Coordination Chemistry Reviews 518 (2024) 216048

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Metal-organic frameworks: A comprehensive review on common

approaches to enhance the energy storage capacity in supercapacitor
Balaji Chettiannan a , Elumalai Dhandapani b , Gowdhaman Arumugam a , Ramesh Rajendran a, * ,
Manickam Selvaraj c, *
a
Department of Physics, Periyar University, Salem, Tamil Nadu 636 011, India
b
Department of Chemistry, J.K.K. Nataraja College of Arts and Science, Komarapalayam, Namakkal, Tamil Nadu 638 183, India
c
Department of Chemistry, Faculty of Science, King Khalid University, PO Box 9004, Abha 61413, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Metal-organic frameworks (MOFs) are a class of crystalline materials formed by the assemblage of inorganic
Metal-organic frameworks metal ions and organic ligands and are known for their porous nature, high surface areas, and tuneable pore
Derivatives sizes. Unfortunately, they are also known for having low conductivity and poor stability making them unde­
Composites
sirable for energy storage applications, especially in batteries and supercapacitors. To combat this issue, several
Morphology
Supercapacitor
strategies are being followed by researchers in the view of improving its conductivity as well as energy storage
properties with a focus on specific capacitance and energy density. In this review, we specifically focussed on
commonly employed approaches which involve integrating MOFs with redox-based metal/linkers and the
combination of MOFs with diverse functional or conductive materials to synthesize composites and utilizing MOF
as templates to generate stable derivatives. Moreover, the focus on the morphology of MOF-based materials and
the factors affecting it are also emphasized. Further, a summary of the challenges and insights associated with
each of these approaches is provided.

1. Introduction to store energy which have been firmly established over time, face
limitations concerning the amount of energy that can be stored per
In an ever-changing and advancing world, the demand for energy volume or mass unit, and lifespan [4–9].
storage solutions that are both efficient and effective has become These difficulties have increased the need for energy storage solu­
increasingly important. As our global society relies more heavily on tions that can smoothly handle the rapid release of power while also
renewable energy sources to fuel our homes, industries, and trans­ storing energy over long periods. This is where supercapacitors emerge
portation systems, the need for adaptable and high-capacity methods of as a promising competitor. Supercapacitors, also called ultracapacitors
storing energy has taken top priority [1–3]. The challenge of bridging or electrochemical capacitors, present a great possibility due to their
the gap between developing renewable energy generation and constant extraordinary capacity for rapidly storing and releasing energy. Unlike
power consumption has driven researchers to pursue innovative solu­ conventional batteries, which rely on chemical reactions to store energy,
tions to meet the energy demand. Supercapacitors have emerged as a supercapacitors work based on principles of electrostatic charge sepa­
new technology offering the potential to revolutionize the field of en­ ration, giving them advantages such as high power density and quick
ergy storage. The global quest for sustainable energy alternatives is charging and discharging. This exceptional resilience not only renders
propelling an unparalleled spread of renewable energy options like solar them a practical choice for immediate energy storage requirements but
panels and wind turbines. While these sources offer eco-friendly solu­ also establishes them as a cost-efficient and lasting investment.
tions, they also present their own distinct set of difficulties. The fluc­ Supercapacitors are currently extensively employed in a variety of
tuation in power generation from renewable sources, reliant on factors sectors, including electric vehicles, portable flexible electronic devices,
such as weather conditions and time of day, emphasizes the critical need airbags, and power backup solutions for mobiles and computers
for efficient energy storage systems. Additionally, traditional techniques [10–13]. In diverse systems, they are integrated to improve cyclic

* Corresponding authors.
E-mail addresses: [email protected] (R. Rajendran), [email protected] (M. Selvaraj).

https://doi.org/10.1016/j.ccr.2024.216048
Received 11 March 2024; Accepted 21 June 2024
Available online 4 July 2024
0010-8545/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

stability, enable flexible packaging, operate over a wide thermal range, our modern world.
reduce weight, and simplify maintenance [14]. Their diverse applica­
tions encompass low-emission hybrid electronic vehicles, fuel cell au­ 2. Classification of supercapacitor
tomobiles, industrial and military sectors, defense applications, medical
fields, flashlights, artificial intelligence, and renewable energy storage Supercapacitors are classified based on their working mechanism as
[15–17]. Often paired with fuel cells or primary batteries, super­ (a) electrochemical double-layer capacitors (EDLC), characterized by
capacitors function as temporary energy storage systems with high electrical charge accumulation at the electrode–electrolyte interface; (b)
power efficiency. This configuration effectively stores energy, demon­ pseudocapacitance (PC), which stems from swift and reversible redox
strating superior energy and power densities when compared to con­ reactions on the surface; and (c) hybrid capacitors, combining features
ventional capacitors and batteries [18,19]. of both EDLC and PC. Fig. 1 displays the distinct categories of super­
Like other emerging technologies, supercapacitor also has scientific capacitors and the specific materials utilized in each category. Table 1
and engineering problems that need innovative approaches. A crucial provides a comprehensive breakdown of the various types of super­
challenge involves improving the energy density of supercapacitors. capacitors based on their energy storage mechanisms.
Researchers are focused on developing new materials and electrode
configurations that can improve the energy density of supercapacitors 2.1. Electric double-layer capacitors (EDLC)
without losing out their power density [20–27].
In this view, metal-organic frameworks (MOFs) emerge as a group of Electric Double Layer Capacitors (EDLCs) boast a more extended
compounds that have attracted significant attention owing to their lifespan of cyclic durability when compared to their rechargeable or
exceptional properties including their adjustable nature, porosity, and lithium-ion counterparts. These devices harness charge distribution
expansive surface area. With the combination of organic ligands and within the double layer interface found at the junction of electrode and
metal ions, MOFs are elaborate networks comprising interconnected electrolyte, where static charges are only a few Angstroms apart.
pores and channels. The appeal of MOFs lies in their inherent ability to Essentially, EDLCs act as supercapacitors that engage in electrostatic
be adjusted, allowing researchers to control their structural character­ charge storage mechanisms. Unlike batteries which can experience
istics finely. This adaptability stems from the wide range of metal ions swelling during their charge/discharge cycles due to electrode expan­
and organic ligands that can be intricately combined to form MOF sion, EDLCs are engineered to avoid such swelling since no Faradaic
frameworks with customized properties. This remarkable versatility reactions occur on their electrodes. Different mediums like aqueous and
enables MOFs to showcase exceptional capabilities for diverse uses, organic electrolytes are viable for ensuring ionic movement across the
including gas storage, separation, catalysis, energy storage and drug electrodes [35]. However, organic electrolytes are preferred within
delivery. Consequently, these frameworks have showcased their excel­ EDLCs because they can store greater amounts of charge through ion
lence in revolutionary material design and demonstrate transformative adsorption granted by their broad voltage window ranging from 2 to 3 V.
prospects in scientific exploration. MOFs introduce an intriguing avenue The formula for determining energy density is,
for tackling the inherent drawbacks associated with electrode materials
utilized in supercapacitors. Their adaptability in structure and potential 1 2
E= CV (1)
for modification provide opportunities for overcoming these challenges. 2
Furthermore, their derivatives including metal oxides, metal sulphides, Equation (1) explains that energy density (E), held by the electrode
metal phosphides, etc. have high surface area and pore distribution, material in a supercapacitor is directly associated with both its capaci­
which is a critical factor for achieving electrochemical performance. tance (C) and the square of its operating voltage (V) [36].
Additionally, the customized design of MOFs allows for the creation of For optimized electrochemical operations in electric double layer
hierarchical structures that facilitate rapid diffusion of ions, thereby supercapacitors, it is crucial to select materials for electrodes that
accelerating both charging and discharging processes [28–34]. feature not only high surface areas but also well-linked mesopores.
Initially, it was thought that pristine MOFs lacked the ability to Porosity alongside surface characteristics must be carefully considered
conduct electrons effectively, making them unsuitable for use in elec­ when selecting materials like activated carbon (AC), carbon nanotubes
trochemical applications. However, significant advancements have been (CNT), and graphene for enhancing the performance capabilities of
achieved in utilizing different successful MOFs, as well as their de­ these supercapacitors [37–39]. Fig. 2 illustrates the electrostatic charge
rivatives and composite materials, in creating electrodes for recharge­ storage mechanism when activated carbon is used as positive and
able batteries, electrochemical sensors, and especially supercapacitors. negative electrodes.
Strategically designing and synthesizing MOFs and their derivatives Activated carbon (AC) is known for its extensive surface area and
with tailored electrochemical properties has become incredibly impor­ cost-effectiveness [40,41]. It exhibits a wide array of pore sizes from 1 to
tant. This is due to the fact that MOFs can be customized at the molec­ 20 nm [42]. Pores ranging from 0 to 1 nm in size can also be acquired
ular level because of their adjustable chemical compositions. Despite the and are commonly referred to as sub-nanometers or ultramicropores.
challenges involved in predicting and controlling the overall topological Several research findings suggest reports on the enhancement of
structures of these frameworks, the incorporation of redox-active metal capacitance based on the pore size. A study by Chmiola et al. [43]
centers, electron-donating/accepting ligands, and specially designed illustrated that pores with average dimensions ranging from 0.6 to 2.25
building blocks into MOFs has allowed them to transform into functional nm, resembling micropores, exhibited superior electrochemical perfor­
materials and they can be derived into oxides, sulfides, etc. suitable for mance compared to larger pore sizes. Similarly, several research works
electrochemical applications. [44,45] indicate that a highly developed carbon structure containing
This review article has multiple objectives, with the aim of covering ultramicro pores (<1 nm) facilitates the smooth transfer and optimal
recent progress and offering a comprehensive review of the common accessibility of electrolyte ions. This phenomenon maximizes the elec­
strategies followed by researchers in designing electrode materials based trochemical performance of the material. This occurs because the size of
on Metal-Organic Frameworks (MOFs) for their application in super­ bare ions typically falls below 1 nm, and the selective adsorption of ions
capacitors. It delves into the strategy of utilizing redox active metal/ with a specific size is only feasible when the pore size matches that of the
linkers, making composites and derivatives of MOF. This review also ions. However, mesopores greater than 2 nm and macropores greater
highlights how morphology of these MOF-based materials influence the than 50 nm impede optimal electrolyte infiltration and result in elec­
electrochemical performance. With right modifications, MOF-based trochemical performance compared to micropores [46]. It can be
materials have the power to redefine the landscape of high- concluded that the micropore features with less than 1 nm pore size offer
performance energy storage systems that align with the demands of better performance in the case of an electrochemical double-layer

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 1. Types of supercapacitors and their corresponding electrode materials.

capacitor (EDLC). mechanism, their structural aspects, and device design [55–57].
The illustration of the electrochemical charge storage mechanism in
the Pseudocapacitor is displayed in Fig. 3.
2.2. Pseudocapacitor (PC) The capacitance levels for pseudocapacitors are maintained consis­
tently across their potential range. The process involves surface-
Pseudocapacitors are type of energy storage device that uses fast and controlled redox reactions. The amount of charge (Q) storable is line­
reversible surface redox reactions or near-surface redox reactions with arly related to voltage (V), shown by Eq. (2):
electrosorption/electrosorption to store electric energy, resulting in
capacitive behavior [47]. These devices combine the physical separation Q = CV (2)
of charges found in capacitors with the chemical reactions of batteries, When observing how charge (Q) changes over time (t), we represent
resulting in higher energy and power density than either capacitors or current (I) using Eq. (3):
batteries alone. The storage of charge is largely due to surface faradic ( )
processes where there’s a transfer of ions between the electrode’s sur­ dQ dV
I= =C (3)
face and electrolytes. However, a battery’s charge storage mechanism dt dt
relies solely on intercalation/deintercalation or diffusive faradic re­
Herein, C stands for specific capacitance, which is measured in F g− 1
actions between the electrode and the electrolyte ions which are often
or F cm− 2.
slow, resulting in longer charging and discharging times [48]. Metal
Pseudocapacitor functionality finds its place on a spectrum lying
oxides, nitrides, sulfides, tellurides, and selenides are commonly
between batteries and electrochemical double-layer capacitors (EDLCs).
referred to as battery-type materials, rather than pseudocapacitive ma­
They offer higher capacitance but generally have a lower power density
terials. However, these materials can also be used as pseudocapacitive
when compared to EDLCs. Processes like under-potential deposition
materials due to their dual functionality [49–51].
(which includes processes like lead being deposited onto gold) represent
For instance, NiO is commonly known as a battery-type material [52]
key aspects of redox-based surface charge transfers [58]. Coupled with
due to its ability to store charge through redox reactions involving the
high power densities and desirable capacitance values reported in lit­
exchange of electrons. Here, the charge storage involves bulk phase
erary sources these materials promise longevity in cycle life while
changes. However, under certain conditions, NiO can also display
maintaining low current density [59].
pseudocapacitive behavior [53,54], particularly when it is in a nano­
structured form or when surface reactions dominate charge storage. In
such cases, charge storage occurs through fast surface reactions rather 2.3. Hybrid supercapacitor (HSC)
than bulk phase changes, resembling the behavior of pseudocapacitors.
Thus, the charge storage mechanism, experimental parameters, The hybrid supercapacitor (HSCs) emerges as an important category
electrode fabrication, electrolytes, and their structures play a crucial in the type of supercapacitor, representing a blend of Electric Double-
role in determining whether the material behaves as a pseudocapacitor Layer Capacitor (EDLC) and pseudocapacitive materials. The promi­
or a battery. Therefore, similar electrode materials are used in both nent EDLC electrode materials include activated carbon (AC), carbon
pseudocapacitors and batteries, the difference is in the charge storage nanotubes (CNT), and graphene, while pseudocapacitive materials

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Table 1
Classification of supercapacitors, their electrode materials and the mechanism
involved in charge storage.
Type of Electrode Charge Merits/
supercapacitor material storage shortcomings
based on charge mechanism
storage
mechanism

Electric double Carbon Electrostatic Good rate

layer capacitor attraction/ capability,
(EDLC) non-Faradaic outstanding
method cyclability, low
capacitance, and
energy density

Pseudocapacitor Redox materials Surface High specific

(metal-oxide/ Faradaic capacitance,
tungstate/ process outstanding
carbide/ sulfide/ (Redox energy/power
etc. or conducting reaction) density, low-rate
polymers) capability

Hybrid Capacitor
(Further classified below based on configuration)
• Asymmetric Terminal 1 Redox reaction High energy
hybrid (Anode/Cathode): density, and power
Redox materials density with
outstanding Fig. 3. Illustration of Pseudocapacitive charge storage.
cyclability
Terminal 2 EDL
(Cathode/Anode): include conducting polymers and metal oxides [60]. The illustration of a
Carbonaceous hybrid capacitor with AC as the negative electrode and MnO2 as the
materials positive electrode is depicted in Fig. 4. Designing a hybrid super­
• Symmetric Redox materials Redox reaction
capacitor involves utilizing a conducting polymer or a metal oxide or a
composite hybrid with carbonaceous plus EDL
materials at both Psuedo-type electrode material in one of the electrodes and EDLC-type
anode and cathode material in the other terminal, with the aim of achieving equilibrium
Anode: Anode: High energy in charge/discharge kinetics.
Li-insertion Lithiation/ density, low cost, As shown in Table 1 [61,62], further categorization of hybrid
material delithiation relatively low
supercapacitors is based on electrode materials: asymmetric hybrids,
cyclability
• Battery-like Cathode: Cathode: EDL High energy battery-type hybrids, and composite hybrids (e.g., Fe3O4/graphene,
hybrid Carbonaceous density, more rGO-f/PANI) [63–65]. Generally, an asymmetric supercapacitor refers
materials expensive to a supercapacitor setup consisting of two different types of electrodes
[66]. Hybrid specifically refers to combining EDLC and Pseudo property
in a single system [67]. In a typical asymmetric hybrid supercapacitor,
usually, the cathode facilitates charge storage through surface

Fig. 2. Illustration of charge storage in EDLC.

Fig. 4. Illustration of hybrid supercapacitor.

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adsorption/desorption, termed the non-faradic process, while the anode of light emission effects. Over recent years, two-dimensional conductive
stores charge through intercalation, known as the faradic process. This MOFs (2D cMOFs) have gained attention as a significant subset of
doesn’t mean that the anode always uses an electrode with faradaic crystalline materials, distinguished by their adjustable porosity and
charge storage process and the cathode utilizes a non-faradic process. elevated electrical conductivity, offering notable advantages in energy-
Since most metal-based electrodes undergo oxidation and reduction related fields. This is attributed to the presence of layered two-
(redox reactions) in positive potential, which is why they are often used dimensional frameworks constructed from flat, fully conjugated li­
in the positive terminal [68]. On the other hand, carbon-based mate­ gands with trigonal geometries, representing a prominent category
rials, which provide a high surface area for efficient ion diffusion and within conductive MOFs [77]. Additionally, Metal-Organic Frameworks
contribute towards higher specific capacitance, are commonly used as (MOFs) incorporating pyrazolate, triazolate, and tetrazolate linkers
negative materials. This arrangement helps to maximize the perfor­ typically display electronic coupling between the metals and the linkers
mance of the supercapacitor [69–72]. Battery-type electrodes exhibit owing to the robust σ-donating and π-accepting properties of azolates.
faradaic charge storage, with specific capacity values fluctuating within Within such frameworks, a prevalent feature involves one-dimensional
the voltage window and typically expressed in C g− 1 or mAh g− 1. chain Secondary Building Units (SBUs) with azolates serving as
Significantly, hybrid supercapacitors amalgamate both faradic and non- bridging components [78]. The short bridging distances of azolates,
faradic processes, overcoming the limitations of EDLC and pseudoca­ combined with their covalent bonding to the metal, account for the
pacitors, offering advantages such as cost-effectiveness, superior per­ favorable conductivities observed in these arrangements.
formance across a broad temperature range, high energy and power One of the earliest mentions of electronically conductive MOFs dates
density, mechanical resilience, cyclic stability, and low resistance. back to 2009 in a report by Kitagawa and colleagues. However, reports
Notably, hybrid supercapacitors find widespread applications in vehic­ on proton conductive MOFs can be traced back to as early as 1979,
ular systems as efficient power sources [73]. Table 2 presents a com­ although the proton conduction mechanism remained unclear due to the
parison of the benefits and drawbacks linked to these three types of lack of crystallinity in MOFs. From 2009 onwards, research groups led
supercapacitors. by Kitagawa and Shimizu delved into proton conduction in crystalline
MOFs. Over the following decade, significant progress was made in
3. Metal-organic frameworks for supercapacitors understanding MOF proton conductors, with studies revealing mecha­
nisms such as the Grotthuss mechanism and the vehicular mechanism,
Metal-organic frameworks (MOFs) which started gaining attention in leading to ultrahigh suprotonic conductivity exceeding 10− 2 S⋅cm− 1
the late 1990 s through the direction of Professor Omar Yaghi, have [79]. In recent years, discussions surrounding MOFs exhibiting excep­
become an area of research that is expanding rapidly. MOFs are intricate tional electrical conductivity have emerged. For example, Ni3(HITP)2
formations that arise from the self-assembly of organic ligands bound to has proven effective as an electrode in Li–S batteries [80], and Cu–BHT
metal ions or clusters, exhibiting complex structures with multiple (butylated hydroxytoluene) MOF has served as an anode in Lithium-ion
binding points. These frameworks possess remarkable characteristics batteries (LIBs) [81]. Notably, the conductive MOF with mixed valency
such as a high surface area, adjustable pores, accessible sites for metal Cu [Cu(pdt)2] has shown conductivity reaching 6 × 10− 4 S⋅cm− 1 at 300
interaction, and modifiable crystal arrangements. Their practical ap­ K [82]. In addition, a series of isoreticular catecholate-based MOFs
plications include a wide range of fields including but not limited to employing hexahydroxytriphenylene (HHTP) as the organic linker,
sensing, catalysis, ion exchange processes, adsorption phenomena, along with various metal nodes (Ni/Cu/Co), have also shown enhanced
separation operations, as well as gas and energy storage [74,75]. conductivity [83].
Moreover, Metal-organic frameworks (MOFs) with conductive Additionally, several conductive MOFs have also shown great po­
properties constitute a distinctive category called conductive MOFs tential specifically in the application of supercapacitors due to their
(cMOFs), which exhibit inherent conductivity and hold considerable unique properties. For example, Ni3(HITP)2 evolved as one of the
potential across diverse technological domains, notably in super­ advanced conductive MOFs with high potential for supercapacitor
capacitors (SCs). The conductivity observed in these MOFs primarily application. It is reported to demonstrate a high surface area and high
stems from pathways that facilitate the transport of ions or electrons electric double-layer capacitance with good stability. Its high electrical
between the framework’s structure and inorganic species. Their utility conductivity eliminates the need for additional conductive additives,
extends to various fields including energy conversion and storage, ensuring efficient charge transport. The material’s volumetric capaci­
electrochemical capture, batteries, sensing, and catalysis [76]. Inter­ tance is competitive with top EDLC materials, and its structure can be
estingly, when subjected to laser irradiation, some conductive MOFs tailored for enhanced performance. Ni3(HITP)2 has also been reported to
even demonstrate changes in electrical conductivity and the emergence maintain its chemical integrity under cycling [84]. Another group of
classical conductive MOFs, HAB MOFs (Ni(HAB) and Co(HAB)), have
shown promising performance in supercapacitors. The Ni-HAB MOF, in
Table 2 particular, exhibits good gravimetric and volumetric capacitance, as
Merits and Demerits associated with these three categories of supercapacitors. well as impressive cycling stability. The Co(HAB) MOF shares similar
Category Merits Demerits advantageous properties due to the strong interaction between the HAB
EDLCs Low cost Low specific capacitance and ligand and metal centers. Unlike many other conductive MOFs, these
Environment-friendly energy density materials exhibit stable redox behavior and are compatible with
Long stand cyclability aqueous electrolytes [85]. Several other conductive MOFs, like the
Rapid charge/dischargeHigh
phthalocyanine-based 2D c-MOF (Ni2[CuPc(NH)8]), exhibit intrinsic
power density
conductivity combined with porosity and high crystallinity. Their good
chemical stability makes them particularly suitable for use in flexible
PCs High energy density Poor cyclability
supercapacitors [86], and also, a conjugated copper(II) catecholate-
High flexibilityHigh specific Low power densityToxic
capacitance (RuO4, V2O5 CuO)High cost based metal-organic framework (Cu-DBC), with redox-active ligand,
exhibits high electrical conductivity at room temperature. Research
HSCs Higher operating voltage –
findings have shown that Cu-DBC, incorporating both the ligand and
High cyclability copper centers, possesses remarkable electrical conductivity, redox
High energy/power density reversibility, and improved performance as a supercapacitor [87].
High specific capacitanceLow self- Nonetheless, majority of the MOFs might not completely satisfy the
discharge
particular criteria of applications like supercapacitors, which necessitate

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not only conductivity but also superior electrochemical performance. As alongside the previously mentioned strategies as the arrangement and
a result, diverse strategies have been implemented to improve both the morphology play a pivotal role in shaping the conductive characteristics
conductive and electrochemical characteristics of MOFs [88]. It’s worth and charge storage mechanisms. It involves the precise regulation of
noting that the properties of these MOFs can be finely adjusted by influential factors like metal ions, organic linkers, and their ratios,
changing the metal ions and organic linkers employed in their synthesis. coupled with chemical modifications of MOFs. The control over
While investigations on exploiting MOFs for efficient energy storage morphology can markedly enhance the electrochemical performance.
and conversion are still in their early stages, the majority of attention The schematic diagram of four common strategies to enhance the
has been directed toward repurposing materials derived from MOFs electrochemical performance of MOF in the field of supercapacitors is
such as metal oxides, carbonaceous porous substances, or nanomaterials shown in Fig. 5.
combining both carbon and metals. The pivotal challenge emerges when
attempting to utilize pure MOFs directly as electrode materials due to 4. Redox approach
their inherent limitations concerning electronic conductivity and poor
electrochemical performance [79]. Redox processes related to the loss and gain of electrons are common
Researchers have utilized multiple approaches to enhance the in nature, and have been employed in different electroactive materials
properties of MOFs to be suitable for energy storage applications. Below for energy, technological and industrial applications. Traditionally,
are the four common strategies that have been used by researchers for MOFs are formed by redox-inactive closed-shell metal centres (e.g. d10
enhancing the performance of MOF and making it suitable for electro­ Zn(II) and d0 Zr(IV) ions) with inaccessible redox couples and organic
chemical charge storage applications [89]. linkers (e.g. carboxylates) that hinder electron transfer between the
(i) Redox approach: Incorporating metal centers or linkers with inorganic nodes. Consequently, the vast majority of MOF materials re­
redox capabilities into the MOF structure is one strategy. These metals ported up to the last decade are insulators (i.e. wide bandgap). Pro­
have the ability to undergo reversible redox reactions, thereby moting redox activity in MOFs can be achieved by rational design of
improving overall material conductivity and performance. both the metal-based nodes and/or the ligands that build up the multi­
(ii) Composite fabrication: Creating composites by integrating dimensional framework [90].
conductive substances like metal oxides, carbon materials, LDH sheets, Utilizing the redox strategy proves highly effective in increasing the
or conductive additives into the MOF structure is another option. These super capacitive performance by enhancing MOF conductivity. There
additional substances establish pathways for electron transfer, resulting are a number of strategies to realize redox activity in MOFs. By
in elevated composite conductivity. embedding redox-active metal centers or organic linkers with inherent
(iii) MOF as templates for Derivatives: The derivatives of MOF reactivity into the MOF matrix (as shown in Fig. 6(a, b)), these materials
demonstrate enhanced durability against environmental factors, chem­ gain the capacity for reversible redox reactions. This process facilitates
ical decomposition, and physical stress. This ground-breaking strategy the exchange of electrons amongst the redox-active components within
has been widely used in recent decades by researchers to design high- the MOF, invariably leading to heightened conductivity. The integration
performance as well as stable electrodes for supercapacitors. of redox-active metal centers introduces supplementary pathways for
(iv) Precise control of MOF structures: This strategy is used metal ions to readily partake in oxidation and reduction processes by

Fig. 5. Four common strategies to enhance the electrochemical properties of MOF.

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Through Bond:
Through-bond approach aims to promote charge transport via
favorable spatial and energetic overlap of the metal and ligand orbitals
in covalent bonding. The archetypal example of this kind is HKUST-1
MOF, where the electron-deficient TCNQ (=7,7,8,8-tetracyanoquinodi­
methane) guest interacts coordinatively with vicinal open-site Cu metal
nodes to pave a through-bond charge transport pathway [95]. Only
recently, the efficient π-conjugation demonstrated in two-dimensional
graphene-like MOFs such as Ni3(HITP)2 and Ni3(BHT)2 supports elec­
tron delocalization in planar sheets. This is translated into an effective
overlap between the metal and ligand frontier orbitals, which results in a
high conductivity [96,97].
Through Space:
Through-space approaches enable charge transport via non-covalent
interactions (such as – stacking) between electroactive fragments that
are held in place by π-π metal–ligand in the MOF, thus compensating the
lack of chemical bonding connection between electroactive building
blocks by their close proximity [98,99]. For example, through-space
interactions have been reported to be observed between the electron
Fig. 6. Illustration of inclusion of redox-active inorganic metal (a) and redox donor (TTFTC) and acceptor (DPNI) ligands in Zn(DMF))2(TTFTC)
active organic linker (b) in MOF. (DPNI) MOF, where partial charge separation is via ligand-based radi­
cals formation. When the donor and acceptor moieties are the same
expediting charge movement within the MOF. Analogously, the infusion entity but only differ in their oxidation state (mixed-valency), a charge
of organic linkers with innate reactivity within the MOF structure can transfer from one moiety to the other can occur, so-called intervalence
also improve redox activity and conductivity. These organic linkers charge transfer (IVCT). Several mixed valence MOFs have been syn­
undergo cyclic redox reactions thereby improving the electron flow thesized to date, and D’Alessandro et al. recently reported the first ev­
within the MOF framework. For example, redox-inactive Zr-based nodes idence of an IVCT process occurring via a through-space mechanism in a
can be replaced by electroactive secondary building units (SBUs) con­ three-dimensional network [100,101].
taining transition metals with partial d-shell occupation, such as Co(II/
III), Cu(I/II), Ni(II/III), etc. Otherwise, redox-inactive carboxylate li­ 4.1. Incorporating redox-active metal centers in MOFs
gands can be substituted by a large variety of π-conjugated ligands that
can promote redox-activity. For instance, the electron-rich TTF unit is Transition metals like nickel (Ni), iron (Fe), manganese (Mn), chro­
one of the most successfully exploited units in building up frameworks mium (Cr), copper (Cu), and cobalt (Co) have different oxidation states,
with new functionalities that extend across interesting donor–acceptor making them useful for synthesizing Metal-Organic Frameworks (MOFs)
charge-transfer phenomena, band-gap modulation, mixed-valency, and with strong electrochemical properties. These MOFs show great poten­
tuneable conductivity [91–94]. tial for replacing expensive precious metals in certain electrochemical
Typically, charges are transferred through two mechanisms, namely: reactions. By including unsaturated open metal sites within MOFs, their
(i) through bond, as shown in Fig. 7(a), and (ii) through space, as shown reactivity can be further improved as these sites act as chemical inter­
in Fig. 7(b). action centres. For instance, C. Yang et al., have successfully created a

Fig. 7. Illustration of through bond(a) and through space (b) mechanisms.

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

new layered Nickel Metal-Organic Framework (Ni-MOF), and tested it as pseudocapacitance reaching 726 F g− 1 at 1 A g− 1, and maintained good
the electrode in three electrode configuration and in a flexible all-solid- stability with a capacity retention of 94.6 % after 1000 cycles. After
state asymmetric supercapacitor. Due to the incorporation of nickel 5000 cycles, the capacitance decreased by 65 % which is mainly
metal as the inorganic metal centre, the three electrode system showed a attributed to repeated insertion and removal of OH− causing structural
excellent capacitance of 1518.8 F g− 1 at 1 A g− 1. One of the important damage and hindering electrolyte interaction with the electrode [105].
factors that causing this enhanced capacitance is the redox activity of In another literature, Ni-MOF was synthesized using a simple hydro­
nickel metal with multiple oxidation states. The cyclic voltammetry (CV) thermal method with a mixed solution of DMF and water. S. Gao et al.,
curves shown in Fig. 8(a) display redox peaks between 0 and 0.5 V, reported that the as-prepared Ni-MOF has a cuboid structure with
indicating pseudocapacitive behavior. These peaks are mainly due to abundant mesopores, beneficial for charge transfer and ion transport. In
pseudocapacitance resulting from the faradic redox reactions of OH– a three-electrode system, Ni-MOF as a working electrode exhibited
intercalation and deintercalation during electrochemical reactions noticeable redox peaks and displayed a specific capacitance of 804 Fg− 1
[102]. at 1 Ag− 1, excellent rate capacitance of 534 Fg− 1 at 10 Ag− 1, and retains
Several researchers utilized this strategy by using Ni-MOF directly as 302 Fg− 1 after 5000 cycles in a 2 M KOH electrolyte. The assembled Ni-
an electrode material. Y. Yan et al., synthesized a unique accordion-like MOF//AC asymmetrical supercapacitor showed a high specific energy
Ni-MOF ([Ni3(OH)2(C8H4O4)2(H2O)4]⋅2H2O) and used it as an electrode (31.5 Wh kg− 1) at 800 W kg− 1 [106].
in supercapacitor. This supercapacitor, featuring the Ni based MOF Moreover, cobalt and manganese are also classified as transition
electrode, demonstrated redox activity which can be confirmed by the metals like nickel and have also been reported to exhibit excellent redox
peaks in the CV curves in Fig. 8(b). This accordion-like redox-active Ni- activity. When utilized as metal centers in MOFs, their incorporation
MOF electrode showed specific capacitances of 988 and 823 F g− 1 at enhances electrochemical performance, owing to their intriguing redox
current densities of 1.4 A g− 1 and 7 A g− 1, respectively, while main­ properties. Zhu et al., presents a hierarchically structured Co-MOF on
taining excellent stability (96.5 % capacitance retention after 5000 cy­ nickel foam (Co-MOF/NF) as a high-performance supercapacitor elec­
cles at 1.4 A g− 1). However, it had limited conductivity due to its highly trode. It achieve an impressive specific capacitance of 13.6F cm− 2 at 2
porous structure [103]. Kang et al. synthesized Ni-MOF using the same mA cm− 2 surpassing previous MOF-based materials. It exhibits excellent
nickel source but a different linker. Ni2(BTC)3 was synthesized using a rate performance at a 79.4 % current density of 20 mA cm− 2. In an
reaction with nickel chloride and pyromellitic acid. The supercapacitor asymmetric supercapacitor, combining Co-MOF/NF as the positive
with this Ni-MOF exhibited redox activity with visible redox peaks as electrode and activated carbon (AC) as the negative electrode, a high
shown in CV curves in Fig. 8(c) and demonstrated excellent energy density of 1.7 mW h cm− 2 at 4.0 mW cm− 2 power density is

Fig. 8. (a) CV curves of Ni-MOF at different scan rates (Reproduced from Ref. [102] with permission from The Royal Society of Chemistry), (b) CV curves of
accordion-like Ni-MOF at different scan rates (Reproduced from Ref. [103] with permission from The Royal Society of Chemistry), (c) CV curves of Ni-MOF with BTC
linker at different scan rates, (Reproduced from Ref. [79] with permission)(d) CV curves of Mn-MOF at different scan rates (Reproduced from Ref. [104] with
permission from The Royal Society of Chemistry).

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

achieved, with 69.7 % capacitance retention after 2000 cycles. This providing the necessary porosity, and chemical and structural stability.
performance is due to the fact that Co-MOF/NF electrode demonstrates Notably, the NDI-core within Zr-NDI-scu-MOF undergoes a reversible
pseudocapacitance behavior, which attributed to redox reactions of redox process, as illustrated in CV studies in Fig. 9(a) (in RED color) with
cobalt metal ions at the electrode–electrolyte interface [107]. Similarly, visible redox peaks, highlighting its potential for maintaining stable
Wang et al. introduced a new layered Mn(II)-based MOF as an electrode supercapacitor performance [111]. In a recent work, Iqbal et al. pre­
material for supercapacitors. The Mn-MOF electrode displayed a good sented a novel Co–B–H-MOF designed with two distinct organic ligands,
electrochemical performances which indicates reversible Mn(II/III) namely pyridine-3,5-dicarboxylic acid and 1,2,4,5-benzene-tetra-car­
processes during oxidation/reduction, and CV curves (in Fig. 8(d)) boxylic acid.
showed pseudocapacitive behavior. In the reported literatures, transi­ 1,2,4,5-Benzene-tetracarboxylic acid, commonly known as BTC or
tion metals are commonly employed as redox-active metal centers due to pyromellitic acid, holds significant importance due to its inherent flex­
their inherent redox properties [104]. Despite this, pristine Metal- ibility. The versatility of BTC arises from its four carboxylic groups,
Organic Frameworks (MOFs), even with redox-active metal centers, allowing for various coordination modes through partial or complete
exhibit poor stability. The observed specific capacitance values cannot deprotonation. BTC exhibits the capability to both accept and donate
be solely attributed to the redox activity of metal centers, but other electrons, forming hydrogen bonds. Transition metal ions can attach to
factors, such as morphology, also play a significant role. Researchers different positions along the aromatic chain, as the carboxylic ends are
must consider these factors, as repeated cycling can lead to structural not situated in the same plane. Notably, BTC contributes to the stabili­
damage arising from redox reactions at the electrode. zation of crystal structures through aromatic rings, facilitated by
π-stacking interactions. This stability of the BTC ligand plays a crucial
4.2. Utilizing redox active ligands in MOFs role in the design of high-dimensional frameworks [113]. Another
organic linker is pyridine-3,5-dicarboxylic acid (H2pdc). H2pdc can
Another strategy, although less commonly used by researchers, is the bond with metal centers through two distinct modes, involving M–O and
utilization of redox-active ligands in Metal-Organic Frameworks M–N bonds. Additionally, the formation of mixed-valent metal com­
(MOFs). The addition of redox active ligand or multivalent metal-node pounds using pyridyl carboxylates proves effective in creating MOFs
gives the MOFs redox activity. Nevertheless, oxidation and reduction with redox properties.
can fail during redox cycling and modify the nature of the coordination The synthesis of this innovative bi-linker Co-MOF involving a soni­
of the ligands into metal centers, or alternatively, the presence of close cation route and the presence of bi-linker actively enhanced the redox
redox-active units may lead to an increase in the Coulomb repulsion that activity of MOF. To conform the activity, the electrochemical properties
would disrupt the MOF structure [108]. The redox-active units, such as of Co–B–H-MOF were systematically examined using a three-electrode
benzoquinone or dithiolenes [109], may lead to production of active assembly, using cyclic voltammetry (CV). The CV results revealed
sites with high reducibility, facilitating charge dispersion, improvement Co–B–H-MOF as a battery-type electrode, demonstrating redox peaks as
in conductivity, and higher stability of the material under given condi­ shown in Fig. 9(b). The MOF also displayed an excellent specific ca­
tions. Similarly, localized charge on some ligand like naphthalene- pacity of 172 C g− 1 at 3 m V s− 1 [112].
diamide or salicylaldehyde-ethylenediamine to produce frameworks So far, research has underscored the effectiveness of using linkers to
that are redox tolerant. Post-synthetic methods can also be utilized in enhance redox activity, improving the performance of supercapacitors.
attaining redox activity by including redox-active guests or ligands However, the incorporation of redox-active linkers is a complex process
within redox-inactive frameworks [110]. that requires careful attention during synthesis. In many cases, the sta­
In the recent study by Mallick et al., a Zr-based MOF featuring a bility of metal-organic frameworks (MOFs) is often compromised,
redox-active core tailored to enhance the electrochemical performance posing a risk of structural damage during charging and discharging cy­
by influencing both double-layer and pseudocapacitance. This is ach­ cles. Even at relatively low temperatures, the organic nature of most
ieved through the integration of the redox core and the utilization of linkers makes them prone to disintegration, negatively affecting redox
organic pillars for structural reinforcement via post-synthetic structure activity and, consequently, electrochemical performance. This raises
rigidification. This leads to a twofold increase in capacitance. The syn­ questions about their suitability for commercial supercapacitors.
thesis of MOF involves using the N, N0-bis(terphenyl-4,400-di-carbox­
ylic acid) naphthalenediimide (H4BTD-NDI) linker with a redox-active 4.3. Insights on redox approach
center known for two-electron redox processes, resulting in the Zr-
NDI-scu-MOF. To ensure prolonged cycle life for supercapacitor per­ The mentioned reports outline the use of redox-active metal ions and
formance, the [Zr6O8(H2O)8]8+ cluster is chosen as a metal node, redox-active linkers in Metal-Organic Frameworks (MOFs) for

Fig. 9. (a) CV curves of Zr-NDI-scu-MOF (red) and Zr-NDI-BPy-sco-MOF (black) at 50 m V s− 1 (Reproduced from Ref. [111] with permission from The Royal Society
of Chemistry) (b) CV curves Co–B–H-MOF at various scan rates (Reproduced from Ref. [112] with permission from Elsevier).

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

applications in supercapacitors. conductivity, and material stability. The reported literature high­
lights the potential challenges associated with redox-active ligands,
• Researchers have explored the incorporation of transition metals like such as the modification of ligand coordination during redox cycling
nickel, cobalt, and manganese into MOFs to leverage their different or the disruption of MOF structures due to Coulomb repulsion.
oxidation states and enhance electrochemical properties. Specif­ Nonetheless, examples like Co–B–H-MOF showcase successful
ically, nickel-based MOFs, such as the layered Ni-MOF and implementations of redox-active ligands, demonstrating improved
accordion-like Ni-MOF, have shown promising outcomes as super­ electrochemical performance and stable supercapacitor behavior.
capacitor electrodes, demonstrating excellent capacitance and sta­
bility. Cobalt and manganese have also been utilized as metal In brief, the use of redox-active metal ions and redox-active linkers in
centers, contributing to high specific capacitance and pseudocapa­ MOFs for supercapacitor applications holds significant promise. Several
citance behavior in MOFs, as seen in the Co-MOF/NF and Mn(II)- successful instances where incorporating transition metals and redox-
based MOF examples. However, it is highlighted that despite the active ligands has led to enhanced pseudocapacitance behavior and
redox activity of metal centers, factors like morphology also play a stable cycling performance. Table 3 compiles recent electrode materials
crucial role in determining the performance and stability of pristine based on Metal-Organic Frameworks (MOFs), employing strategies
MOFs. involving either redox-active metals/ redox-active ligands, along with
• Another strategy discussed involves the use of redox-active ligands in their electrochemical performance. While many research studies have
MOFs, though less commonly explored. This approach introduces adopted this redox approach, several significant challenges have also
redox activity by incorporating ligands with redox-active units, such been highlighted in various literature sources. For example, the poor
as benzoquinone or dithiolenes, enhancing charge dispersion, structural stability of MOFs, especially under high charge and discharge

Table 3
Recent MOF-based electrode materials with redox active metal/linker and their performance in supercapacitor.
Name of the MOF Inorganic Metal Organic Linker Specific Power Energy Retention Reference
Material capacitance density density capability
2
Ni3(HITP)2 Nickel 2, 3, 6, 7, 10, 11-hexaiminotriphenylene (HITP) 18 μF cm− – – 90 % after 10,000 [84]
c-MOF cycles
− 1
Ni-HAB Nickel hexaaminobenzene 420 F g at – – 90 % after 12,000 [115]
c-MOF 1 m V s− 1 cycles
2
2D (Ni2[CuPc Nickel, Cobalt Phthalocyanine 18.9 mF cm− 16 mW 1.7 μWh 91.4 % after 5000 [86]
(NH)8]) c-MOF cm− 2 cm− 2 cycles
Cu-DBC Copper dibenzo-[g,p]chrysene-2,3,6,7,10,11,14,15- 479 F g− 1 at 0.2 A 0.1 kW 13.8 Wh 80 % after 2000 [87]
c-MOF octao g− 1 kg− 1 kg− 1 cycles
Cu3(HHTP)2 Copper 2,3,6,7,10,11-hexahydroxytriphenylene 135 C g− 1 2100 W 32 Wh 99 % after 1000 [116]
c-MOF kg− 1 kg− 1 cycles
Ni-MOF Nickel Terephthalic acid (TPA) with monocarboxylic 2.38C cm− 2 at 1 2550 W 50.1 Wh 95 % after 1000 [117]
benzoic acid (BA) mA cm− 2 kg− 1 kg− 1 cycles
Ni-MOF Nickel Terephthalic acid (TPA) 1276 F g− 1 at 0.5 407.4 W 30.4 Wh 92.1 % after [118]
A g− 1 kg− 1 kg− 1 20,000 cycles
Co-MOF Cobalt Pyridine-3,5-dicarboxylic acid and 1,2,4,5-ben­ 177.3 C g− 1 at 0.3 4250 W kg 42.5 Wh 95 % after 10,000 [112]
zene-tetra-carboxylic acid A g− 1 − 1
kg− 1 cycles
Ni/Co-MOF Nickel and Trimesic acid 828 C g− 1 at 1 A – – – [119]
Cobalt g− 1
Cu-MOF Copper 451 C g− 1 at 3 m V 510 W kg− 1
41 Wh g− 1
92 % after 5000 [120]
s− 1 cycles
Cu-MOF Copper Isonicotinic acid 781.87 F g− 1 at 1105 W 48.50 Wh 93.4 % after [121]
0.6 A g− 1 kg− 1 kg− 1 10,000 cycles
Cu@Fe-MOF Copper and 2-amino terephthalic acid 420.54 F g− 1 at 3 2.743 kW 44.20 Wh 88 % after 5000 [122]
Iron A g− 1 kg− 1 kg− 1 cycles
Cu-MOF Copper 4-aminopyridine (4-APy) and 1,3,5-benzenetri­ 547 F g− 1 at 2 m V – – – [123]
carboxylic acid (H3BTC) s− 1
Cu-MOF Copper Terephthalic acid (BDC) 892 C g− 1 at 1 A 15.7 kW 88.2 Wh 120 % after 10 [124]
g− 1 kg− 1 kg− 1 000
cycles
Fe-MOF Iron Benzene dicarboxylic acid (BDC) 752 F g− 1 at 4 A – – – [125]
g− 1
Ni/Co-MOF Nickel and benzene-1, 4-dicarboxylic acid/Terephthalic 594.24 C g− 1at 1 775.13 kW 66.2 Wh 92.7 % after 5000 [126]
Cobalt acid (TPA) A g− 1 kg− 1 kg− 1 cycles
Co-V-MOF Cobalt and 4,5-imidazole dicarboxylic acid (H3IMDC) and 1711.1 F g− 1 at 1 835 W kg− 1 70.65 Wh 92.1 % after [127]
Vanadium Trimesic acid A g− 1 kg− 1 10,000 cycles
Mn-MOF Manganese BTC (Benzene-1,3,5-tricarboxylic acid) 357.6 C g− 1 at 6 A 60.01 Wh 851 W 98.6 % after 1000 [128]
g− 1 kg− 1 kg− 1 cycles
Mn-MOF Manganese 1,3,5-Benzenetricarboxylic Acid 248.3 C g− 1 2550 W 60 Wh 98.57 % [129]
kg− 1 kg− 1 after 1000 cycles
Cu-B-MI MOF Copper 1,2,4,5-Benzenetetracarboxylic acid (BTC) and 156 C g− 1 at 0.8 A 4000 W 52 Wh 93 % after 3000 [130]
2-mthylimidazole (C4H6N2) g− 1 kg− 1 kg− 1 cycles
Cu-MOF Copper 2,3,6,7,10,11-hexahydroxytriphenylene 135 C g− 1 2100 W 32 Wh 99 % after 1000 [116]
(HHTP) kg− 1 kg− 1 GCD cycles
− 1
Cu – MOF Copper Redox Tetrathiafulvalene ligand 266.5 C g 1.1 kW 62.9 Wh – [131]
kg− 1 kg− 1
Ni-TTC MOF Nickel Tetrathia[8]circulene-2,3,5,6,8,9,11,12-octaol 249 F g− 1at 0.2 A – – – [132]
(8OH-TTC) g− 1
Cu–Co NH2 Cobalt and 2-Aminoterephthalic acid – 750.0 W 3.39 Wh 86 % after 10,000 [133]
Copper kg− 1 kg− 1 cycles

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

rates, hasn’t received adequate attention and optimization in much of their vast availability, eco-friendliness, accessibility, and other
the literature. Even MOFs with redox metal centers or ligands often compelling properties which include unique structures, high surface
exhibit narrower potential windows and shorter cycle life compared to areas, chemical robustness, and considerable theoretical specific
other materials used in supercapacitors. In some cases, the presence of capacitance values. It is important to note that among the choice of
hard metal ions and redox-inactive ligands in MOFs creates a high en­ electrodes of electrochemical supercapacitors, the metal oxides are
ergy barrier for charge transport, leading to poor performance in energy widely used for increasing capacitance through precise nanoscale
applications [101,114]. These challenges highlight the ongoing need for modification and tuning of defects as well as surfaces/interfaces. It has
research to address these limitations and refine the design for practical become increasingly common for researchers to use metal oxides with
use in supercapacitors. Metal-Organic Frameworks (MOFs) to create composite materials aimed
Our strategic hypotheses for enhancing performance go beyond at enhancing the overall specific capacitance while simultaneously
solely focusing on redox activity. Despite successful integration of maintaining cyclic stability. Even though many metal oxides act as
transition metals and redox-active ligands, MOFs frequently demon­ semiconductors with relatively low electrical conductivity, their addi­
strate constrained potential windows and cycle life. Prioritizing struc­ tion to MOFs can still enhance conductivity and electrochemical per­
tural stability, especially under high charge/discharge rates, is crucial. formance to a certain level. However, this improvement may not fully
Introducing structurally robust MOFs, such as azolate MOFs known for overcome the conductivity limitations of pristine MOFs. Although the
their chemical stability across diverse conditions, alongside redox ac­ incorporation of metal oxides into MOFs can enhance conductivity to
tivity, could extend cycle life and broaden the potential window. some extent, it may not fully resolve the conductivity challenges of
MOFs. However, it is noted to enhance the overall stability of the
5. MOF composites material.
The combined effects derived from compositing transitional metal
While pristine metal-organic frameworks also possess some impres­ oxides with MOFs by adding on their individual advantages elevate the
sive characteristics, they often lack adequate electrical conductivity. efficiency of supercapacitors [135]. Xiong et al., ingeniously engineered
This issue has restricted the capabilities that MOFs might otherwise have a hybrid by integrating NiO with Ni-MOF, an approach for synthesizing
offered. In response to the limitations, several researchers have devel­ metal oxide@MOF arrays employing metal oxides as disposable tem­
oped MOF composites by combining MOFs with a variety of functional plates. Through a sequential hydrothermal technique, ordered MOF
materials. These hybrid composites merge the advantageous properties arrays are converted into metal oxide@MOF. They aimed at advancing
of MOFs with other functional substances to overcome individual the performance of supercapacitors without binders. This configuration
shortcomings. The process to synthesize these composites is simple and improves electrode conductivity and promotes electron and ion trans­
allow us to merge the positive qualities while neglecting the less desir­ port because of the synergetic properties of both NiO and Ni-MOF
able traits. This collaborative effect unlocks new possibilities that components. They also exhibited a high specific capacity (1853 C
standalone pristine MOFs cannot achieve. These MOF composite mate­ cm− 2 at 1 mA cm− 2) compared to pure NiO/NF (242 C cm− 2) with low
rials are particularly impactful in energy storage advancements. En­ impedance. The hybrid supercapacitor (HSC) made with NiO@Ni-MOF/
hancements in electric conductivity and general functionality become NF and carbon nanotube (CNT) electrodes exhibited a impressive spe­
possible when integrating conductive or redox active additives like cific capacitance of 144 F g− 1 when discharged at 1 A g− 1 current
metal ions, metallic oxides, or conducting polymers into MOFs or other density, matched with elevated energy and power densities of 39.2 Wh
compounds such as layered double hydroxides, MXenes, etc. Such in­ kg− 1 and 7000 W kg− 1, respectively. It also maintained 94 % of capacity
tegrations not only increase the electrical conductivity but also signifi­ retaining its initial capacitance after over 3000 charge–discharge cycles
cantly improve the electrochemical performance of MOFs [134]. The [136]. In another research, Zheng et al., engineered a Co3O4
schematic diagram illustrating the commonly used MOF composite nanocube@Co-MOF composite characterized by superior alkaline
materials is shown in Fig. 10. resilience and elevated energy storage capacity. This composite material
preserved its integrity in demanding alkaline environments particularly
in 3.0 M KOH for a minimum duration of 15 days, which a pristine MOF
5.1. Metal oxides@MOF can’t hold. Due to its distinctive structural properties and an high sur­
face area, the fabricated composite demonstrated a good specific
Transition metal oxide materials have recently gained attention as capacitance value reaching 1020 F g− 1 at current density of 0.5 A g− 1
viable options for electrodes in energy storage applications, owing to

Fig. 10. Illustrative diagram of various prominent MOF composites.

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

and it sustained its high cycling stability experiencing mere a 3.3 % loss transition metals (TMO-based QDs) have been reported to exhibit
after 5000 cycles at a current density of 5 A g− 1. Furthermore, when elevated levels of conductivity and a diverse spectrum of valence states,
utilized within a solid-state flexible device, this metal oxide@MOF serving to mitigate the limitations in MOFs’ conduction attributes and
composite delivered an peak energy density that reached up to 21.6 structural robustness [141]. Gao et al., successfully synthesized SnO2
mWh cm− 3 [137]. quantum dots@ZIF-8 using a simple in-situ method and explored its use
Nonetheless, the predominant factor contributing to the suboptimal as an electrochemical pseudo-capacitor material in a KOH electrolyte.
enhancement of energy density is the considerable distance required for The structural analysis showed well-dispersed SnO2 quantum dots
mass transfer and failure to attain the anticipated conductivity [138]. within ZIF-8. The combination of the porous structure of the ZIF-8
H. Duan et al., tackled this common issue by synthesizing micro- framework composited with SnO2 quantum dots maximizes active ma­
nanocrystalline Mn-HHTP@MnO2 (MHMO-x) by inducing a reaction terial utilization, resulting in a high specific capacitance. SnO2 quantum
between HHTP and MnO2, thereby overcoming issues related to mass dots@ZIF-8 demonstrated a maximum specific capacitance of 931 F g− 1,
transfer limitations. Through fine-tuning the quantity of HHTP and surpassing pure SnO2 quantum dots (241 F g− 1) and the MOF, ZIF-8 (99
MnO2, and the duration of the reaction, they refined the self-assembly F g− 1). Additionally, it exhibited good cycling stability over 500 cycles,
method, achieving MHMO-x variants characterized by reduced mass attributed to the synergistic electrochemical behavior of ZIF-8 and SnO2
transfer pathways and enhanced electrical conductivity. This high­ quantum dots, enabled by ZIF-8′s three-dimensional structure and large
lighted the importance of exposing specific facets as well as maintaining surface area facilitating the dispersion of SnO2 quantum dots [142]. This
small sizes for attaining elevated levels of capacitance. When assembled research paves a new way for exploring Metal oxides@MOFs as elec­
into an aqueous asymmetric supercapacitor, MHMO-4//AC delivered an trode materials to enhance the conductive, stability, and capacitive
energy density of 51.1 Wh kg− 1 at a power density of 650 W kg− 1. properties of MOFs.
Notably, retaining 89.1 % its capacitance is ascribed to size and
morphological engineering being major factors in enhancing electro­ 5.2. Metal-doped MOF
chemical performance. However, due to the trace quantities of Mn2+
originating from MnO2, the extension of Mn-HHTP nanoarrays is Several researchers have integrated additional metals into MOFs to
considerably constrained [139]. boost electrical conductivity. Through effective coordination with the
Alternatively, Yang et al. developed a bimetallic oxide derivative, linkers, these metal elements facilitate the formation of MOFs with
which is then composited with MOF. The composite (MnCo2O4/Ni- multiple metallic centers. While this classification could be included in
MOF) electrode is synthesized through the conversion of a Co/Mn dual- the composite section due to its amalgamated nature, it is more accu­
metal MOF into MnCo2O4, followed by the in-situ growth of Ni-MOF on rately termed as metal-doped MOFs and not composite. For instance,
its surface to form a nano-flower-like configuration with reaction con­ Pang et al., used a one-step coprecipitation method to create a unique
ditions as shown in Fig. 11. This structure displayed excellent electro­ manganese-doped cobalt-zeolitic imidazolate framework (ZIF-67) that is
chemical performance owing to its significant active site availability, larger in size compared to other ZIF-67 using the same process. The
vast surface area, and porous nature. The integration of Ni-MOF with addition of manganese ions, which is larger than cobalt ions, cause a
MnCo2O4 brought forth enhanced kinetic performance and decreased structural defect in MOF that facilitates better contact with the elec­
electrical resistance while merging metal oxide and MOF benefits from trolyte, promoting ion dispersion and electron transfer. The conductivity
improved stability of MOF. Also, its distinct nano-flower shape pro­ of the samples is also significantly improved due to the coupling effect of
moted effective ion movement and utilization of active matter for different metals. In supercapacitor testing, the Co/Mn-ZIF material
elevated electrochemical efficacy. With capabilities including high achieved a capacity of 926.25 F g− 1 at 0.5 A g− 1, retaining 64.1 % of its
specific capacitance reaching up to 957.11 F g− 1 at a charge rate of 1 initial capacity even after 1500 cycles at 10 A g− 1 [143]. Yuanxun Chen
Ag− 1, remarkable rate capacity retaining at least 93.41 % at heightened et al. used the same approach but with different metal (Zn). They
currents of 10 A g− 1, plus consistent cycle stability with over 83 % ca­ developed a Zn-doped Ni-based metal-organic framework (Ni-MOF)
pacity post-16,000 cycles, the composite stood out significantly. The with a honeycomb-like spherical structure using a microwave-assisted
assembled asymmetric supercapacitor also achieved a high energy method and HCl as a modulator. By adjusting the amount of Zn ions,
density of 35.60 Wh kg− 1 at 749.91 W kg− 1, with minimal capacitance they obtained an optimal Zn-doped Ni-MOF electrode material with
loss (5.26 %) after 20,000 cycles [140]. Quantum dots based on outstanding electrochemical performance, boasting a specific capacity
of 237.4 mAh g− 1 at 1 A g− 1 and 122.3 mAh g− 1 at 2 A g− 1 which is
among the highest reported for MOFs composites [144]. However, these
exceptional properties are not only attributed to the doped-metal ions
but also their unique crystal structure and special morphology, which
need to be addressed individually.

5.3. Conducting polymers@MOF

Within the array of composite materials, conducting polymers (CPs)

are regarded with considerable interest due to their electrical conduc­
tivity and mechanical characteristics. Notably, these include high spe­
cific capacitance, simple synthesis processes, robustness against
environmental degradation, and superior properties for forming films
[145]. Iqbal et al. synthesized a copper-based MOF-199 and enhanced
its electrochemical efficacy by integrating it with graphene and poly­
aniline (PANI). The specific capacity of MOF-199 significantly increased
from 88 C g− 1 to 766 C g− 1 with the addition of PANI. Combining MOF-
199/PANI with activated carbon in a hybrid supercapacitor achieved
excellent energy and power density of 64 Wh kg− 1 and 7200 W kg− 1,
Fig. 11. Schematic diagram of two-step synthesis of MnCo2O4/NiMOF com­ respectively, with 92 % capacity retention after 1000 cycles. This study
posite (Reproduced from Ref. [140] with permission from John Wiley suggests MOF-199, especially in combination with PANI, is a promising
and Sons). electrode material for high-performance energy storage devices. The

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

findings suggest that MOF-199, especially in conjunction with PANI, capacitance value of 715.6 F g− 1 at a current density rate of 0.3 A g− 1.
provides a conductive structure for MOF [146]. Wang et al. also tackled Furthermore, they engineered an asymmetrical supercapacitor using
the issue of suboptimal electrical conductivity within metal-organic PPy-MOF as a positive electrode and activated carbon (AC) as a negative
frameworks (MOFs) through an innovative approach. They incorpo­ electrode, which exhibited impressive capacitive behavior including
rated MOF crystals with polyaniline (PANI) strands and electrochemi­ achieving an energy density of 40.1 Wh kg− 1 when operating at a power
cally deposited them on carbon cloth substrates. Compared to other density of 1500.6 W kg− 1. This highlights the strong prospect for this
composites, conducting polymers specifically improved conductivity in MOF-PPy composite in energy storage solutions due to the elevated
MOF, rather than a noticeable stability. electron transfer and cumulative benefits stemming from integrating Ni-
The schematic diagram illustrating the conduction by MOF shown in MOF and PPy [150]. Qin et al. did a very similar work of Ni-MOF@PPy,
Fig. 12(a) highlights that electronic mobility is severely restricted along by combining a Ni-based metal-organic framework (Ni-MOF) with PPy
the framework or when attempting to penetrate the crystalline structure in the view of improving its electron transfer properties. However, un­
of MOFs, although the electrolyte retains its ability to permeate and exit like previous work, they additionally added K4Fe(CN)6 in the electrolyte
the porous MOF structures by diffusion effect. But, as shown in Fig. 12 to further improve the redox characteristics. The composite showed a
(b), by integrating conductive PANI within this matrix, conductive heightened specific capacitance of 1815.4 F g− 1 at 1 A g− 1 when used
pathways were established for both electron and electrolyte movement with K4Fe(CN)6 electrolyte when compared with KOH electrolyte. It can
across MOF surfaces, thereby generating an electrochemical double- be inferred that along with PPy, adding K4Fe(CN)6 to the KOH electro­
layer on the surface of the constructed PANI-ZIF-67-CC interface. The lyte increased the system’s capacitance by 6.1 %. Using Ni-MOF@PPy as
synthesized PANI-ZIF-67-CC electrode preserved the inherent architec­ the positive and active carbon (AC) as the negative electrode, they
ture of ZIF-based MOFs while demonstrating a remarkable enhancement assembled an asymmetric supercapacitor that displayed a high energy
in electrochemical activity. Electrochemical tests demonstrated that ZIF- density of 38.5 Wh kg− 1 at a power density of 7001 W kg− 1 and also
67 immersed onto carbon cloth without PANI integration attained displayed 90.2 % capacitance retention of its initial value after 3000
merely inferior values of capacitance, specifically, 1.47 mF cm− 2, which cycles [151].
reflects its naturally insulating characteristics. Furthermore, electrodes These studies suggest that MOF@conductive polymer is an innova­
solely composed of PANI deposited on carbon cloth showcased over one- tive approach for enhancing the electrochemical as well as conductive
third of areal capacitance at 727 mF cm− 2 than that seen in composites properties of pristine MOFs.
with ZIF-67 interlaced with PANI chains. This clearly dictates a coop­
erative synergistic benefit that optimizes electric double-layer capacitor 5.4. Carbon nanotubes (CNTs) @MOF
(EDLC) actions alongside pseudocapacitive behavior developed from
such composite efforts [147]. Recognizing these advantages, in a recent In-depth studies have focused on the use of sophisticated carbon-
study, Le et al., synthesized composites using reduced graphene oxide based electrodes in supercapacitors owing to their superior character­
(rGO), manganese/copper metal-organic framework (Mn/Cu-MOF), and istics, such as extensive surface area, exceptional electrical conductivity,
polyaniline (PANI) for use as supercapacitor electrodes. The rGO/Cu- and good electrochemical stability. Carbon materials like carbon nano­
MOF@PANI electrodes outshined the rest in performance metrics. By tubes (CNTs), carbon nanofibers, composite materials containing car­
incorporating Cu-MOF during the reaction, it served as an accelerant for bon, and those based on graphene form part of this group. These
the polymerization of aniline which increases the amounts of PANI substances show promise in high-efficiency supercapacitor electrodes,
synthesized, subsequently enhancing the overall functionality of the however, they typically originate from various chemicals or fossil
electrode. The enhancement is mainly due to both PANI’s pseudocapa­ sources and are manufactured through complex, expensive procedures.
citive properties and a collaborative effect between rGO and Cu-MOF. Nonetheless, among these efficient conductive carbons, CNTs emerge as
These composite materials offered optimal architectures to facilitate a comparatively economical option [152]. Thus, the hybridization of
swift ion movement. Consequently, with this configuration, an impres­ CNT with MOF is an interesting solution to improve the electrochemical
sive specific capacitance of 276 F g− 1 was obtained at a current density performance since poor conductivity and stability degrade the capaci­
of 0.5 A g− 1 [148]. tive performance of MOFs.
Moreover, other conducting polymers like polypyrrole was also used Sun et al. engineered a novel composite made of nickel-based metal-
as composite for MOF due to their outstanding electronic properties organic framework (MOF(Ni)) with corrugated layers and carbon
[149]. Wang et al. synthesized a PPy-MOF composite through a simple nanotubes (CNTs) using a solvothermal process. This layered configu­
wet-chemical technique by employing a nickel metal-organic framework ration provides a high area for storing electrolytes and quick pathways
(Ni-MOF) with PPy. The electrochemical activity of the Ni foam altered for ion movement. This area is provided by textured-layer architecture
with PPy-MOF outperformed that of standalone Ni-MOF and PPy. of MOF(Ni), while CNT’s one-dimensional structure enhances electrical
This enhanced performance led to a considerable specific conductivity and structural stability. Relative to standalone MOF(Ni),

Fig. 12. Schematic Representation of Electron and Electrolyte Conduction in (a) MOF and (b) MOF Interwoven by PANI (Reprinted with permission from [147].
Copyright 2015 American Chemical Society.)

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

the hybrid material MOF(Ni)/CNT features improved electrochemical individual MOFs, while also introducing additional features like the
behavior at various weight percentages. In particular, MOF(Ni)/CNT template effect. The benefits presented by these novel MOF/MXene
with 10 % CNT content shows outstanding specific capacitance levels composites unlock their potential for utilization in various applications
and excels in rate capability as it maintains 88.6 % performance even including supercapacitors [157]. Leveraging these beneficial charac­
when discharged at 10 A g− 1. This indicates that reaction parameters teristics, Zhang and colleagues engineered an enhanced energy storage
such as the quantity of precursors for the composite also determine the mechanism by crafting Ti3C2Tx-MXenes/Ni-based metal-organic frame­
capacitance outcome. When constructed into an asymmetric super­ work composites (Ti3C2Tx/Ni-MOFs) for high performance in super­
capacitor together with activated carbon (MOF(Ni)/CNT(10 %)//AC), capacitors. The schematic diagram of the formation of MOF with and
the unit displays a capacitance value of 97 F g− 1 at a discharge current of without MXene is shown in Fig. 13(a). The unique 2D architecture of
0.5 A g− 1 and sustains cycle life by preserving 83.2 % capacity over 5000 MXenes and their surface functionality with oxygen elements steer the
cycles, and it also demonstrates a good energy density reaching up to formation of Ni-MOFs into thin, 2D microbelts. This modification of
32.6 Wh kg− 1at an appreciable power efficiency of 476.5 W kg− 1 [153]. template effect not only amplifies conductivity but also contributes both
In a similar study by Anwer et al., ternary metallic Metal-Organic electric double-layer capacitance and pseudocapacitance through fara­
Framework (MOF) was synthesized with the incorporation of carbon daic processes. These newly fashioned 2D Ni-MOF microbelts serve as
nanotubes (CNTs) at varying ratios, meticulously engineered to enhance prolific sites enabling redox activities while simultaneously simplifying
performance in electrochemical supercapacitors. The composite mate­ the transfer of ions within them. As tested, the Ti3C2Tx/Ni-MOFs elec­
rial developed a layered architecture that promotes swift ion movement trode exhibits impressive electrochemical performance of 1124 F g− 1
and effective electrolyte absorption. The synergistic interplay of CNT specific capacitance at a current density of 1 A g− 1 and retaining an
with MOF, enhanced by the redox activities involving multiple metal adaptable performance capability of 62 % at a current density of 20 A
ions, results in good charge retention capabilities. Notably, the one- g− 1. Both samples display conventional cyclic voltammetry (CV) curves
dimensional nanostructure of CNTs confers both stability and conduc­ featuring peaks indicative of faradaic pseudocapacitance (Fig. 13(b)).
tive properties upon the composite. Particularly, when analyzing MOF However, the Ti3C2Tx/Ni-MOFs exhibited significantly larger CV areas
with 5 % CNT, a significant increase in the capacitive property over pure compared to Ni-MOFs, implying higher specific capacitance and supe­
MOFs is observed due to eminent specific capacitance as well as robust rior rate capability for Ti3C2Tx/Ni-MOFs. It is confirmed that embedding
rate capability. It retains 86.1 % of capacitance at the current density of Ti3C2Tx MXenes into MOF structures, there is an elevation in ion ex­
5 A g− 1. When used asymmetrically into a supercapacitor with activated change speed which catapults charge storage capacity forward consid­
carbon as the negative electrode, opposite to MOF-CNT(5 %), this erably [158]. In order to address the limitations of standalone MXene or
combination delivered a notable capacitance of 166.4 F g− 1 at the cur­ MOF materials, such as restricted redox-active sites, weak electronic
rent density of 1 A g− 1 and maintained an impressive stability, shielding conductivity, and instability, Xu et al. developed NiCo-MOF/MXene
against decay across 10,000 energy cycles where it experienced only heterostructures by stacking ultrathin 2D NiCo-MOF nanosheets onto
minimal decrease down to 79.2 %. Additionally, it showed an energy exfoliated MXene nanosheets through ultrasonic treatment. These
density of 23.6 Wh kg− 1 at a power density of 501.5 W kg− 1 [154]. These combined MOF/MXene structures harness the advantages of MOFs,
reports suggest that the composited amount of CNT when used in lower MXene, and their hierarchical design, providing a high surface area,
percentages (5 % & 10 %) improved the performance of MOF. electrical conductivity, fast ion movement, and structural durability. As
In the view of further improving the energy density, Han et al., a result, the electrode exhibited a markedly improved capacitance of
synthesized a composite, designated as Mn/Ni-MOF@MWCNTs, by 1176.8 F g− 1 compared to the pure MOF’s 653.4 F g− 1, along with a
integrating bimetallic manganese (Mn) and nickel (Ni) metal-organic cycle stability of 72.5 % versus the pure MOF’s 50.5 %. This underscores
frameworks (MOFs) with multi-walled carbon nanotubes (MWCNTs). that the development of MXene/MOF heterostructures is one of the
Since MWCNTs were pivotal in maintaining the electron transport and strategical approaches to enhancing MOF performance [159].
the compound’s structural framework, it led to the realization of a
notable specific capacitance reaching 793.6 F g− 1 at a current density of 5.6. Layered double hydroxides(LDH)@MOF
1 A g− 1 coupled with a commendable capacitance retention rate of
74.92 % subsequent to 1000 charging cycles. In addition, when assessed Layered double hydroxides (LDHs), due to their unique two-
within symmetric supercapacitor setups, this composite material dimensional (2D) layered configurations, show considerable potential
demonstrated superior energy storage capabilities marked by an energy for use in the advanced supercapacitors of the next era. This architecture
density of 33.2 Wh kg− 1 and maintained a stable capacitance retention provides a high surface area as well as accommodating for adjustable
of 78.3 % even after 2000 cycles [155]. This implies that employing CNT composition concerning both the host layers and the species intercalated
as a composite with MOF is a promising strategy; however, careful within them [160]. In a research, Zheng et al. designed an advanced
consideration of the appropriate ratio is essential. composite (NiAl-LDH/Ni MOF/S) designed for use in supercapacitor
electrodes, which was fabricated through a three-step procedure:
5.5. Mxenes@MOF
i. The first step involved synthesizing LDH nanoplates via a hy­
In the past decade, a significant amount of study has been dedicated drothermal technique.
to MXenes, an emerging class of two-dimensional ultra-functional ii. This was then followed by the nucleation of MOF nanosheets on
nanomaterials. These materials have gained considerable interest for these plates to increase the specific capacitance.
their wide-ranging applications in fields like renewable energy and iii. To further enhance electrical conductivity, they administered a
sustainable fuel generation. MXenes’ unique layered structure serves a sulfidation process.
dual purpose by enhancing the movement of ions in electrolytes while
also delivering active sites for transition metal redox reactions on their This innovative NiAl-LDH/Ni MOF/S composite demonstrated su­
exterior surface. Owing to these attributes, MXenes are seen as highly perior specific capacitance characteristics achieving 1670 F g− 1 at 1 A
capable candidates for electrode materials in electrochemical storage g− 1 with high integral area under CV curve as shown in Fig. 14(a) (blue-
devices, especially supercapacitors [156]. Given that certain classic coloured curve) coupled with an admirable rate capability with main­
MOFs are hindered by low conductivity and stability concerns, inte­ taining 65 % of its initial capacitance as the current density increased
grating MXenes, which boast excellent electrical conductivity and an from 1 to 30 A g− 1 as displayed in Fig. 14(b) (blue-coloured line). By
abundance of surface functional groups, can address these issues. utilizing the combined strengths of LDH and MOF, they were able to
MXenes serve to improve the stability and conductive properties of construct an asymmetric supercapacitor which achieved a substantial

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 13. (a) Schematic illustration of the synthetic process of Ni-MOF with and without Ti3C2Tx, (b) CV curves of Ni-MOF and Ti3C2Tx/Ni-MOF at the constant scan
rate of 5 m V s− 1. (Reproduced from Ref. [158] with permission from Elsevier).

Fig. 14. (a) Comparative CV curves (b) Plot of specific capacitance values of NiAl-LDH, Ni-MOF, NiAl-LDH/Ni-MOF and NiAl-LDH/Ni-MOF/S (Reproduced from
Ref. [161] with permission from John Wiley and Sons).

energy density of 35.4 Wh kg− 1 and sustained performance showing also aims to address the electrical conductivity limitations of MOFs.
negligible degradation with 96.4 % capacity retention after 10,000 These doped structures offer improved electrolyte contact, enhanced
charge–discharge cycles at 10 A g − 1 [161]. ion dispersion, and electron transfer, resulting in heightened specific
capacitance and cyclic stability. Nevertheless, challenges emerge in
precisely controlling the crystal structure and morphology. In the
5.7. Insights on MOF composites
case of the Co/Mn-ZIF, optimizing the coprecipitation method for
enhanced electrical conductivity while preserving the desired crystal
The strategy of compositing Metal-Organic Frameworks (MOFs) with
structure presents a notable challenge. Additionally, understanding
various materials represents a promising path to overcome the inherent
the complicated interplay among composited metal ions, crystal
limitations of pristine MOFs and enhance their application in super­
structure, and morphology is crucial to fully exploit the potential of
capacitors. Upon reviewing the literature, it becomes evident that MOF
these composites. Moreover, achieving scalability and cost-
composites offer numerous advantages, yet they also present certain
effectiveness in synthesizing metal-doped MOF for practical super­
limitations that require overcoming.
capacitor applications also demands careful consideration.
3) Combining conducting polymers with MOFs in composites like PANI-
1) Combining metal oxides with Metal-Organic Frameworks (MOFs) is a
ZIF-67-CC and rGO/Cu-MOF@PANI benefits from electrical con­
strategy aimed at enhancing the conductivity of pristine MOFs to
ductivity and mechanical properties of conducting polymers. These
some degree, though it may not be the most optimal approach. They
composites establish pathways for both electron and electrolyte
have improved the electrical conductivity of MOF and expanded the
movement, enhancing both electric double-layer capacitor (EDLC)
operational voltage range. For example, NiO@Ni-MOF demonstrated
and pseudocapacitive behavior. The inclusion of conducting poly­
improved electrode conductivity, efficient electron and ion trans­
mers leads to improved specific capacitance and energy density.
port, and a high specific capacity. Despite these benefits, challenges
Nevertheless, challenges arise in achieving a synergistic balance
persist in maintaining the stability of metal oxide-MOF interfaces
between MOFs and conducting polymers. Precise control over syn­
over numerous charge–discharge cycles which demand further
thesis conditions is very important for the uniform incorporation of
exploration into the long-term durability of these composites.
conducting polymers into the MOF structure (as observed in the
2) Integrating metals with MOFs, as observed in manganese-doped
PANI-ZIF-67-CC composite). Guaranteeing stability during dynamic
zeolitic imidazolate framework-67 (ZIF-67) and Zn-doped Ni-MOF,

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

electrochemical processes and extended cycling poses challenges, conjectures for improving MOF-based composite performance include,
particularly concerning the potential degradation of conducting (i) Investigating novel surface modification techniques, like surface
polymers. Additionally, optimizing the loading ratio of conducting passivation or interlayer insertion, to enhance the stability of metal
polymers to MOFs for optimal electrochemical performance remains oxide-MOF interfaces and mitigate degradation. (ii) Utilizing advanced
an ongoing challenge. yet cost-effective synthesis methods such as template-directed synthesis
4) The incorporation of carbon nanotubes (CNTs) into MOFs effectively to precisely control crystal structure and morphology. (iii) Developing
tackles the challenges of poor conductivity and stability associated scalable production methods such as continuous flow synthesis and
with pristine MOFs. In the work of MOF(Ni)/CNT composite, this continuous batch-type synthesis to facilitate commercialization. (iv)
strategy results in enhanced electrochemical behavior, remarkable Lastly, integrating materials with additional functionalities or modifying
specific capacitance, and notable rate capability. The composite’s the linkers to broaden the applicability of MOFs. These can help over­
design offers a spacious area for electrolyte storage and efficient come limitations and pave the way for future advancements.
pathways for ion movement, showcasing the synergistic advantages Recently reported literature on MOF composites and their electro­
of combining MOFs with CNTs. Moreover, composites like Mn/Ni- chemical performance is depicted in Table 4.
MOF@MWCNTs further amplify electron transport but with a pre­
cise amount of usage. 6. MOF derivatives
Despite these benefits, challenges persist in achieving a well-
dispersed and stable CNT-MOF composite. The solvothermal pro­ Metal-organic frameworks, known for their vast specific surface
cess used in the synthesis of MOF(Ni)/CNT and ternary metallic areas and modifiable porous structures, act as templates for the forma­
MOF-CNT composites requires careful optimization to ensure ho­ tion of metal oxides, sulfides, phosphides etc. that are used in electrodes.
mogeneity and prevent CNT agglomeration. Achieving a consistent These MOF-based derivatives feature an array of metal ion species and
distribution of CNTs throughout the MOF matrix and establishing a valence states. The interaction among various metal ions leads to syn­
robust interface between CNTs and MOFs are critical for maximizing ergistic outcomes that boost ion adsorption, movement, and transfer
electrical conductivity and structural stability. Overcoming these leading to enhanced electrochemical capabilities in supercapacitors. The
challenges will necessitate advancements in synthesis techniques remarkable electrical conductance and high presence of metal ions
and a deeper understanding of the interactions between CNTs and within these MOF derivatives widely establish them as prominent ma­
MOFs. terials in supercapacitor applications [181,182]. Researchers usually opt
5) The amalgamation of MXenes with MOFs also emerges as a remedy for Cobalt, Nickel, Iron, Manganese, and Copper as their preferred
to address the low conductivity in MOFs. The 2D architecture of metals when synthesizing derivatives based on Metal-Organic Frame­
MXenes plays a pivotal role in forming thin, 2D micro belts within works (MOFs), due to their easy availability and low cost. A flowchart
Ni-MOFs, boosting conductivity and providing additional redox ac­ containing the breakdown of common MOF derivatives is shown in
tivity sites. However, integrating MXenes with MOFs introduces Fig. 15.
challenges related to the intricate design of the composite. For
instance, achieving the controlled formation of thin, 2D micro belts, 6.1. MOF-derived metal oxides
as observed in the Ti3C2Tx/Ni-MOFs composite, needs precise con­
trol over synthesis conditions. Additionally, stabilizing and scaling Metal oxides derived from MOFs effectively retain the distinctive
up the synthesis of such composites for practical applications may microstructural features of their precursors yet demonstrate a dimin­
encounter challenges in terms of cost and production scalability. ished crystalline nature, thereby improving the diffusion of electrolytes.
6) The incorporation of layered double hydroxides (LDHs) into MOF In contrast to conventional bulk metal oxides, these MOF-originated
composites improves specific capacitance considerably. For example, counterparts exhibit a high specific surface area that lends itself bene­
in NiAl-LDH/Ni MOF/S composite, this strategy showcases superior ficially to ensuring the better interaction between active substances and
specific capacitance, admirable rate capability, and substantial en­ electrolytes. When metal-organic frameworks (MOFs) undergo ther­
ergy density. The layered structure of LDHs contributes to an high molysis, they yield metal oxides endowed with traits beneficial for
surface area, and their synergistic combination with MOFs enhances supercapacitors. This includes a large surface area, structure of pores on
specific capacitance and overall performance. However, challenges multiple levels, and improved electrical conductivity [183].
arise in the multi-step synthesis process involved in this strategy.
Achieving seamless integration of LDH nanoplates with MOF nano­ 6.1.1. Cobalt-based oxides
sheets, as demonstrated in the NiAl-LDH/Ni MOF/S composite, de­ Oxides of cobalt are highly regarded for their use in supercapacitor
mands careful optimization at each synthesis step. The significant applications, owing to beneficial features such as high theoretical
challenge lies in ensuring that the sulfidation process enhances capacitance, reversible oxidation–reduction reactions, strong conduc­
electrical conductivity without compromising the composite’s tivity, durable stability, cost efficiency, eco-friendliness, and positive
overall stability. redox attributes [184]. Based on this, Salunkhe et al., transformed a
single metal-organic framework (MOF), ZIF-67 into nanoporous cobalt
As outlined in the above section, several disadvantages have also oxide (Co3O4) by finely tuning the annealing process. The precise
been faced by MOF-based composite materials in commercial super­ thermal protocol for deriving Co3O4 with an evenly shaped 3D poly­
capacitor applications. They include:- (i) Maintaining stability at the hedral morphology involves heating in a nitrogen atmosphere at 500 ◦ C
interfaces between MOF and its composite, (ii) While many reports for 30 min, which prevented collapse of its porous structure. The
successfully prepare composites on a lab scale, achieving scalability and resulting ZIF-derived nanoporous Co3O4 has a high surface area of 148
cost-effectiveness on an industrial scale remains uncertain, (iii) Control m2/g. As supercapacitor electrode, it exhibited impressive capacitance
over the loading of MOF and composite is feasible at the laboratory level value of 508 F g− 1 at a scan rate of 5 mV⋅s− 1. They further constructed a
but becomes problematic at the commercial level, (iv) Agglomeration of asymmetric supercapacitors (Co3O4//Carbon) and it showed a superior
materials can occur, (v) In some studies, an increase in conductivity performance with a high specific energy of 36 Wh kg− 1 at specific power
compromises stability, which is unacceptable for commercial super­ of 8000 W kg− 1, and excellent stability over 2000 cycles [185]. Few
capacitors. Future research should address these disadvantages in order researchers coupled Co-based oxides with other metals like Ni, Cu, Zn
to facilitate the scale-up of MOF-based composites for industrial-level etc., in the view of further improvements. In a study, Lim et al., devel­
supercapacitor applications. oped a bi-metal oxide, ZnCo2O4, by transforming a Cobalt- MOF with an
Furthermore, after reviewing numerous literature, our proposed infusion of zinc in a Co:Zn = 2:1 ratio onto carbon cloth, followed by

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Table 4
Recent reports on MOF composites and their electrochemical performance.
Name of the MOF material Type of composite Specific capacitance Power density Energy density Retention capability Reference
− 1 − 1 − 1 − 1
MOF@GO MOF@GO 840 F g at 2 A g 388.5 W kg 30.7 Wh kg 84 % after 7000 cycles [162]
Ni-MOF@PPy MOF@PPy 1815.4 F g− 1 at 1 A g− 1
7001 W kg− 1 38.5 Wh kg− 1 90.2 % after 3000 cycles [151]
Cu-MOF/rGO MOF@ rGO 867.09 F g− 1 at 1 A g− 1
0.6 kW kg− 1 30.56 Wh kg− 1 90.07 % after 10,000 [163]
cycles
Fe-MOF@AC MOF@AC 628.5 F g− 1 at 1 A.g− 1 897.5 W kg− 1
16.24 Wh kg− 1 82 % after 10,000 cycles [164]
rGO@ CoFe-MOF Bimetallic MOF@ rGO 2069.1 F g− 1 at 0.5 A 700 W kg− 1 75.8 Wh kg− 1 91.3 % after 5000 cycles [165]
g− 1
Ni-Co-V-MOF/CNT TrimetallicMOF/CNT 166.4 F g− 1 at 1 A g− 1 501.5 W kg− 1 23.6 Wh kg− 1
79.2 % after 10,000 cycles [154]
rGO/Ni-MOF@PANI rGO/MOF@Conducting polymer 204 F g− 1 at 0.5 A g− 1 – – 81 % after 5000 cycles [166]
Cu-MOF/PANI MOF/PANI 766 C g− 1 7200 W kg− 1 64 Wh kg− 1 92 % after 1000 cycles [146]
Ti3C2TX/ZIF-67/CoV2O6 3D Mxene/MOF 285.5 F g− 1 – – – [167]
Co-MOF@MX-CNF MOF@Mxene-CNF 426.7 F g− 1 832.4 W kg− 1 72.5 Wh kg− 1
90.36 % after 1000 cycles [168]
MXene@Ni-MOF Mxene@MOF 979 F g− 1at 0.5 A g− 1 – – 98 % after 5000 cycles [169]
Ni-MOFs/V2CTx–MXene MOF@Mxene 1103.9 C g− 1 at 1 A g− 1 746.8 W kg− 1 46.3 Wh kg− 1
118.1 % after 15 000 [170]
cycles
Ni-ZIF-67 on MXene MOF@Mxene 557 C g− 1 at 0.5 A g− 1 400 W Kg− 1 27.48 Wh Kg− 1 66 % after 5000 [171]
FeCu MOF/MXene Bimetallic MOF@Mxene 440 mAh g− 1 – 33.3 Wh kg− 1 89 % after 10,000 [172]
Ni-MOF/PEDOT MOF@Conducting polymer 1401 F g− 1at 10 A g− 1 450 W kg− 1 40.6 Wh kg− 1 80 % after 1000 cycles [173]
ZnCo-MOF/PPy/Ag2O Bimetallic MOF/Mxene/Metal oxide 420 F g− 1 at 1 A g− 1 501.74 μW 82.23 μW h 84.5 % after 10,000 cycles [174]
cm− 2 cm− 2
1 1 1
NiCo-MOF-74 @t-PPY Bimetallic MOF@Conducting 849 C g− at 1 A g− 747.6 W kg− 58.4 Wh kg− 1 90.0 % after 10,000 [175]
polymer
− 1 − 1 − 1 − 1
ZnO@MOF@PPy MOF@Conducting polymer 1181 F g at 2 A g 2156.4 W kg 61.1 Wh kg 92 % after 10,000 [176]
d-MOF-808@PANI MOF@Conducting polymer 188 F g− 1 at 30 m V s− 1
– – 99.8 % after 10,000 cycles [177]
NiAl LDH@Mn3O4@Co- LDH@Metakl Oxide@MOF 1311 C g− 1 at 1 A g− 1 849.91 W kg− 1
60.91 Wh kg− 1
82.9 % after 5000 cycles [178]
MOF
Mo–Co–OH/Co-MOF) LDH@MOF 1927.44 F g− 1 at 1 A g− 1
8000 W kg− 1 51.60 Wh kg− 1 96.59 % after 5000 cycles [179]
(MOF(Ni)/CNT) MOF@CNT 97 F g− 1at 0.5 A g− 1 476.5 W kg− 1 32.6 Wh kg− 1 83.2 % after 5000 cycles [153]
Co-BTC@GO MOF@GO 1144 F g− 1 at 1 Ag− 1 – – 88.1 % [180]
after 20,000 cycles

Fig. 15. Flowchart of breakdown of prominently used MOF derivatives.

calcining it at 350 ◦ C for two hours under ambient conditions. The specific capacitance values are 25.9 mAh g− 1 at the current density of 2
integration of zinc was found to significantly alter the morphology of the A cm− 2 for ZnCo2O4, and Co3O4 shows a specific capacity of 17.7 mAh
synthesized nanocrystalline bimetallic oxide when compared with its g− 1 at the same current density. This enhancing performance is achieved
single-metal counterpart, Co3O4 deriving from solely cobalt-MOFs. through pre-oxidative annealing of these MOFs at 500 ◦ C under an N2
Experimental analyses revealed that ZnCo2O4 electrode exhibits a atmosphere prior to air exposure showcased in Fig. 16. Such strategic
fourfold increase in specific capacity when compared with pristine annealing induces additional conducive surface defects alongside an
Co3O4 samples derived from MOFs while retaining robust stability with abundance of cation species including Co2+ and Co3+, along with oxy­
only a minimal 5.2 % loss in capacity after 2000 cycles. The obtained gen voids which together increase conductivity and improve electron

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 16. (a) Formation process of M-Co-Oxide from Co/M-MOF (a) (Reproduced from Ref. [186] with permission from Elsevier), (b) Synthesis process of hollow
porous CuO/g-C3N4 from Cu-BTC (Reproduced from Ref. [167] with permission from the Royal Society of Chemistry).

movement, collectively increasing overall charge transport efficiency capabilities, reaching 842 F g− 1 at a current density of 1 A g− 1 while
[186]. preserving its integrity at 96.4 % over 10,000 charging cycles. More­
Kiey et al. focused on using a simple pyrolysis process to turn cobalt- over, when used in a two-electrode supercapacitor configuration with
based metal-organic frameworks (MOF) into Co3O4@N-doped C com­ Co-O-NSs@CFC acting as the positive electrode and activated carbon the
posites. They first made a porous structure called zeolitic imidazolate negative electrode, it displayed an impressive energy density of 55.7 Wh
framework (ZIF-67) using a method with triethylamine in water at room kg− 1 at a power density of 1125.9 W kg− 1 [189]. Moreover, hollow
temperature. This ZIF-67 was then used as a starting material to make structured metal oxides derived from metal-organic frameworks hold
Co3O4@N-doped C. The resulting material showed improved perfor­ great potential. For example, Niknam et, al., implied the importance of
mance in supercapacitors, with a high specific capacitance of 709 F g− 1 using hollow structures containing multiple transition metal oxides for
at 1 A g− 1 and good stability after 5000 cycles. The study suggests that high-performance energy. They focused on synthesizing MOF-derived
this simple direct template method could lead to formation of efficient Co3O4 through heat treatment and then doping it with vanadium (V)
MOF-derivative for supercapacitors. Here, the use of triethylamine to form multi-shelled V-doped Co3O4 hollow spheres. The resulting
surfactant helped create a porous structure with optimal sizes for electrode, called MS-V-CO, demonstrated excellent electrochemical
enhancing electron and ion transport, contributing to the improved properties, such as low internal resistance, fast kinetics, and a very high
performance of the Co3O4@N-doped C electrode. This indicates that specific capacitance of 1593 F g− 1. The electrode’s structure, charac­
surfactant also plays a important role in the enhancement [187]. Tanka terized by a large surface area, multiple shells, and a wrinkled surface
et al., have developed an innovative technique for forming structured obtained from its MOF precursor contributed to its success. When used
nanoarchitectures by employing nitrogen-infused carbon nanotubes (N- in an asymmetric supercapacitor with activated carbon as the negative
CNTs) alongside small Co3O4 particles upon electro spun carbon nano­ electrode, the MS-V-CO//AC demonstrated a maximum energy density
fibers (CNF). Through a self-templating approach using metal-organic of 66.88 Wh kg− 1 at a power density of 240 Wkg− 1 at 0.3 A g− 1 [190].
frameworks (MOFs), they facilitate the formation of N-CNTs and This is one of the simple yet effective derivative strategies to obtain
Co3O4 nanoparticles at reduced temperatures, removing the require­ high specific capacitance and high energy density.
ment for external reducing agents. The resultant 3D Co3O4/N-
CNTs@CNF structure, which contains elements of MOFs, exhibits 6.1.2. Copper-based oxides
outstanding electrical storage capabilities as evidenced by its significant Copper oxide has been widely investigated as a promising material
specific capacity, extended durability, and superior charge–discharge for energy storage systems, due to its high theoretical specific capaci­
rates. This is an economical and simple production strategy. Specifically, tance, low cost and ecological benefits. As a metal oxide family, copper
this arranged 3D complex of conductive and electroactive materials oxide also has attracted notable attention as an pseudocapacitive elec­
rooted in MOF technology results in a notable specific capacity reaching trode material for super capacitors, due to its high theoretical specific
238 mAh g− 1 at a current density of 1 A g− 1. Additionally, it maintains capacitance of 1800 F g− 1 [191]. Metal-Organic Frameworks (MOFs)
stability coupled with robust rate performance. The constructed asym­ have shown significant advantages in making porous materials by con­
metric supercapacitor device offers substantial energy density values of trolling pore size and the adjusting electrochemical properties through
52.9 Wh kg− 1 while maintaining exceptional power output of 873.5 W synthetic parameters [192]. Due to these reasons, several researchers
kg− 1, further demonstrating cyclic stability with over 90 % capacity find MOF-derived copper oxide based materials to be a promising
retention after 10,000 cycles [188]. candidate. For instance, Wu et al converted a three-dimensional copper
Similarly, Mateen et al., concentrated their efforts on pioneering an (II) metal-organic framework (Cu-MOF) into nanosheets of Cu2O/Cu@C
economical electrode material with substantial capacity for super­ via a calcination process of heating at 600 ◦ C for 2 h at a ramping rate of
capacitors by utilizing MOF-derived cobalt-oxide. They synthesized 1.5 ◦ C min− 1. Due the slowing temperature rising rates, the rapid
walnut-shaped nanosheets of cobalt oxide (Co-O-NSs) on a skeleton of breakdown of MOF structure is preserved resulting in nanosheets feature
carbon fiber cloth (CFC) via an efficient hydrothermal process. Owing to with evenly dispersed Cu2O/Cu@C nanoparticles on carbon sheets dis­
its origin as a modified metal-organic framework derivative, this sub­ playing hierarchical porous structures. Moreover, the specific surface
stance showcased advantageous properties such as large surface area area (336.3 m2/g) and the total pore volume (3.41 cm3 g− 1) were found
and well-defined crystallinity that made it appropriate as an electrode to be higher than those of pristine Cu-MOF. At 0.5 A g− 1, the specific
for supercapacitors. The electrode exhibited superior charge retention capacitance was determined to be 665 F g− 1, which was higher than that

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

of Cu-MOF. However, the nanosheets of Cu2O/Cu@C exhibited sub- treatment.

optimal cycling stability (53.5 % retention) after 5000 cycles. By
assembling Cu2O/Cu@C //AC asymmetric supercapacitors, they ob­ 6.1.3. Iron-based oxides
tained the maximum energy density of 38.6 Wh kg− 1 at a power density Iron-based oxide materials have attracted considerable attention due
of 466.5 W kg− 1 [193]. Other than the reaction temperature, the reac­ to their exploration for energy storage applications. Among metal-
tion time also affects the performance of material. Aljaafari et al., organic frameworks (MOFs), Fe-based oxides derived from MOFs are
developed a framework of cuprous oxide (Cu2O) derived from a Metal- highly reported by researchers, compared to iron sulfides and phos­
Organic Framework using a simple one-step method. They carefully phides, due to their high stability and toxicity issues. For example, Zhou
studied the impact of reaction time on the structure and growth of Cu2O, et al. established a low-cost path to fabricate a superior anode, i.e.
discovering that the cubic Cu2O synthesized in 12 h showed superior spindle-like α-Fe2O3@C derived from the MIL-88-Fe MOF, directly
performance in terms of capacitance compared to those synthesized in 8 growing on oxidized carbon nanotube fiber (S-α-Fe2O3@C/OCNTF),
and 10 h. The cubic Cu2O-12 h electrode showed the maximum specific resulting in an electrode which exhibited an impressive performance
capacitance of approximately 365 Fg− 1 as compared with cubic Cu2O-8 with 1232.4 mF cm− 2 at 2 mA cm− 2. With Na-doped MnO2 nanosheet on
h (151 Fg− 1) and cubic Cu2O-10 h (195 Fg− 1) at the current density of CNTF as cathode and the prepared material as an anode, the highest
0.75 Ag− 1. The energy density of cubic Cu2O-12 h was found to be specific capacitance (201.3 mF cm− 2) and energy density (135.3 μW h
approximately 16.95 Wh Kg− 1 at a power density of 235.4 W Kg− 1 cm− 2) are obtained [198]. To boost conductivity and enhance capacitive
[194]. To specifically, enhance the specific capacitance and energy storage, Yu et al., fabricated a porous hollow α- Fe2O3 micro boxes with
density, researchers employed a strategy that involves the combination uniformly distributed Ag nanoclusters (NCs) coated on the surface. The
of carbon-0based materials like carbon, GO, rGO, and g-C3N4, or con­ obtained α- Fe2O3@Ag micro box electrode exhibits a high specific
ducting polymers like PANI, with copper oxide derived from a metal- capacitance of 701 F g− 1 at 0.1 A g− 1, and remains 191 F g− 1 at a high
organic framework (MOF). In particular, Zhu et al. successfully pre­ current density of 10 A g− 1 as a pseudocapacitive electrode. It retains 80
pared a distinct composite incorporating graphite carbon nitride (g- % of the specific capacitance after 2000 charge–discharge cycles, and
C3N4) into copper oxide (CuO). Specifically, a Cu-BTC MOF material was 72 % after 10 000 cycles at 10 A g− 1. When assembling the
prepared at the beginning, and then g-C3N4 was introduced via ultra­ α-Fe2O3@Ag//AC ASC, it demonstrates the highest specific capacitance
sonic treatment and rapid thermal annealing as shown in Fig. 16(b). of 123 F g− 1 and energy density of 41.8 Wh kg− 1 [199]. Similarly, Chen
Consequently, a unique hollow porous CuO/g-C3N4 composite with et al. creatively resolved energy storage limitations of hematite Fe2O3 in
an octahedral structure has been successfully developed and it main­ supercapacitors through the synthesis of innovative core–shell super­
tained the original shape, additionally, with uniform carbon layer. CuO/ structures to mimic a pinecone, containing vertically aligned MnO2
g-C3N4 exhibited an outstanding reversible specific capacity of 1530.4 F nanosheets onto the surface of the Fe2O3. This is synthesized through the
g− 1 as an anode material. Furthermore, the asymmetric supercapacitor use of a sacrificial Fe-MOF (MIL-88A) template. This enhanced the en­
device was constructed with NiCo-MOF cathode and CuO/g-C3N4 anode, ergy storage, exhibiting a remarkable specific capacitance of 908.5 F
in which the remarkable energy density of 50.8 Wh kg− 1 at 800 W kg− 1 g− 1, and when used along with NiCo2O4 as cathode in hybrid super­
and stable cycling performance (70.1 % retention over 3000 cycles) capacitor, M–Fe2O3@ MnO2 reaches a remarkable energy density of
were achieved. These superior properties are ascribed to the synergistic 86.8 Wh kg− 1 at a high power density of 804.1 W kg− 1 [198].
interaction between transition metal oxides and carbon-based materials
via the specific structure of the composites. In this work, the authors 6.1.4. Manganese based oxides
provide practical architecture how carbon materials are employed to The growing interest in manganese oxides is mainly due to their
manipulate the electronic structure and morphology of MOF-derived theoretical specific capacitance as high as 1370 F g− 1 [200], which
transition metal oxide [195]. Similarly, He et al. employed a strategy makes them highly promising supercapacitor electrode materials. In
in which they combined copper metal-organic framework (MOF)- terms of exploring the preparation of MnO2 from metal-organic frame­
derived copper oxide with mesoporous carbon (CuOx@mC). This com­ works (MOFs) as supercapacitor electrode materials, recently a lot of
posite was further modified by embedding polyaniline (PANI) and researchers started paying attention to it. As a representative work on
reduced graphene oxide (rGO). The resultant CuOx@mC@PANI@rGO this path, Chen and his co-authors have published two articles which
composites exhibited a well-organized interface layer of PANI and rGO greatly demonstrate the potential of MOF-derived MnO2 as super­
on the CuOx@mC framework, leading to improved ion diffusion and capacitor electrode materials.
redox reactions. By adjusting the pyrolysis temperature of Cu-MOF, the They employed diverse methodologies:
ternary CuOx@mC@PANI@rGO composite (synthesized at 700 ◦ C)
demonstrated the highest capacitance of 534.5 F g− 1, coupled with 1. They synthesized Mn-MOF and, through calcination, transformed the
excellent cycling stability. In contrast, the CuOx@mC@PANI composite MOF into MnO2 using two distinct temperatures: 500 ◦ C and 600 ◦ C.
without rGO only showed a capacitance of 456.0 F g− 1 at 1 Ag− 1 [196]. 2. In an alternative approach, they directly cultivated MOF-derived
Other than rGO, an improvement in performance was also achieved MnO2 on carbon sheets, calcinating at a temperature of 600 ◦ C.
when graphene oxide (GO) was used with MOF-derived copper oxide.
Islam et al. developed a low temperature methodology to synthesize In the first work, they showed that Mn3(MA)(H2O)2(IPA)3, an Mn-
sheet-like CuO nanostructures supported on graphene oxide (GO) using MOF, can be converted to different forms of manganese oxide by
copper based metal organic framework (Cu-(BDC)-MOF) engineered calcination and tested electrochemical performance in a sodium sulfate
onto graphene-oxide. The synthesis route of hybrid nano materials electrolyte. It was found that the material derived at 500 ◦ C had much
consists of deposition of Cu-(BDC)-MOF crystals on exfoliated graphene higher capacity than a material made at 600 ◦ C. The 500 ◦ C made ma­
layers and alkali aging in NaOH. The CuO/GO hybrid nanostructures terial has a porous architecture, which helps with long-term stability and
were characterized by various techniques and revealed that the ho­ increased capacitance of 150 F g− 1 for a current density of 1.0 A g− 1
mogenous sheet-like CuO nanostructures exfoliate on graphene oxide [201].
with tremendous supercapacitor performance. The resulting GO/CuO In the second work, combined manganese oxide derived from Mn-
hybrid nanostructures deliver a high specific capacitance of 606 F g− 1 at MOF with carbon sheets to produce nanocomposites known as MnOx-
a scan rate of 2 m V s− 1, in addition to excellent cycling stability of 93 % CSs. These nanocomposites consist of mixed-valent manganese oxide
of the initial capacitance [197]. nanoparticles grown on ultra-thin carbon sheets. Specifically, the MnOx-
Here, low temperature and slow treatment methods provided better CSs produced at 600 ◦ C (MnOx-CSs –600) exhibited excellent perfor­
capacitance and cyclic stability than that of high temperature and rapid mance in supercapacitors (SCs). This nanocomposite achieved a notable

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

specific capacitance of 220 F g− 1 at a current density of 1 A g− 1 and The resulting NiO exhibited a specific capacitance of 485 F g− 1 at a
demonstrated an impressive energy density of 27.5 Wh kg− 1 in an current of 1 A g− 1, with an impressive capacity retention of 87 % after
asymmetric supercapacitor. The success can be attributed to its ultra- 5000 cycles. The success of this approach can be attributed to the hex­
thin carbon sheets, providing robust support for manganese oxide, agonal flaky structure of NiO which is derived from the precursor MOF,
ensuring a large surface area, high electrical conductivity, and pre­ characterized by a rougher surface and smaller particles, rendering it
venting dissolution during cycling. Additionally, the mixed-valent particularly advantageous for electrochemical processes [209]. In
manganese cations within the nanocomposite contribute to its addition to these reports, Ramachandran et al. incorporated titanium
outstanding electrochemical performance. Notably, the synthesis carbide into Ni-MOF-derived NiO. The synthesis involved heating a
method is straightforward, cost-effective, and environmentally friendly, distinct MOF/MXene composite (Ni-MOF/Ti3C2Tx) in the air to obtain
making it a promising approach for large-scale production compared to Porous NiO/Ti3C2Tx. The resulting electrode exhibited a heightened
previous methodologies [202]. specific capacity of 630.9 C g− 1 at a current density of 1 A g− 1, sur­
passing the performance of pure NiO (376.8 C g− 1) in the context of
6.1.5. Nickel-based oxides supercapacitor applications [210].
Recent studies have centered on economical transition metal oxides,
with particular attention to NiO materials. These materials have 6.1.6. Multi-metallic oxides
garnered significant interest due to their cost-effectiveness, low toxicity, Multi-metallic MOF derived oxides have known to provide promising
and environmentally friendly attributes, along with a higher theoretical electrochemical performance due to the presence multi-metal species.
capacitance (2573 F g− 1). However, the practical application of NiO For instance, Patil et al., aimed to synthesis various shapes of NiFe2O4
electrodes in supercapacitors is hindered by their high resistivity (NFO) as advanced electrode materials of supercapacitors through al­
[203,204]. MOFs are recognized as compelling active materials in terations of calcination temperature. The process involved solvothermal
electrochemical processes, given their unique compositional and struc­ method followed by annealing. Different morphologies including
tural advantages, as well as their dual role as templates and precursors threads, mesh-like structure and the grain shape of cubic spinel struc­
for diverse functional materials in energy conversion and storage. The tured bimetal MOF derived NFOs were acquired at 460 ◦ C, 500 ◦ C and
use of MOF-derived NiO, characterized by a porous nature and ordered 550 ◦ C, respectively, while the structure decomposes with rising tem­
arrangement, holds promise for enhanced conductivity and superior perature greater than 550 ◦ C. Cuboid shape of MOF derived NFO500
electrochemical performance compared to pristine NiO [205]. Jiang (MOF-MNFO) has specific area of 38.17 m2/g which is quite favorable
et al. created composite NiO/Ni@C materials from a pillared MOF for fast charge-transfer and enhancing the high storage of energy. The
named Ni2(BDC)2(DABCO) through the calcination method at 500 ◦ C. mesh-like structure help in diffusion of OH– ion accessible to entire
The metal oxide derivatives from the MOF with features containing NiO, electrode with reasonable low charge transfer resistance. The MOF-
Ni, and Carbon constituted the multiple active sites in which the supe­ MNFO electrode delivered high specific capacitance of 833 F g− 1 and
rior energy storage capability could be introduced. Metal oxide de­ specific energy of 42 Wh kg− 1 at a specific power of 154 W kg− 1 at a
rivatives from MOF showed a significant specific capacitance of 805.3 F density of 1 M KOH. It retained 74 % after 3000 cycles at 3 A g− 1 and the
g− 1 at 0.5 A g− 1 and 576.2 F g− 1 at 10 A g− 1. The assembled ASC, NiO/ coulombic efficiency value of 84 % [211]. Ting et al., synthesized
Ni@C//PEDOT-AC (poly(3,4-ethylenedioxy-thiophene)-activated car­ nanoporous electrode with metals like nickel, cobalt, and a combination
bon) demonstrated its specific energy of 20.7 Wh kg− 1, superior specific of nickel and cobalt by deriving MOF-74. Among them, the nickel–cobalt
power 12,920 W kg− 1 and held 69.7 % of its capacitance after 10,000 combination showed exceptional performance with high capacitance
cycles, accompanied by a wide working voltage window from 0 to 1.7 V (684 F g− 1) and stable cycling (86 % retention after 3000 cycles). This is
[206]. In similar way, Shin et al. raised the prospect of using a self- attributed to the nanoporous structure, which enhances the material’s
standing NiO electrode fabricated by directly transforming a Ni-MOF ability to store energy and withstand repeated use [212].
derived from nickel oxide and carbon as well as the uniform distribu­ Xijun Wei, employed a metal-organic framework (MOF) to fabricate
tion of them onto a conductive carbon nanofiber (CNF) film. The CNF a Co-Fe mixed metal oxide nanocube (CFNC) material with a composi­
film ensured the mechanical robustness and excellent electrical con­ tion of Co3O4/Fe2O3 was fabricated by employing a metal-organic
ductivity of the electrode. The resulting self-standing NiO/C@CNF framework (MOF) as a precursor. The CFNC was used as both the
electrode possessed remarkable specific capacitances of 742.2 F g− 1 at 1 anode and the cathode in symmetric supercapacitors, and exhibited
A g− 1 and 671.1 F g− 1 at 10 A g− 1. When employing the self-standing good electrochemical performances with an energy density as high as
NiO electrode as the positive electrode with activated carbon, the 35.15 Wh kg− 1 under a power density of 1125 W kg− 1 [214]. In a similar
fabricated supercapacitor device showed the excellent electrochemical fashion, Acharya et al. employed a direct approach to derive metal ox­
energy storage with high energy density and power density of 58.43 Wh ides from bimetallic MOF using a solution-based method and modified it
kg− 1 and 1,947 W kg− 1, respectively [207]. into a trimetallic oxide through a series of techniques involving chemical
In the further quest for heightened energy density, Jiao et al. crea­ reduction, ageing, etching and calcination as shown in Fig. 17. The
tively enhanced the reactivity of nickel-based nanoparticles (Ni/NiO) by process yielded hollow Zn-Ni-Co-oxide (ZNCO) nanosheet arrays on Ni
meticulously adjusting the temperature by 300, 350, 400 and 450 ◦ C foam covered with reduced graphene oxide (rGO). Initially, 2D Zn-Co-
during the synthesis process. At 400 ◦ C, the complete MOF to derivative MOF-derived nanoleaf arrays were fabricated, followed by a sequence
conversion incorporates a distinctive nickel form (Ni3+) into the nano­ of ion exchange, etching, and post-annealing steps to achieve the desired
particles where they initiated atom rearrangement, resulting in the hollow and porous ZNCO nanostructure. The resulting hierarchical
formation of numerous active sites conducive to chemical reactions. The ZNCO nanosheet array electrode exhibited notable characteristics,
flexible supercapacitor that employed these modified nanoparticles including a high specific capacity of 267 mAh g− 1, an ultra-high rate
demonstrated a specific capacitance of 136.4 F g− 1 at 2 A g− 1 and an capability (83.82 % at 50 A g− 1), and an extended cycling life (~90.16
impressive energy density of 61.3 Wh kg− 1 at power density of 900 W %). Furthermore, this electrode was assembled into a ZNCO//rGO-
kg− 1. This successful strategy underscores the importance of tempera­ MDPC hybrid supercapacitor, showcasing a higher energy density of
ture and structural modifications in materials to optimize energy storage 61.25 Wh kg− 1 at a power density of 750 W kg− 1 under a current density
and conversion. The introduction of subtle distortions in the lattice of of 1 A g− 1, with a capacitance retention of 94.52 % of its initial specific
the nanoparticles effectively augmented surface area and active sites, capacitance even after 6,000 cycles, highlighting its exceptional long-
leading to an enhancement in overall performance [208]. term durability [213].
Gao et al. similarly employed Ni-MOF-derived NiO, achieving Further, a facile post-thermal pyrolysis method has been employed
outstanding electrochemical performance at a temperature of 350 ◦ C. by Chettiannan et al., to exploit the merits of multimetallic oxides

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 17. Schematic representation for the synthesis of MOF-derived zinc-nickel–cobalt oxide on reduced graphene oxide (rGO) decorated Ni foam (rGO-NF)
(Reproduced from Ref. [213] with permission from Elsevier).

derived from metal-organic frameworks (MOFs) to synthesize NiO/ to the structure, leading to the high specific surface area of MnNi2O4
Co3O4/NiCo2O4 from NiMOF and CoMOF. Using a slow heating treat­ [216].
ment up to 600 ◦ C, they attained the preferable multimetallic oxide Chameh et al., successfully made a multi-metal oxide material by
material. The careful optimization of various NiMOF and CoMOF ratios mixing two metal oxides derived from a metal-organic framework
revealed superior outcomes, with the 4:1 ratio (NC41) demonstrating (MOF). They, then added different amounts of pure and oxidized g-C3N4
the most favorable results. NC41 composite displayed the highest spe­ to this mix to enhance its properties. Among different percentages, 10 %
cific capacity 1108.9 C g− 1 at 2 A g− 1, and sustained 95.3 % capacity Ox-g-C3N4/CeO2/CoFe2O4 combination performed exceptionally well as
retention over 5000 cycles at 10 A g− 1. The betterment of the specific a supercapacitor, showing a high specific capacitance (255.5 F g− 1). In
capacity is due to the presence of multifaceted metal oxidation, surface an asymmetric device, using the promising 10 % Ox-g-C3N4/CeO2/
oxygen defects, and reduced solvation effects as a result of solid meso­ CoFe2O4 as the cathode and activated carbon as the anode, they ach­
porous structure and larger specific surface area. When employed as an ieved a wide potential window, high-power density, and good cycling
electrode material for constructing an assembled hybridized asymmetric performance. This success is attributed to the collaboration between the
supercapacitor (NiO/NiCo2O4/Co3O4//Carbon Black), it demonstrated, porous g-C3N4 sheets and CeO2/CoFe2O4, indicating that adding g-C3N4
significant specific capacity 416.95 C g− 1 at 0.5 A g− 1, and satisfied 89.1 to MOF-derived multimetallic metal oxide is a useful strategy for
% retention over 5000 cycles at 10 A g− 1 still combined with higher improving the performance of energy storage devices like
energy density 89.81 Wh kg− 1 at a power density 387.49 W kg− 1. This supercapacitors.
demonstrates that reaction parameters like precursor ratios, tempera­
ture, choice of precursor highly influence the output efficiency [215].
Lan et al. explored an alternative material and achieved significantly 6.2. MOF derived sulfides
enhanced energy density. A flower-like nanostructured MnNi2O4
composed of porous nanosheets has been prepared through a rapid and Several researches explore the potential of MOF-derived sulfides for
simple MOF-induced thermal synthesis. Such intriguing micro/nano the application as supercapacitor electrode. A remarkable attribute of
structure can guarantee a large surface area and a great amount of active these MOF-derived sulfide materials is their increased electrical con­
sites, thus leading to the outstanding performance of MnNi2O4 as a ductivity, which stems from sulfur’s relatively lower electronegativity in
supercapacitor electrode. The electrode exhibited a high specific comparison with oxygen. However, these advantageous properties are
capacitance of 2848 F g− 1 at 1 A g− 1, and excellent rate capability and hindered by constraints such as slow charging/discharging kinetics and
very good cycle stability, with 93.25 % of capacitance retention after poor cycle life. To boost the capabilities of transition metal sulfides, it is
5000 charge–discharge cycles at 10 A g− 1. Moreover, an asymmetric possible to introduce defects or voids that capitalize on the unique
supercapacitor device using MnNi2O4 as the positive electrode and structural properties native to MOFs.
active carbon as the negative electrode has been fabricated, delivering a
very high energy density of 142.8 Wh kg− 1 at a remarkable power 6.2.1. Cobalt-based sulfides
density of 800 W kg− 1. Even operated at a high power density of 16 kW Xiao et al. put forward a new approach by sulfurizing the Co-MOF
kg− 1 the energy density goes up to 56.8 Wh kg− 1. electrode, which is the first report of sulfurizing with Co-MOFs. Sulfu­
The flower like unique structure and multi-metal composition of the rized MOF samples showed various morphologies. The Co-MOF sample
MnNi2O4 electrode is an important basis of success in this work and treated with thiourea (S67/CC-thiourea) shows wrinkled morphology
differentiate from the existing works. The homogeneous MOF-derived and connected aggregation between particles, resulting in the apparent
metal oxide strategy can successfully inherit the flower-like increment of the specific surface area and the electrical conductivity.
morphology of Mn/Ni-MOF precursor, and many pores are introduced And, the S67/CC-thiourea exhibit good specific capacitance (469.5 F g− 1
at 4 A g− 1), which was approximately 50 times as that of the pristine Co-

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

MOF electrode (8.0 F g− 1). However, when the researchers constructed 2) In the second study by the same team, Tao et al. focused on syn­
an asymmetric supercapacitor with an activated carbon as a negative thesizing a porous zinc cobalt sulfide nanosheet array on Ni foam
electrode and the S67/CC-thiourea as positive electrode, the achieved (Zn-Co-S/NF) by growing 2D zinc/cobalt-based metal-organic
maximum energy density was 3.25 Wh kg− 1 at 275 W kg− 1, falling framework (Zn/Co-MOF) nanosheets on NF, followed by additional
somewhat below expectations. Consequently, the focus has shifted to­ sulfurization as shown in Fig. 18(b). The resulting Zn-Co-S/NF
wards exploring MOF-derived sulfides instead of employing composites nanosheet array directly served as a supercapacitor electrode and
or direct sulfuration of pristine MOFs. This strategic shift aims to exhibited superior electrochemical performance compared to zinc
enhance the electrochemical performance of supercapacitors [217]. cobalt sulfide powder. The Zn-Co-S/NF nanosheet array as super­
Han et al., explored the amalgamation of oxides with sulfides, capacitor electrode exhibits superior electrochemical performance
revealing that cobalt nickel sulfide’s electrochemical behavior can (2354.3 F g− 1 and 88.6 % retention over 1000 cycles), much better
greatly benefit from the synergistic effect provided by a Co-MOF-derived than zinc cobalt sulfide powder (355.3 F g− 1 and 75.8 % retention
Co3O4 framework. Even though ternary cobalt nickel sulfide holds po­ over 1000 cycles). The asymmetric supercapacitor device assembled
tential as an electrode material for supercapacitors, barrier to its wide from Zn-Co-S/NF and activated carbon electrodes achieved an
usage include poor electrochemical durability, diminished rate capa­ impressive energy density of 31.9 Wh kg− 1 and a maximum power
bility, and undesired nano-configuration. The properties inherent to density of 8.5 kW kg− 1. Notably, this ASC demonstrated robust
MOF-originating metal oxides owe much to their large surface area ar­ cycling stability, retaining 71.0 % of its capacity over 10,000 cycles
chitectures, such structures render them conducive to surface transport [220].
processes and provide shorter routes for electrolyte diffusion. To tap into
these benefits, they engineered petal-shaped Co3O4@CoNi2S4 nanowall Tao et al.’s research highlights the effectiveness of MOF-derived
arrays on carbon cloth designing a free standing electrode for asym­ metal sulfides in enhancing the electrochemical performance of super­
metric supercapacitors. This specially designed Co3O4@CoNi2S4 pre­ capacitors, offering promising advancements in energy storage tech­
sents an impressive specific capacity of 244.4 mAh g− 1 at 1 A g− 1 current nology. Similarly, Gong et al., designed a core–shell structure of NiCo2S4
density and maintains remarkable rate performance, preserving 81.3 % on nickel foam by using MOF as precursor. This material displayed a
capacity even at a 16 A g− 1 current density. Moreover, when assembled specific capacity of 850.2 C g− 1 at 1 A g− 1 and maintaining 93.6 % of its
into a Co3O4@CoNi2S4//AC ASC, this configuration delivers high energy original capacity after 5000 cycles [221].
density of 55.6 Wh kg− 1 at power output of 884.4 W kg− 1. It showed a
86 % capacity retention after enduring 10,000 charge–discharge cycles 6.2.2. Copper-based sulfides
[218]. The copper sulfides, due to their distinctive applications in various
Tao et al. conducted two consecutive research studies focusing on the high-tech technological fields such as electronics, sensors, catalysis,
utilization of metal-organic frameworks (MOFs) to fabricate specialized photovoltaics, energy storage etc., are considered as highly relevant
materials for supercapacitors. materials [222]. A number of researchers focused on the electrode
performance of MOF-derived copper-based sulfides to refine the elec­
1) In the first study, they developed a hierarchical nickel–cobalt sulfide trochemical performance of MOF. In their work, Wu et al., presented an
nanosheet array on a conductive nickel foam (Ni–Co–S/NF) without innovative and environmentally friendly synthesis of Cu1.96S/C hybrid
the need for binders. The synthesis process involved the in-situ composites by using metal-organic framework (Cu3(1,3,5-benzene­
growth of uniform 2D Co-based MOF nanowalls on Ni foam, fol­ benzene-triyl)-benzenesulfonate) as a precursor. They used sulfidation
lowed by their transformation into hierarchical Ni-Co-S nano­ method to uniformly incorporate ultrafine Cu1.96S NPs into porous
architectures through etching and ion-exchange reactions with Ni carbon octahedra with in situ formation. This strategy retains the
(NO3)2, and subsequent solvothermal sulfurization as shown in octahedral structure of MOFs to the final Cu1.96S /C composite even
Fig. 18(a). This Ni-Co-S/NF electrode demonstrated exceptional during the process of sulfidation and carbonization. The electrochemical
electrochemical capacitive performance, with a high specific measurements were also performed in the 1 M KOH aqueous electrolyte
capacitance of 1406.9 F g− 1 at 0.5 A g− 1, 53.9 % retention at 10 A and Cu1.96S /C-650 demonstrated great capacitance stability, leading to
g− 1, and an impressive cycling stability of 88.6 % retention over a smaller capacitance value than that in H2SO4 electrolyte (34.2 F g− 1 vs
1000 cycles. Furthermore, ASC assembled with Ni-Co-S/NF as the 63.8 F g− 1 at a scan rate of 100 m V s− 1, respectively) [223]. Just like
positive electrode and activated carbon as the negative electrode previously mentioned report, carbon-coated copper sulfide (Cu7S4) have
exhibited a high energy density of 24.8 Wh kg− 1 at a power density of also been synthesized via one-step sulfuration of copper trimesate
849.5 W kg− 1 [219]. (Cu3(BTC)2). Li et al. prepared Cu7S4 hybrid materials on a large scale by

Fig. 18. (a) Schematic diagram of the formation process of Ni-Co-S (Reproduced from Ref. [219] with permission from the Royal Society of Chemistry), (b)
Schematic diagram for the synthesis of Zn-Co-S/NF and Zn-Co-S-P. (Reproduced from Ref. [220] with permission from John Wiley and Sons).

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

pyrolysis of Cu3(BTC)2 metal-organic framework (MOF) under a sulfur higher specific capacitance of 1128 F g− 1 at 2 A g− 1. Furthermore, Ni-
atmosphere at 600 ◦ C. The synthesized Cu7S4nanoparticles with a size of MOF@NiS2 was also used to fabricate an all-solid-state asymmetric
approximately 100 nm show a cobble-like morphology, which are supercapacitor (ASC) with AC as the negative electrode which offered a
encapsulated by amorphous carbon. When being used as electro­ reasonable energy density of 23.5 Wh kg− 1 and excellent cycling sta­
chemical capacitor, Cu7S4/C electrode exhibited excellent electro­ bility (95.2 % capacitance retention after 10,000 discharge–charge cy­
chemical performance, the highest capacitance reached 321.9 F g− 1 cles). This work offer an exclusive strategy of using MOF as composite as
with a specific capacity of 80.5 mAh g− 1, at a current density of 0.5 A well as derivative [229].
g− 1, which is superior to reported Cu7S4-based electrode materials. More Tian et al., were able to achieve a high porosity in the material with a
importantly, the electrode has nearly 78.1 % of its capacitance retained large exposed surface area, by combining carbon nano fibers (CNF) with
after 3000 cycles, demonstrating its good cyclic stability [224]. Another MOF derived Ni3S2. By growing metal-organic frameworks (MOFs) on
interesting method was devised by Niu et al., which involved the syn­ pre-oxidized electrospun polyacrylonitrile (PAN) nanofibers and later
thesis of HKUST-1 derived copper sulfide (CuS) polyhedrons and carbon carbonization and sulfurization developed hierarchical Ni/Ni3S2 deco­
nanotubes (CNT) and their use as a binder-free flexible composite rated carbon nanofibers (CNFs) materials. With these particular process
electrode. A peculiar synergistic interaction between such constituents conditions, synthesis of Ni3S2 nanoparticles of 14 nm nucleating uni­
markedly enhanced the electrochemical performance of the composite formly onto the PAN-derived CNF surface was successful. The hierar­
thin film used for supercapacitor electrode. The composite thin film chical hybrid materials exhibited excellent electrochemical
demonstrated specific capacitance of 606.7 F g− 1 with a current density performances as supercapacitor electrodes with high specific capaci­
of 1 A g− 1 for the asymmetric supercapacitors, while energy density of tance of 830 F g− 1 at 0.2 A g− 1. Solid-state supercapacitor assembled
the device was efficiently increased to 38.4 Wh kg− 1 at a power density with Ni/Ni3S2@ CNFs delivered energy density of 31.6 Wh kg− 1 at a
of 750 W kg− 1 by assembling the HKUST-1 derived CuS polyhedrons and power density of 1800 W kg− 1 and maintained high capacitance reten­
N-doped carbon polyhedrons into CNT films for positive and negative tion of 95.7 % after 5000 charge–discharge cycles [230]. This indicates
electrodes. Most impressively, these supercapacitors showed highly along with sulfuration, particle size also greatly influence its
remarkable cycle stability with a capacity retention of 87.0 % after 6000 performance.
cycles [225]. In similar fashion, Liu et al., also utilized HKUST-1 to Moreover, several researches insist that incorporation of sulfur va­
derive copper sulfide (CuS). They applied a calcination-vulcanization cancies into lattice is an effective way to enhance the interface reaction
technique to prepare Cu9S8@C in carbon fiber cloth. HKUST-1 was activity and acceleration reaction kinetics through optimized electronic
transformed into Cu9S8 nanoparticles and organic ligand contribute in conductivity. The design of transition metal sulfides with sulfur vacancy
the production of amorphous carbon in Cu9S8@C after calcination at defects dispersed on network-like structures can improve the electro­
high temperature and vulcanization. With addition of conducting chemical performance of electrode materials [231].
polymer (ppy), PPy/Cu9S8@C-CC nanocomposite electrode was devel­ In their work, Qu et al. improved the performance of MOFs derived
oped with the help of electrochemical deposition method. PPy/ metal sulfides for supercapacitor application by introducing sulfur va­
Cu9S8@C-CC electrode demonstrates 270.72 F g− 1 specific capacitance cancies. The authors prepared the porous nickel sulfide derived from Ni-
with 80.36 % retention rate after 3000 cycles [226]. based MOF and converted it into r-Ni3S2 (nickel sulphide after reduction
Nevertheless, these investigations on MOF-derives copper sulfide treatment) with a unique tailored structure of folded nanoparticles
based materials have yet to yield significant improvements in achieving composed of petal-like flakes, which could not only provide increasing
a satisfactory level of specific capacitance. To address this, Zhao et al. the specific surface area but also more active sites were exposed. After
have pioneered the development of a three-dimensional hierarchical reduction by using sodium borohydride, the specific capacitance became
hollow electrode material, namely Cu(NiCo)2S4/Ni3S4, achieved 1571.8 F g− 1 at the current density of 1 A g− 1 which increased 32 % after
through the etching of a precisely defined bimetal organic framework 5000 cycles. The asymmetric supercapacitor (r-Ni3S2//AC) was also
(CuCo-MOF). This trimetallic sulfide structure, with its large surface assembled, which delivered a specific energy of 33.7 Wh kg− 1 at a power
area, hierarchical pore distribution, and enhanced conductivity, offers density of 1167.8 W kg− 1. This study reveals the promising value of
abundant active sites for redox reactions and facilitates rapid charge tuning the crystal structure and adding sulfur vacancies in order to
transfer. The Cu(NiCo)2S4/Ni3S4 electrode displayed a high specific enhance their unsatisfied cycle performance and low specific capaci­
capacitance of 1320 F g− 1 at 1 A g− 1, retaining 85 % of capacitance after tance in MOF-derived sulfide [232]. In a similar strategical approach,
5000 cycles. Moreover, in a hybrid supercapacitor with activated car­ Huang et al. focused their research on the development of high-
bon, it achieved a notable energy density of 40.8 Wh kg− 1 and a performance battery-type electrode materials with a specific emphasis
remarkable power density of 7859.2 W kg− 1 [227]. on metal sulfides, particularly transition metal sulfides (TMS). TMS have
been considered for the next generation of electrode materials due to
6.2.3. Nickel-based sulfides their merits as there are plenty of transition metals that can participate
Nickel and cobalt sulfides have recently been the subject of increased in the intercalation/deintercalation reaction, have affordable prices, and
research attention due to their robust Faradic redox activity, high the processing flexibility. However, there has been a great challenge in
capacitance, low cost, and the low environmental cost involved in their using TMS due to their poor conductivity and sluggish redox reactions.
processing. The band gaps of sulfides can be tuned, and different phases Therefore, in their work, they adopted the employment of nanosized
of sulfides can be realized, providing significantly broadened choices for hollow-structured Ni-based MOFs to prepare hollow-constructed nano-
the study’s investigation. Compared with metal oxides, sulfides possess size carbon-coated nickel sulfide nanocrystal (H-NiS1− x/C) with effec­
higher ductility and more complicated crystal structures, which can be tive sulfur vacancies through straightforward ion exchange and thermal
attributed to the higher electronegativity of sulfur. This property of annealing. The as-prepared H-NiS1− x /C-50 showed an excellent elec­
sulfides is critical and beneficial for stability and can increase the control trochemical performance of a high capacity of 1728 F g− 1, robust cycling
level of volume effect. The MOF-derived Nickel sulfur is one of the performance (72 % capacity retention after 8000 cycles), and high rate
candidates with great promise [228]. To address the limitation on the performance. As an asymmetric supercapacitor, it also demonstrated a
application of MOF due to the poor electrical conductivity and stability, high energy density of 36.88 Wh kg− 1 owing to the improved conduc­
Jiawei Zhang et al. designed a rational heterogeneous structure to tivity via desired sulfur vacancies and unique structure [233].
construct ultra-thin Ni-MOF@NiS2 nanosheet arrays derived from a Ni-
MOF self-sacrificed template and precursor. The novel-designed heter­ 6.2.4. Multimetallic sulfides
ostructure not only enhanced the conductivity but also possessed porous Just like multi-metal oxides, MOF precursors have also been
Ni-MOF structure. Meanwhile, the Ni-MOF@NiS2 electrode displayed employed to synthesis multi metal sulphides. Kang et al. have published

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

a new strategy for the synthesis of the hollow rod-like NiCoMn ternary capacitance increases with the increasing of the NiS2 content. In addi­
metal sulfides nanosheets (NiCoMn-S). NiCoMn-S with an internal tion, assembled asymmetric supercapacitors (ASCs) are constructed
porous structure was fabricated by etching/ion-exchange reaction and a with the NiS2/CoS2/NC-500 as positive electrode and Activated carbon
subsequent sulfurization process through metal-organic frameworks as negative electrode, the operated ASC achieves a high-energy density
(MOFs) template. It is addressed that the unique hollow structure with of 53.93 Wh kg− 1 at power density of 800 W kg− 1 and remarkable cycle
three-metals in combination dramatically facilitate the electrolyte stability of 85.71 % capacitance retention after 20,000 cycles at 5 Ag− 1.
penetration and electron/ion transportation. The as-constructed NiC­ The significant specific capacitance and were attributed to the stable
oMn-S material shows very good electrochemical performance, and the structure formed at 500 ◦ C, presence of sulfur, combination of multiple
NiCoMn-S electrode delivers better specific capacitance (2098.2F g− 1 at metals which resulted in the efficient charge transfer [235].
1 A g− 1) than those of other controlled sulfides. The asymmetric
supercapacitor (ASC) built with NiCoMn-S exhibits a good specific 6.3. MOF derived phosphides
capacitance of 124.5 F g− 1 at 1 A g− 1, and a maximum energy density of
50.0 Wh kg− 1 at 850.0 W kg− 1, and a good capacitance retention (73.6 Metal phosphides have emerged as one of the most important elec­
% after 6000 cycles) [234]. Liu et. al. prepared a sulfide-based mono­ trode for supercapacitor due to their high active sites, unique physical
metal composites (NiS2/CoS2/NC) by carbonization and sulfuration of and chemical property and porous structure. Several studies clearly
Ni/Co based MOF via incorporating nitrogen-doped carbon(NC) to indicate that the metal phosphides obtained from the MOFs have
optimize electrical conductivity. Remarkably, NiS2/CoS2/NC material excellent electrochemical performances compared to other metal phos­
(NiS2/CoS2/NC-500) fabricated at 500 ◦ C showed a distinctive rod-like phides because of the enhanced capacitance, specific surface area, better
structure. Benefiting from the unique nanostructure and the pore-sized stability, excellent electrical conductivity, large pseudo capacity, high
distribution, the specific capacitance of NiS2/CoS2/NC –500 reached rate capability and many other results [236]. Moreover, the MOFs
up to 1325 F g− 1 at 1 Ag− 1 and excellent capacitance retention of 75 % derived metal phosphides have a high performance as well as scale
remains after 5000 cycles at 5 Ag− 1. Interestingly, the specific synthesize, which are very important for the commercial applications.

Fig. 19. (a) Schematic illustration of etching of ZIF-67 and phosphorization of NiCo-LDH (Reproduced from Ref. [237] with permission from Elsevier), (b) Schematic
illustration of oxidation of CuCo-ZIF and phosphorization of Cu:Co3O4 (Reproduced from Ref. [238] with permission from Elsevier).

24
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

For instance, Xu et al. focused on the synthesis of a cobalt-based kW kg− 1 [238].

phosphide, employing a cost-effective approach to create hollow bime­ Using the combination of multimetallic phosphate and multimetallic
tallic phosphide (NixCo1− xP). This involved the etching of ZIF-67 and sufide, Zardkhoshoui et al., have achieved a remarkable breakthrough in
subsequent low-temperature phosphorization of NiCo-LDH with supercapacitor technology, attaining an ultrahigh energy density of
NaH2PO2 in a N2 atmosphere, as illustrated in the Fig. 19(a). The posi­ 158.4 Wh kg− 1, which stands as one of the highest reported values to
tive outcomes were attributed to effective electrode–electrolyte date. Their approach involved the synthesis of yolk-shell Cu-Co-P hollow
connection, the distinctive hollow structure, and the favorable con­ nanospheres through a cost-effective hydrothermal method. Recog­
ductivity of NixCo1− xP. The NixCo1− xP composites displayed an nizing the challenge of low specific capacitances in both positive
enhanced specific capacity of 548 C g− 1 at a current density of 1 A g− 1A (cathode) and negative (anode) electrode materials as a significant
g− 1, with a substantial capacity retention of 66.2 % even as the current obstacle for asymmetric supercapacitors (ASCs), the researchers
density increased to 40 A g− 1. Furthermore, the hybrid supercapacitors, employed yolk–shell Cu–Co–P hollow nanospheres (Y-CCP HN) as the
utilizing NixCo1− xP as the anode and active carbon as the cathode, positive electrode, utilizing a metal-organic framework (MOF). Simul­
exhibited a broad applied potential window of 0–1.4 V and demon­ taneously, they utilized CuFeS2 nanosheet (CFS NS) arrays as the
strated prolonged cycling performance, retaining 98.3 % capacitance negative electrode, employing a low-cost and simple hydrothermal route
after 10,000 cycles. This configuration achieved a high gravimetric en­ for ASCs. The Y-CCP HN and CFS NS electrodes demonstrated substan­
ergy density of 31.52 Wh kg− 1 at a gravimetric power density of 700 W tial specific capacitances of 2043.3 F g− 1 (340.55 mAh g− 1) and 654.3 F
kg− 1, maintaining 8.96 Wh kg− 1 at 7000 W kg− 1 [237]. Elayappan et al. g− 1 (218.1 mAh g− 1), respectively, impressive rate performances
employed a another distinct approach to create a phosphate-based (~77.55 % and 63.2 %, respectively, even at 24 A g− 1), and outstanding
metal-organic framework (MOF) derivative. They developed a com­ durability (96.7 % and 95.3 % after 8000 cycles, respectively). Notably,
posite material (CoP–CoNC/CC) by integrating MOF-derived cobalt the Y-CCP HN//CFS device exhibited a remarkable energy density of
phosphide and cobalt nanoparticles into nitrogen-doped nanoporous 158.4 Wh kg− 1 at a power density of 900.3 W kg− 1, along with a notable
carbon. The fabrication process involved simple precipitation followed specific capacitance of 352.1 F g− 1 (176.05 mAh g− 1), and excellent
by pyrolysis–phosphatization. The resulting CoP–CoNC/CC demon­ cyclability (96.1 % after 8000 cycles). This research showcases an
strated a high surface area with adjustable pores, contributing to effective strategy for constructing metal phosphides alongside metal
enhanced supercapacitor performance. Notably, it exhibited a high sulfides with porous characteristics [241].
capacitance of 975 F g− 1 at 1 mA cm− 2. When utilized as a positive Utilizing a straightforward calcination technique, Kavian et al. syn­
electrode in a hybrid supercapacitor alongside activated carbon as the thesized nickel phosphide (NiP) and bimetallic nickel–cobalt phosphide
negative electrode, it showcased a specific capacitance of 144 F g− 1, a (NiCoP) from Ni-MOF and NiCo-MOF, respectively. The NiCoP com­
remarkable energy density of 39.2 Wh kg− 1, and stability of 86.5 % pound proved to have a very good performance in which a high specific
retention even after 5000 cycles. This result is attributed to the syner­ capacitance of 1456 F g− 1 was obtained at a current density of 2 A g− 1,
gistic effects of MOF-derived CoP, cobalt metal, and nitrogen-doped and a favorable capacitance retention of 968 F g− 1 was achieved at 100
nanoporous carbon on a three-dimensional carbon cloth [239]. How­ A g− 1. This extraordinary behavior is due to the existence of cobalt metal
ever, Wang et al., have conducted a study on how temperature in­ in the redox processes, and the effect of nickel–cobalt synergistic in­
fluences performance by creating MOF derived-CoP-T microcubes at teractions during charge–discharge process. And, a supercapacitor using
different temperatures of T = 300, 350, and 400 ◦ C, featuring both solid NiCoP/NF as a positive electrode, activated carbon as negative electrode
and hollow structures. These microcubes were produced via a phos­ showcased an energy density of 36.87 Wh kg− 1 at a power density of
phidation process using the [CH3NH3][Co(HCOO)3] precursor at the 2250 W kg− 1 [242].
aforementioned temperatures. The hollow microcubes created at 350 ◦ C
notably offered a much larger specific surface area (25.9 m2/g) than 6.4. MOF-derived Hydroxides
their solid counterparts, which measured only 16.1 m2/g. When assessed
for use in supercapacitors, the electrode made from hollow CoP micro­ Hydroxides derived from MOFs have a layered structure, high spe­
cubes at 350 ◦ C exhibited enhanced electrochemical capabilities (560 F cific capacitance, high specific surface area, and many active sites. In
g− 1) in contrast with the solid sample (427.6 F g− 1), at an applied cur­ addition, they possess special properties for ion exchange and excellent
rent density of 1 A g− 1. This improvement in the supercapacitor’s redox activity. Hydroxides derived from MOFs are widely used as elec­
characteristics can be ascribed to the increased surface area after trode materials in supercapacitors. MOF-derived hydroxides not only
phospidation at that specific optimal temperature. Further, an asym­ inherit the advantages of the precursor MOFs but also overcome the
metric supercapacitor device was engineered using hollow CoP-350 ◦ C shortcomings of common hydroxides, such as instability, poor conduc­
microcubes as the anode and Nitrogen-doped graphene serving as the tivity and agglomeration [243].
cathode, but it displayed a bit poor capacitive retention of 69 % when Generally, Acidic and alkaline process have been recognized as the
the current increased from 0.5 to 8 A g− 1. It also offered an energy most common approaches for stripping precursors of LDHs. Li et al., for
density of 21.4 Wh kg− 1 at a power density of 373 W kg− 1, and excep­ the first time designed a facile alkaline process for removing the pre­
tional durability, with 81.2 % capacity retention even after 6000 cycles cursors to prepare LDH derived from bimetallic MOFs (Ni-MOF@Co-
[240]. Sun et al. addressed the challenges associated with lower capacity MOF). It is worth noting that many types of redox reaction centres
and durability in transition metal phosphides. To tackle these issues, present in such LDH derived from MOF, contributing to the high ca­
they devised a straightforward method involving the treatment of metal- pacity, and the redox reaction area is greatly expanded owing to the
organic frameworks (MOFs) to create mesoporous Cu-doped CoP formation of hollow nanoflowers, which have a higher circumference as
nanosheet arrays on carbon cloth. The incorporation of copper (Cu) into compared to the bulk. Furthermore, exfoliated sheets with high specific
the CoP matrix significantly enhanced the overall electrochemical per­ surfaces caused by alkali peeling have more reactive sites to make better
formance of the electrode. The synthesis process, depicted in the Fig. 19 contact with the electrolyte and facilitate the redox reactions. This LDH
(b), involves in-situ growth, oxidation of CuCo-ZIF, and phosphorization derived from the bimetallic MOF inherits the structure of MOF, inher­
of Cu:Co3O4 to yield Cu: CoP. The optimized Cu: CoP electrode exhibited iting the stable structure, excellent performance, and improved capac­
a notable capacity of 113.3 mAh g− 1, improved rate capability (61.6 % ity, but also overcame the disadvantage of poor conductivity, low rate
retention at 80 A g− 1), and excellent cycling stability (85.7 % retention ability, and serious agglomeration of hydroxides. As a result, the fabri­
over 5000 cycles at 16 A g− 1). In the hybrid supercapacitor (HSC) de­ cated electrode showed exceptional gravimetric capacitance of 1088 C
vice, pairing the optimized Cu: CoP with activated carbon resulted in a g− 1at 1 A g− 1 with a good cyclability of 94 % retention after 12,000
remarkable energy density of 31.5 Wh kg− 1 at a power density of 15.9 cycles. Furthermore, it is worth noting that the assembled B-SH device

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

displayed an ultrahigh energy density of 66.5 Wh kg− 1 at the power its capacitance decreased by only 6.8 % [248].
density of 825 W kg− 1, much better than those of some symmetric These studies emphasize a promising concept of employing metal
hybrid capacitors reported from the same perspective and higher cycle hydroxide materials derived from MOFs, possessing optimal character­
retention and coulombic efficiency of 86 % and 95 % after storing istics for facilitating effective electron transport and electrolyte
18,000 h [243]. Huang et al., revealed a new outlook for green energy accessibility.
storage research by using metal-organic framework MIL-88A as the
precursor. For the positive electrode, they derived iron-cobalt–nickel 6.5. Insights on MOF derivatives
hydroxides (Fe-Co-Ni-OH), which showed a specific capacitance of
1065 F g− 1 with excellent rate performance and stability. The negative MOF derivatives like metal oxides, sulfides, phosphides, and hy­
electrode was MOF-derived Fe2O3 compounded with reduced graphene droxides are promising. Notably, various synthesis methods, such as
oxide (Fe2O3/RGO-1), which led to a specific capacitance of 734 F g− 1 thermal decomposition, calcination, sulfurization, and phosphorization,
with much improved cycle stability. The energy density of the Fe-Co-Ni- have been employed to transform MOFs into metal oxides, sulfides,
OH// Fe2O3/RGO-1 ASC reached 43.11 Wh kg− 1 even at a high power phosphides, and hydroxides, respectively.
density of 800 W kg− 1, outperforming other recently reported devices. To obtain MOF-derived metal oxides, the thermal decomposition or
This research offers a new approach using the same precursor material calcination of MOFs has been essential. Examples include the trans­
(MIL-88A) to derive materials that can be used for both positive and formation of ZIF-67 into nanoporous cobalt oxide (Co3O4) and the
negative electrodes [244]. synthesis of hollow Zn-Ni-Co-oxide (ZNCO) nanosheet arrays mentioned
In similar manner, Xiao et al, did two works: earlier. By tailoring the annealing process with specific temperatures
and durations, the desired properties can be attained by preventing
1. In the first work, in their initial study, Xiao et al. synthesized hier­ collapse and optimizing electrochemical capabilities. The challenges
archical Ni(OH)2 structure for supercapacitors by using a Ni-based include achieving a gentle balance between high specific capacitance
metal-organic framework (MCF-35) as a template. Precise control and stability over extended cycling. The selection of precursors, control
of the reaction time and acid concentration in the mixture allowed over reaction conditions, and understanding the synthesis process are
them to tune the structure of the Ni(OH)2 to a range of perfection key aspects demanding attention. In the realm of metal sulfides, inno­
somewhere between highly crystalline and highly porous, and the vative sulfurization techniques and controlled synthesis methods have
optimal structure showed large adsorption capacity for active species led to notable advancements. The sulfurization of Co-MOF electrodes
and excellent ion and electron diffusion rate. The hierarchical Ni and the subsequent formation of Co3O4@CoNi2S4 nanowall arrays
(OH)2 exhibited a high specific capacitance of 2255 F g− 1 at 0.5 A demonstrate the potential of MOF-derived structures. Challenges persist
g− 1. The integration of the optimized Ni(OH)2 with active carbon in a in achieving high energy density, and addressing electrochemical
hybrid supercapacitor led to a remarkable gravimetric energy den­ durability. The integration of additional elements and the use of carbon-
sity of 42.54 Wh kg− 1 at a high power density. The superior per­ based materials, such as graphene oxide and carbon nanotubes, aim to
formance on the energy storage performance of the porous Ni(OH)2 improve specific capacitance, stability, and energy density. Challenges
electrode indicated the significant application potential of the MCF- include refining synthesis techniques and optimizing reaction conditions
35 template [245]. for enhanced electrochemical performance. Metal phosphides derived
2. In the second work, they described the rational design of controlled from MOFs, showcase high active sites, unique properties, and a porous
alkaline hydrolysis routes to achieve MOF-to-LDH via a pseudo­ structure. The synthesis of cobalt-based phosphide (NixCo1− xP) and the
morphic transformation. The reaction of MOF75(Ni) and Co-MOF development of a composite material (CoP–CoNC/CC) demonstrate
with KOH affords a phase-pure LDH material with preserved MOF effective electrode–electrolyte connection and a distinctive hollow
morphology. Ni3(μ3-OH) and Co3(μ3-OH) clusters were critically structure, contributing to superior supercapacitor performance. Chal­
involved in the structural assembly of LDH materials affording lenges lie in the multi-step synthesis processes, such as etching, phos­
exquisite control over leaching of metal cations and uncontrolled phorization, and pyrolysis–phosphatization, requiring careful
growth of hydroxides. The resulting LDHs exhibited a hierarchical optimization for seamless integration and desired properties. Achieving
pore structure and retained sphere shaped morphology after con­ a well-controlled synthesis for stability, scalability, and cost-
version. The optimized LDH was examined for supercapacitor ap­ effectiveness remains a challenge.
plications and displayed a specific capacitance of about 1652 F g− 1 at MOF-derived hydroxides, characterized by a layered structure, high
1 A g− 1, excellent cycle performance (with a capacitance retention of specific capacitance, and abundant active sites, present significant ad­
nearly 100 % over 2000 cycles) [246]. vantages. Alkaline processes, such as pseudomorphic transformations
from MOFs to layered double hydroxides (LDHs), have been explored by
Unlike previous study, Liu et al, included manganese instead of co­ researchers. Challenges include addressing low rate capability, and
balt by synthesizing manganese-nickel double hydroxide (MnNiDH) by agglomeration of hydroxides. Achieving a balance between crystallinity
alkalizing the precursor Mn/Ni-MOF-74. The resulting MnNiDH with a and porosity is also important for enhancing ion and electron diffusion
spear-shaped structure exhibited a small particle size and abundant rates.
microporous structure after activation by using potassium hydroxide. Among the MOF-derivatives discussed in various literature sources
The small size and rich structure improve the path for ion transport, above, several disadvantages have been highlighted, underscoring the
which is beneficial for its electrochemical activity. As a result, the need for more targeted research in the future. For instance, many studies
MnNiDH shows a capacitance of 2498 Fg− 1 at a current density of indicate that synthesizing MOF-derivatives often involves multi-step
1Ag− 1, and an aqueous device displays a high energy density of 58.53 processes and costly precursor materials. The expense can further in­
Wh kg− 1 [247]. In another study, Bi et al. addressed the challenges with crease when specific MOFs like M-BTC, M-DHTP, M-PTA, and zeolitic
individual LDHs like low conductivity and tendency to agglomerate by imidazolate frameworks (ZIFs) are required, given their prominence in
developing MOF-derived hierarchical CuO@NiCo-LDH hollow nano­ recent MOF research. These cost factors impede their progress toward
cage heterostructures developed through etching and oxidation of cop­ scalability [249,250]. As mentioned in this section, many derivatives
per foam (CF). They displayed a high specific capacitance of 5607 necessitate high to very high temperatures for their formation, which
mF cm− 2 at 1 mA cm− 2, and remarkable cycling stability with 93.1 % not only adds to the cost but also demands specialized high-temperature
capacitance retention after 5000 cycles. Furthermore, an asymmetrical equipment. Addressing these disadvantages in future research can lead
supercapacitor comprising CuO@NiCo-LDH/CF and activated carbon to the development of more cost-effective and stable high-performance
showed a peak energy density of 47.3 Wh kg− 1. Even after 10,000 cycles, MOF derivatives suitable for supercapacitor applications.

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Furthermore, certain newly discovered MOFs exhibit remarkable suitability for a wide range of energy-related applications.
conductivity in their pristine state, potentially surpassing the perfor­ Recently reported MOF derivatives and their electrochemical per­
mance of MOF derivatives. This suggests a pathway for utilizing MOFs formance including specific capacitance, energy density, and power
directly without the need for extensive modification. However, density are given in Table 5.
achieving mechanical and chemical stability comparable to that of de­
rivatives will necessitate significant research efforts in the coming years. 7. Morphology-controlled MOF-based materials
Currently, our understanding of these MOFs is limited. The application
of advanced and adaptable synthetic methods is anticipated to expand The strategies explored in the previous section includes the inte­
the understanding of MOFs and their derivatives, increasing their gration of redox metal/linker, MOF composites, and deriving electrode

Table 5
Recent reports on MOF derivatives and their electrochemical performance.
Name of the MOF material Type of derivative Specific Power density Energy density Retention capability Reference
capacitance

MOF-derived NiZnCo-P nano-array MOF- derived Ternary 2816 F g− 1 750 W kg− 1

62.5 Wh kg− 1
89.5 % after 10,000 [251]
Metal phosphate at 1 A g− 1 cycles
MOF-derived V2O5 electrode MOF- derived Metal oxide 12.27 mF cm− 2 – 2.21 × 10− 3 50 % after 7000 cycles [252]
at 0.05 mA cm− 2 mW h cm− 2
MOF-derived NiO/Ni MOF derived Metal oxide/ 104.6 mAh g− 1 2393 Wkg− 1
26 90 % after 1000 cycles [253]
metal Wh kg− 1
− 1 − 1
Bi-metallic MOF Derived MOF derived Binary 1392 F g at 1 A 8238.2Wkg 62.7 92.4 % after 10,000 [254]
(Ni-Fe)-P-C metal g− 1 Wh kg− 1 cycles
phosphate
Bimetallic MOF derived Ni–Fe–O/NPC on MOf derived Binarymetal oxide 1419Fg− 1 892.2 41.3 88.5 % after 10,000 [255]
porous carbon nanofibers at 1Ag− 1 Wkg− 1 Wh kg− 1
cycles
Ni-MOF derived NiO/Ni/r-GO Metal Oxide/metal/r-Go 649.22 4.136 39.59 81.1 % after 5,000 [256]
composite Cg− 1 kWkg− 1 Wh kg− 1
cycles
at 3 A g− 1
Co-MOF-derived Co3O4@ MOF derived Ternary 3393.8 5000.0 W. 4.9 93.0 % after 1000 [257]
Co/N-CNTs/Ag Nps/r-Go composite F g− 1 kg− 1 W h.kg− 1
cycles
at 5 m V s− 1
MOF-derived ZnCo2O4/ZnO MOF derived Bimetallic oxide/ 803 Fg− 1 710.49Wkg− 1
50.41 91.04 % after 10,000 [258]
metal oxide at 1 A g− 1 Wh kg− 1
cycles.
Cu3P/C–Ni MOF derived Metal phosphide/ 283.8 C g− 1 at 1 A 800.1 W kg− 1
15.2 60 % [259]
c-doped metal g− 1 Wh kg− 1
after 10 000 cycles
Cu3P/Cu@NC MOF derived Metal phosphide 540 C g− 1 at 1 A 7.98 kW kg − 1
45.5 91 % after 10,000 [260]
g− 1 Wh kg− 1
cycles
MOF derived ZnCo2O4 particles on MXene MOF derived Metal oxide/ 260 mAhg− 1 at 1 3512.2 W 63.8 91.3 % after 15,000 [261]
nanosheets Mxene composite mA g− 1 kg− 1 Wh kg− 1
cycles
MOF-derived hierarchical core–shell Metal phosphide 6.34F cm− 2 at 2 A 799.3 W kg− 1
35.7 85.7 % after 10,000 [262]
hollow Co3S4@ @ bimetallic oxide cm− 2 Wh kg− 1
cycles
NiCo2O4
MOF Metal-oxide/ metal composite 709Fg− 1 – – – [187]
1
derived Co3O4@N- at 1 A g−
doped carbon
MOF-derived NiS2@ MOF derived Metal sulfide/ 1572 F g− 1 402.1 21.6 94.8 % after 10,000 [263]
carbon microspheres wrapped with CNTs at 0.5 A g− 1 W kg− 1
Wh kg− 1
cycles
carbon nanotubes
MOF derived CNTs/ MOF derived Nickel–cobalt 734 C g− 1 852 42.15 88.46 % after 10,000 [264]
Ni–Co–S3 composites bimetallic sulfide at 1 A g− 1 W kg− 1
Wh kg− 1
cycles
MOF-derived Ni-Co sulfide nanotubes/ MOF derived Binary metal 2506 F g− 1 at 0.5 A – – 58 % after 6000 cycles [265]
GO sulfide/ GO g− 1
MOF-derived double-shell hollow Ni-Fe- MOF derived Ternary metal 1433Fg− 1 791 66.8 85 % after 8000 cycles [266]
Mn-Se selenide at 1 A g− 1. Wkg− 1 Wh kg− 1

MOF-derived CoP-NP@C MOF derived Metal phosphide/ 540 F g− 1 649.93 W 20.22 92.4 % capacitance [267]
C at 1.0 A g− 1 kg− 1 Wh kg− 1
retention after
10, 000 cycles
1
MOF derived NiCo2O4 MOF derived Binary metal 188 mAh g− at 5 1185 84.26 83.23 % after 10,000 [268]
oxide Ag− 1 Wkg− 1 Wh kg− 1
cycles
MOF- derived MOF derived Metal oxide/rGO 420Fg− 1 3.0 22.1 90.1 % after 5000 [269]
Mn3O4/ at 0.5Ag− 1 kW kg− 1
Wh kg− 1
cycles
r-GO
MOF-derived MnO/C MOF derived Metal oxide/C 421 F g− 1 at 0.5 A 680 15.5 94 % [270]
g− 1 W kg− 1 Wh kg− 1
after 5,000 cycles
MOF-derived NiCoP/rGO MOF derived Binary metal 250.9 749 60.6 83.7 % after 10,000 [271]
phosphide/rGO mAh g− 1 Wkg− 1 Wh kg− 1
cycles
at 1 A g− 1
P-doped NiCo-MOF MOF derived Binary metal 1168.2 C g− 1 at 1 A 800.0 W kg− 1
55.8 75.7 % [272]
derived phosphide/C g− 1 Wh kg− 1
after 10,000
P-NiCoS@C cycles
2
MOF-derived MOF derived Binary metal 5.67C cm− at 1 – 0.164 91.67 % [273]
Co–Fe-P@NiCo phosphide/NiCo LDH mA cm− 2 mW h cm− 2
after 5,000
cycles
MOF-derived walnut-like hierarchical Co- MOF derived Metal oxide 178 F g− 1 1125.9 W/kg 55.7 94.5 % [189]
1
O-nanosheets at 1.5 A g− Wh/kg after 5,000
cycles

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

materials from MOFs, clearly underscore the essential role of morphology enhances the interaction between electrode materials and
morphology control in enhancing performance. Many of these concepts electrolytes, facilitating rapid ion diffusion. The unique flower-like
converge in the strategy of obtaining different arrangements in materials structure contributes to efficient charge storage, resulting in higher
through the assembly of nanometric building units [274]. This impor­ capacitance and exhibit improved cycling stability, ensuring the
tance on the structure of MOFs, their derivatives, or composite materials longevity of supercapacitors. The hierarchical arrangement of nano­
has yielded particularly promising results, marking a growing field with flowers promotes effective electron transport, reducing internal resis­
numerous research groups actively involved. The design of various tance and enhancing overall conductivity [280,281]. Given these
micro/nanostructured MOFs, showcasing one-dimensional (1D), two- impressive characteristics, integrating flower-like structures, especially
dimensional (2D), and more complex three-dimensional (3D) architec­ in metal-organic frameworks (MOFs) and their derivatives, has proven
tures, is recognized as a promising avenue to enhance electrochemical to be a strategic approach for enhancing electrochemical performance.
performance. Recent progress in this area involves the utilization of tiny For example, Yang conducted the synthesis of hierarchical ZnO/NiO
MOF building blocks as structural templates, leading to significant ad­ microstructures with diverse shapes by utilizing zinc and nickel metal-
vancements in fabricating sophisticated structures and designing MOF- organic frameworks (MOFs) as precursors. Through precise adjust­
based materials at the micro/nanoscale without altering the chemical ments in the quantities of zinc and nickel, various microstructures,
composition of MOFs. These innovative approaches highlight the including hollow spheres and seaweed-like flowers, were obtained.
versatility of MOF materials [275,276]. Nanostructures like tubes/rods, Notably, the seaweed-like flower structures exhibited superior energy
sheets, flakes, plates, wires, spheres, flowers and other intricate mor­ storage performance, showcasing a specific capacitance of 435.1 F g− 1 at
phologies help create advanced paths for ions and electrons, acceler­ a current density of 1 A g− 1. The distinctive structure, coupled with the
ating the charging and discharging processes by enhancing composition derived from MOFs, enhanced the material’s conductivity
electrolyte–electrode interactions, improving contact, and reducing for ions and electrons, thereby providing additional sites for energy-
duration [277]. The integrity of supercapacitors is maintained during related chemical reactions [282].
these processes due to the reinforcing effects of nanostructures. The Within the area of research on MOF-based nanoflower-like struc­
concept of 2D materials, constituted by atom-thin sheets bonded in- tures, Lei et al. reported a noteworthy study showcasing a high specific
plane by strong covalent or ionic forces, has attracted considerable in­ capacitance.
terest. This robust bonding immobilizes atoms or molecules in place, In order to design electrode material with outstanding capacitive
while weak van der Waals forces hold the reduced-dimensional layers performance, a core–shell nanoflower-like CuO/CF@NiCoMn–OH as a
together. In recent years, two-dimensional (2D) materials, especially flat positive electrode was constructed on a copper foam (CF) substrate by
materials, have garnered increased attention for their exceptional the assistance of Metal-organic framework (MOF) assisted growth, and a
properties such as transparency, large surface area, and excellent ther­ simple hydrothermal treatment as shown in the schematic Fig. 21(a).
mal/electrical conductivity. Their atomic thinness provides significant The SEM and TEM images as shown in Fig. 21 (b and c) respectively.
flexibility and transparency, making them ideal candidates for flexible In Fig. 21(b), it is clearly presented that the presence of Mn and Ni
and transparent electronic devices when compared to other bulk mate­ ions along with Co shares the development of CuO/CF@NiCoMn–OH in
rials [278,279]. Besides, MOF-based 2D sheet-like materials, nano­ nanoflower-like structure. The TEM image (Fig. 21(c)) manifests the
spheres, nanowires have also been gaining attention in recent decades. shell-on-core architecture constituted of the CuO nanowire core sur­
Fig. 20 shows the various commonly utilized MOF-based structures for rounded by NiCoMn–OH nanoflower shells. The CuO/CF@NiCoMn–OH
energy storage applications. shows the exceptional specific capacity of 26.8 Fcm− 2 at 8 mAcm− 2 that
is equivalent to 3356 Fg− 1 at 1 Ag− 1. The remarkable performance of
CuO/CF@NiCoMn–OH can be attributed by the synergistic composition
7.1. Nanoflowers as well as the specific structure of the materials.

Nano/micro flower-like structures emerge from the organized or • Firstly, CF acts as a copper source for doping and as substrate, which
irregular arrangement of nanosheet-like particles. Researchers in the enhances the conductivity and structural stability.
field of energy storage consistently highlight the promising nature of • Secondly, the formation of nanowires increases the close connection
these flower-like structures. Numerous studies stress the advantageous with KOH electrolyte, the nature of nanowires increase the rate of ion
qualities of nanoflowers, particularly their high surface area that pro­ diffusion. The nanoflower surface has large surface area, which
vides abundant active sites for electrochemical reactions. This complex

Fig. 20. Illustration of various morphologies commonly employed for energy storage applications.

28
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 21. (a) Schematic illustration of formation of CuO/CF@NiCoMn–OH and its (b) SEM and (c) TEM image (Reprinted with permission from [283]. Copyright 2021
American Chemical Society), (d) Schematic representation of formation of flower-like structure of Ni-MOPh (Reproduced from Ref. [252] with permission
from Elsevier).

reduces the transport distance of electrons and provides number of 482 F g− 1 at 10 m V s− 1, with cyclic stability of 93.8 % at 1000 cycles. In
sites for reactions. two electrode setup with Cu-MO F g− 1 (positive) and Activated carbon
• Finally, Ni, Co and Mn with different valences in the assembly pro­ (AC), the device exhibited an energy density of 34.5 Wh kg− 1 and a
vide excellent electrochemical properties. specific power of 1350 W kg− 1 at a current density of 0.5 A g− 1. This
performance is attributed to nano-flower morphology and the inclusion
Moreover, the assembled CuO/CF@NiCoMn–OH//AC system ex­ of graphene which improved the charge storage characteristics [284].
hibits a high energy density of 37.28 Wh kg− 1 with power density of 170 In a study conducted by Cheng et al., a flower-like three-dimensional
W kg− 1 in a 1.5 V potential window [283]. In another work, Azadfalah structure of nickel metal-organic phosphate (Ni-MOPh) layered nano­
et al., used pristine Cu-MOF and mixed it with graphene. The electro­ sheets were synthesized. When this framework material is heated to
chemical performance revealed that it achieved a specific capacitance of 600 ◦ C in air, an amorphous derivative, A-(Ni-MOPh)-D, retains the

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

three-dimensional architecture of the MOF with a homogeneous array of Bahaa et al., suggested a unique technique for the synthesis of
pores. With low lattice energy, A(Ni-MOPh)-D’s high amorphousness advanced specialized copper cobalt sulfide nanosheet arrays (CuCo2S4
enables fast, reversible chemical reactions and readily allows for NS). The structure of the electrode design process is shown schemati­
movement of ions. Upon further heating at 100 ◦ C for 2 h, the Ni-MOPh cally in Fig. 23(a). These unique nanosheets with a large surface area
sample developed a well-defined, complete flower configuration, as and interconnected porous network structure. The hierarchical structure
shown in Fig. 21(d). By superimposing and extending the layer of sheets of CuCo2S4 NS arrays provides extensive electroactive sites and reduces
from the central position, three-dimensional flower-like architecture the ion/electron diffusion length. The SEM images in Fig. 23(b, c) depict
was formed, which enlarged the surface area of the sample significantly. that CuCo2S4 NS nano-sheets with an ultra-thin structure have grown
Due to the high degree of order, and thus the relatively low lattice en­ evenly on highly porous Ni foam in 3D. Notably, this indicate that the
ergies, the rate of the movement of ions is increased considerably and CuCo2S4 NS nano-sheets are 3D nanostructure that is vertically arranged
the times at which the reactions take place on the surfaces of the elec­ on Ni foam as a substrate. Furthermore, the original structure of
trodes are shortened. Electrochemical measurements reveals that the CuCo2S4 NS remained intact after efficient exchanging the anion, doc­
structure exhibits a specific capacitance of 804.0 F g− 1 at 0.5 A g− 1 in a umenting excellent compatibility of the original structure and the
three-electrode setup with about 83.5 % capacity retention after 2000 precursors.
cycles. Moreover, in a two-electrode configuration, A-(Ni-MOPh)-D // Moreover, the CuCo2S4 NSs electrode delivered remarkable electro­
AC cell delivered high was measured as 258.8 F g− 1 at 0.5 A g− 1. The chemical performance with superior specific capacity of 409.2 mAh g− 1
incredible conductivity could be ascribed to its unique structured and areal capacity of 0.96 mA h cm− 2 at a current density of 3 mA cm− 2,
porosity, benefiting from the facile diffusion of electrolyte into the bulk excellent rate capability (77.9 % capacity retention at 50 mA cm− 2), and
and fast electron transfers. The abundant pore architecture also leads to outstanding cycling stability (94.2 % capacity retention after 10 000
more sites of electrochemical activity and the lower lattice energy of the cycles). Especially, an assembled CuCo2S4 NS//Fe2O3/NG solid-state
amorphous derivative facilitates quicker chemical reactions [285]. asymmetric SC delivered an ultra-high volumetric capacity of 2.1 mA
h cm− 3 at a current density of 3 mA cm− 2 and an excellent energy
density of 89.6 Wh kg− 1 at a power density of ~663 W kg− 1 with 1.6 V
7.2. Nanosheets superior operating potential window and preserving high rate and good
cyclability (~91.5 % capacity retention after 10 000 cycles). The per­
Nanosheets demonstrate diminished volume variability, heightened formance is attributed to its unique sheet like morphology [288]. In a
accessibility of active sites, and shorter diffusion lengths in comparison similar fashion, Tan et al. also synthesized nanosheet-like arrays of
to alternative nanostructures. These attributes significantly contribute Co3S4 derived from MOFs and enhanced its energy storage capabilities
to the enhancement of electrochemical energy storage performance, through room-temperature treatment with NaBH4. This treatment
improving cycling stability, specific capacity, surface area, and capaci­ simultaneously adjusted sulfur vacancies and surface morphology,
tance retention [286]. As a result, there is a noteworthy fascination with leading to improved performance [290]. Similar morphology has also
nanosheets based MOF materials. been explored by Wang et al. NiCo-MOF (NCM) nanosheets were pre­
To solve the urgent challenge of low capacitance and slow kinetics, pared by a hydrothermal method on nickel foam to be used as a pre­
zinc–cobalt sulfide nanosheet arrays (ZnCoS-NSs) were explored by Sun cursor. A solution of MXene and electrolyte solution of the mixture of
et al. Firstly, the MOF arrays were converted into ZnCoS-NS arrays as a Ni2+ and Co2+ are mixed for the electrodeposition and to produce
backbone to form a three-dimensional (3D) continuous electrical and MXene-Ni-Co@NiCo-MOF/NF (M-NC@NCM/NF) nanosheets as shown
ionic conduction network for the growth of active materials. Then Ni in Fig. 23(d). Obvious hexagon nanosheet would create a good porous
(OH)2 was grown on ZnCoS-NSs as positive material and Vanadium structure to improve electrochemical performance. The capacity reten­
nitride (VN) was grown on it as negative electrode. The Ni(OH)2@Zn­ tion could maintain at 75.3 % even after 5000 cycles and specific ca­
CoS-NS (8.1 F cm− 2 at 3 mA cm− 2, corresponds to 2730 F g− 1) was pacity reached 855.0 C g− 1 in 1 A g− 1. The smooth nano sheets on the
verified a highly capacitive positive electrode, which is in parallel with nickel foam were found in the SEM images in Fig. 23(e). M-NC@NCM/
VN@ZnCoS-NS, a highly capacitive negative electrode (1.35 F cm− 2 at 3 NF nanosheets were furnished sturdy supports by growing NiCo-MOF
mA cm− 2). The reaction and charge transfer mechanisms in these and were conducive to deposit materials. The vague long block of e-
nanosheet arrays was demonstrated in the Fig. 22. The assembled ASC NC@NCM/NF materials showed in Fig. 23(f) with low surface area and
device has demonstrated the high energy density (75 Wh kg− 1 at 0.4 kW less active sites because the lack of MXene would disturb electron
kg− 1), long-time stability (82 % capacitance retention even after 10 000 transmission. Without excellent polymerization, there would be hard
full cycles), and superior flexibility (92 % capacitance retention even grain bond among molecular chains. Despite, with higher reaction
after 4000 times bending) [287].

Fig. 22. Charge storage mechanism of Ni(OH)2@ZnCoS-NSs positive electrode and VN@ZnCoS-NSs negative electrode (Reproduced from Ref. [287] with permission
from the Royal Society of Chemistry.)

30
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 23. (a) Schematic illustration of the design and fabrication of CuCo2S4 NS, and its (b) Low and (c) High magnification SEM images (Reproduced from Ref. [288]
with permission from the Royal Society of Chemistry.), (d) Schematic illustration of electrodeposition process for the formation of MXene-Ni-Co@NiCo-MOF/NF, and
its its corresponding (e, f, and g) SEM images (Reproduced from Ref. [289] with permission from Elsevier), (h) Scheme of synthesis process of CNT@CoSe2
nanosheets, and their corresponding (i and j) SEM images and (k) TEM image (Reproduced from Ref. [259] with permission from Elsevier).

31
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

times, materials resulted in better outcomes and Fig. 23(g) shows the M- et al., certain MOFs, such as Co-MOF, exhibit remarkable improvements
NC@NCM/NF nanosheets possessing the deposition of 240 s with in energy density. The research conducted by Q Liu and colleagues
hexagon shape that could improve ion transfer paths and have more stands out, representing one of the highest reported values for specific
active sites. capacitance and energy density in the existing body of literature. This
This nanosheet arrangement enhances active sites, amplifies energy achievement underscores the significance of morphological adjustments
density, hastens ion transport, and supports cycle stability. It can be in MOFs for optimizing their electrochemical properties, with potential
inferred that the material’s morphology is susceptible to control through implications for advancing energy storage technologies. The nanosheet-
ion adsorption by MXene layers [289]. like architecture of Co-MOF not only contributes to excellent energy
Researchers have also reported the effectiveness of hollow nano­ density but also signifies a noteworthy stride in the quest for high-
sheets in enhancing capacitive performance. As an example, C. Miao performance materials in the field of energy storage. They prepared a
et al. engineered arrays of hollow cobalt molybdenum selenide 2D metal-organic framework (MOF) nanosheet using a liquid–liquid
(Co–Mo–Se) nanosheets through an ion exchange and selenization pro­ interface method. Schematic illustration and topological structure of the
cess. This method provided an abundance of electroactive sites, spacious nanosheet Co-BTB-LB derived from Co2+ ion and H3BTB (ligand) is
areas for electrolytes, and short paths for ion movement. The resulting shown in Fig. 24(a). As shown in SEM image in Fig. 24(b), it displays a
material demonstrated outstanding energy storage properties, including sheet-like structure. The Co-BTB-LB electrode demonstrates an impres­
a high capacity of 221.7 mAh g− 1, commendable rate performance, and sive capacity of 4969.3 F g− 1 at 1 A g− 1 and maintains 75 % capacity
remarkable stability (maintaining 95 % capacity after 8000 cycles). In after 1000 cycles. In an asymmetric supercapacitor, it achieves a
combination with active carbon (AC) in Co–Mo–Se//AC, it achieved a excellent energy density of 150.2 Wh kg− 1 at 1619.2 W kg− 1 with
notable energy density of 44.7 Wh kg− 1 [291]. excellent stability, retaining 97.1 % capacitance after 10,000 cycles.
To enhance areal capacitance, energy density, and facilitate the This advancement marks a notable achievement in the performance of
development of a flexible electrode, a novel approach involving the asymmetric supercapacitors, showcasing the potential of such 2D
incorporation of 2D nanosheets onto 1D carbon nanotubes was imple­ nanomaterials [293].
mented by Wang et al. CoSe2 nanosheets two-dimensional (2D) were Further work in this area has been described by Zheng et al. They
grown on carbon nanotube (CNT) films in this study through an in situ reported the synthesis of ultrathin two-dimensional (2D) nanosheets of
route with using Co-based Metal-Organic Frameworks (MOFs) as the cobalt-organic frameworks (Co-MOFs) by a surfactant assisted simple
sacrificial template. Through DFT simulations, it is observed that CoSe2/ hydrothermal synthesis. They are excellent ultrathin layers of cobalt
CNT is more conductive than Co3O4/CNT. The nanocomposite elec­ based 2D nanosheets with appealing electrical properties. In a three-
trode, combining self-supported CoSe2 nanosheets and one-dimensional electrode system, these ultrathin 2D Co-MOF nanosheets evident a
(1D) CNT, enables the fast transportation of ions/electrons and reduces maximum specific capacitance of 1159 F g− 1 at the current density of 0.5
the diffusion pathway of ions/electrons. As shown in Fig. 23(h), they A g− 1. Impressively, the electrode retains 96.7 % of its original specific
synthesized well-dispersed 2D nanosheets of CoSe2 on CNT films capacitance after 6000 cycles, demonstrating good stability.
through a two-step hydrothermal process using metal-organic- Major influences on supercapacitor performance include ion diffu­
frameworks (MOF)-derived Co-MOF nanowall arrays as templates pre- sion and electron transport.
coated onto CNT substrate. The obtained nanoplates remain 2D shape The key roles played by the ion diffusion coefficient and length are
and have more ordered, further vertically aligned less thickness after demonstrated by the ion diffusion process illustrated in Fig. 25(a). The
selenization. Meanwhile, the nanosheets consisting of nanoparticles host material properties set the ion diffusion coefficient, whereas these
which could also be clearly seen in the SEM images (Fig. 23(i, j)) and properties can be adjusted through artificial treatment can result ion
TEM image (Fig. 23(k)). The nanoparticles were closely packed and diffusion length. Therefore, reduction in particle size to decrease ion
formed nanosheet arrays with a typical size ~10 nm and abundant diffusion length seems to be an efficient approach to increase the
pores. The assembled flexible asymmetric SC (ASC) exhibits a high areal operational efficiency of supercapacitor electrodes. Importantly,
energy density of 0.25 mW h cm− 2 and long-term cycling stability (about compared with bulk or even micro-nano-sized Co-MOF, the ultra-thin
85.29 % capacitance retention over 4000 cycles). Furthermore, the 2D CoMOF NS showed significantly shorter ion diffusion length
flexible ASC-device yields an area capacitance of 593.5 mF cm− 2 at a derived by its ultrathin thickness. This property probably contributes to
current density of 5 mA cm− 2 [292]. the electrode capabilities of ultrathin Co-MOF nanosheets.
Enhancing the performance of pristine Metal-Organic Frameworks Furthermore, the ultrathin flaky construction of Co-MOF nanosheets
(MOFs) can be achieved by carefully tuning their morphology. Notably, can also cut Co-deficient electrons, reducing the electron cloud density
when engineered into nanosheet structures, as demonstrated by Q Liu and often making available more exposed active sites on the surface of

Fig. 24. (a) Schematic illustration of topological structure of the nanosheet Co-BTB-LB and its (b) SEM image (Reproduced from Ref. [293] with permission from
John Wiley and Sons).

32
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 25. (a) Illustration of influence of ion diffusion length in diffusion process, and (b) illustration of inclusion of carbon black for reduced electron transport length
(Reproduced from Ref. [294] with permission from Elsevier).

Cobalt oxide material. This helps in the easy interaction of the substrate capacitance and the faradaic pseudocapacitance of PPy [295].
molecules consequently improve electrical properties. In another work, Wu et al., made a sandwich-like hybrid film by
It is vital to address the electronic transport challenge. Improving the combining 2D metal-organic framework (MOF) nanoflakes and gra­
electrical conductivity of electrode materials is limited by the interface phene oxide (GO) through a process involving zeolitic imidazolate-67
resistance present between nanoparticles. One commonly utilized (ZIF-67) nanocubes. The hybrid film, post-sulfidation, exhibited
method to address this is through the implementation of a carbon ad­ outstanding electrochemical performance by effectively merging the
ditive in improving electrical conductivity, as seen in Fig. 25(b). In favorable pseudocapacitor characteristics of cobalt sulfide with the
addition, the ultrathin 2D Co MOF nanosheets mixed well with carbon excellent conductivity provided by rGO. As shown by SEM images in
solve the successful formation of a short electron transport length. The Fig. 26(e, f, g, h), distinctive morphologies of ZIF-67 and ZIF-GO have
accessibility of electrons to traverse through the porous morphology of been obtained. ZIF-67 crystallizes in the cube shape, as shown in Fig. 26
the carbon additive gives the 2D Co-MOF enhanced electrical perfor­ (e). However, there are no cubes of ZIF-GO obtained but only wrinkle
mance over other distinct nanostructures in thin regions. Given the nanoflakes have been observed, as shown in Fig. 26(f), indicating the
substantial specific surface area attributable to numerous active sites strong interaction between ZIF-67 and GO. The porous structure of rGO/
provided via the inherent functional groups, ultrathin nanosheets CoSx-rGO/rGO was produced by the subsequent freeze-drying process.
remain a leading option as an electrode material candidate for super­ The SEM image in Fig. 26(g) show the cross-sectional view of rGO/CoSx-
capacitors [294]. rGO/rGO hybrid film which displays that the sandwich structure of the
hybrid film is formed, where bare rGO nanosheets act as the electrode
and the two layers of rGO coating are used as protection for the active
7.3. Nanoflakes
material. Compared with CoSx on top and bottom layers, the SEM images
from Fig. 26(h) suggest that the top and bottom rGO on glassy carbon
The term ’flake’ is usually used to describe a flat, thin and small
electrode is too fragile to be detected. The as-prepared ASC using this
structure, which refers to pieces or fragments of material with a flat or
film as positive electrode and AC as negative electrode delivered the
thin profile. Expanding on the same concept, nanoflakes structure is
energy density of 10.56 Wh kg− 1, power density of 2250 W kg− 1 and
wide and composed of layers or fragments at nanometer scale. Such
exhibited an excellent flexibility. Particularly, the ASC still maintained
flake like structures same as nanosheet are also recently incorporated to
92.8 % capacitance of its initial capacitance even after 10,000 cycles
MOF-based materials especially composites or derivatives to improve
[296].
the electro-chemical performance of MOFs.
In contrast to previous approaches, Ma et al., enhanced cyclic sta­
Yue et al. introduced a hybrid configuration featuring a conductive
bility by cultivating a flake-like structure of metal-organic framework
Cu-CAT MOF on a porous flake-like polypyrrole scaffold (p-PPy) to
(MOF) on carbon cloth (CC). They grew cobalt-based MOF-67 (ZIF-67)
enhance capacitance. The preparation of p-PPy/Cu-CAT MOF is illus­
on a flexible and conductive carbon cloth, resulting in a ZIF-67 with an
trated in Fig. 26(a). In this design, short rod-shaped Cu-CAT crystals
integrated flake-like structure on the carbon cloth, significantly boosting
were stacked on PPy flakes and introduced into the pores of the p-PPy
conductivity. The uniqueness of the helical carbon fibers with wrinkles
scaffold. While this arrangement reduces surface area, it establishes a
in the carbon cloth facilitates increased contact with Cobalt, aiding the
hierarchical pore structure, promoting improved charge transfer. The
growth of ZIF-67 on the carbon cloth. The hybrid electrode exhibited
porous PPy scaffold, loaded with the conductive Cu-CAT MOF, serves as
remarkable performance, achieving a high capacitance of 1756 mF cm− 2
an active material for flexible solid-state supercapacitors. This scaffold
and demonstrating excellent cycling stability with 103 % capacitance
provides loading areas and conductive support for Cu-CAT crystals,
retention after 15,000 cycles at a high current density of 40 mA cm− 2 in
thereby enhancing capacitance. The PFTA template guides the adsorp­
a KOH solution. Even after 5000 cycles, the TC-ZIF-67 electrode main­
tion of pyrrole monomers and the polymerization of ultrathin PPy
tained its flake-like structure, albeit with slight deterioration due to the
nanoflakes, resulting in a smooth surface with wavy wrinkles, as
shortened ion diffusion length. This deterioration was outweighed by
depicted in the TEM image in Fig. 26(b). SEM images of p-PPy and p-
significantly improved electrode conductivity and a capacitive charge
PPy/Cu-CAT MOF are shown in Fig. 26(c) and (d), respectively. Fig. 26
storage mechanism enhanced by its flake-like morphology [297]. Wang
(c) reveals that p-PPy, based on cross-linked PPy nanoflakes, exhibits
et al., did a different approach of first preparing the NiO nanoflakes and
uniformly interconnected pores with a diameter of approximately 5 μm.
then in situ formation of Ni-MOF over NiO. Particularly, the conversion
In Fig. 26(d), high-density short rod-shaped Cu-CAT crystals are grown
degree of Ni-MOF from NiO was conveniently tuned by altering the
onto PPy nanoflakes, uniformly dispersed in both the outer and inner
amount of terephthalic acid added in the hydrothermal process. NiO/Ni-
pores of p-PPy. This uniform dispersion maintains the original porous
MOF-25 with 25 % of the conversion ratio of NiO to Ni-MOF possessed
structure of p-PPy, with the porous flake-like structure enhancing

33
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 26. (a) Illustration of preparation of p-PPy/Cu-CAT MOF, and their corresponding (b) TEM image and (c and d) SEM images (Reprinted (adapted) with
permission from [295]. Copyright 2020 American Chemical Society), SEM images of (e) ZIF-67, (f) ZIF-GO, (g) rGO/CoSx-rGO/rGO (cross-sectional view), and (h)
rGO/CoSx-rGO/rGO (top–bottom view). (Reproduced from Ref. [296] with permission from Elsevier).

superior electrochemical performance with a specific capacity of 163.4 shaped plates. Through a careful process involving the heating of a
mAh g− 1 (1176.6 F g− 1) at a current density of 1 A g− 1 [298]. Nickel-iron bimetallic metal-organic framework at different tempera­
tures, they successfully achieved diverse NFO structures, including
7.4. Nanoplates threads, mesh-like configurations, and grains. From Fig. 27(a,b), the
transmission electron microscopy (TEM) micrographs of the NFO syn­
There has been a growing interest in the design and utilization of thesized at 500 ◦ C (NFO500) revealed rhombus plates, showcasing the
nanoplate-like structures as electrode materials for supercapacitor ap­ effectiveness of their method. Due to its rhombus plate-like morphology
plications. The work of Patil et al. represents a significant contribution to and mesh-like structure, it exhibited superior supercapacitive perfor­
this, as they sought to engineer various shapes of NiFe2O4 (NFO) for mance. The porous nature and extensive surface area of NFO500 were
supercapacitors with distinct morphologies, such as flat rhombus- identified as key factors enhancing charge transfer and providing

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 27. (a,b) TEM images of NFO500 (Reproduced from Ref. [211] with permission from Elsevier).

abundant sites for energy storage. With an impressive capacitance of precise manipulation of MOF growth but also enables the exploration of
833 F g− 1, surpassing other NFO samples, and demonstrating excep­ dynamic pathways, leading to the development of MOFs with unique
tional stability over 3000 cycles, this study underscores the pivotal role and tailored properties. The utilization of modulator-driven modulation
of tailored nanoplate-like structures in advancing supercapacitor tech­ strategies not only enhances the fundamental understanding of MOF
nology. The findings of this research underscore the importance of formation but also opens up new avenues for the rational design and
morphology engineering in optimizing the electrochemical properties of synthesis of MOFs for application in energy storage [299].
electrode materials for supercapacitors [211]. Based on this, S.Wang et al, reported that adding pyridine as a
Since achieving a precise control over the synthesis of metal-organic modulator in the solvothermal process resulted in thin and wide nickel-
frameworks (MOFs) is paramount for ensuring reproducibility and metal organic framework (Ni-MOF) nanoplates. Fig. 29(a) illustrates the
tailoring the physical properties, the modulation of self-assembly pro­ scanning electron micrographs (SEMs) of as-synthesized two-dimen­
cesses has emerged as a foundational principle offering a adaptable sional (2D) Ni-MOF nanoplates. It can be observed that the nanoplates
strategy to influence vital characteristics such as crystallinity, particle are smooth, rectangular and uniform in their shapes, with dimensions
size, morphology, porosity, defectivity, and surface chemistry in MOFs. ranging from 250 nm to 1 µm. In Fig. 29(b), the transmission electron
The important aspect of this approach is the strategic incorporation of micrographs (TEMs) of the same nanoplates also show flat, thin tem­
modulator molecules into synthetic mixtures, which acts as a steering plate. The thicknesses of nanoplates measure up to approximately 23
mechanism for the formation of MOFs with desired attributes. The nm, which are in accordance with the nanometer range of their widths.
careful manipulation of the interplay between modulator molecules and It showed a high capacitance of 222.5 F g− 1 in a three-electrode setup
metal-organic components allows one to gain fine-tuned control over the and 178.3 mF cm− 2 in a two-electrode system. Even after 1000 char­
structural evolution during MOF synthesis The uniformity and repro­ ge–discharge cycles, it maintained a capacitance of 128 F g− 1 at 2 A g− 1.
ducibility of Metal Organic Framework (MOF) properties can only be The nanoplate structure displayed higher specific surface area, allowing
achieved if this modulation strategy is employed. Fig. 28 illustrates the better access to the electrolyte [300].
outcomes of introducing a modulator during synthesis. Reaction time plays an important role in precise control of MOF
Moreover, the role of modulation extends beyond achieving static morphology. Zhao et al., synthesized a unique design of CoP/Mo-NiCoP
control. It is increasingly recognized for its ability to exert kinetic con­ nanoplates derived from Co-MOF on a carbon cloth. The resultant 3D
trol over the self-assembly process. By introducing modulators at spe­ structure with plate like layers has a large surface area, making it easy
cific stages of MOF synthesis, researchers can influence the reaction for the active sites to store energy effectively. Doping molybdenum (Mo)
kinetics, dictating the rate at which precursor molecules assemble into into CoP/NiCoP nanoplates enhances electronic transfer capability. The
the final MOF structure. This kinetic modulation not only allows for the CoP/Mo-NiCoP electrode exhibited a superior capacity, surpassing that
of numerous other counterparts. The schematic diagram of synthesis
process involving MOF formation, hydrolysis, etching, MOF/LDH com­
posite formation and Mo-doping and final phosphorylation is shown in
Fig. 30(a). The nanoplates underwent a change, organizing themselves
into an interconnected three-dimensional (3D) network that uniformly
covered the CC fibers, as evident in the SEM images presented in Fig. 30
(b,c). Upon a more detailed examination using higher magnification
SEM imaging (Fig. 30(d)), it became apparent that the CoP/Mo-NiCoP
nanoplates were uniformly distributed, showing no observable clus­
tering or collapse. Upon closer scrutiny, it was revealed that numerous
small cross-linked nanosheets, each with a thickness of approximately
10 nm, emerged and clustered on a nanoplate, forming a 3D network
structure with a distinctive hierarchical organization (Fig. 30(e)). These
nanosheets exhibited a polycrystalline nature, featuring relatively small
polycrystalline domains averaging around 15 nm, as depicted in Fig. 30
(f,g).
It is concluded that maintaining a short reaction time of approxi­
mately 30 min was crucial for achieving partial hydrolysis and preser­
ving the desired nanoplate geometry. Extending the reaction time to
around 6 h proved detrimental, leading to severe etching of the Co-MOF
Fig. 28. Outcomes of application of modulators in MOF synthesis.

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 29. (a) SEM and (b) TEM images of Ni-MOF nanoplates (Reproduced from Ref. [300] with permission from Elsevier).

Fig. 30. (a) Schematic diagram of synthesis process of CoP/Mo-NiCoP, and their corresponding (b,c) Lower and (d) higher magnification SEM images, and (e, f)
Lower and (g) higher magnification TEM images (h) schematic of electron transportation and OH− ion penetration in CoP/Mo-NiCoP (Reproduced from Ref. [301]
with permission from Elsevier).

template and subsequent destruction of the nanoplate array. Fig. 30(h) • The high aspect ratio and large surface area of nanorods significantly
shows the schematic of electron transportation and OH– ion penetration affect the charge storage and transfer process that takes place during
in the prepared electrode. This highlights the delicate balance between the charging and discharging process in supercapacitors.
reaction duration and preserving the structural integrity of the nano­ • In MOF based materials, through the control synthesis of nanorods,
plates in the synthesis process [301]. the shape modulation could be achieved via programmed self-
As per the findings by Shen et al., achieving a stable morphology assembly. The nanorod structure in MOFs is responsible for effi­
depends on both the reaction time and temperature. In their work, they cient electrolyte penetration and ion accessible diffusion into the
synthesized Ni-MOFs at different temperatures – 60, 80, 100, and material, attributed to its lengthened geometry, which provides
120 ◦ C. Notably, the Ni-MOF produced at 80 ◦ C showcased a hexagonal larger interparticle spaces, relaxation of diffusion limitations, and
plate-like morphology adorned with a unique cross-network structure the superior overall charge/discharge kinetics.
on its surface, featuring a superior surface area when compared to ma­ • Further, the exposed nanorod positive planer sites have a greater
terials prepared at alternative temperatures [302]. density of an electrochemical active surface area, creating larger
capacitance. Essentially, morphological tuning to nanorods mor­
7.5. Nanorods phologies in MOF materials will maximize the full potential elec­
trochemical performance of the electrode materials in
The shape of nanorods in supercapacitor electrodes is significantly supercapacitors, by enhancing the specific capacitance, rate capa­
importance because the morphologies of nanorods can enhance the bility, and cycling stability.
electrochemical performance of supercapacitor electrode materials by
providing the following advantages [303]. For example, Yue and colleagues developed a unique yarn electrode
by cultivating arrays of conductive metal–organic framework (MOF)

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

nanorods on a polyester yarn coated with reduced graphene oxide (rGO/ heightened adsorption of electrolyte ions, consequently boosting the
PET). The schematic representation of this process is illustrated in specific capacitance of the Ni-MOF. The porous and nanorod
Fig. 31(a). This conductive yarn serves as a robust foundation for the morphology played a crucial role in facilitating ion diffusion, positively
growth of active materials, boasting exceptional properties such as a influencing the specific capacitance of the Ni-MOF [307]. The findings
high surface area, good conductivity, and a well-structured porous suggest that the performance of the MOF material can be substantially
design. The 3D nanostructured array layer on the fiber surface consists enhanced by adopting a nanorod-like morphology.
of numerous Cu-MOF nanorods, each with an average diameter of 20
nm. This arrangement enhances the exposure of active surfaces and 7.6. Nanowires
establishes an efficient pathway for electrolyte ions. In supercapacitor
tests, the yarn electrode demonstrated outstanding performance, Nanowires and nanorods, both belonging to the category of 1D-elon­
exhibiting high capacitance (151.9 F g− 1 at 3 m V s− 1), remarkable gated nanostructures, share similarities yet feature distinct character­
mechanical flexibility, and an extended cycling life. The nanorod istics in terms of geometry and applications. While nanorods maintain a
structure plays a pivotal role in exposing substantial active surfaces and cylindrical form with a uniform diameter along their length, nanowires
facilitating the efficient movement of electrolyte ions [304]. exhibit a longer structure with the potential for a variable diameter
In a study led by Yu et al., researchers have utilized the distinctive along their length. Nanowires can be considered analogues to nanorods
porous structures of nanorods-stacked hollow microtubes to advance but with a higher aspect ratio, emphasizing the ratio of length to
innovative applications. Employing a straightforward synthesis method diameter [308]. This variability in diameter, coupled with the elongated
with bismuth-based metal-organic frameworks, the team successfully structure, provides nanowires with unique properties that find appli­
created these structures. Notably, these microtubes with stacked nano­ cations in various fields. The longer length of nanowires contributes to
rods exhibit remarkable features, including a substantial surface area of enhanced pathways for charge transport and increased surface area,
54.3 m2 g− 1 and an specific capacity of 532 C g− 1 at 1 A g− 1 when making them valuable in applications such as electronics, sensors, and
applied as negative electrodes in supercapacitors, surpassing the per­ energy storage devices. Additionally, when nanowires take on a hollow
formance of other reported Bi2S3 materials. The hollow architecture of form, they are referred to as nanotubes [309].
the microtubes facilitates efficient ion movement, contributing to Wang et al. reported the use of the nanowire morphology by
outstanding capacity and stability, with an impressive 91.0 % retention assembling the conductive Cu-MOF nanowires on the rGO fibers to
observed after 3000 cycles. In the domain of hybrid supercapacitors, fabricate an rGO/Cu-MOF fiber electrode material. The schematic
pairing Bi2S3 as the negative electrode with CoNi-LDH as the positive illustration of the preparation process is shown in Fig. 32(a). SEM and
electrode achieves a notably energy density of 27.8 Wh kg− 1 at 806.5 W TEM images in Fig. 32(b, c, d) depict the Cu-MOF nanowires on the rGO
kg− 1 [305]. In a similar fashion, Xu et al., synthesized a new nanorod- fiber surface, forming a 3D nanowire array layer. These 35 μm wide fi­
shaped manganese-based metal-organic frameworks (Mn-MOFs) using bers comprised of nanowires, each having a diameter of 68 nm and a
a solvothermal method. When used as a electrode, these Mn-MOFs length of 530 nm. The interspacing between nanowires served as elec­
showed a capacitance of 371 F g− 1 at 0.5 A g− 1 and performed well trolyte reservoirs, reducing ion diffusion paths and facilitating ion
even at higher current densities. In asymmetric supercapacitors, where migration. The Cu-MOF nanowires featured 1D open channels, pro­
Mn-MOFs served as the cathode and graphene as the anode, they ach­ moting efficient charge/discharge transfer reactions and enlarging the
ieved an energy density of 31.6 Wh kg− 1. The main thing is that, it electrode/electrolyte interface for improved high-rate performance. The
maintained 91.8 % of their initial capacitance after 10,000 char­ material’s open porous structure and the bendy conductive wires formed
ge–discharge cycles at 1 A g− 1 [306]. by the Cu-MOF nanowire layer effectively accommodated stress and
This indicates that the nanorod-shaped Mn-MOF, despite being a structural changes, while also increasing the active components in
pristine MOF, maintains its stability due to its unique nanorod-like contact with electrolytes and enhancing electrical conductivity. This
structure. unique material structure amalgamates the advantages of rGO fibers and
Unlike conventional preparation methods employed in previous conductive Cu-MOF, resulting in a capacitance of 202 F g− 1, exceptional
studies, Bhosale et al. utilized an economical reflux condensation tech­ bending flexibility, and an good areal energy density of 0.51 mW h cm− 2
nique to fabricate a rod-shaped Ni-MOF. The preparation is shown in in the assembled supercapacitor [310]. A further improved capacitance
Fig. 31(b). This material exhibited exceptional specific capacitance and in MOF derived sulphide is reported by Gong et al., in their work of
a remarkably high energy density. The prepared Ni-MOF exhibited a designing a stable volume-expansion controlled NiCo2S4 electrode
rod-like structure, creating favorable pathways for electrolyte ion micro-porous structure on nickel foam. The schematic illustration of
penetration and improving the interaction between the active material formation process is shown in Fig. 32(e). The fabrication process initi­
and electrolyte. With a substantial specific surface area of 398.4 m2 g− 1 ates with the hydrothermal and annealed growth of NiCo2O4 (NCO)
and a highly porous architecture, the Ni-MOF demonstrated exceptional nanowire arrays directly on nickel foam (NF). Subsequently, NCO un­
performance as a supercapacitor. It showed a specific capacitance of dergoes immersion in a mixed solution of NiCo-zeolitic imidazolate
1956.3F g− 1 at a current density of 5 mA cm− 2, retaining 81.13 % of its framework-67 (NiCo-ZIF-67). During this stage, Co2+ ions, in conjunc­
initial capacitance after 3000 cycles at a 35 mA cm− 2 current density. In tion with 2-methylimidazole, undergo an exchange with high concen­
a Ni-MOF//activated carbon hybrid supercapacitor (HSC), the fabri­ trations of Ni2+, leading to the conversion of Co-ZIF-67 into NiCo-MOF
cated system displayed a very high specific energy of 98.15 Wh kg− 1 at a (referred to as NCMA) nanosheets. These nanosheets interconnect,
specific power of 1253.47 W kg− 1, with remarkable capacity retention of forming a network-like structure on the surface of NCO nanowires. The
99.29 % over 3000 cycles. core–shell structure is intentionally designed with NCO nanowires as the
The SEM images, as illustrated in Fig. 31(c,d), unveiled a nanorod- core and interconnected NiCo-MOF nanosheets as the shell. Following
like configuration and porous attributes of the Ni-MOF, contributing sulfidation, the NiCo2S4 core layer develops numerous micro-pores,
to an enlarged surface area and increased specific capacitance. These augmenting the contact space between the electrolyte and the mate­
nanorods, with an average length of around 19 nm, displayed varied rial and substantially increasing the number of active sites, thereby
lengths and diameters, resulting in an enhanced aspect ratio. Further­ enhancing capacity performance. Simultaneously, the NiCo2S4 shell
more, the interconnected porous nanorods offered additional active sites layer, derived from NiCo-ZIF-67 under specific reaction conditions,
for charging kinetics, diminishing the diffusion length of the electrolyte ensures the electrode material maintains its capacity, mitigating long-
and augmenting energy storage and high-rate capability. When term charge–discharge-induced volume expansion and improving
observed from a top-down perspective in the SEM images, the overlap of cycling stability. SEM images in Fig. 32(f and g) depict the NiCo2S4
both small and large nanorods, interspersed with voids, facilitated nanowire-like structure. The NiCo2S4 electrode exhibits a noteworthy

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 31. (a) Schematic representation of formation of Cu-MOF/rGO/PET yarn and their application as supercapacitor (Reprinted (adapted) with permission from
[304]. Copyright 2020 American Chemical Society), (b) Schematic illustration of synthesis process of Ni-MOF and their corresponding (c, d) SEM images (Repro­
duced from Ref. [279] with permission from the Royal Society of Chemistry.)

38
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 32. (a) Schematic illustration of preparation of rGO/Cu-MOF fiber and their corresponding (b, c and d) SEM images at different magnification (Reproduced from
Ref. [310] with permission from Elsevier), (e) Illustration of growth of NiCo2S4 on Ni-foam and its (f, and g) SEM images (Reproduced from Ref. [221] with
permission from Elsevier).

specific capacitance of 850.2 C g− 1 at 1 A g− 1 and retains 93.6 % of its related to the high sublimation temperatures of organic ligands and the
original capacitance after 5000 cycles. When combined with Active low decomposition temperatures of conductive MOFs. Facilitated by
Carbon (AC), the system attains an energy density of 38.1 Wh kg− 1 at oxygenated water (O-H2O), the growth process of crystalline
700 W kg− 1, showcasing an impressive 84.3 % capacity retention after Cu3(HHTP)2 NWAs follows a base-growth mode. The key components of
5000 cycles [221]. this process are emphasized in the preparation setup and the illustrated
The effective management of volume expansion during sulfuration coordination stacking growth (Fig. 33(a)). Analysis of scanning electron
reactions through this morphology-oriented approach suggests prom­ microscopy (SEM) images (Fig. 33(b) and (c)) post-synthesis reveals the
ising potential for applications in supercapacitors. consistent and dense growth of aligned nanowires on the polished Cu
Introducing an innovative dual-temperature zone chemical vapor foil surface. These nanowires exhibit a diameter of approximately 200
deposition (CVD) technique, Du and colleagues enable on-site growth of nm and a length of around 2 μm. Further examination (Fig. 33(d))
conductive Cu3(HHTP)2 metal-organic framework (MOF) nanowire ar­ highlights the prevalent hexagonal column structure with a hexagonal
rays (NWAs) at the interface between a solid Cu foil and a solid organic top facet among most nanowires. Additional insights from Fig. 33(e) and
precursor. This groundbreaking method effectively tackles challenges (f) disclose a hexagonal layer structure composed of multiple 2D

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 33. (a) Schematic diagram of dual-temperature zone CVD synthesis of Cu3(HHTP)2 NWAs on Cu foils (The procedure includes an organic ligand sublimation step
(high temperature zone) and a solid–solid reaction step (low temperature zone)), and illustration of the crystal structure of Cu3(HHTP)2 from slipped-parallel AB
stacking of hexagonal layers (b) SEM images and digital photographs (inset of (b) the blank polished Cu foil), (c) Cu3(HHTP)2 NWAs grown on the Cu foil. (d) High-
magnification SEM image of Cu3(HHTP)2 NWAs grown on the Cu foil, Enlarged images: in the red dotted box in (e) the green dotted box in (f). (g) Layered structure
of Cu3(HHTP)2 nanowire from slipped-parallel AB stacking of hexagonal layers. (Reproduced from Ref. [311] with permission from the Royal Society of Chemistry).

Cu3(HHTP)2 nanosheets. The stacking process for the formation of electrochemical attributes of CC/SiCNWs@NiCo2O4 NAs can be ascribed
nanowire arrays is depicted in Fig. 33(g). In practical applications, the to its binder-free, freestanding structure. The presence of open nano­
utilization of Cu3(HHTP)2 on the Cu foil in a symmetrical supercapacitor sheet arrays on a nanowire network facilitates electrolyte contact, and
demonstrates an impressive specific surface area-normalized capaci­ the establishment of a conductive network through SiCNWs enhances
tance of 41.1 μF cm− 2 at 0.5 A g− 1. This performance surpasses that of overall performance. Additionally, the intercrossing triangular forma­
most carbon materials, showcasing an enhancement of 2 to 5 times tion provides an augmented number of reaction sites, contributing to
[311]. both enhanced electrochemical reactivity and structural stability [313].
In similar approach, Hou et al, also combined conductive Cu-MOF Furthermore, T. Wang et al., designed a hierarchical nanowire array
nanowire arrays with a self-supported polypyrrole (PPy) membrane featuring a core–shell structure of NiCoO@NiCo–OH on flexible carbon
using hydrothermal treatment. The nanowire array of Cu-MOFs provide fiber clothes. This innovative design employed a cobalt-based metal-
high conductivity and an active surface, while the PPy membrane adds organic framework (Co-MOF) as an intermediary. The resulting struc­
mechanical flexibility, efficient charge transfer, and extra capacitance ture not only provides a substantial surface area but also offers abundant
[312]. In alignment with prior methodologies, Yin et al., employed a active sites, facilitates swift electron transport, and ensures efficient
comparable approach to synthesize a hierarchical core–shell structure. diffusion of electrolyte ions. The material exhibited a specific capaci­
This involved utilizing metal-organic framework nanoarrays (MOFNAs) tance of 1792 F g− 1 at 5 mA cm− 2, which is ascribed to its unique
as templates and SiC nanowires (SiCNWs) as conductive skeletons. The structure [314].
resulting electrode, CC/SiCNWs@NiCo2O4 NAs on a carbon cloth sub­
strate, showcased remarkable electrochemical performance in a binder-
free supercapacitor, boasting a high specific capacitance of 1604.7 F 7.7. Nanospheres
g− 1, commendable rate performance, and excellent cycling stability.
Moreover, a hybrid supercapacitor incorporating this electrode Spherical particles exhibit a consistent and rounded diameter, of­
demonstrated a substantial energy density of 49.9 Wh kg− 1, exhibiting fering ample contact points for interactions. When these particles are
stable cycling performance and excellent flexibility. The improved reduced to the nanoscale, they result in higher the surface-to-volume
ratio. For a same volume, the surface interaction is 1000 times

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

heightened as shown in Fig. 34, resulting in an increase in active sites. electrode material plays a crucial role in dictating the storage of elec­
This morphology is widely favoured when selecting electrode materials, trolyte ions and the conduction of electrons. In their study, they syn­
being both common and desirable [315]. Numerous materials based on thesized nanocomposites of zirconium oxide/carbon (ZrO2/C) with a
Metal-Organic Frameworks (MOFs) with a spherical morphology have spherical morphology through the pyrolysis of UiO-66, a zirconium-
been reported to date. based metal-organic framework (MOF). Notably, unlike some other
As an example, Reddy et al. fabricated porous hollow spheres and MOFs, our ZrO2/C material exhibits self-sufficiency for supercapacitor
flower-shaped NiO structures using a Metal-Organic Framework (MOF) applications, eliminating the need for additional conductive agents. The
through a simple solvothermal synthesis followed by heat treatment. ZrO2/C electrode showcased remarkable electrochemical performance,
Through the manipulation of linkers in this process, they successfully attaining a specific capacitance of 241.5 F g− 1 at a rate of 1 A g− 1 [317].
preserved the distinctive flower-like and hollow spherical configura­ In a similar manner to the previously mentioned report, Y. Zhong and
tions of NiO nanoparticles inherited from the original MOF-based tem­ collaborators achieved a nano-sphere configuration by utilizing the TPA
plates. Surface morphological features play a crucial role in influencing (terephthalic acid) linker but by adjusting temperatures. Their method
the performance of electrode materials. The integration of novel nano­ involved the synthesis of nickel metal-organic framework microspheres
structures, such as hollow nanospheres and nanoflowers, not only boosts directly affixed to reduced graphene oxide (Ni-MOF/rGO) through a
the conductivity and active surface area of NiO but also augments the simple hydrothermal and calcining procedure. Noteworthy is the
number of diffusion channels within the material structure, ultimately annealing step at 300 ◦ C, which yielded outstanding conductivity,
leading to an overall improvement in performance. cycling stability, and a considerable ion-accessible surface area. This
resulted in an impressive specific capacitance of 954 F g− 1 at 1 A g− 1 and
• The utilization of the HmIM (2-methyl imidazole) linke]r in Ni-MOF a noteworthy rate capability of 80.25 % at 5 A g− 1. Additionally, when
(NMF-1) results in a flower-like structure, displaying numerous integrated into an asymmetric supercapacitor (ASC) alongside activated
disordered nanosheets. This distinctive morphology is clearly carbon, the assembled Ni-MOF/rGO-300 showcased a energy density of
evident in the SEM images presented in Fig. 35(a, b). 17.13 Wh kg− 1 at 750 W kg− 1. Notably, the material retained 81.63 %
• On the contrary, when employing the TPA (terephthalic acid) linker capacitance even after undergoing 4000 cycles at a high current density
in the synthesis of Ni-MOF (NMF-2), the resulting structure takes the of 5 A g− 1. The exceptional electrochemical performance is ascribed to
form of distorted spheres with an average diameter measuring 1.5 the synergistic effects arising from the unique structures of Ni-MOF and
μm. This specific morphology is well depicted in the SEM images rGO, along with the nanosphere morphology of the Ni-MOF [318].
provided in Fig. 35(c, d). Another study focusing on achieving a nanosphere morphology also
documents the utilization of TPA as the linking agent. The application of
The results of the electrochemical investigations indicate that the nanosphere morphology in Metal-Organic Framework (MOF)-derived
supercapacitive performance of porous NiO hollow spheres surpasses metal oxides, as demonstrated by the work of Z. Zhang et al., presents a
that of porous NiO flowers. Specifically, the former exhibits a specific highly promising avenue for advanced energy storage applications. In
capacitance (Cs) of 1058 F g− 1 at a current density (j) of 2 A g− 1, while their study, the researchers successfully engineered a unique hybrid
the latter demonstrates a lower specific capacitance (Cs = 857 F g− 1 at j material featuring nickel oxide (NiO) nanospheres embedded within a
= 2 A g− 1). Remarkably, the porous NiO hollow spheres display spherical carbon matrix, grown on reduced graphene oxide (rGO)
exceptional capacity retention, retaining over 93 % of their initial ca­ through a pyrolysis process utilizing a nickel MOF precursor with ter­
pacity even after undergoing 5000 cycles. Moreover, the successful ephthalic acid (TPA) as the ligand. This distinctive structure signifi­
fabrication of an asymmetric supercapacitor using NiO//Fe2O3 dem­ cantly enhances the surface area of NiO, providing superior
onstrates remarkable stability over 3000 cycles. This asymmetric pseudocapacitance, efficient electronic transmission pathways, and
supercapacitor achieves an impressive energy density (E) of 35.75 Wh improved ionic absorbability and conductivity. The resulting NiO/C/
kg− 1 at a power density (P) of 780 W kg− 1. rGO hybrid electrode exhibited outstanding electrochemical perfor­
The distinctive structural attributes of the porous spherical NiO mance, demonstrating a high specific capacity of 496 C g− 1 at a current
particles play a pivotal role in enhancing their electrochemical proper­ density of 1 A g− 1, remarkable cycling stability, and an impressive en­
ties. These characteristics provide an abundance of active sites and ergy density of 35.9 Wh kg− 1 in a hybrid supercapacitor. The nano­
numerous transport channels for electroactive species, thereby sphere morphology, facilitated by the MOF-derived synthesis, played a
contributing to an overall improvement in electrochemical performance vital role in optimizing NiO’s specific capacity, lifespan, and overall
[316]. Likewise, according to Shrivastav et al., the configuration of an electrochemical performance.
Furthermore, the introduction of size-controlled NiO nanoparticles
(2–3 nm) uniformly distributed in a spherical carbon matrix supported
by rGO represents a strategic design to enhance the contact area be­
tween NiO and the carbon/electrolyte interface. This innovative
approach minimizes ionic diffusion resistance, improves conductivity,
and mitigates ion diffusion paths, contributing to exceptional cycling
stability and prolonged lifespan during long-term cycling. These results
showcases the potential of nanosphere morphology in MOF-derived
metal oxides for practical applications, particularly as a positive mate­
rial for high-performance supercapacitors with impressive energy stor­
age capabilities and durability [319].

7.8. Insights on morphology

The morphology of MOF-based materials stands as a essential factor,

influencing their performance in supercapacitors. The diverse shapes
including nanoflowers, nanosheets, nanoflakes, nanoplates, nanorods,
nanowires, and nanospheres have been explored and reported. Re­
Fig. 34. Illustration of increase in surface-to-volume ratio when the size of the searchers have investigated into the special details in these morphol­
particle is reduced from microscale to nanoscale. ogies to understand their specific advantages and applications,

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Fig. 35. (a,b) SEM images of Flower-like Ni-MOF (NMF-1) and (c,d) SEM images of sphere-like Ni-MOF (NMF-2). (Reproduced from Ref. [316] with permission
from Elsevier).

particularly in supercapacitors. Nanoplate structures, like those observed in NiFe2O4 rhombus plates,
For instance, the use of MOF-derived nanoflowers, as demonstrated are achieved through the heating of a Nickel-iron bimetallic metal-
by the synthesis of NiO nanoflowers, involves tailored fabrication. The organic framework at different temperatures. The modulation of self-
integration of terephthalic acid (TPA) as the ligand in MOF precursor assembly processes, including the strategic incorporation of modulator
synthesis and adjusting the temperature contributes to the formation of molecules, influences MOF formation and morphology. Achieving static
disordered nanosheets, creating a flower-like structure. Solvothermal and kinetic control through modulation strategies requires careful
synthesis followed by heat treatment is employed to manipulate linkers, manipulation of the interaction between modulator molecules and
preserving the distinctive flower-like configuration of NiO nano­ metal-organic components. Ensuring uniformity and reproducibility of
particles. Temperature control, synthesis method and linker choice are MOF properties is challenging without employing modulation
critical factors influencing the morphology of the resulting nanoflowers. strategies.
However, achieving a consistent and controlled synthesis of nanoflowers Reports with nanorod-like structures involve solvothermal processes
can be challenging which requiring precise modulation of reaction pa­ with modulators like pyridine. The nanorod structure contributes to
rameters. The reproducibility in flower-like structures may pose chal­ high capacitance, uniformity, and stability in supercapacitor applica­
lenges due to sensitivity to synthesis conditions, where temperature may tions. Achieving nanorod morphology involves meticulous control of
fluctuate. reaction time and temperature. The challenge lies in balancing reaction
Nanosheets in MOF-based materials, such as Co-MOF/NiCo-LDH duration to prevent structural integrity loss while ensuring desired
nanosheets, are synthesized by a multi-step process involving MOF nanorod geometry.
formation, hydrolysis, etching, composite formation, and final phos­ Nanowire arrays, such as those composed of conductive Cu-MOF
phorylation. The process involves the growth of interconnected nano­ nanowires, are synthesized through innovative dual-temperature zone
sheets on a carbon cloth substrate, forming a 3D network structure with chemical vapor deposition (CVD) techniques. Oxygenated water facili­
hierarchical organization. Modulation strategies during MOF synthesis tates the base-growth mode of crystalline Cu3(HHTP)2 nanowires,
and careful control of reaction time are essential for achieving desired ensuring consistent and dense growth on the substrate. Combining
nanosheet structures. But, maintaining a delicate balance in reaction conductive Cu3(HHTP)2 nanowires with a self-supported polypyrrole
duration, achieving uniformity in nanosheet distribution and preventing (PPy) membrane provides flexibility and efficient charge transfer.
clustering or collapse during synthesis are challenging. Challenges include addressing high sublimation temperatures of ligands
Nanoflake structures, as observed in Co-MOF/NiCoP nanoflakes, and low decomposition temperatures of conductive MOFs. Also, uniform
involve a synthesis process that includes MOF formation, hydrolysis, growth should also be considered.
etching, composite formation, Mo-doping, and final phosphorylation. A Nanosphere structures, like those observed in nickel oxide (NiO)
short reaction time is crucial for achieving partial hydrolysis and pre­ nanospheres embedded in a carbon matrix, are engineered through
serving the desired nanoflake geometry. The nanoflakes form an inter­ pyrolysis processes with MOF precursors. In several works, the use of
connected 3D network on carbon cloth, enhancing surface area and terephthalic acid (TPA) as a linking agent contributes to the nanosphere
electron transfer capability. Prolonged reaction times can lead to severe morphology, enhancing the electrochemical performance of NiO. The
etching, destroying the desired nanoflake array, which pose a challenge. controlled use of specific linkers and maintaining the uniformity and

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

nano-size distribution of nanospheres poses challenges. The synthesis of morphology.

MOF-based materials with diverse morphologies for supercapacitor ap­ Recently reported MOF-based materials with different morphologies
plications involves a proper control of synthesis parameters, modulation and their electrochemical performance including Specific capacitance,
strategies, and precursor materials. energy density and power density is given in Table 6.
Additionally, to enhance the performance of MOF-based super­
capacitors through morphological variation, we propose a hypothesis, 8. Commercialization – Prospects and challenges
which is conducting a comprehensive analysis to correlate the perfor­
mance of MOF-based supercapacitors with their specific morphologies. Metal-organic frameworks are known to offer considerable advances
This involves integrating experimental studies with computational in electrochemical performance and stability when subjected to pre- and
simulations to discern how various morphologies, such as nanoflowers, post-treatment techniques. These structures conserve the signature
nanosheets, and nanorods, impact critical performance parameters like features typical to the initial MOFs which proves the impressive
capacitance, cycling stability, and rate capability. Such an analysis is adaptability for different applications, and also sometimes outperforms
essential to clarify the specific morphologies that contribute to enhanced the traditional counterparts. However, the industrial application of
performance, as conflicting research findings exist. After elucidating the MOFs for supercapacitors is still restricted by several barriers
benefits of specific morphologies, it facilitates the development of [85,344,345].
tailored synthetic strategies. These strategies would involve exploring Since MOF-based materials hold the inherent porosity and structure,
novel solvent systems and templating agents to exert precise control the use of binders in the manufacturing process of MOF derivatives and
over the nucleation and growth of MOF structures, thus addressing compounds based electrodes may induce the aggregation of MOFs or
challenges related to reproducibility and uniformity. other particles, hence diminishing the accessible active surface area and
Based on insights from the literature, a visual representation in the collapsing the inherent structure [346,347]. This can be addressed by
form of an illustrative figure highlighting the common factors influ­ focussing research on determining scaling-up techniques of binder-free
encing morphology is shown in Fig. 36. electrodes. Furthermore, it is imperative to ensure suitable reaction
Each morphology offers unique advantages, such as increased sur­ conditions, like temperature and rate of heating, while employing
face area, enhanced charge storage, and improved kinetics. However, calcination and pyrolysis methodologies for post-treatments. Further­
challenges persist in achieving reproducibility, uniformity, and stability. more, the practical utility of MOF materials in industrial settings is
The careful balance of reaction conditions, choice of ligands, and limited by their susceptibility to hydrolysis [348,349]. While certain
innovative synthesis techniques can help in achieving the desired MOFs derived from Zirconium and Hafnium have demonstrated

Fig. 36. Illustration of the common factors influencing morphology of MOF based materials.

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

Table 6
Recent reports on MOF-based materials, their morphology and electrochemical performance.
Name of the material Morphology Specific capacitance Energy density Power density Stability Reference
− 1 − 1 − 1 − 1
MOF derived NiCo-LDH Nanosheets 723 C g at 1 A g 40.26 Wh kg 850 W kg 74 % after [320]
10,000 cycles
− 1 − 1 − 1 − 1
Nickel-Metal Organic Framework Nanosheets 536 F g at 1 A g 45.6 Wh kg 750 W kg 85 % after [321]
10,000 cycles
(Ni, Co)3S4have been decorated on metal–organic Nanosheets 1319 F g− 1 at a current 34.2 Wh kg− 1
849.2 W kg− 1
84.8 % after [322]
framework (MOF)-derived straw-bundle-like CeO2 density of 1 A g− 1 10,000 cycles
Metal–organic framework (MOF) derived cobalt Nanosheets 842 F g− 1 (421 C g− 1) at 1 55.7 Wh kg− 1
1125.9 W kg− 1
94.5 % after [189]
oxide (Co-O) hierarchical walnut A g− 1 5000 cycles
Metal-organic framework derived Co-Mo-S Nanosheets 1805.28 F g− 1 at a current 169.73 Wh kg − 1
371.44 W kg − 1
94.44 % after [323]
density of 0.5 A g− 1 50,000 cycles
Metal-organic-frameworks Nanosheets 770.4 C g− 1 at 1 A g− 1 40.6 Wh kg − 1
266.6 W kg − 1
85 % after [324]
Defective ZnCoNiP 5000 cycles
1 − 1 1 1
Nickel-Metal Organic Framework (Ni-MOF) Nanosheets 536 F g− at 1 A g 45.6 Wh kg− 750 W kg− 85 % after [321]
synthesized 10,000 cycles
1 1 1 1
MOF derived NiCo2S4@NC Nanoflower 1021.6 F g− at 1 A g− 61.5 Wh kg− 426.6 W kg− 92.7 % over [325]
5000 cycles
− 1 − 1 − 1 − 1
Hierarchical NiCo-Layered Double Hydroxide Nanoflower 2210.6 F g at 1 A g 45.02 Wh kg 799.96 W kg – [326]
Integrated with Metal–Organic Framework-
Derived Co@C
Metal-organic framework-derived (Mn-CoxSy@ Nanoflower 2.19 mA h cm− 2 at 1 95.25 Wh kg− 1
963.2 W kg− 1
92.08 % after [327]
(Ni–Cu)OHs mA cm− 2 10,000 cycles
NiCo metal–organic framework (MOF) Nanoflower 927.1 F g− 1 at 1 A g− 1 28.5 W hkg− 1
400.5 W kg− 1
95.4 % after [328]
5000 cycles
− 1 − 1 − 1
NiCo2S4, nickel–cobalt layered double hydroxides Nanoflower 2934 mAh g at a current 38.8 Wh kg 993.0 W kg 81.2 % after [329]
(NiCo-LDH) and CoS2 electrodes density of 1 A g− 1 10,000 cycles
Nickel-Metal Organic Framework (Ni-MOF) derived Nanoflower 613 F g− 1 27.58 Wh kg− 1
1320 W kg− 1
97 % after [330]
NiS 5000 cycles
1 1 1 1
Metal–organic framework-derived Co3S4 @ V2O5 Nanowires 1493.6 F g− at 1 A g− 40.7 Wh kg− 800 W kg− 85.9 % after [331]
10,000 cycles
− 1 − 1
Metal-organic frameworks (MOFs)-derived Nanowires 709 F g at 1 A g – – 83 % after [187]
Co3O4@N-doped carbon 5000 cycles
− 1 − 1 − 1 − 1
Synthesis of copper/chromium metal organic Nanowires 535.1 F g at 0.7 A g 36.7 Wh kg 2600 W kg 90.3 % after [332]
frameworks DerivativesCu/Cr-MOF-D 5000 cycles
MOF derived hierarchical ZnNiCo-LDH on vapor Nanowires 378.10 mAh g− 1 at 1 A 117.5 Wh kg− 1
576.9 W kg− 1
94 % after [333]
solid phase grown CuxO g− 1 10,000 cycles
Optimized Fabrication of Bimetallic ZnCo Nanowires 1611 F g− 1 at 2 A g− 1 44.5 Wh Kg− 1
876.7 W Kg− 1
– [334]
Metal–Organic Framework at NiCo-Layered
Double Hydroxides
1 1 1
Ni-MOF Nano flakes 21 mA h at 1 A g− 11 Wh kg− 6396 W kg− 89 % after 3400 [335]
cycles
1 2 1 1
Ni-Co MOF Nano flakes 1385 F g− at 4 mA cm− 7.8 Wh kg− 173.07 W kg− 88.4 % after [336]
3000 cycles
1 1 1 1
CNT/nickel–cobalt bimetallic sulfide (CNTs/ Nano flakes 734 C g− at 1 A g− 42.15 Wh kg− 852 W kg− 88.46 % [264]
Ni–Co–S3) composites after10000
cycles
1 1
Cobalt-metal–organic frameworks (MOFs) Nano flakes 1726 Fg− at 1 Ag− – – 97.4 % after [337]
3000 cycles
MOF–derived hollow double–shelled NiO Nanosphere 473 F g− 1 at the current 21.4 Wh kg− 1
375.8 W kg− 1
94 % after 3000 [338]
density of 0.5 A g− 1 cycles
Bifunctional metal–organic framework-derived Nanosphere 1259 F g− 1 at 0.5 A g− 1 87.3 Wh kg− 1
825 W kg− 1
81.3 % after [339]
nitrogen-doped porous multishell CuCoS@NiCoS 8400 cycles
− 1 − 1 − 1 − 1
nickel phosphide encapsulated in carbon Nansphere 1622 F g at 1 A g 47.46 Wh kg 0.397 kW kg 75.2 % after [340]
microsphere from a spherical MOF 8000 cycles
Nickel-metal–organic framework (Ni-MOF) Nanorod 1956.3 F g− 1 at 5 mA 98.15 Wh kg− 1
1253.47 W kg− 1
99.29 % over [307]
cm− 2 3000 cycles
Co(OH)2/Ni(OH)2nanorods derived from Nanorod 1957 F g− 1 at 0.5 A g− 1
– – 88 % after 4000 [341]
metal–organic framework (MOF)
− 1 − 1 − 1 − 1
nickel cobalt manganese ternary metal–organic Nanorod 1428 F g at 1 A g 38.10 Wh kg 884.38 W kg 83.5 % after [342]
frameworks 3000 cycles
− 2 − 2
Two-dimension nickel cobalt metal–organic Nanosheets 4.31 F cm at 1 199.4 μWh cm −
801.9 μW cm 92.51 % after [343]
frameworks/reduced graphene oxide hybrid films mA cm− 2 2
5000 cycles
(2D/2D NiCo-MOFs/rGO)
1 1 1
Defective ZnCoNiP nanosheets derived from metal- Nanosheets 770.4 C g− at 1 A g− 266.6 W kg− 85 % of specific 90.5 % after [324]
organic-frameworks capacitance after 10,000 cycles
5000 cycles

promising aqueous durability, extensive studies have primarily focused frameworks compared to their two-dimensional counterparts [350,351].
on assessing the stability of traditional available MOFs like imidazole- While numerous three-dimensional water-stable MOFs have shown
based zeolitic imidazolate frameworks (ZIFs), MOFs with infinite varying pH stability, there remains a lack of research on the pH stability
length (MILs), and porous coordination networks (PCNs). However, it’s of two-dimensional MOFs. Electrochemical setups and asymmetric
important to note a lack of recent research investigating water-stable supercapacitor (ASC) devices often rely on aqueous alkaline solutions as
MOFs. Moreover, majority of water-stable MOFs primarily feature electrolytes, requiring that MOFs used as electrode materials maintain
three-dimensional structures, attributed to the inherent rigidity of such their natural crystalline structure and porosity to ensure stability in

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B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

these solutions. The presence of layered structures in two-dimensional contain potentially toxic materials like sulfur or phosphide, raising
MOF-based materials holds significant promise for various applica­ questions about their safety standards on a larger scale. Consequently,
tions due to their intriguing atomic-scale characteristics [352,353]. It’s there’s an urgent need for more research to establish safe handling and
anticipated that in industrial applications, electrode materials derived storage protocols for MOF-based materials and devices. Moreover,
from two-dimensional MOFs with exceptional porosity and thermody­ ensuring the long-term stability of MOF-based electrode materials in
namic stability, will demonstrate improved performance. It’s important practical applications is one of the major challenges. Extensive dura­
to highlight the necessity for further research to assess the practical bility tests should be conducted to assess the performance of MOF-based
suitability of stable MOF-based materials and their derivatives for electrodes under diverse conditions, including repeated cycling, tem­
industrial-scale supercapacitor applications, indicating that there is still perature variations, and exposure to various chemical pollutants.
significant progress to be made in this area. Moreover, the integration of MOF-based energy storage materials into
practical devices and systems also presents some challenges. This in­
9. Summary volves tackling design considerations, scalability issues, and ensuring
compatibility with current technologies. Therefore, research efforts
In summary, metal-organic frameworks (MOFs) have been investi­ should not only focus on material advancements but also on system-level
gated by various researchers for their application as electrode materials integration and the design aspects of energy storage systems [355–357].
in supercapacitors. However, pristine MOFs have limitations that pre­ As far, this review highlights the significance of careful control over
vent their application in conventional energy storage systems. Their synthesis parameters, modulation strategies, precursor materials, and
primary drawback lies in poor electrical properties arising from the reaction conditions to achieve the desired morphology and optimize
insulating nature of organic ligands in MOFs that restrict electron electrochemical performance. While redox-active pure MOFs, MOF
transport within the MOF structure. Additionally, MOFs are mechani­ composites and derivatives each present advantages, the derivatives
cally unstable, making them prone to damage or structural degradation stand out for their stability than pure MOF, due to the evaporated
under mechanical stress or with prolonged use. This mechanical insta­ organic ligands during thermal treatment without compromising the
bility can compromise long-term efficiency and durability. Conse­ MOF structure. From this review comparing various report, it can be
quently, these challenges lead to reduced strength and poor energy interpreted and concluded that the strategic selection of redox-active
storage characteristics of MOFs compared to other materials. While metals, preferably in a bimetallic metals coupled with derivation into
MOFs offer benefits like high porosity and surface area, they often need metal oxides or sulfides, with a preference for nanosheet-like, plate-like,
improvements in conductivity, mechanical strength, capacitance, and or flower-like 2D morphologies on a 3D substrate holds potential for
energy density to align with traditional energy storage systems [354]. By enhancing the electrochemical performance of MOFs in supercapacitors.
exploiting the distinctive characteristics of MOFs, researchers have This comprehensive review details the transformative potential of
adopted a range of strategies to enhance their utilization in super­ MOFs in shaping high-performance supercapacitors. The synthesis
capacitors. Four key strategies including the redox approach, composite techniques, reaction parameters, use of additives, and innovative ap­
fabrication, MOF as templates for derivatives, and precise control of proaches discussed herein lay the groundwork for future research
MOF structures have played an important role in enhancing the elec­ addressing the evolving demands of our modern world. The intricate
trochemical performance. Researchers strategically incorporated redox- interplay of material design, synthesis strategies, and morphological
active metal centers/ligands for developing MOF with redox properties, control places MOFs at the forefront of supercapacitor technology
employed composite fabrications to enhance capacitance and stability, contributing to sustainable and efficient energy storage solutions.
explored MOF derivatives through post-synthetic modification (POSM),
and exercised precise control over the morphological features of MOF CRediT authorship contribution statement
and their derivatives to tailor them to improve their performance in
supercapacitor. Among the strategies, the synthesis of MOF derivatives, Balaji Chettiannan: Investigation, Conceptualization, Methodol­
including metal oxides, sulfides, phosphides, and hydroxides, has shown ogy, Data curation, Writing – original draft. Elumalai Dhandapani:
promise in overcoming challenges related to energy density, stability, Data curation, Resources, Writing – review & editing. Gowdhaman
and scalability. Various synthesis methods, such as thermal decompo­ Arumugam: Data curation, Resources, Writing – review & editing.
sition, calcination, sulfurization, and phosphorization, have been Ramesh Rajendran: Conceptualization, Methodology, Writing – review
deployed to transform MOFs into functional derivatives suitable for & editing, Supervision. Manickam Selvaraj: Funding acquisition, Re­
supercapacitor applications. Moreover, the exploration of morpholog­ sources, Writing – review & editing.
ical aspects in MOF-based materials, ranging from nanoflowers to
nanospheres, has provided insights into their specific advantages and Declaration of competing interest
applications in supercapacitors. Each morphology offers unique bene­
fits, including increased surface area, enhanced charge storage, and The authors declare that they have no known competing financial
improved kinetics. Despite the impressive attributes, challenges remain interests or personal relationships that could have appeared to influence
in achieving consistency, uniformity, and long-term stability in MOF- the work reported in this paper.
based electrode materials. The large-scale synthesis of MOFs presents
challenges that limit their practical industrial-level. Scalability and cost- Data availability
effectiveness are very important for making MOFs suitable for broader
use. For example, maintaining hydrolytic stability and consistent The authors do not have permission to share data.
morphology in MOF-based electrodes can be challenging with slight
variations in reaction conditions on a larger scale along with concerns Acknowledgments
about precursor costs. Moreover, techniques like doping, or post-
synthetic modification, may require varied temperatures which adds The authors extend their appreciation to the Deanship of Research
to the cost. This underscores the need for cost-effective and scalable and Graduate Studies at King Khalid University for funding this work
production techniques, with a focus on collaboration between materials through the Large Research Group project under grant number, R.G.P.2/
scientists and engineers. Safety is also a major consideration, given that 329/45. And, this research was supported by financial assistance from
these materials can present risks in energy storage environments, the Department of Science and Technology, New Delhi under the DST-
particularly when under extreme temperatures or in chemically reactive INSPIRE FELLOWSHIP award (INSPIRE fellow registration number:
conditions. Additionally, some MOF-based composite electrodes may IF210236).

45
B. Chettiannan et al. Coordination Chemistry Reviews 518 (2024) 216048

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