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MOF/graphene oxide based composites in smart

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supercapacitors: a comprehensive review on the
electrochemical evaluation and material
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development for advanced energy storage devices

Sanjeev Gautam, *a Shruti Rialach, bc
Surinder Paulb and Navdeep Goyald

The surge in interest surrounding energy storage solutions, driven by the demand for electric vehicles and
the global energy crisis, has spotlighted the effectiveness of carbon-based supercapacitors in meeting high-
power requirements. Concurrently, metal–organic frameworks (MOFs) have gained attention as a template
for their integration with graphene oxide (GO) in composite materials which have emerged as a promising
Received 9th February 2024
Accepted 18th April 2024
avenue for developing high-power supercapacitors, elevating smart supercapacitor efficiency, cyclic
stability, and durability, providing crucial insights for overcoming contemporary energy storage obstacles.
DOI: 10.1039/d4ra01027b
The identified combination leverages the strengths of both materials, showcasing significant potential for
rsc.li/rsc-advances advancing energy storage technologies in a sustainable and efficient manner. In this research, an in-

a
Advanced Functional Materials Lab, Dr S.S. Bhatnagar University Institute of c
Energy Research Centre, Panjab University, Chandigarh-160014, India
Chemical Engineering & Technology, Panjab University, Chandigarh-160014, d
Department of Physics, Panjab University, Chandigarh-160014, India
India. E-mail: [email protected]; Tel: +91 97797 13212
b
Department of Physics and Astronomical Science, Central University of Himachal
Pradesh, Dharamshala, 176215, India

054610Dr Sanjeev Gautam 070485Ms Shruti Rialach is

leads an independent research a research scholar at Central
group, the Advanced Functional University of Himachal Pradesh
Materials Lab., at Panjab who is conducting her research
University, India. He has 25+ work at Energy Research Centre,
years of experience with over Panjab University, Chandigarh.
161+ (h-index = 33) interna- Currently, her focus lies in
tional publications. He exploring MOF/GO composites
completed his PhD (2007) in for the enhancement of smart
condensed matter physics at the supercapacitors, targeting their
Department of Physics, Panjab application in advanced energy
University, Chandigarh, India. storage devices. Ms Rialach
He also worked as a grid earned her MSc Physics from
Sanjeev Gautam Shruti Rialach
computing administrator for the Department of Physics, Panjab
CMS (LHC) research project and then as beamline scientist at University, Chandigarh, and persuing her PhD from Department of
Pohang Accelerator Lab, with Korea Institute of Science and Physics and Astronomical Science, Central University of Himachal
Technology (star post-doc), South Korea (2007–2014), where he got Pradesh. Her research interests include smart supercapacitors,
expertise in synchrotron radiation research in materials. As Panjab advanced energy storage devices, electric vehicles.
University faculty (2014 onwards), he received international and
national grants, and advanced his research in the eld of nano-
technology, sustainable energy, food technology, catalysts, and
environmental safety. He supervised 8 PhD students along with
several UG/PG researchers, and served as an editorial board
member for Scientic Reports, Materials Letters, Materials Letters:
X and Heliyon.

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depth review has been presented, in which properties, rationale and integration of MOF/GO composites
have been critically examined. Various fabrication techniques have been thoroughly analyzed,
emphasizing the specific attributes of MOFs, such as high surface area and modifiable porosity, in
tandem with the conductive and stabilizing features of graphene oxide. Electrochemical
characterizations and physicochemical mechanisms underlying MOF/GO composites have been
examined, emphasizing their synergistic interaction, leading to superior electrical conductivity,
mechanical robustness, and energy storage capacity. The article concludes by identifying future research
directions, emphasizing sustainable production, material optimization, and integration strategies to
address the persistent challenges in the field of energy storage. In essence, this research article aims to
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offer a concise and insightful resource for researchers engaged in overcoming the pressing energy
storage issues of our time through the exploration of MOF/GO composites in smart supercapacitors.
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plays a crucial role in ensuring a continuous and reliable supply of

1 Introduction renewable energy to power systems, even during periods of no
The vitality of life hinges on the acquisition and conversion of sunlight and low wind speeds. Growing storage systems are crucial
energy from the environment, a fundamental process in which to the global deployment of renewable energy, and when
human actively participate by transforming less desirable combined with variable renewable like wind and solar, they can
energy forms into essential resources such as meat, heat from help replace expensive and environmentally harmful fossil fuel-
wood, and electricity from fossil fuels. Human energy
consumption evolved from primitive reliance on food to more
efficient hunting and primitive agriculture. The 1875 onset of
industrialization and the steam engine led to a threefold
increase in energy consumption, unlocking access to concen-
trated solar energy storage in fossil fuels. Industrialization
revolutionized energy dynamics; by 1970, daily energy
consumption was 115 times higher than in prehistoric societies
due to technological advancements. Fig. 1 below illustrates how
patterns of energy usage have changed throughout time.
The burgeoning global demand for energy underscores its
pivotal signicance in enhancing societal well-being, mitigating
climate change, and ensuring the requisites for sustainable
human existence.2 The International Energy Agency (IEA) predicts
a yearly increase of 3% in global energy demand throughout the
period from 2023 to 2025. The question that now needs to be
answered is: How are we going to sustainably meet these
demands? The answer lies in energy storage! Yes, energy storage Fig. 1 The change in energy consumption patterns over time.1
Adapted from the source: Sci. Am., 1971, 225, 134–147. Copyright 1971
technologies allow us to store excess energy and discharge it when
JSTOR.
there is too little generation or too much demand. Energy storage

Dr Surinder Paul is an associate Prof. Navdeep Goyal is a leading

Professor at the Department of professor at the Department of
Physics and Astronomical Physics, Panjab University,
Science, Central University of India, with 35+ years of experi-
Himachal Pradesh, India, with ence. He did his postdoc at TIFR,
12+ years of experience in Mumbai (1992–93). His main
research. His main area of area of work is in experimental
research is materials science, solid-state physics, especially
mainly synthesis of perovskite the dielectric properties of chal-
material for electrode applica- cogenide glasses, device appli-
tion of solid oxide fuel cell. cation of high critical
temperature superconductors,
magnetic properties of layered
Surinder Paul Navdeep Goyal
superconductors and power
electronics. He has published more than 150 international publi-
cations and has a h-index of 21.

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generated electricity while boosting supply security. In this era of Fig. 2(c) provides a comprehensive overview of research articles
rapid technological advancement and growing energy demands, published over the past 15 years, highlighting the advancements
the need to store energy has never been more apparent. and trends in MOF/GO composite materials for energy storage
Capacitors and widely available batteries constitute prominent devices.
energy storage devices within the electric market. Capacitors store In this paper, we have delved deeply into the dynamic world of
energy through charge accumulation, creating a potential differ- MOF/GO composites for supercapacitor applications, pushing the
ence across plates. However, their energy density is constrained by boundaries of energy storage technology to new frontiers. The
dielectric limitations. In contrast, batteries store energy through article commences by explaining the fabrication and charge
reversible chemical reactions, yet face challenges with low power storage mechanism in various types of supercapacitors, further
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density during rapid cycles. Because of this restriction, scientists examining the rationale and properties of MOFs and GO,
have been investigating supercapacitors, which provide a unique emphasizing their individual contributions to enhancing super-
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combination of outstanding power density, long cycle life, and capacitor performance. Notable features of MOFs, including their
swi charging/discharging times. These attributes render super- elevated surface area and modiable porosity, are discussed
capacitors well-suited for various applications, viz., power elec- alongside the conductive and stabilizing characteristics of gra-
tronics, power ampliers, etc., necessitating expeditious energy phene oxide. Subsequent sections explore fabrication techniques,
discharges and frequent cycling. Silicon carbide (SiC) and gallium energy storage mechanism and physicochemical mechanisms of
nitride (GaN) have become integral components in power elec- MOF/GO composites, highlighting their synergistic effects on
tronics, as depicted in Fig. 2(a), owing to their inherent properties. electrical conductivity, mechanical robustness, and energy storage
The surge in demand, however, has presented supply challenges, capacity. This research stands in stark contrast to conventional
necessitating a thorough exploration of strategies to meet the energy storage devices, providing a promising trajectory for the
escalating needs of the rapidly expanding market. Carbon, unlike evolution of high-performance supercapacitor technologies.
silicon and gallium, is abundant in nature. The planet's vast Several characterization techniques frequently used to study the
forests, peat bogs, and even carbon dioxide from the atmosphere electrochemical behavior of supercapacitor materials and devices
can be harnessed for carbon-based materials. Fig. 2(b) illustrates have also been discussed in the latter sections for comprehensive
recent studies on carbon allotropes employed as electrode mate- understanding of the performance and limitations of super-
rials. Among the most promising candidates for supercapacitor capacitors, facilitating the development of improved energy
electrodes are carbon derivatives and composite materials. MOF/ storage devices. Through a comprehensive discussion, this review
GO composites are gaining signicant traction among delves into advancements that cater to the unique requirements of
researchers for energy storage applications owing to their unique each application, emphasizing the evolving landscape of MOF/GO
combination of properties as this synergistic combination enables composites in smart supercapacitors. In conclusion, the review
precise control over ion transport kinetics and electrochemical anticipates future research directions by underscoring the imper-
reactions, thus promising advancements in the development of ative for sustainable and scalable production methods, continued
high-performance energy storage devices such as supercapacitors. material optimization, and innovative integration strategies. These
identied avenues not only hold the potential to address current
challenges but also pave the way for the continual advancement of
supercapacitor technologies, ensuring their relevance and efficacy
in evolving energy storage landscapes.

Fig. 2 (a) The current status, forecast, and size of the global market for
gallium nitride (GaN) and silicon carbide (SiC) power semiconductors,3
(b) recent breakthroughs in carbon allotropes as electrode materials,4
and (c) research articles published regarding the advancements and
trends in MOF/GO composite materials for energy storage devices
over the past 15 years. (a) Adapted from the source: openPR. Copyright
2022 openPR, and (b) adapted with permission from source: Nano Fig. 3 Illustration of the mechanisms for storing charge in (a) electric
Energy, 2014, 9, 128–141. Copyright 2014 Elsevier. double-layer capacitor, (b) pseudocapacitor, and (c) hybrid capacitor.

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2 Supercapacitors The total capacitance (Ctotal) of the EDLC can be calculated as

the sum of inverse of the double-layer capacitance of each
2.1 Types and operation electrode:
A supercapacitor, alternatively referred to as an ultracapacitor 1 1
or electrochemical capacitor, functions as an electrical energy ¼2 (3)
Ctotal Cdl
storage device that stores energy via electrostatic charge sepa-
ration at the interface of porous electrodes and an electrolyte. It where “2” is used because there are two electrodes in an EDLC.
offers a unique set of advantages, such as rapid charging and When a voltage (V) is applied across the EDLC, we can
discharging abilities,5 an extended cycle life,6 and high power calculate the amount of charge (Q) it can store employing the
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density.7 These remarkable attributes make supercapacitors initial equation. The energy (E) stored in the EDLC can be
a crucial component in addressing a multitude of contemporary computed utilizing the subsequent equation:
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

challenges, from powering electric vehicles8 and renewable

E = 0.5 × Ctotal × V2 (4)
energy systems9 to enhancing the performance of portable
electronics.10,11 A captivating recent application of super-
These equations provide a mathematical framework for
capacitors involves ABB ash charging Swiss buses. Every time
understanding how charge, capacitance, voltage, and energy are
a bus smoothly comes to a stop, a contact ascends to connect
related in an EDLC. The actual capacitance and energy storage
with a supercapacitor ash charger, providing a rapid delivery
capabilities depend on the specic design and materials used in
of 600 kilowatts in just 15 seconds.12 In this age of innovation
the EDLC, as well as the operating conditions. The process is
and environmental consciousness, the importance of super-
purely electrostatic and does not involve chemical reactions,
capacitors as a key enabler of our energy-efficient, sustainable
making EDLCs capable of rapid energy storage and release,
future cannot be overstated. Based on how these super-
along with sustaining an enormous number of cycles of charge
capacitors store energy, as seen in Fig. 3, supercapacitors are
and discharge. However, these devices' energy density is
categorized into three distinct types.
somewhat constrained because of their charge storing
(1) Electrochemical double-layer capacitor
technique.14
(2) Pseudocapacitor
2.1.2 Pseudocapacitor. A pseudocapacitor is an energy
(3) Hybrid capacitor
storage system that functions as a transitional step between
2.1.1 Electrochemical double-layer capacitor. EDLCs,
a battery and a traditional electrolytic capacitor. Pseudocapa-
known as electric double-layer capacitors, represent a category of
citors store charge through a combination of processes,
energy storage devices that store electrical energy by electrostati-
including faradaic reactions and non-faradaic (electrostatic)
cally separating charges at the interface between an electrolyte and
mechanisms. The mathematical mechanism of charge reten-
an electrode material that possesses a high surface area. Ions, both
tion in pseudocapacitors can be elucidated by considering the
positive and negative, from the electrolyte are attracted to the
following components:
surface of the opposing electrode when a voltage is applied, which
1. Faradaic reactions: pseudocapacitors oen use materials
is the charge accumulation mechanism in EDLCs. This division of
with redox-active properties, such as conductive polymers or
charges creates an electrostatic double-layer at each electrode–
oxides of transition metals, as the components in their elec-
electrolyte interface. The energy is stored as accumulated charge in
trodes. Charge gets accumulated in these materials through
the electrostatic double-layer. Ions move to the double layer's
redox (reduction–oxidation) reactions. The faradaic reactions
surface when voltage is applied to the electrodes, charging the
involve the passage of electrons between the electrode and the
capacitor. On the other hand, when a capacitor is discharged, ions
electrolytic solution. Such reactions are typically described
are repelled. This is how the EDLC charges and discharges.13
using the Butler–Volmer equation:
EDLCs accumulate energy following the fundamental capacitor
equation: I = k(Cox − Cred) (5)

Q=C×V (1) In this equation, I represents the current (charging/

discharging), k is the rate constant for the redox reaction, Cox
In this equation, Q represents the stored charge, C denotes
denotes the concentration of the oxidized form of the redox
the capacitance, and V stands for the applied voltage.
species across the electrode, and Cred is the concentration of the
The double-layer capacitance (Cdl) in EDLCs is given by:
reduced state of the redox molecules across the electrode.
3A 2. Non-faradaic (electrostatic) mechanisms: apart from fara-
Cdl ¼ (2)
d h daic reactions, pseudocapacitors also rely on the electrostatic
storage of charge. This mechanism entails the adsorption and
desorption of ions, typically cations, at the juncture where the
In this context, 3 signies the permittivity of the electrolyte, A
electrode and the electrolyte interface. The mathematical
corresponds to the surface area of electrodes, d represents the
description of this mechanism oen relies on the Gouy-
distance between electrodes, and h stands for the viscosity of the
Chapman-Stern (GCS) model or the Helmholtz double-layer
electrolyte.
capacitance model.

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 Gouy-Chapman-Stern Model: the GCS model considers the In this equation, Q signies the stored charge, Cp represents
distribution of ions in the electrical double layer formed at the the pseudocapacitance, and DE is the potential difference
juncture contacting the electrode and the electrolyte. It uses the associated with the redox reaction.
Poisson–Boltzmann equation to describe the capacitance and Concerning a hybrid supercapacitor, we have both EDLC and
distribution of charges in the double layer. pseudocapacitance contributions. Subsequently, the combined
 Helmholtz double-layer capacitance: this model simplies contribution from the two mechanisms results in the total
the GCS model and considers a more compact double layer with charge (Qtotal) contained in the hybrid supercapacitor:
a constant capacitance value.
Combining both faradaic and non-faradaic mechanisms, the Qtotal = QEDLC + Qp (9)
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overall charge storage in pseudocapacitors can be mathemati-

cally described as the sum of the contributions from faradaic where, QEDLC is the charge stored due to EDLC, and Qp is the
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reactions and the double-layer capacitance. The total capaci- charge stored due to pseudocapacitance.
tance (Ctotal) of a pseudocapacitor can be expressed as: The materials used in hybrid capacitors can vary depending
on the specic design and application, but they typically involve
1 1 1
¼ þ (6) the utilization of transition metal oxides and compounds based
Ctotal Cdl Cfaradaic on carbon as the electrode components in view of their elec-
trical conductivity and elevated surface area. Carbon-based
In this context, Ctotal represents the overall capacitance of the materials comprise activated carbon,34–37 graphene,38–41 carbon
pseudocapacitor, Cdl is the double-layer capacitance, and Cf nanotubes,42–45 and other carbon derivatives.46–49 Transition
aradaic is the capacitance arising from faradaic redox reactions. metal oxides, viz., RuO2,50–52 and MnO2,53–56 can be used in the
Nowadays, most of the pseudocapacitors store electrical positive electrode of hybrid capacitors to increase energy
energy using electrochemically active materials like conducting storage capacity.
polymers, viz., polyaniline (PANI),15–17 poly(3,4-propylene diox-
ythiophene) (PProDOT),18,19 poly(3,4-ethylene dioxythiophene) 2.2 Fabrication
(PEDOT),20–22 polypyrrole23–25 and polythiophene (PT),26–28 and The fabrication of different types of supercapacitors with
various transition metal oxides29–31 for fabricating the elec- respect to the electrode materials, specic capacitance, cycling
trodes. Giving the active electrode material more specic stability, energy density and power density values has been
capacitance and better energy densities is the primary benet of showcased in Table 1. In general, conducting polymers and
the pseudocapacitor. Notwithstanding their impressive elec- transition metal oxides are commonly employed in the fabri-
trical characteristics, pseudocapacitors exhibit restricted elec- cation of pseudocapacitors, whereas carbon-based materials are
trical conductivity of the electrode material.32 frequently utilized for EDLC electrodes.57 Carbon-based EDLCs
2.1.3 Hybrid capacitor. A hybrid capacitor is an assorted offer high power density and good cycling stability owing to
device for storing energy that combines the characteristics of their distinct working processes, yet they typically exhibit lower
a supercapacitor and a battery. It typically features electrodes capacitance and energy density. Conversely, pseudocapacitors
with both electrostatic double-layer capacitance (EDLC) and operate differently, with the electrode chemical reactions
pseudocapacitance properties, allowing it to offer quick charge/ leading to the accumulation of irreversible components during
discharge times and a substantial amount of power density, cycling, thereby causing performance degradation over time.
similar to supercapacitors, while also providing higher energy Hybrid supercapacitors (SCs) combine the charge-storage
density, resembling batteries.33 A hybrid supercapacitor's mechanisms of both EDLCs and pseudocapacitors, resulting
charge storage methodology integrates electrostatic double- in higher capacitance compared to EDLCs and improved cycling
layer capacitance (EDLC) with pseudocapacitance, which is stability relative to pseudocapacitors. They maintain high power
frequently connected to redox reactions. The mathematical density while also achieving an increase in energy density.
equations for these two mechanisms are as follows: Ren et al. initially developed MWCNT/ordered mesoporous
The EDLC component is associated with the physical sepa- carbon (OMC) composite bers as electrodes for wire-shaped
ration of charges at the electrode–electrolyte juncture. The supercapacitors (WSS).58 OMC particles grew within the inter-
stored charge (Q) in an EDLC is determined by the equation: stices of MWCNTs, enhancing conductivity and enlarging the
effective surface area for ion adsorption, thereby potentially
Q = CEDLC × V (7)
increasing energy and power density. By leveraging the advan-
tageous structures and properties of each component, the
where, in this equation, Q represents the stored charge, CEDLC
composite ber was engineered. Subsequently, two aligned
denotes the EDLC capacitance, and V is the applied voltage.
MWCNT/OMC composite bers coated with H3PO4-PVA elec-
Pseudocapacitance results from redox processes at the elec-
trolyte were twisted to fabricate a exible wire-shaped EDLC.
trode material's surface. The stored charge (Q) resulting from
Carbon microbers (CMFs) have emerged as effective alterna-
pseudocapacitance can be expressed using the equation:
tives to metal wire current collectors. MWCNTs were spray-
Q = Cp × DE (8) coated onto CMFs using a simple method. The resulting
MWCNT/CMFs bundle served as electrodes, current collectors,
and substrates or active materials for EDLCs, thus constituting

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Table 1 Comparison between fabrication of EDLCs, pseudocapacitors and hybrid supercapacitors

Specic
Electrode capacitance Cycling
Supercapacitor materials (F g−1) stability (%) Energy density Power density Applications

EDLC Carbon-based 11.25–174 92–100 Moderate High Mainly in high power

materials applications (e.g.,
(e.g., activated regenerative braking in
carbon) vehicles)
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Pseudocapacitor MOx conducting 60–1280 67–98 Moderate to high Moderate to high Energy storage in
polymers portable electronics,
renewable energy
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systems
Hybrid Carbon-MOx/ 258–2377 75–99 Higher than EDLCs Higher than EDLCs Diverse applications
supercapacitor conducting typically lower than typically lower than requiring a balance
polymers pseudocapacitors pseudocapacitors between high power
and energy density

Free-standing, exible graphene lms with a 3D inter-

a WSS. Due to the elevated effective surface area and exceptional connected porous structure have also been highlighted in some
conductivity of carbon microbers, the resulting super- studies as the perfect substrates for creating hybrid SCs. Meng
capacitors achieved heightened capacitance, power, and energy et al. generated a homogeneous mixture by incorporating CaCl2
densities. Additionally, the fabrication of highly conductive into a GO dispersion. Upon bubbling CO2 through the mixture,
lms and bers, such as super-aligned CNT (SACNT) arrays, is CaCO3 particles encapsulated within GO sheets were formed.61
feasible. These materials possess versatility, serving as Following vacuum ltration, a GO/CaCO3 hybrid lm was ob-
substrates or active materials for EDLCs, as well as highly tained. Subsequent reduction of GO using hydrazine and
conductive exible current collectors. removal of CaCO3 using diluted acid resulted in the formation
Cui et al. reported the fabrication of exible conductive of a exible 3D graphene skeletal sheet. A hierarchical 3D PANI/
textiles produced on cellulose cotton textile substrates by graphene composite lm was then prepared by uniformly
a straightforward “dipping and drying” method employing growing PANI nanowire arrays on both the interior and exterior
aqueous single-walled carbon nanotube (SWCNT) ink.59 Despite surfaces of the 3D graphene substrate. Due to its interconnected
a high areal capacitance of 0.48 F cm−2, minimal capacitance porous structure, the composite lm retained 88% of its initial
loss was observed aer 130 000 cycles. Traditionally, metal foils capacitance aer 5000 cycles at a current density of 5 A g−1.
and wires have been utilized as current collectors to enhance Moreover, the SC based on the composite lm exhibited excel-
performance; however, their weight and susceptibility to fatigue lent exibility and rate performance, highlighting the potential
under repeated bending limit their applicability in exible utility of exible hybrid supercapacitors.
power sources. In contrast, the conductive CNT networks in this
study serve as three-dimensional exible current collectors,
effectively reducing the overall bulk of the device and stream- 3 Metal–organic frameworks (MOFs)
lining its construction.
MnO2 stands out as a top-tier pseudocapacitance material 3.1 Introduction to MOFs
due to its exceptional properties, including a high theoretical Ever since the inception of highly porous MOF materials in the
specic capacitance of approximately 1400 F g−1, cost- mid-1990s, the eld of applied nanomaterials has garnered
effectiveness, low toxicity, and abundance in nature. Flexible a tremendous interest in chemistry, material science, chemical
substrates, such as sponges comprised of interconnected engineering, and related areas.62–68 MOFs, as already discussed,
cellulose or polymer bers with hierarchical macroporous are crystallized substances comprising metal ions or clusters
characteristics, were employed for loading active ingredients by which are connected to each other by organic linker molecules.
Chen et al.60 Utilizing a simple and scalable “dipping and They are also sometimes referred to as porous coordination
drying” technique, carbon nanotubes (CNTs) were coated, fol- polymers or coordination network solids. Here's a brief intro-
lowed by MnO2 electrodeposition, resulting in the fabrication of duction to MOFs:
a MnO2/CNT/sponge electrode. The synergistic combination of Structure: the metal nodes or clusters that are linked together
the highly conductive and porous CNT-coated sponge with the by organic ligands in MOFs form a three-dimensional, periodic
porous electrodeposited MnO2 yielded impressive outcomes, lattice structure. The metal nodes act as coordination centers,
including a higher specic capacitance of 1230 F g−1, a specic the organic ligands serve as connecting struts and the modular
power density of 63 kW kg−1, a specic energy density of 31 design allows for a wide variety of metals and organic linkers to
kW h kg−1, and consistent cycling stability over 10 000 cycles be used, leading to an extensive array of MOF structures. Fig. 4
with minimal capacitance decay. shows the MOF structure in three dimensions where the metal
ion/cluster has been wrapped by the organic linker molecules.

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separation, waste–water treatment, photocatalysis, sensors,

batteries, and, lately, supercapacitors.70–78

3.2 MOFs in supercapacitors

MOFs are attracting attention in applications involving super-
capacitors because of their distinctive attributes that render
them well-suited for energy storage materials. Due of their
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substantial surface area, consistent and permanent porosity,

and controllable pore dimensions and shapes, MOFs are perfect
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for increasing the power density and charge storage capacity of

supercapacitors.79 Additionally, it is possible to engineer some
MOFs with enhanced stability and electrical conductivity in
electrolytes. This combination of features makes MOFs a mate-
rial with great potential for advancing supercapacitor tech-
nology, with the potential for higher energy storage and faster
charge–discharge rates. A lot of research has been done in the
last several years on functionalizing pristine MOFs for use as
supercapacitor electrode materials directly. For instance, Lee
et al. developed pure metal–organic frameworks (Co-MOF)
based on cobalt, which show promise as a material for super-
capacitors. With a specic capacitance of up to 206.76 F g−1, the
Fig. 4 Architecture of metal–organic frameworks, weaving the metal doctor bladed Co-MOF lm demonstrated commendable
ions/clusters and organic linkers. pseudocapacitor performance.80 On the other hand, using
a straightforward solvothermal technique, Kang et al. synthe-
sized Ni-MOF materials created using Ni3(1,3,5-benzene-
tricarboxylic acid)2$12H2O. Aer 1000 cycles, it maintained
Porosity: one of the most remarkable features of MOFs is
a strong capacitance retention rate of 94.6% and a boosted
their high porosity. The consistent placement of organic linkers
specic capacitance of 726 F g−1.81 Despite all the features,
and metal nodes creates a network of pores or cavities within
a number of signicant drawbacks have prevented MOFs from
the material. This porous structure is also thought of as an
being used in practical application elds, including insufficient
electrolyte membrane that permits charge transfer.69 These
conductivity, inadequate chemical stability, and oen high
pores can be of various sizes and shapes, making MOFs suitable
manufacturing costs.82,83 Making metal oxides or carbonaceous
for a lot of applications.
compounds from MOFs has shown promise as a solution to
Tunability: MOFs are highly tunable materials. Researchers
these pristine MOF constraints.84 The low conductivity intrinsic
can design and synthesize MOFs with specic properties by
problem of pure MOFs, which hinders the achievement of
choosing numerous available metal ions and organic linkers
appropriate charge transfer levels in supercapacitors, is
arrangements. The prescribed tunability allows for the cus-
resolved by these composite materials, a few of which have been
tomization of MOFs to meet the requirements of various
discussed below and tabulated in Table 2.
applications.
(a) MOF/carbon nano-tube composites: amalgamation of
Applications: various potential applications of MOFs have
metal–organic frameworks (MOFs) with carbon nanotubes
been recognized across numerous industries, including drug
(CNTs) has been explored via several methodologies, charac-
delivery, pharmaceuticals, medical imaging, gas adsorption and
terized by their remarkable electrical properties, unique pore

Table 2 Different types of MOF-composites exhibiting varying power densities, energy densities, and specific capacitance values

Energy density Power density Cycling stability Specic capacitance

Electrode material Synthesis route (W h kg−1) (W kg−1) (%)/cycles (F g−1) Ref.

MOF-CNT (10%) In situ 20.2 750 89.5%/8000 431.6@1 A g−1 85

Trimetallic MOF-CNT Solvothermal 23.6 501.5 79.2%/10 000 978.54@2 A g−1 86
Co-MOF/PANI Hydrothermal 23.2 4480 100%/3000 162.5C g−1@2 A g−1 87
MOF-PEDOT Chemical vapor 40.6 450 80.6%/1000 [email protected] A g−1 88
polymerization (CVP)
Cu-MOF@d-MnO2 Electrodeposition — — 95%/6000 340@1 A g−1 90
MOF-LaFeO3 MOF-gel method 34 900 92.2%/5000 241.3@1 A g−1 91
65Ni-MDH Hydrothermal 81 1900 91.3%/10 000 875C g−1@1 A g−1 92

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architecture, and robust mechanical and thermal properties. successfully synthesized by Shi et al. via an in situ chemical
Very recently, a green in situ physical mixing technique was vapor polymerization (CVP) method.88 The composites exhibi-
proposed by Zhang et al. to enhance the architecture of MOF/ ted a very high specic capacitance of 1401 F g−1 at 0.5 A g−1,
CNT (10%).85 Optimal composite structure depicted a notable and following 1000 cycles at 10 A g−1, the specic capacitance of
increase in specic capacitance to 431.6 F g−1 at a current the Ni-MOF/PEDOT composites retained 80.6% of its initial
density of 1 A g−1 (based on 1 M Li2SO4 electrolyte), surpassing capacitance. Ni-MOF contributes to a high specic capacitance,
that of the pristine MOF (143.1 F g−1), anticipating that the while PEDOT positively inuences the structural stability of Ni-
addition of CNTs could enhance the specic capacitance and MOF, thereby signicantly enhancing the cycle life of the
rate performance of the pristine MOF gel. Moreover, the device composites. Additionally, an asymmetric supercapacitor (ASC)
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showcased an extended cycle life, retaining 89.5% of its capac- was constructed using activated carbon (AC) and Ni-MOF/
itance aer 8000 charge–discharge cycles at 10 A g−1, alongside PEDOT composite electrodes which achieved a relatively high
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

a high energy density of 20.2 W h kg−1 at a power density of energy density of 40.6 W h kg−1 at a power density of 450 W
750 W kg−1, suggesting that this enhancement primarily stems kg−1, which can be ascribed to the fact that PEDOT endows the
from the fact that an appropriate ratio of CNTs can signicantly composites with the ability to facilitate rapid charge transfer,
augment the electrical conductivity and ion transmission effi- thereby enhancing the dynamic response properties of ions and
ciency of MOFs. Anwer et al. also presented a trimetallic-based reducing interface resistance.
MOF/CNT (5%) featuring hierarchical/dual-layered structures (c) MOF/graphene nanocomposites: graphene and its deriv-
synthesized via a straightforward solvothermal method.86 The atives, including graphene oxide (GO) and reduced graphene
hybrid supercapacitor demonstrated a signicant power density oxide (rGO), have garnered signicant attention and have
of 501.5 W kg−1 and an energy density of 23.6 W h kg−1, which largely been reported among the materials recently introduced
might be attributed to the synergistic features of the MOF-based for supercapacitors. An effective solution proposed for
composite contributing to enhanced electrochemical capabil- addressing the energy issue involves combining metal–organic
ities, including increased electro-active locations, shortened frameworks (MOFs) with graphene structures.89 The favorable
diffusion paths for electrolytes, and a higher number of redox characteristics of graphene-based materials, coupled with their
reactions in the KOH electrolyte. ease of processability and functionalization, make them highly
(b) MOF/conducting polymers: the intercalation of MOFs promising candidates for integration with MOFs for various
with conducting polymers (CPs) such as polyaniline (PANI), functional materials which has been discussed in detail in the
polypyrrole (Ppy), and polyethylene dioxythiophene (PEDOT) sections to follow.
has been approached in a number of ways as the CPs have been
reported to offer favorable device stability, high pseudocapaci-
tance, and straightforward synthesis procedures. Iqbal et al.
4 Metal–organic frameworks and
utilized a hydrothermal approach to synthesize a unique Co- graphene oxide (MOF/GO) composites
MOF material, which was subsequently physically infused for supercapacitors
with polyaniline (PANI) to enhance the performance of the
4.1 Rationale and properties of MOF/GO composite
pristine material.87 Operating at 1 A g−1, parallel operation
materials
yielded a maximum specic energy of 23.11 W h kg−1, accom-
panied by a specic power of 1600 W kg−1 for MOF-PANI Energy storage has shown a great deal of interest in MOF/GO
assembly. Similarly, at 4 A g−1, achieving a specic energy of composites, especially in the advancement of supercapacitors.
8.906 W h kg−1 corresponded to an outstanding specic power The rationale for developing MOF/GO composites lies in the
of 6400 W kg−1, with a specic capacitance retention of 146% desire to harness the advantageous properties of both MOFs
aer 3000 cycles which is substantiated by a theoretical Dunn's and GO while mitigating their individual limitations. Table 4
model capable of distinguishing between faradaic (diffusive) shows the comparison of electrode material, electrolyte, elec-
and non-faradaic (capacitive) contributions. In a different work, trochemical performances and synthesis routes employed for
a highly conductive and stable MOF-PEDOT composite was MOF/GO based supercapacitors. As discussed in the previous
section, MOFs have exceptional surface area and tunable

Table 3 Different types of composites with graphene derivatives exhibiting varying power densities, energy densities, and specific capacitance
values

Energy density Power density Cycling stability Specic

Electrode material Synthesis route (W h kg−1) (W kg−1) (%)/cycles capacitance (F g−1) Ref.

rGO/MXene-PPy Vacuum-assisted ltration 11.3 500 67.7%/10 000 408.2@10 A g−1 93

Chitosan/GO hydrogel Microwave-assisted hydrothermal 31 150 98.6%/10 000 [email protected] A g−1 94
GO/ZHS Ultrasonication 158.1 236.9 73.7%/50 000 [email protected] A g−1 95
GQDs (graphene quantum dots) Chemical treatment 17.36 191.7 96%/3000 257@3 A g−1 96
3D graphene/MnO2 Electrodeposition 6.8 62 82%/5000 130@2 A g−1 97
composite network

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Table 4 Electrochemical behaviour comparison of MOF/GO based supercapacitors

Energy Power Cycling Specic

density density stability (%)/ capacitance
Electrode material Electrolyte Synthesis route (W h kg−1) (W kg−1) cycles (F g−1) Ref.

Mo-MOF/GO 1 M H2SO4 Mixing 55 400 87.5%/6000 617@1 A g−1 101

HPNCs/rGO-80 6 M KOH Precipitation 18 475 90%/10 000 245@1 A g−1 102
Fe2O3-MOF/GO 1 M H2SO4 Mixing 79.2 405 96.3%/5000 869.2@1 A g−1 103
Ni/Co-MOF-rGO 6 M KOH Reux 72.8 42.5 91.6%/6000 860@1 A g−1 104
250.6 mA h g−1@1 A g−1
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Ni-BPDC/CNF 1 M H2SO4 Precipitation 48.1 1064.7 92%/5000 105

Ni-MOF/rGO 1 M KOH Ultrasonication 37.8 227 59%/500 [email protected] F cm2 106
Cu-MOF/G 6 M KOH Solvothermal 34.5 1350 93.8%/1000 482@10 mV s−1 107
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

Ni-MOF/GO 6 M KOH Solvothermal 39.43 34.29 93.5%/1000 1017@10 mV s−1 108

CuOx@mC@PANI@rGO 1 M H2SO4 Polymerization — — 70%/500 534.5@1 A g−1 109
Ni-MOF/rGO 6 M KOH Hydrothermal 16.5 250 82.4%/5000 630@1 A g−1 99
Co-MOF/GO 6 M KOH Precipitation 8.10 850 78.8%/1000 549.9@10 mV s−1 110
Zn-MOF/rGO 3 M KOH Hydrothermal 7.1 400 87%/5000 82.5@10 mV s−1 111
ZIF-8/GO 6 M KOH In situ growth 12.7 447 96.6%/10 000 [email protected] A g−1 112
Ce-MOF/GO 3 M KOH + 0.2 M K3Fe(CN)6 Wet chemical 111 449.7 85%/5000 2221.2@10 mV s−1 113
HMRL-1/rGO 1 M Na2SO4 Ultrasonication 57.2 4380 83.3%/4000 366.6@1 A g−1 114

porosity, owing to which they can signicantly increase the attributes in the MOF/GO composites, including high specic
charge storage capacity of supercapacitors, which leads to surface area, well-dispersed pore sizes, and enhanced conduc-
higher energy density – a crucial parameter for energy storage tivity. It is widely anticipated that these innovative materials
devices. On the other hand, GO, as a component of the hold signicant promise for applications as electrodes in the
composite, boasts excellent electrical conductivity, improving development of highly effective supercapacitors.
the movement of electrons within the supercapacitor and We can use both magnetic and non-magnetic metals in the
facilitating efficient energy transfer. synthesis of MOF/GO composites depending on the specic
Besides integration with MOFs, GO has also been infused goals and the intended use. The choice of the metal component
with various other materials for energy storage solutions, viz., in the MOF/GO composite will signicantly impact the
chitosan/graphene oxide hybrid hydrogel electrode,94 reduced composite's characteristics and functionality. Fig. 5 illustrates
graphene oxide/MXene-polypyrrole composite lm,93 PPAC- various metal MOF/GO composites, both non-magnetic and
graphene hydrogel electrode,98 and many other composites magnetic, that can be employed in supercapacitor applications.
which have been listed in Table 3. Increased research endeavors
are directed towards harnessing the synergistic potential of 4.2 MOF/GO composites
combining multiple MOFs with diverse types of graphene. This
is driven by the recognition of numerous desirable structural 4.2.1 Magnetic metal MOF/GO composites. Magnetic MOF/
GO composites incorporate magnetic metal ions or clusters into
their structures. Magnetic metals impart magnetic properties to
the composite, making it responsive to external magnetic elds,
and can be used as the primary materials for charge trans-
mission and storage. In addition to providing efficient ion
transport channels, the thick shell of porous MOFs can guar-
antee the structure's mechanical durability. In the recent years,
substantial amount of research has been done in this regard.
(a) Nickel-MOF/GO: in a recent work, He et al. synthesized Ni-
BPDC/GO by employing hydrothermally produced self-made
graphene oxide (via modied Hummer's and Offeman's
method) as a substrate and 4,49-biphenyldicarboxylic acid
(BPDC) to serve as an organic binder.99 There was no effect of
GO on the growth and crystalline arrangement of Ni-BPDC
(NiB). Various samples with different GO concentrations were
synthesized and the calculations show that at 1 A g−1, the
specic capacitances of NiB, NiB/GO-1, NiB/GO-3, and NiB/GO-5
are, respectively, 460 F g−1, 265 F g−1, 630 F g−1, and 228 F g−1. It
Fig. 5 Various magnetic and non-magnetic metal MOF/GO
is evident that NiB/GO-3 exhibits a larger portion of capacitance
composites used widely for supercapacitor applications in advanced compared to the other two (NiB/GO-1 and NiB/GO-5), primarily
energy storage materials. because of the enhanced uniformity and even distribution

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achieved through its composite structure of BPDC and GO. The capacitance (Cs) of 549.96 F g−1 was recorded in a three-
cyclic stability of the three-electrode system was found to be electrode system when the cyclic voltammetry test scan rate
56.5% within the rst 2400 cycles and thereaer it had was 10 mV s−1. This value was notably larger than the observed
a constant stability of 100% aer 10 000 cycles. The NiB/GO-3 specic capacitance (Cs) of 260.75 F g−1 for CoM due to the
composites showed high energy density value going up to addition of graphene to it which made more active sites avail-
16.5 W h kg−1 with respect to a power density value of 250 W able thus causing an increase in the nanocomposite's specic
kg−1, which must be attributed to the inclusion of GO in the capacitance by enhancing the diffusion and proximity amongst
sample which offered abundant active sites for its functionali- the electroactive materials and electrolyte ions. High power
zation with MOF molecules, which improved the specic density value of 850 W kg−1 and energy density value of
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capacitance, operational current density and rate capability in 8.10 W h kg−1 were also demonstrated by CoM/G which is
MOFs by reducing intrinsic resistance, ion diffusion imped- ascribed by the synergistic action of CoM and graphene in the
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

ance, and charge-transfer resistance, indicating that NiB/GO-3 nanocomposite. CoM/G also demonstrated an excellent cycle
composites are an appealing material for electrodes in super- lifespan; that is, 78.85% of its original specic capacitance
capacitor applications. remained unchanged aer 1000 cycles of charging and dis-
Following the development of Ni-BPDC/GO, Ibrahim's group charging at 1 A g−1, which is due to the composite structure's
reported the development of a hierarchical structure of Ni-MOF/ mechanical stability and the type of faradaic charge storage it
GO encompassing graphene nanoplatelet (GNP) adopting a mix possesses.
of microwave-assisted synthesis and in situ approach.100 Initial Chen's team has recently introduced an innovative method
research looked at the Ni-MOF/GO/GNP nanocomposites with for developing graphene oxide-based cobalt–metal organic
varying GO amounts (Ni-M/GOx/GNP) as an electrode material framework (Co-BTC@GO) aimed at enhancing the super-
for supercapacitors; Ni-M/GO3/GNP performed the best. Next, capacitor performance.115 This approach is initiated through
using a current density of 1 A g−1, the authors built Ni-M/GO3/ the utilization of GO made using improved Hummer's method.
GNP coin cell and pouch cell supercapacitors with specic Different GO dosages were injected into Co-BTC and the best
capacitance values of 102.24 F g−1 and 70.41 F g−1, respectively, results were acquired at GO dosage of 0.02 g (Co-BTC@GO:2).
because GO provided a large surface area that made the elec- Demonstrating excellent rate capability, the highest specic
trolyte ions highly accessible. Notably, compared to the pouch capacitance reached 1144 F g−1 at 1 A g−1, marking a notable
cell conguration, the coin cell conguration had a 1.5-fold increase compared to the specic capacitance of 759.2 F g−1
longer discharge time and a 50-fold greater surface under the observed in the sample without GO, ascribed by the superior
CV curve. This is ascribed by the fact that pouch cells are put electron transport resistance, ion diffusion rate, and stereo-
together using the polyethylene bags which leads to unwanted scopic structure of the Co-BTC@GO:2 composite as compared
volume expansion throughout the charge–discharge process to Co-BTC. Moreover, Co-BTC@GO:2 demonstrated an excep-
which negatively impacts the supercapacitor's performance. tional cycle performance aer 2000 cycles, keeping 88.1% of its
Both the cells exhibited remarkable capacitance retentions of baseline capacity aer 2000 cycles, compared to 78.5% for Co-
85.6% and 82.5%, respectively, aer more than 20 000 cycles, BTC, showing superior electron and charge transfer capabil-
indicating that the substrate matrices of Ni-MOF remained ities due to the fusion of three-dimensional architecture of Co-
stable throughout the electrochemical procedures. In the coin BTC microspheres with the two-dimensional lamellar
cell assembly, the addition of GNP as well as GO has demon- membrane architecture of GO. This material is expected to
strated an improvement in discharging time of approximately provide insights into the development of electrochemically
six and three times greater than that of the pristine Ni-MOF sound supercapacitor electrodes.
electrode, respectively. The improved conductivity and compo- (c) Iron-MOF/GO: Xu's group, in 2017, came up with
sitional durability of Ni-MOF might be largely accredited to the a straightforward mixing procedure to create a generic and easy
peculiar synergistic interaction that exists among the two way to make different three-dimensional GO/MOF composites
different graphitic carbon networks included in the Ni-M/GO3/ on a large scale.103 Orange coloured Fe-MOF crystals were
GNP composite. Additionally, at 993.54 W kg−1 power density prepared using a simple mixing method. Thereaer, to create
and a noticeably larger energy density of 14.02 W h kg−1, the a Fe-MOF/GO composite hydrogel, in brief, the produced 20 mg
samples demonstrated why they are an ideal electrode material of iron-MOF crystals were promptly added to an aqueous GO
to feed coin cell and pouch cell systems. dispersion while being vigorously shaken with a vortex mixer.
(b) Cobalt-MOF/GO: cobalt based MOF/GO composites have Following that, a freeze-dry procedure was applied to the
also shown promising results as supercapacitor electrodes. generated composite hydrogel in order to expel the water while
Azadfalah et al. created a novel Co-MOF/G, using the metal producing the composite aerogel (FeM/GO). At 1 A g−1, the FeM/
linker 2-methylimidazole (2-MeIm) employing a straightforward GO composite electrode produced an elevated specic capaci-
one-step precipitation process, named as CoM/G.110 Owing to tance of 869.2 F g−1, while the electrode composed solely of
the integration of CoM and graphene, the electrochemical tests Fe2O3 produced a signicantly lower Cs of 258.5 F g−1 at 1 A g−1,
suggested that the available surface area, electrical conductivity, which is due to a substantial electric double-layer capacitance
and area under the CV curves of CoM/G were signicantly provided by the networks made of connected GO sheets. High
higher compared to those of CoM. When employed as the power densities of 8010 W kg−1 and 79.2 W h kg−1, respectively,
material for a supercapacitor electrode, an excellent specic were obtained by the FeM/GO electrode at energy densities of

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25.8 W h kg−1 and 405 W kg−1, which is explained by the density measurements maintained 6.5 W h kg−1 even when the
addition of GO, which improves the electrical conductivity and power density levels rose to 15 126 W kg−1 as the ZIF-8 nuclei
three-dimensional structure of the FeM/GO composite. The effectively prevented the restacking of GO sheets. Besides this,
composite electrode's electrochemical stability was also evalu- aer 10 000 cycles, the symmetry supercapacitor demonstrated
ated by continuous charging/discharging tests at 20 A g−1 outstanding cyclic stability, retaining 96.6% of its initial
spanning 5000 cycles. The composite electrode had good capacitance at 2 A g−1, indicating excellent electrochemical
cycling performance in the subsequent cycles, with no notice- behaviour using GO as substrate.
able shi in specic capacitance aer a modest increase during (b) Copper-MOF/GO: Singh et al., in 2021, synthesized a new
the rst 500 cycles, which is ascribed by the signicant biporous blue coloured crystals of Cu-MOF by solvothermal
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concentration of active surface area of the nanoparticles which route whose composite with GO was made using simple ultra-
provides faradaic capacitance to the composite. sonication technique.114 The composite exhibited good
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

4.2.2 Non-magnetic metal MOF/GO composites. Non- measurements of specic capacitance value of 366.6 F g−1 and
magnetic MOF/GO composites do not contain magnetic metal showed a dual capacitive behavior at 1 A g−1 current density
ions but instead use non-magnetic metals or metal clusters (e.g., range, falling to 83.30% spanning 4000 cycles, displaying the
Zn, Cu, Pb, Al) and do not contribute magnetic properties to the improved electrochemical properties brought about by the
composite. combination of rGO and MOF, without compromising thermal
(a) Zinc-MOF/GO: for a supercapacitor to be commercialized, or mechanical stability. In view of achieving better charge
the electrode material needs to possess a superior structure, be storage performance, the symmetrical supercapacitor device
relatively straightforward to synthesize, be abundantly avail- demonstrated an optimal power density of 21.10 kW kg−1 at
able, and exhibit outstanding performance. Thi et al. synthe- 14.66 W h kg−1 and an optimal energy density value of
sized Zn-MOF/rGO hybrid composites produced using 57.2 W h kg−1 at 4.38 kW kg−1, ascribed by the permeable
a hydrothermal process that have visually appealing wrinkled MOF's redox-active Cu2+ centers, which have appropriate
nanosheet-like architectural electrodes.111 Zinc-MOF was channel architectures to aid in ion transport. The observed
synthesized using p-benzenedicarboxylic acid (H2BDC), and two outcomes suggest that the freshly developed Cu-MOF/GO might
types of composites – Zn-BDC/rGO10 and Zn-BDC/rGO20 – were be a promising component that can be composited with other
made depending on the amount of rGO. With a three-electrode conducting matrices.
conguration, the electrochemical capacitive efficiency was Recently, Sarathkumar's group prepared nitrogen-rich Cu-
evaluated in a 3 M aqueous KOH electrolyte. At 1 A g−1, Zn-BDC/ MOFs decorated on reduced GO nanosheets (Cu-MOF/rGO).116
rGO20 had a greater specic capacity than Zn-BDC/rGO10 and The 3D porous Cu-MOFs were synthesized by facile ultra-
pure Zn-BDC, with respective values of 205, 153, and 54C g−1, sonication over the rGO surface. The developed binder-free
and it is evident that the incorporation of rGO raised the elec- electrode had an excellent specic capacitance value of 867.09
trodes' specic capacitance. Specically, Zn-BDC/rGO20 had F g−1 at 1 A g−1, which is attributed to the narrow microporous
a specic capacity that was almost twice as high as pure Zn- distribution in addition to a multimodal mesoporous distri-
BDC. In addition, the Zn-BDC/rGO20 symmetric device bution of Cu-MOF. Given that they lower the material's internal
showed a specic capacitance value of 82.5 F g−1 at a power impedance and promote ion transport, these meso- and
density level of 0.4 kW kg−1 and an energy density level of micropores are crucial textural features that improve the
7.1 W h kg−1 owing to the engagement of metal centers in material's supercapacitive performance. Given that they lower
graphene nanosheet-mediated fast electron transfer processes. the material's internal impedance and promote ion transport,
Zn-BDC/rGO composites exhibit excellent electrochemical these meso- and micropores are crucial textural features that
performance and can be easily synthesized, making them improve the material's supercapacitive performance. Aer 5000
promising materials for supercapacitor electrodes. charging–discharging cycles, the device was observed to have
In a different report, Wang et al. developed Zn-MOF/GO a capacity retention of 131.65%, conrming its outstanding
using 2-methylimidazole as an organic linker.112 Self-made GO cycle stability as a consequence of the frequent cycling that
by modied Hummers' method was mixed with Zn-MOF and activates it electrochemically. Moreover, the constructed
the solution was named ZIF-8/GO. The sample yielded an symmetric supercapacitor device exhibited high energy density
enormous surface area of 816.4 m2 g−1 owing to the large measurements of 30.56 W h kg−1 and power density measure-
accessible electrolytic surface provided by ZIF-8 nanoparticles. ments of 12 kW kg−1 because of the presence of Cu(II) centers,
High specic capacitance levels of 225.0 F g−1 at 0.5 A g−1, which enables GO's redox activity to produce high energy
improved rate capabilities, and outstanding electrochemical density in addition to providing a high surface area for
reliability exhibiting 96.8% preservation when subjected to improved ion adsorption. The composite's exceptional electro-
10 A g−1 were all displayed by the electrode material. This is chemical properties validate its viability for use in energy
attributed to the presence of negatively charged GO sheets storage.
which have a lot of functional groups that contain oxygen which (c) Cerium-MOF/GO: Ramachandran et al. developed the
interact with positively charged ZIF-8 nuclei to support the ZIF-8 large mesoporous structured Ce-MOF/GO composites with little
structure anchoring on GO sheets electrostatically. An energy alteration of literature,117 with Ce-MOF forming a uniform sized
density value of 12.7 W h kg−1 with a specic power of 447 W nanorod structure.113 The SEM analyses revealed that the Ce-
kg−1 was provided by the symmetry supercapacitor. The energy MOF nanorods had been utilized to embellish the wrinkled

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GO sheets. For the prepared composite, an optimal specic

capacitance value of 2221.2 F g−1 and an energy density value of
111.05 W h kg−1 were achieved in 3 M KOH + 0.2 M K3Fe(CN)6
electrolyte for a current density range of 1 A g−1, owing to the
incorporation of redox additives. The extensive mesoporous
framework of Ce-MOF and the pseudocapacitance that comes
from GO sheet are responsible for this increased electro-
chemical performance. Ce-MOF/GO composite demonstrated
exceptional long-term stability, indicating that it is an
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intriguing material for electrodes to feed applications involving

supercapacitors.
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

5 Synthesis of integrated MOF/GO

composites
MOFs are obtained from metallic clusters linked by organic Fig. 7 (a) Schematic presentation of synthesis of Nd-MOF/GO
composites via hydrothermal method, (b) cyclic voltammetry of Nd-
ligands, while GO is derived from graphite and consists of oxygen-
MOF/GO, (c) scanning electron microscopy micrograph of Nd-MOF/
functionalized carbon sheets. The synthesis of MOF/GO GO, and (d) galvanostatic charge/discharge of Nd-MOF/GO.141 (b)–(d)
composites typically involves integrating MOF crystals onto the Adapted with permission from source: Mater. Sci. Eng., B, 2023, 295,
surface of GO sheets, enhancing their capabilities. Fig. 6 shows 116530. Copyright 2023 Elsevier.
the energy storage mechanism of a supercapacitor based on MOF/
GO composites which can be made using a variety of techniques,
each with its own benets and drawbacks. These include post- Hydrothermal method is a synthesis technique that uses high-
synthesis,118–121 in situ growth,122–126 solvothermal,127–131 co-precip- temperature and high-pressure water as a reaction medium to
itation,132,133 mixing,134,135 and ultrasonication.136–140 create or modify materials. Whereas, water is substituted with
Supercapacitor applications require careful consideration of organic solvents in the solvothermal technique to conduct high-
various factors in order to make certain that the nished product temperature and high-pressure reactions for material synthesis
possesses the appropriate electrochemical properties and or modication.
performance. Quite a few methods for composite synthesis are Recently, Siddiqui et al. reported the development of rod-
suitable for this specic application due to material compati- shaped neodymium-MOF/GO composites using simple and
bility, structural control, scalability and electrochemical perfor- economical hydrothermal technique.141 Firstly, GO was made by
mance. The methods that are used commonly have been listed them using the modied Hummers' method. The nal mixture of
below because they offer better control over the composite's Nd-MOF precursors and GO solution was poured into an auto-
properties and are more suited for supercapacitor applications. clave lined with Teon and baked for 18 hours at 200 °C celsius.
Besides these conventional methods, some unconventional Precipitates with a grey hue were produced as the autoclave
approaches have also been discussed alongside. cooled to ambient temperature. To maintain a pH of about 7, the
precipitates were thoroughly cleaned several times and were
5.1 Hydrothermal and solvothermal methods centrifuged at 4000 rpm for about 10 minutes using a solution of
ethanol and DI water. Aer washing, the precipitates were put in
Hydrothermal and solvothermal methods are two of the most an oven and aged in a Petri dish for 12 hours at 80 °C to obtain
commonly used methods for MOF/GO composite synthesis. Nd-MOF/GO, as the illustration in Fig. 7(a) shows. The Nd-MOF/
GO composite's SEM picture, displayed in Fig. 7(c), features rod-
like structures with a diameter of roughly 10 mm and a length of
60 mm. The electrode made up of these composites demonstrated
a cyclic stability of 88.67% spanning 4000 cycles and a coulombic
efficiency of 95.1%, presenting it as an appealing active material
to feed supercapacitor electrodes. It also had a specic capaci-
tance level of 633.5 F g−1 during a current density value of
0.3 A g−1, which was quite enormous. The superior capacitive
response can be ascribed to the noble interconnections formed
by the Nd-MOFs/GO composite, which improve its potential in
a pseudo-capacitive response by enhancing the poor conductivity
of the needle-like structures of Nd-MOFs. This mainly initiates
the charge transport process, which leads to a stable dynamics
and steady method for handling ions in the electrolyte, hence
Fig. 6 Energy storage mechanism of a supercapacitor based on MOF/
lowering diffusion resistance.
GO composites.

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Fig. 8 (a) Scanning electron microscopy micrograph of NiM-OH/rGO,

(b) cyclic voltammetry curves of NiM-OH/rGO at different scan rates in
2 M KOH, (c) cyclic voltammetry curves of NiM-C/rGO at different scan
rates in 2 M KOH, (d) galvanostatic charge/discharge curves of NiM-
OH/rGO, and (e) galvanostatic charge/discharge curves of NiM-C/rGO
spanning various current densities.142 (a)–(e) Adapted with permission
from source: ACS Appl. Energy Mater., 2019, 2, 5029–5038. Copyright
2023 American Chemical Society.

In a different work reported by Jiao's group, by using a one-

pot solvothermal procedure, nickel-based pillared MOFs con- Fig. 9 (a) and (b) Scanning electron microscopy images of mono-
disperse and uniform Ni-MOF nanospheres at different magnifications
taining rGO (NiM-rGO) composites were created.142 Using MOF-
and angles, (c) and (d) scanning electron microscopy images of porous
rGO as the precursor, various treatments were applied to Ni-M/rGO300 nanospheres at different magnifications and angles, (e)
produce both positive (NiM-OH/rGO) and negative (NiM-C/rGO) the asymmetric supercapacitor's cyclic voltage measurement curves
electrodes. Upon alkaline treatment, solid microrods in OH/ spanning various scan rates, (f) galvanostatic charge/discharge curves
rGO underwent a structural transition into hollow microrods, of the asymmetric supercapacitor spanning various current densities,
and (g) obtained specific capacitance values of the asymmetric
as demonstrated by SEM analysis (Fig. 8(a)). The resulting
supercapacitor.143 (a)–(f) Adapted with permission from source: J.
hybrid supercapacitor demonstrated high energy value of Colloid Interface Sci., 2022, 286, 116032. Copyright 2022 Elsevier.
59 W h kg−1 and power density value of 15.5 kW kg−1, showing
a positive connection with rising scan rates, owing to the
device's good rate capability. Additionally, it demonstrated a hydrothermal reaction for six hours at 120 °C. Eventually,
remarkable stability during cycling with 95% capacity preser- centrifuging was used to produce the black precipitate, which
vation spanning 10 000 cycles at 20 A g−1 and a decent rate was then recovered aer being repeatedly washed with DMF
ability (19% capacity loss ranging 1 to 20 A g−1), which is and then further dried at 60 °C. The resulting black precipitate
ascribed to the integration of conducting graphene sheets and was further calcined for one hour at 200 °C, 300 °C, and 400 °C
seeded N species, offering an efficient electrode material. in a pure nitrogen environment, ramping at a rate of 1 °C per
Fig. 8(b)–(e) displays the GCD and CV plots for the positive minute. These products were designated as Ni-M/rGO200, Ni-M/
(NiM-OH/rGO) and negative (NiM-C/rGO) electrodes. The rGO300, and Ni-M/rGO400, respectively. The morphologies of
results from this study indicated that the addition of rGO to the acquired samples were analysed by SEM. The Ni-MOF
pillared MOFs markedly improved the electrochemical func- spheres were uniform and monodisperse, with a typical diam-
tionality of the derived electrode materials. eter of particles of about 300 nm, as seen in Fig. 9(a) and (b). The
Zhong et al. also utilized a straightforward hydrothermal and as-formed Ni-M/rGO300 (Fig. 9(c) and (d)) displayed an
sequential calcining route to design and produce nickel-MOF increasingly permeable morphology aer annealing, whereas
microspheres that are rmly anchored upon rGO.143 Using rGO displayed a more compact structure of layers. Ni-M/rGO300
a modied Hummers' technique, they used pristine graphite showed more folds with rGO and a relatively more consistent
powder to create GO. The hydrothermal route was employed to arrangement of Ni-MOF when compared to other morphologies.
create the Ni-MOF composite. A dark suspension was typically An asymmetric supercapacitor (ASC) was constructed with the
produced by mixing certain quantities of dried GO, Ni(NO3)2- Ni-M/rGO300 composite as the cathode, the anode was acti-
$6H2O, and PTA in DMF and ethylene glycol solution while vated carbon (AC), and the electrolyte was KOH aqueous solu-
stirring continuously for three days. Then the nal product was tion (6 mM) in order to assess the possible applications of the
enclosed within a Teon-lined 50 mL autoclave and subjected to prepared Ni-M/rGO300 composite. Fig. 9(e) displays the CVs of

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the ASC at various scan speeds ranging from 20 mV s−1 to

100 mV s−1, covering a wide potential window of 0 to 1.5 V. The
operating window of ASC gadget is three times wider than that
of the Ni-M/rGO300 electrode in a conguration of three-
electrode system, and it is evident that the CV curves of the
device maintain their original forms as scan rates increase.
Relatively fewer devices are needed to reach the requisite high
voltage window thanks to the high voltage. The completed Ni-
M/rGO300/AC ASC device's galvanostatic charge–discharge
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plots at varied currents of 1 to 2 A g−1 have been displayed in

Fig. 9(f). All of the GCD curves' identical forms reect how well
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the storage of charge is balanced. Additionally, the specic

capacitance level of the ASC was established using the dis-
charging times indicated in the GCD curves. The completed
ASC, as depicted in Fig. 9(g), demonstrated a remarkable
specic capacitance of 954 F g−1 at an initial current density
level of 1 A g−1 and sustained at 720 F g−1 at 5 A g−1, demon-
strating a good rate capability of 75.47%. This research envi-
sions a wide range of opportunities for the creation of novel
electrode materials that satisfy strict requirements for power
density and energy content needed for devices to store energy.

5.2 Co-precipitation method

Co-precipitation is a method in which two or more precursor
chemicals are dissolved in a solvent, and a precipitating reagent
is introduced to induce the simultaneous formation of solid
Fig. 10 (a) Diagram illustrating the Co-M/GX nanocomposites'
particles containing both components. In the context of MOF/
manufacturing process, (b) Co-M/G5 nanocomposite's micrograph
GO composite preparation, co-precipitation process involves obtained using field effect scanning electron microscopy, (c) the Co-
the precipitation of both the metal ions (for MOF) and graphene M/G5 electrodes' cyclic voltammetry measurements in 6 M KOH at
oxide in a single step. This method is preferred to hydrothermal various scan rates (10–100 mV s−1) (d) plots illustrating the cell's gal-
synthesis because it is simpler, cost-effective, results in better vanostatic charging and discharging at a current density of 1 A g−1, (e)
dispersion of graphene oxide within the MOF matrix, and offers the red LED illuminated by the Co-M/G5//CA device, and (f) electrode
design of the Co-M/G5//CA asymmetric supercapacitor.110 (a)–(f)
better authority over the architecture and chemistry of the Adapted with permission from source: J. Energy Storage, 2021, 33,
resulting MOF/GO composite. 101925. Copyright 2021 Elsevier.
Azadfalah et al. employed a one-step basic precipitation
route to synthesize nanocomposites of Co-based MOF/gra-
phene.110 Co(NO3)2$6H2O was introduced into methanol, and produced a specic capacity of 50.20 F g−1 at 20 mV s−1, an
the mixture was agitated for 15 minutes. The synthesis media energy density value of 8.1 W h kg−1, and a power density value
were then mixed with varying concentrations of graphene (2.5 of 850 W kg−1 spanning 1 A g−1. This result indicates that the
and 5.0 mg), and the resulting slurry was ultrasonically treated addition of graphene to CoM enhances CoMG5's surface area,
for 30 minutes. Next, 2-MeIm was gradually added to the prior improving the electrolyte ion diffusion and electroactive mate-
solution aer being dissolved in methanol. The solution that rial contact area, and ultimately raising the specic capacitance.
started out dark pink quickly turned dark purple and was stirred A satisfactory cyclic stability of 78.85% was also demonstrated
for 24 hours at 25 °C. So as to create the nished products, the aer 1000 cycles of charging and discharging, proving that the
precipitates were nally recovered by centrifugation. They were nanocomposite's enhanced supercapacitive performance was
rinsed repeatedly with DI–water and then ethanol, following due to the synergistic action of graphene and Co-MOF. Elec-
which they were further dried at 80 °C for 24 h. The different trochemical investigations revealed that the combination of
samples were labeled as Co-M, Co-M/G2.5 and Co-M/G5. The graphene and Co-MOF worked synergistically to enhance the
schematic production procedure of the nanocomposites is supercapacitive performance of the nanocomposite.
shown in Fig. 10(a). The nanocomposites having different Recently, Safari and Mazloom also observed magnicent
compositions were adopted as the electrode materials, and the energy storage performance in Co + Fe bimetallic MOF la-
Co-M/G5 electrode displayed the maximum capacity, measuring ments decorated over reduced GO nanosheets.144 Firstly, they
549.96 F g−1, which is attributed to the presence of defects in prepared GO using modied Hummers' method and then
the structure's architecture allowing electric charge carriers to applied an ultrasonic-assisted solvothermal approach to
ow more freely which increases the specic capacity. Inside develop the Co + Fe-MOF electrodes. Then they prepared Co +
the voltage operation of 1.7 V, the Co-M/G5 asymmetric cell

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Table 5 Sample texture parameters assessed using BET, and charge transfer resistance (Rct) and equivalent series resistance (Rs) established
using EIS measurements.144 Adapted with permission from source: J. Energy Storage, 2023, 58, 106390. Copyright 2023 Elsevier

Active material SBET (m2 g−1) Vp (cm3 g−1) rp (nm) Rs (U) Rct (U)

Co + Fe-MOF 52.7 0.017 1.32 1.01 23.07

3% Co + Fe-MOF/rGO 149.0 0.054 1.79 0.79 5.03
5% Co + Fe-MOF/rGO 112.0 0.027 1.57 0.93 8.04
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Fe-MOF/rGO electrodes, using 3 and 5 wt% of rGO, showing are displayed in Fig. 11(d). The reduction peaks correlate to
spindle-like morphology. The highest specic capacitance of the reduction of Co4+ to Co3+ to Co2+ and Ni3+ to Ni2+, whereas
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2069.1 F g−1 at a current density spanning 0.5 A g−1 was eval- the redox peaks were formed during state transition of Co2+ to
uated for 3% Co + Fe-MOF/rGO and aer 5000 cycles, it showed Co3+ and Ni2+/Ni3+. Consequently, the overall oxidation and
excellent stability during cycling with 91.3% capacitance pres- reduction of peak current densities of both the materials are
ervation at an elevated current density of 10 A g−1. This can be raised by their various oxidation states. Initially, with the rising
ascribed by the considerable increase in the integrated area of quantity of rGO precursor in the sample (NCM/rGO0 < NCM/
3% Co + Fe-MOF/rGO as compared to the pristine Co + Fe rGO1 < NCM/rGO2), the CV comparison result revealed that
bimetallic MOF as can be seen from the CV curves, which the samples' CV area increased and eventually decreased as the
caused enhancement in the electrochemical properties owing to amount of rGO increased (NCM/rGO3 < NCM/rGO2). Relative
the coating of rGO over the sample. The asymmetric super- GCD diagrams of all the samples are illustrated in Fig. 11(e). It
capacitor device exhibited good energy density level of
75.8 W h kg−1 at power density level of 700 W kg−1 that explains
the pseudocapacitive property and is ascribed to the faradaic
redox processes on the electrode surface during OH− insertion/
extraction. Table 5 displays the results of the calculations for
average pore size (rp), specic surface area (SBET), and pore
volume (Vp). When compared to the pristine MOF, the Co + Fe-
MOF/rGO demonstrated increased BET surface area and
porosity. The boost in SBET of Co + Fe-MOF/rGO over raw MOF
could be attributed to the generation of greater permeability at
the point of interaction between rGO and MOF. Because the
rGO sheets stack around the permeable spindles of Co + Fe-
MOF, SBET and rp drop as the rGO content increases from 3 to
5%. The results exhibited that the 3% Co + Fe-MOF/rGO might
make an intriguing electrode material to feed the energy storage
devices.
A different work reported by Beka's group, in 2019, grew
ultrathin NiCo-MOF 2D nanosheets on rGO substrates using
conventional room temperature precipitation method.145 The
growth of nanosheets via this route has been illustrated in
Fig. 11(a). In specics, methanol, 2 methylimidazole, cobalt
nitrate, nickel nitrate, and the self-made rGO utilizing sulfur as
template precursor were combined and blended into a homo-
geneous solution. The group prepared samples using different
concentration of rGO. Thereaer, the solution was allowed to
stay at room temperature for a full day. Ultimately, the nal
product was produced as 2D NiCo-MOF/rGO (NCM/rGO) aer
centrifugation, washing, and drying. Fig. 11(b) and (c) displays
a homogeneous distribution of MOF nanosheets generating
a framework resembling a ower, using FE-SEM and TEM
Fig. 11 (a) Diagram illustrating the development phase of NCM/rGO
analyses, respectively. Aer adjusting the rGO to MOF ratio, through straightforward precipitation at ambient temperature, (b) field
NCM/rGO2 (comprising 10 mg rGO) was used as the best per- effect – scanning electron microscopy image of NCM/rGO2 nano
forming hybrid material as compared to other compositions. At sheets, (c) transmission electron microscope image of NCM/rGO nano
a current density spanning 1 A g−1, an excellent specic sheets, (d) relative cyclic voltammetry plots at scan rate of 1 mV s−1 for
capacitance value of 1553 F g−1 was attained for NCM/rGO2. NCM/rGO2, and (e) relative galvanostatic charge/discharge plots at
4 mA g−1 for NCM/rGO2.145 (b)–(e) Adapted with permission from
The relative cyclic voltammetry analyses for each of the four source: RSC Adv., 2019, 9, 36123–36135. Copyright 2019 Royal Society
samples (NCM/rGO0, NCM/rGO1, NCM/rGO2, and NCM/rGO3) of Chemistry.

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was found that all samples' GCD curves show two different nanosheets. The rst stage involved continually stirring MOF
phases of discharge: the potential lowers quickly at rst, and and GO to create three-dimensional porous hydrogel nano-
then it discharges slowly in the later stages. Furthermore, structures. The second stage involved freeze-drying the gener-
following 5000 cycles of charging and discharging, the sample ated hydrogel of the GO/MOF composite in order to
demonstrated an exceptional cyclic capacity of 83.6%. This may immediately transform it into an aerogel-like nanomaterial.
have to do with rGO's benet as a conducting backbone. Lastly, in step 3, the produced nanomaterials were heated in
Therefore, a spike in the ratio of rGO results in an increase in nitrogen and air atmospheres, respectively, to transform to
the hybrid material's conductivity, higher active material a pure stage of rGO/MOF. It should be noted that the double-
consumption, and improved rate capability. Remarkably, the step annealing procedure helps preserve the 3D porous struc-
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constructed asymmetric gadget exhibited an exceptional energy ture and can stop the generated composite aerogels made from
density level of 44 W h kg−1 at a power density level of 3168 W rGO and MOF from collapsing. Iron-MOF, nickel-MOF, ZIF8 (Zn
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kg−1, which is attributed to our porous rGO's exceptional and cations linked together with 2-methylimidazolate anions),
special qualities, which improve the ionic and electrical MOF5, tin-MOF, cobalt-MOF, and iron-MOF/nickel-MOF
conductivity connected to two-dimensional NCS redox nano- hybrids were among the several composite aerogels created
sheet materials that are active to boost the pseudocapacitive from GO (Fig. 12(a)–(i)) based on this simple and general mixing
characteristic, and are the primary cause of its exceptional method illustrated in Fig. 12(j). According to the electro-
performance. This report's electrochemical performance shows chemical data, at a constant current density spanning 1 A g−1,
that MOF nanosheet hybridization with carbon materials is the rGO/Fe2O3 nanocomposite electrode produced an enor-
a viable strategy for next-gen supercapacitors. mous specic capacitance of levels 869.2 F g−1 as compared to
rGO (360.8 F g−1) and Fe2O3 (258.5 F g−1), respectively.
5.3 Mixing method Primarily, the 3D networks comprising interconnected reduced
rGO sheets contribute signicantly to the substantial electric
The simple mixing method for synthesizing GO/MOFs involves
combining a graphene oxide suspension with MOF crystals
through gentle mixing. The process typically includes
dispersing GO and MOF in suitable solvents, slowly combining
them while stirring to ensure uniform distribution. This prep-
aration technique is able to produce MOF/GO composites in
just a few minutes with controlled composition.
In a paper reported by Xu's group, massive production of
several 3D MOF/GO composites was reported utilizing an
elementary mixing technique.103 The group synthesized the
composite in three phases using blended MOF and GO

Fig. 12 Images showing (a) GO dispersion, (b) iron-MOF/GO hydrogel, Fig. 13 Morphologies of the PCF: (a) and (b) scanning electron
(c) iron-MOF/GO aerogel, (d)–(i) additional GO/MOF composite aer- microscope images, (c) scanning transmission electron microscope
ogels (d–i, scale bar = 0.35 cm), and (j) a schematic representation of image, (d) transmission electron microscope image, (e) high resolution
the process of making MOF/GO and MOF/rGO-derived composite – transmission electron microscope image, (f) cyclic voltammetry
aerogels via mixing process.103 (a)–(i) Adapted with permission from curves spanning a scan rate of 0.1 mV s−1, and (g) galvanostatic charge/
source: Chem. Mater., 2017, 29, 106390. Copyright 2017 American discharge profiles.146 (a)–(g) Adapted with permission from source:
Chemical Society. Small Methods, 2019, 3, 106390. Copyright 2019 Wiley Online Library.

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double-layer capacitance and exceptional electrical conduc-

tivity. Secondly, the structures composed of Fe2O3 derived from
MOFs are comprised of numerous Fe2O3 nanoparticles, each
measuring less than 10 nm. These nanoparticles exhibit
a heightened concentration of active surface area, thereby
imparting faradaic capacitance to the composite material.
In a different report, Ding et al. used MOF particles of zeolitic
imidazolate frameworks (ZIF-8) with GO nanosheets to fabricate
the composite structure via mixing.146 The positively charged ZIF
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polyhedra (zeta potential, Vz = +3.1 mV) were dynamically

enveloped by the negatively charged nanosheets of GO (Vz =
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−45.8 mV). The solution's Vz dropped to −7.3 mV when the two

were incorporated together, suggesting that a portion of the
charge is neutralized by the interaction involving ZIF and GO.
The hybrid framework of ZIF/GO composite was created
following vacuum ltering. Pyrolyzing the structure in question Fig. 14 (a) The schematic diagram illustrates the preparation process
generated a three-dimensional carbon porous framework (PCF) of the GO-MOFs (HKUST-1) composite. It entails mechanically
consisting of polyhedral vacuous carbon plated with reduced GO, blending MOFs and GO in an aqueous solution, followed by laser
as can be seen in Fig. 13(a)–(e). The hybrid electrode exhibited treatment (scribing), resulting in the formation of a highly porous 3D
nanostructured composite utilized as an electrode in supercapacitors
a substantial discharge ability of 1151 mA h g−1, and aer 650
and (b) a schematic illustrating the preparation process of the Al-MOF/
cycles, it demonstrated a modest capacity collapse of 0.035% per graphene composite is depicted, where positive and negative charges
cycle. Several potentially synergistic features in the design of the are denoted by the symbols “+” and “−“, respectively, on the surfaces
PCF/S electrode contribute to its remarkable cycling efficiency. of Al-MOF and graphene oxide. (a) Adapted with permission from
Firstly, the utilization of highly conductive and mechanically source: Electrochim. Acta, 2020, 329, 135104. Copyright 2020 Elsev-
ier. (b) Adapted with permission from source: Nano Energy, 2019, 65,
robust graphene facilitates the deposition of sulfur and enables
104032. Copyright 2019 Elsevier.
the efficient transfer of electrons between layers within the active
material. Secondly, the volume expansion of the sulfur
composite during charge and discharge phases is accommo- HKUST-1 microrods act as spacers within the GO matrix, pre-
dated, and the accessibility of the electrolyte to sulfur is venting agglomeration and restacking of GO sheets, which is
enhanced through the geometrically structured channels crucial for the formation of robust three-dimensional struc-
inherent in the three-dimensional carbon scaffolding. tures. Additional processing of the composite lm was carried
Fig. 13(d)–(f) shows the cyclic voltammetry and galvanostatic out to enhance its conductive properties, enabling it to function
charge/discharge proles for the synthesized composites. effectively as an electrode for supercapacitors. In this subse-
Therefore, by offering straightforward, scalable methods to quent stage, GO was transformed into the conductive and
create 3D porous designs with heterostructured interfaces, these porous material known as laser-induced reduced graphene
materials can be a promise in the eld of energy storage avenues. oxide (L-rGO) using CO2 laser scribing to produce a lm. Aer
5000 cycles, the produced lm exhibited a cyclic stability of
97.8% at 10 A g−1 and a high capacitance of 390 F g−1 at 5 mV
5.4 Mechanical shear blending with scribing
s−1. Furthermore, with an exceptional energy density of
Mechanical shear blending followed by scribing is a method 22.3 W h kg−1 and an outstanding power density of 8037.5 W
used to produce nanocomposite materials with controlled kg−1, the symmetrical supercapacitor validated a new pathway
dispersion and alignment of nanollers (GO) within the MOF for fabricating 3D porous graphene-MOF composites for high-
matrix. A novel porous 3D-structured carbon composite mate- performance energy storage devices. This approach differs
rial, incorporating carbonized metal–organic framework (C- from traditional methods of converting GO to rGO, which
MOF) microrods derived from HKUST-1, and graphene, was typically involve heat or chemical reduction, processes that may
developed by Van et al. for high-performing supercapacitors.147 damage or degrade the delicate HKUST-1 microrods.
The combination of HKUST-1 microrods' 1D structure and
graphene's 2D structure yields a composite material with
enhanced electron and charge transportation capabilities. The 5.5 Ex situ synthesis
proposed concept depicted in Fig. 14(a) is based on two inno- Ex situ approach enables the synthesis of MOF and graphene
vative strategies. Firstly, to achieve a unique three-dimensional composites by incorporating specic chemicals. The synthesis
composite structure, HKUST-1 microrods and GO were process may be time-consuming, and the ex situ approach
combined using a straightforward synthetic technique known could potentially alter the characteristics of the composite
as mechanical grinding. Upon combining these two compo- material. While the qualities of the two substances being
nents in an aqueous shear mixing environment, the HKUST-1 combined and their interaction must meet certain conditions,
fragments or seeds rapidly grew into rods with diameters the direct mixing approach is easier to manipulate. Following
ranging from nano-to-microns. The uniformly dispersed this approach, Gao et al. synthesized Al-MOF particles and

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thereaer graphene was uniformly coated onto them to form

the Al-MOF/graphene composite.148 Subsequently, the
composite underwent lithiation and delithiation processes,
leading to a signicant structural alteration of the Al-MOF
particles characterized by an order–disorder transition
(Fig. 14(b)). This transition facilitated the diffusion and
storage of Li+ ions by creating more open channels. At
a current density of 100 mA g−1, the composite exhibited
a continuous increase in capacity from 60 to 400 mA h g−1. The
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remarkable enhancement observed in Li+ ion migration and

storage can be attributed to the lithiation/delithiation-
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induced structural disordering in MOF crystals, which

creates additional channels for ion transport. The presence of
graphene sheets enables the MOF particles to maintain their
electrical conductivity with the current collector. Moreover,
these sheets facilitate charge transfer processes and Li+ ion
migration kinetics across the Solid Electrolyte Interphase (SEI)
layer, thereby enhancing electronic conductivity. The study
suggests that enhancing the capacity and cycling stability of
anode materials requires both the lithiation/delithiation-
induced order–disorder transition in MOFs and the optimal
encapsulation of MOF by graphene.

6 Characterization techniques
6.1 Structural and morphological characterizations
The structural and morphological characterization of MOF/GO Fig. 15 Powder X-ray diffraction patterns of G, Co-M, Co-M/G2.5 and
composites involves various analytical techniques to under- Co-M/G5 samples.110 Adapted with permission from source: J. Energy
Storage, 2021, 33, 101925. Copyright 2021 Elsevier.
stand their composition, crystal structure, morphology, and
surface features.
One of the common techniques employed for this purpose is To further characterize the morphology of the synthesized
X-ray diffraction. XRD is an effective tool for establishing crystal composites visually, Scanning Electron Microscopy (SEM) and
structure of materials. By subjecting the MOF/GO composite to Transmission Electron Microscopy (TEM) were employed. SEM
X-rays, the arising diffraction pattern can be analyzed to scru-
tinize the crystalline phases that are existing and obtain infor-
mation about the unit cell parameters, crystallite size, and
preferred orientation. Azadfalah's group used a facile one-step
precipitation method to create Co-MOF/graphene nano-
composites.110 They employed XRD for the analysis of graphene
(G) with different compositions of ZIF-67, namely, Co-M, Co-M/
G2.5, and Co-M/G5. As we can see in Fig. 15, two diffraction
peaks (2 q = 26.5° and 2 q = 43°) were visible in the XRD pattern
of G. These peaks matched JCPDS no. 0284-25 and corre-
sponded to reections originating from the graphitic structure
in accordance with (002) and (101) planes, respectively. The
peaks in the Co-M XRD pattern at 2 q = 7.44°, 10.56°, 12.92°,
14.89°, 16.55°, 18.13°, 22.18°, 24.66°, 25.22°, 26.83°, 82.29°,
30.70° and 32.63° corresponded, respectively, to the reections
arising from (011), (002), (112), (022), (013), (222), (114), (233),
(224), (134), (044), (334), (244), and (345) planes, showing that
there is good agreement between the XRD pattern of the ZIF-67 Fig. 16 Scanning electron microscope images of (a)–(c) the graphene
single crystal and the diffraction pattern of the synthesized Co- nanosheets completely encapsulated and adhered to the Ni-MOFs
under diverse magnifications, which achieves a 3D porous architecture,
M. The Debye-Scherrer equation yielded crystallite sizes of 25,
(d) and (e) uniform sized nanorod structure of CeMOF@CNT composites,
18, and 22 nm for the Co-M, Co-M/G2.5, and Co-M/G5 samples, (f) and (g) uniform sized nanorod structure of CeMOF@GO compos-
respectively. Evidently, the inclusion of graphene is the cause of ites.113 (a)–(g) Adapted with permission from source: RSC Adv., 2018, 8,
this size reduction. 3462–3469. Copyright 2018 Royal Society of Chemistry.

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and TEM provide high-resolution images of the surface and spacers, the deposited nanorods can also prevent GO sheets
internal structure of materials. These techniques can reveal from stacking again. Conversely, the GO sheets may aid in
information about the morphology, particle dimensions, and stopping the Ce-MOF nanorods from clumping together.
spatial arrangement of MOF nanoparticles on the graphene TEM provides even higher resolution images than SEM,
oxide sheets. enabling researchers to visualize the internal structure of MOF/
SEM allows researchers to observe the surface morphology GO composites, including the arrangement of nanoparticles,
and topography of MOF/GO composites at high resolution. It layers, and any defects present. A nanocomposite was formed by
provides insights into the particle size, distribution, and the combining chromium-centered MOF nanoparticles and GO
overall structure of the composite. Zong's group, recently in using a simple ultrasonication method by Cui et al., which was
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2023, developed 3-D porous aerogels that had superior capaci- governed by the dendrimerpolyamidoamine (PAMAM).140 TEM
tive characteristics for adaptable energy storage by embedding pictures of CrMOF, CrMOF@PAMAM, and CrMOF/
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

open-hollow Ni-MOF microspheres onto rGO nanosheets.149 GO@PAMAM nanocomposites show their textures in
SEM analysis revealed that the prepared composites had Fig. 17(a)–(c). The micrographs show a substantial quantity of
a rough surface, an average diameter of around 2 mm, and an well-crystallized regular octahedrons. The CrMOF@PAMAM
open-hollow structure with a homogeneous spherical shape. images demonstrated some pronounced wrinkles consistent
Moreover, the graphene nanosheets were completely wrapped with GO's properties, evenly coated across the surface of
and attached to the composite surface, as seen in Fig. 16(a)–(c), CrMOF. This showed that the morphology had been well-
resulting in a 3D porous architecture. The pace of electron/ion maintained, creating certain three-dimensional hole forma-
transport can be greatly accelerated by both graphene nano- tions. In other report, Beka's group prepared a Ni + Co/
sheets and composites, and the resulting three-dimensional MOF@rGO hybrid material using a level precipitation proce-
porous architecture can greatly reduce the length of ion dure at ambient temperature.145 Fig. 17(d)–(g) the TEM pictures
dissemination pathways, increase the amount of specic of Ni + Co/MOF@rGO hybrid material which make it evident
surface area, and provide an abundance of exposed sites for how rGO sheets are formed onto ultrathin MOF nanosheets. It
activity. In a different report by Ramachandran et al., wet is amazing how its excellent elasticity is revealed by the creases
chemical synthesis of CeMOF@GO and CeMOF@CNT and folds.
composites was carried out at room temperature.113 Besides these techniques, thermogravimetric analysis (TGA)
Fig. 16(d)–(g) shows their SEM images. The resulting CeMOFs in is also employed by researchers, which measures the weight
GO and CNT are evenly scaled nanorod structures with a length changes of a material as a function of temperature. It can be
of few micrometers and a diameter of about 150 nm, as used to scrutinize the thermal stability of MOF/GO composites
demonstrated by the SEM pictures. In addition to serving as and ascertain the content of different components based on
their decomposition temperatures.

Fig. 17 Transmission electron microscope micrographs of (a) CrMOF,

(b) CrMOF@PAMAM, (c) CrMOF/GO@PAMAM showing regular octa-
hedrons with excellent crystallinity,140 and (d) to (g) transmission
electron microscope images of Ni + Co/MOF@rGO nanosheets at Fig. 18 A comparison of the electrochemical behavior of conven-
different magnification exhibiting the translucent GO blending with ZIF tional supercapacitors can be illustrated through cyclic voltammetry
particles where its excellent flexibility is made apparent by the pres- (CV) and galvanostatic charge–discharge (GCD) curves, as shown in
ence of creases and folds.145 (a)–(c) Adapted with permission from panels (a) and (d) for electric double-layer capacitors (EDLCs), panels
source: ACS Omega, 2021, 6, 31184–31195. Copyright 2021 American (b) and (e) for Pseudocapacitors, and panels (c) and (f) for hybrid
Chemical Society, and (d)–(g) Adapted with permission from source: capacitors, respectively. (a)–(f) Adapted with permission from source:
RSC Adv., 2019, 9, 36123–36135. Copyright 2019 Royal Society of Adv. Funct. Mater., 2022, 32, 2108107. Copyright 2022 Wiley Online
Chemistry. Library.

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6.2 Electrochemical characterizations discharge curve, and (V2 − V1) represents the working potential
window (in V).
Electrochemical characterizations play an essential role in
One can compute a supercapacitor's energy density (E) and
assessing the effectiveness of MOF/GO composites for various
power density (P) using the following formula:
applications. The results obtained from these techniques
contribute to optimizing the design and performance of MOF/ CðV2  V 1Þ2
C¼ (12)
GO composites for diverse electrochemical applications. 2  3:6
Fig. 18 shows the comparison between CV and GCD curves of
and
different types of supercapacitors.150 Here's how each technique
3600E
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is applied to different types of supercapacitors. P¼ (13)

6.2.1 Cyclic voltametry (CV). CV is a widely used electro- t
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chemical technique that provides information about the redox

behavior and electrochemical stability of MOF/GO composites. Here's an outline discussing the galvanostatic charge/
By applying a potential sweep, CV generates current–voltage discharge characterization for different types of
curves that can reveal details about the electrochemical supercapacitors.
processes, capacitance, and the presence of specic redox (a) Electrochemical Double-Layer Capacitors (EDLCs): GCD
couples. The following formula could be used to get an elec- curves for EDLCs are linear, reecting the capacitive behavior
trode's specic capacitance (C) from cyclic voltammetry: with a constant slope. The slope of the discharge curve provides
Ð V2 information about the equivalent series resistance (ESR) of the

1
 IðV ÞdV
C F g ¼ V1 (10) supercapacitor.
mnðV 2  V 1Þ
(b) Pseudocapacitors: GCD curves for pseudocapacitors may
exhibit non-linear behavior, with voltage plateaus or slopes
In the provided context, where C represents the specic corresponding to the redox reactions in addition to the capac-
capacitance (in F g−1), m is the mass of the active electrode (in itive behavior.
g), n is the scan rate (in V s−1), and V1 and V2 are the potential (c) Hybrid capacitors: GCD curves for hybrid capacitors may
Ð V2
limits (in V), the expression V1 IðV ÞdV signies the area under show a combination of linear behavior and non-linear features
the cyclic voltammetry (CV) curve within the specied voltage corresponding to both capacitive and faradaic processes.
range. Here's an outline discussing the cyclic voltammetry 6.2.3 Electrochemical impedance spectroscopy (EIS). EIS is
characterization for different types of supercapacitors. a technique used to study the electrical properties and imped-
(a) Electrochemical Double-Layer Capacitors (EDLCs): ance of MOF/GO composites. By applying a small alternating
EDLCs typically exhibit rectangular-shaped CV curves, indi- current at different frequencies, EIS provides information on
cating ideal capacitive behavior. The area under the CV curve the resistive and capacitive components of the composite,
represents the charge storage capacity of the supercapacitor. helping to understand the charge transfer processes, interfacial
(b) Pseudocapacitors: pseudocapacitors exhibit non-linear resistance, and overall electrochemical behavior. Here's an
CV curves due to faradaic redox reactions occurring at the outline discussing the electrochemical impedance spectroscopy
electrode surface. The curves may show peaks or humps cor- characterization for different types of supercapacitors.
responding to redox processes. (a) Electrochemical Double-Layer Capacitors (EDLCs): EIS of
(c) Hybrid capacitors: hybrid capacitors may exhibit EDLCs typically shows a semicircle in the high-frequency
a combination of capacitive and faradaic behavior in the CV region, representing the charge transfer resistance at the elec-
curves, reecting the contribution from both EDLC and pseu- trode–electrolyte interface. At low frequencies, a linear portion
docapacitive components. corresponds to diffusion-controlled processes in the electrolyte.
6.2.2 Galvanostatic charge/discharge (GCD). GCD is (b) Pseudocapacitors: EIS of pseudocapacitors may show
commonly employed to investigate the energy storage perfor- additional features such as Warburg impedance, indicating the
mance of MOF/GO composites, particularly in supercapacitors diffusion of ions within the electrode material. The presence of
and batteries. By applying a constant current, GCD measures faradaic processes introduces additional elements in the
the charging and discharging characteristics, providing infor- impedance spectrum.
mation on capacitance, charge storage, and overall electro- (c) Hybrid capacitors: EIS of hybrid capacitors may reveal
chemical performance. The following formula can be utilized to a combination of semicircles, linear portions, and additional
determine the specic capacitance from the galvanostatic features corresponding to both charge transfer resistance and
charge–discharge (GCD) investigation: ion diffusion processes associated with EDLC and pseudoca-
Ð pacitive components.

 I V ðtÞdt
C F g1 ¼ (11) Thi et al., in 2022, synthesized a low-cost nanocomposite of
mðV 2  V 1Þ Zn-MOF-rGO (ZM@rGO) by hydrothermal technique which
depicted a porous wrinkled nanosheet-like network.111 They
In the provided equation, where I represents the steady prepared two types of composites on account of the rGO's
discharge current during GCD measurement, m is the mass of concentration: ZM@rGO10 and ZM@rGO20. The electro-
Ð
the active electrode (in g), V ðtÞdt denotes the area under the chemical properties of Zn-MOF, ZM@rGO10, and ZM@rGO20

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Fig. 19 (a) ZnMOF, ZM@rGO10, and ZM@rGO20 cyclic voltammetry

profiles at a 10 mV s−1 scan rate; patterns of cyclic voltammetry
monitoring at different scan rates of (b) ZnMOF, (c) ZM@rGO10, and (d)
[email protected] (a)–(d) Adapted with permission from source: Synth.
Met., 2022, 290, 117155. Copyright 2022 Elsevier.

composite electrodes were ascertained by employing a three-

electrode setup in a 3 M aqueous KOH electrolyte for CV,
GCD, and EIS investigations. With a 10 mV s−1 scan rate, the Zn-
MOF, ZM@rGO10, and ZM@rGO20 nanocomposites' CV plots
are displayed in Fig. 19(a) inside the potential zone of −0.2 V
and +0.5 V. The redox peaks of all three electrodes are clearly Fig. 20 (a) Galvanostatic charge/discharge curves for ZnMOF,
apparent on the CV curves, suggesting that the faradaic reaction ZM@rGO10, ZM@rGO20 at a current density of 1 A g−1, (b) galvano-
static charge/discharge plots for ZM@rGO20, (c) ZM@rGO10, (d)
is occurring as the procedure is being carried out. It's important
ZnMOF at various current densities, (e) graph of specific capacity
to note that, out of the three CV curves, the ZM@rGO20 curve versus current density, and (f) electrochemical impedance spectra (EIS)
had the largest area, indicating that it performs better electro- (enlarged view image of Nyquist plot and connected circuit of EIS
chemically than Zn-MOF and ZM@rGO10. Additionally, the CV shown in the inset).111 (a)–(f) Adapted with permission from source:
curves demonstrated a wide range of interaction between Synth. Met., 2022, 290, 117155. Copyright 2022 Elsevier.
extremely reactive material sites and electrolytic ions, suggest-
ing that the surface faradaic redox reaction may be primarily
responsible for the materials' capacitance properties. The a unique plateau area beneath the current density, and their
results are consistent with a recurring observation regarding very symmetrical shape indicates signicant reversibility.
MOF-based supercapacitors' hybrid battery-like and Additionally, ZnMOF and the composites ZM@rGO10 and
pseudocapacitive-like functionality.151–153 Cyclic voltammetry ZM@rGO20 were subjected to electrochemical impedance
(CV) proles for ZnMOF, ZM@rGO10, and ZM@rGO20 elec- spectroscopy (EIS) (Fig. 20(e)) and the Nyquist plot, along with
trodes in Fig. 19(b)–(d) demonstrate increased integrated CV the area inset gure that corresponds to a connected circuit, is
curve areas at higher scan rates (10–50 mV s−1), indicating displayed in Fig. 20(f). ZM@rGO20 exhibits a lower charge
improved electrochemical performance for all three electrodes transfer resistance (Rct) of 1.23 U cm−2, which can be attributed
by the addition of GO to ZnMOF in certain amount. to the rapid rate of reactions amongst the active electrode and
The galvanostatic charge–discharge (GCD) curves for electrolyte than ZM@rGO10 (1.7 U cm−2) and ZnMOF (1.85 U
ZnMOF, ZM@rGO10, and ZM@rGO20 at a current density of cm−2). Notably, the decreased resistance value also shows that
1 A g−1 are illustrated in Fig. 20(a) to assess the electrochemical KOH electrolytes and active electrodes are well suited to one
behavior within the potential operation of −0.15 to 0.5 V. In another.
comparison to ZM@rGO10 and pristine ZnMOF, it is evident Recently, in 2023, Chen's group presented a newly developed
that the ZM@rGO20 electrode has achieved a longer discharge in situ synthesis technique for GO/MOF composites (Ni-BTC/
time, which suggests that the functionality of the super- GO) for high-performance supercapacitors.154 Ni-BTC/GO 0, 1,
capacitor is considerably affected by the appropriate amount of 2, and 4 are the series hybrid materials that were developed by
rGO in pure ZnMOF. Fig. 20(b)–(d) shows graphical represen- altering the GO dosage (0, 0.01, 0.02, and 0.04 g of GO). Their
tations depicting the GCD contours for all the electrodes esti- group also conducted CV, GCD and EIS analyses using a system
mated for the current density levels that fall between 1–5 A g−1 of three electrodes in a 3 molar KOH solution to assess the
region, wherein each of the three electrodes' voltage lines shows electrochemical capacitance outcomes. According to the tests,

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Fig. 21 (a) Cyclic voltammetry curves of NiBTC and NiBTC@GO Fig. 22 (a) Specific capacitance of NiBTC and NiBTC@GO2 spanning
composites spanning 2 mV s−1, (b) galvanostatic charge/discharge various levels of current densities, (b) specific capacitance as a function
curves of NiBTC and NiBTC@GO composites spanning 1 A g−1, (c) of GO mass at a current density of 1 A g−1, (c) NiBTC and NiBTC@GO2
galvanostatic charge/discharge curves of NiBTC@GO2 spanning 2– electrochemical impedance spectroscopy (EIS) plots in the frequency
100 mV s−1, and (d) galvanostatic charge/discharge curves of range of 0.01 Hz to 100 kHz, and (d) performance of NiBTC and
NiBTC@GO2 spanning 1–20 A g−1.154 (a)–(d) Adapted with permission NiBTC@GO2 cycling in 3 M KOH electrolyte spanning 1 A g−1 of
from source: ACS Omega, 2023, 8, 10888–10898. Copyright 2023 current density.154 (a)–(d) Adapted with permission from source: ACS
American Chemical Society. Omega, 2023, 8, 10888–10898. Copyright 2023 American Chemical
Society.

GO had a specic capacitance value of 180 F g−1, which can be

ascribed to the characteristic pseudocapacitive behavior, which decrease as the amount of GO increases. This indicates that the
stems from the reversible Faraday reaction caused by Ni2+ in GO level in NiBTC@GO1 is unsaturated, which is why it has
alkaline solution, showing distinct redox peaks (Fig. 21(a)) a lower specic capacitance and conductivity than
instead of rectangular forms. When NiBTC@GO2 is contrasted NiBTC@GO2. However, an overabundance of GO in
with alternative electrodes, a larger peak current is produced, NiBTC@GO4 would result in worsening GO agglomeration and
indicating a considerable increase in electrochemical activity. reduced conductivity performance. NiBTC@GO2 shows up
Fig. 21(a) depicts the integrated area under the CV curves for all more prominent redox peak levels, indicating a signicant
electrodes in order: NiBTC < NiBTC@GO1 < NiBTC@GO4 < increase in capacitance. The specic capacitance levels recor-
NiBTC@GO2. This order also corresponds to the specic ded for NiBTC@GO2 are 1199, 1058.6, 1000.8, 927, 815, and 676
capacitance levels of the electrodes, which is further supported F g−1 at 1, 2, 3, 5, 10, and 20 A g−1, respectively.
by the GCD curves spanning 1 A g−1 in Fig. 21(b), which Nyquist plots for electrochemical impedance spectroscopy
demonstrate that NiBTC@GO2 offers a prolonged charging and (EIS) results were also evaluated in the 0.01–100 kHz frequency
discharging duration. Furthermore, each and every GCD curve span, and the outcomes are shown in Fig. 22(a). Half-circles and
clearly shows charging and discharging plateaus, illustrating arcs and lines that are situated in high and low-frequency zones
the characteristic pseudocapacitive behavior. The NiBTC@GO2 make up the Nyquist plot. Ion diffusion is illustrated by lines
CV curves are displayed in Fig. 21(b) wherein it is observed that and is related to the Warburg resistance (Zw). The Zw value
more prominent redox peaks are seen in NiBTC@GO2, indi- decreases as the line slope increases.155 The NiBTC@GO hybrid
cating a signicant increase in capacitance owing to the supercapacitor electrode's specic capacitance is plotted
synergistic effects between Ni-BTC and GO. For current density against GO concentration in Fig. 22(b). The GO concentration is
ranging between 1–20 A g−1, the GCD values of NiBTC@GO2 inuenced by the Ni element's concentration. Compared to
were measured (Fig. 21(d)). The perceived potential region NiBTC, the slope of NiBTC@GO2 is noticeably steeper. Fig. 22(c)
spanning 0 and 0.5 V in the GCD slopes of NiBTC@GO2 illus- contains an illustration of the corresponding analog circuit.
trates typical pseudocapacitive behavior. Good coulombic effi- Owing to the simulated ndings, the aggregate electrolytic
ciency is demonstrated by NiBTC@GO2, as seen by the solution resistance (Rs) corresponding to NiBTC and
symmetrical form of the arcs throughout the quick charge– NiBTC@GO2 are 0.6602 U and 0.7911 U, respectively. The
discharge operation. NiBTC, NiBTC@GO1, NiBTC@GO2, and diameter that denes the semicircle in the a high-frequency
NiBTC@GO4 have specic capacitances of 625.6, 691.6, 1199, domain demonstrates the charge transfer resistance (Rct)
and 945.4 F g−1, respectively. By shortening the ion transport resulting from the redox processes. The lowest semicircle
channel and raising the specic capacitance, layers of GO on the diameter is found in NiBTC@GO2. The equivalent electrical
exterior can greatly increase the conductive properties of Ni- conductivity values of NiBTC and NiBTC@GO2 are 0.131 and
BTC. The charging and discharging times increase rst, then 0.142 S m−1, respectively, and their respective Rct values are
7.649 U and 7.065 U. Interestingly, NiBTC@GO2 has good

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cycling performance; even aer 5000 cycles, it maintains appropriate sensing elements, smart supercapacitors can detect
84.47% of its initially generated capacity as opposed to 75.81% specic analytes or environmental conditions while simulta-
for NiBTC (Fig. 22(d)). In a nutshell NiBTC@GO2 indicates neously storing energy. GO, well known for its exibility, makes
outstanding impedance properties, with the electrolyte's OH− MOF/GO composites well-suited for integration into exible
ions possessing a more rapid ability to diffuse to the electrode and wearable electronics,157 and smart supercapacitors based
surface. GO can improve the composites' conductivity and offer on these composites can be conformably integrated into various
sufficient OH− embedding and dis-embedding space, whereas form factors, enabling applications in Internet of Things (IoT)
Ni-BTC can reduce GO aggregation and provide a uniformly stiff devices (i.e. Articially Intelligent devices),158,159 renewable
framework for GO adhesion. energy160 and beyond.161–163
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Fu et al. synthesized a metal organic framework (UiO-66), as

7 Smart supercapacitor and artificial an illustration, based on zirconium and inscribed onto a carbon
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nanotube membrane (CNTF), which is referred to as 66-C.164

intelligence (AI) energy storage devices Aer that, PEDOT-GO or poly(3,4-ethylenedioxythiophene)-
Smart supercapacitors refer to advanced energy storage devices graphene oxide (PGO) was codeposited electrochemically on
that go beyond the traditional capabilities of conventional 66-C to obtain a porous electrode that was extensible
supercapacitors. While energy storage remains a primary (PGO@66C), which had excellent properties for exible super-
function, smart supercapacitors must possess additional func- capacitors. There has never been a report on the composites
tionalities and features, making them “smart” in the context of that combine MOFs with PGO as electrode materials used in
modern technological advancements that enable them to sense, solid-state supercapacitor devices that offer exibility. The
adapt, or respond to changes in their environment or user morphology and microstructure of the developed samples were
requirements. Smart supercapacitors require the electrode and examined by SEM. Fig. 23(a) and (b) displays the P@66C SEM
electrolyte materials to exhibit not just high conductivity and images. We can observe that, upon electrodeposition, conduc-
wide surface area, but also intelligent behaviors.156 MOF/GO tive PEDOT covered and connected UiO-66, and the lms
composites benet from the mechanical robustness of gra- display the porosity feature. The PGO@66C SEM micrographs
phene oxide and exhibit stimuli-responsive behavior, such as in Fig. 23(c) and (d) reveal a considerable shi in morphology
reversible structural changes in response to external stimuli like compared to Fig. 23(a) and (b). The interface of the sheets
temperature, pressure, or chemical exposure. MOFs can also displays a curled bend that is compatible with the microstruc-
serve as sensors due to their ability to selectively adsorb target ture of GO when the composites undergo polymerization in the
molecules, and thus by combining MOF/GO composites with presence of GO. The degree of porosity of P@66C can be raised
by the loose exible microstructure resembling a sheet of
PGO@66C, which would enhance electrochemical characteris-
tics and facilitate electrolyte access. Fu's group fabricated
a solid-state symmetrical SC device and employed two-electrode
system to examine its functioning and efficiency. The CV curves
of the PGO@66C device at various speeds of scans extending
from 5 to 500 mV s−1 are illustrated in Fig. 23(e). It is evident
that the PGO@66C device's CV curves exhibit quasi-rectangular
proles with a signicant rise in current as scan speeds
increase. The PGO@66C gadget exhibits an enormous rate
capability, according to the results. Areal capacitance contrary
to CV scan rates for the PGO@66C device is displayed in
Fig. 23(f). As the scan rates increase, the areal capacitance
values decline. At 5 mV s−1, the device's areal capacitance values
reach 30 mF cm−2. Fig. 23(g) shows the device's triangular GCD
curves with a current density between 0.4–5 mA cm−2. For all
GCD current densities, the PGO@66C device shows a reduced iR
drop. The solid-state capacitor device's strong capacitive quali-
Fig. 23 (a) Scanning electron microscopy images of (a) and (b) P@66C, ties are demonstrated by the symmetry and linear contour of the
(c) and (d) PGO@66C, (e) the PGO@66C solid-state SC device's cyclic
charging and discharging curves. An energy density of 0.0022
voltammetry curves spanning from 5 mV s−1 to 500 mV s−1 at various
scan speeds, (f) relationship between the PGO@66C solid-state SC mW h cm−2 and a power density of 0.2 mW cm−2 were attained
device's areal capacitance and cyclic voltammetry scan rates, (g) the at a current density of 0.4 mA cm−2. As depicted in Fig. 23(h),
solid-state SC device PGO@66C's galvanostatic charge/discharge the solid-state capacitive component was evaluated at a scan-
curves at various GCD current densities (a: 5, b: 2, c: 1, d: 0.8, e: 0.5, f: ning rate of 50 mV s−1 in a range of various bending and
0.4 mA cm−2), and (h) cyclic voltammetry curves obtained for the
twisting situations. Because of its extreme exibility and light
PGO@66C solid-state SC device under various curvature (a: flat; b, c:
bent; and d: twisted) circumstances at a scan rate of 50 mV s−1.164 weight, the SC may be bent and twisted in any way without
(a)–(h) Adapted with permission from source: ChemistrySelect, 2016, losing its structural integrity. Additionally, the CV prole
1, 285–289. Copyright 2016 Wiley Online Library. (Fig. 23(h)) showed the device's exceptional mechanical

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qualities as it stays constant and even gets larger at various pseudocapacitive behavior is a component of the electro-
bending angles. The characteristics of PGO@66C indicate that chemical mechanism. The symmetric redox peaks demonstrate
MOF-based solid-state capacitors hold great promise for appli- the high reversibility of the CuMOF/PET@rGO electrode. Even
cations in exible and wearable AI electronics. at high scan rates, the CV curve morphologies remained similar,
Yue et al. synthesized yarn electrode by cultivating conduc- suggesting strong rate performance. When the scan speeds were
tive clusters of MOF nanorods covered in reduced graphene raised, there was a possible shi in the anodic and cathodic
oxide-coated polyester (PET@rGO) yarn.165 They synthesized GO peaks, which is connected to the electrode polarization. The
sheets using modied Hummers' method and then immersed GCD curves acquired at different current densities are displayed
the cleaned PET yarn in a well-dispersed GO solution to create in Fig. 24(c). Their almost triangular shape suggests strong
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an incredibly thin GO layer over its surface. Thereaer, it was electrochemical activity and the pseudocapacitive contribution
dried in a vacuum at 50 °C for 3 hours and this procedure of could be the cause of the GCD curves' divergence from linearity.
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

dipping sheets and subsequently drying them was replicated for The determined specic capacitances are plotted in Fig. 24(d)
ten cycles. In an ascorbic acid solution, the GO lm was based on the outcome of the CV measurement. With the
chemically decomposed at 90 °C while being stirred. The CuMOF/PET@rGO electrode's superior structural characteris-
resultant PET@rGO yarn was rinsed aer four hours by vacuum- tics providing assistance, a specic capacitance of 151.9 F g−1 at
drying it at 50 °C and washing it three times in DI water. Then 3 mV s−1 was established. To assess the cycling stability of the
they synthesized CuMOF/PET@rGO yarn electrodes by adding CuMOF/PET@rGO electrode, it was continuously charged and
Cu(C2H3O2)2$H2O and HHTP in DMF/DI water mixture in discharged (Fig. 24(f)). Despite a noticeable decrease in capac-
certain ratios. In the above solution, the PET@rGO yarn was itance performance due to structural fatigue, the CuMOF/
introduced. Aer undergoing a 12 hour reaction at 85 °C, the PET@rGO electrode maintained 74% of its initial capacitance
CuMOF/PET@rGO yarn was carefully washed three times with following 2000 cycles. For 500 cycles, the CuMOF/PET@rGO
deionized water and allowed to naturally dry at room tempera- electrode was bent regularly, and as can be seen in Fig. 24(g),
ture. A 3D nanostructured array layer made up of many CuMOF there was an overlap in the recorded CV curves. Retentions of
nanorods is visible on the PET@rGO ber surface in Fig. 24(a) capacitance above 92% were computed (Fig. 24(h)), resulting
and (b). The average diameter of these nanorods is 20 nm. Large from which the assembled yarn SC was used to supply electricity
active surfaces can be exposed more easily because of this for small electrical gadgets, as well as an electronic calculator
special shape, which also creates an effective diffusion path for could be powered by two yarn SCs connected in series to carry
electrolyte ions. At varying scanning rates, the CV curves have out a mathematical calculation (Fig. 24(i) and (j)). Further xing
been described in Fig. 24(e). Each curve exhibited two mild of these yarn SCs was done on a wool glove (Fig. 24(k) and (l))
anodic and cathodic peaks, suggesting that Cu2+/Cu+'s and they were also able to activate the electronic calculator aer
bending it numerous times. Based on these ndings, our yarn
SCs appear to be a potential energy storage solution for wear-
able and exible electronics.

7.1 IoT energy storage devices

Smart electronic articial intelligence (AI) devices with a range
of functions,166–169 including shape memory, electrochromism,
photodetection, sensing capability, adaptability and self-
monitoring, self-diagnostic and health monitoring, energy
harvesting and storage, safety and fault tolerance, and user
interface and human–machine interaction, have been devel-
oped recently.170,171 By incorporating responsive MOFs into the
composite, smart supercapacitors can be designed to adapt
their performance or trigger specic functionalities in response
to environmental changes. Graphene oxide, despite being an
insulator, can be functionalized or reduced to graphene to
improve its electrical conductivity. Furthermore, graphene is
Fig. 24 (a) and (b) Scanning electron microscopy micrographs of
more favorable for storing the charge than other carbon mate-
CuMOF/PET@rGO yarns, (c) galvanostatic charging/discharging
curves of CuMOF/PET@rGO electrode, (d) specific capacitances of rials because of its enormous specic surface area (2630 m2
CuMOF/PET@rGO electrode, (e) cyclic voltammetry curves of g−1), which remains constant regardless of the pore size varia-
CuMOF/PET@rGO electrode, (f) cycling stability of the CuMOF/ tion.172,173 Incorporating graphene oxide into MOF-based
PET@rGO electrode for 2000 cycles, (g) mechanical bending's impact composites helps create a conductive network throughout the
on the CV curves, (h) effect of mechanical bending on capacitances,
material, facilitating rapid electron transfer and improving the
and pictures of an electronic calculator in the (i) and (j) fixed state, (k)
and (l) bending state, with the assembled yarn SCs serving as the power overall performance of the supercapacitor.
source.165 (a)–(l) Adapted with permission from source: Energy Fuels, Very recently, in the treatment of colorectal cancer, Shen
2020, 34, 16879–16884. Copyright 2020 American Chemical Society. et al. introduced a pH-responsive Fe-MOF@GO composite drug

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delivery system characterized by a stable structure and uniform responsive and efficient smart supercapacitors. Ongoing
particle size distribution.174 The incorporation of GO and MOF, research focuses on optimizing scalability and cost-
both possessing lamellar structures, enhances drug retention effectiveness for practical applications in modern AI energy
and permeability, thereby promoting drug absorption. This storage systems. This integration could open exciting possibil-
study effectively demonstrates the potential of MOF@GO drug ities for the evolution of smart supercapacitors with improved
delivery systems in healthcare, including drug loading and anti- performance.
tumor applications. Furthermore, there were challenges in
using 2D-MOFs for electrode preparation because of the strong 8 Conclusion and outlook
van der Waals attraction of neighbouring nanosheets, which
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may cause the massive 2D-MOF lms to aggregate and self- In this review, we gave a thorough rundown of the most recent
restack next to each other. This may seriously compromise advancements in MOF/GO-based electrode materials tailored
Open Access Article. Published on 30 April 2024. Downloaded on 5/25/2024 8:07:27 AM.

their ease of access to electrolyte ions and could negatively for advanced energy storage applications. The discussion
impact devices' electrochemical performance.175 By carefully encompassed diverse characteristics, ranging from chemical
incorporating strongly conductive graphene layers into 2D-MOF synthesis methods to magnetic and non-magnetic metal-based
lms to create a switching graphene/MOF multilayer arrange- MOFs, and various composites like MOF/G, MOF/GO, MOF/
ment, Cheng's group suggested a method to improve the rGO. Emphasis was placed on their properties in the context
characteristics of 2D-MOF electrode materials.176 They showed of advanced energy storage applications of smart super-
how to develop hybrid electrodes using the electrostatic self- capacitors, shedding light on how these materials can propel
assembly method, which included self-assembled 2D Co-MOF/ progress in developing energy storage solutions with height-
rGO paper. They also suggested a one-to-two approach, which ened performance and capabilities. To overcome the limitation
involves employing a synthesis process developed from MOF to posed by the low conductivity of organic linkers in MOFs, gra-
generate two different kinds of electrodes with good porosity for phene and its derivatives are strategically combined with MOFs,
FSSCs: CoMOF@rGO and NiMOF@rGO. This process merely enabling the enhancement of electrochemical properties
requires the metal ion precursors to be altered. An extensive through improved conductivity.
asymmetric all-solid-state supercapacitor was created utilizing Various types of MOF/GO composites have been discussed
a negative NiMOF@rGO40 electrode, a positive CoMOF@rGO40 herein, including Mo-MOF/GO, Fe2O3-MOF/GO, Ni/Co-MOF-
electrode, and an electrolyte made up of PVA-H2SO4, in order to rGO, ZIF-8/GO, Ce-MOF/GO, HMRL-1/rGO, and others. These
create customizable supercapacitors possessing a large energy composites are of great interest to researchers due to their
density. A remarkable areal capacitance of 426.5 mF cm−2 and exceptional electrochemical performance and other properties
a volumetric capacitance of 22.45 F cm−3 at 1.2 mA cm−2 were resulting from the synergistic interaction between MOF and GO
displayed by the constructed paper-based CM/rGO40//NM/ architectures. Conversely, various composites of GO with other
rGO40 E-SCs. GCD experiments under various bending angles materials have been outlined, such as GO/ZHS, Chitosan/GO
were performed to evaluate the device's exibility. As compared hydrogel, graphene quantum dots (GQDs), rGO/MXene-PPy,
to the original state, the specic capacitance could retain 97.5% and others, that have also demonstrated promising potential
during the procedure. Specically, the specic capacitance in the realm of energy storage devices. Furthermore, discus-
remained at 93.9% regardless of 100 twisting rounds at a 180° sions have extended to composites of MOFs with other mate-
bending angle which can be ascribed to the interconnections rials, including trimetallic MOF-CNT, Co-MOF/PANI, MOF-
formed by the CM/rGO40//NM/rGO40 E-SC. The exible gadget, PEDOT, MOF-LaFeO3, Cu-MOF@d-MnO2, among others.
measuring 35 mm by 20 mm, is remarkably thin at just 1.9 mm This article covers the types and operation of superconduc-
in thickness and so light that even a delicate ower stamen may tors, rationale and properties of MOF/GO composites, their
li it up. Notably, modifying the E-SCs device's design allowed surface engineering, three-electrode, and two-electrode elec-
for a demonstration of its modiable performance, wherein the trochemical characteristics, and their applications in smart
E-SCs could continue to light the LED even aer being cut supercapacitors. Selecting appropriate metal cations and
multiple times. Thus, the above-described results amply show linkers aids in ne-tuning the nal structural characteristics for
that the paper-based CM/rGO40//NM/rGO40 E-SCs, which are improved ion migration, as the covalent connection between
all-solid-state, may function as a dependable and customizable MOF and GO is facilitated by a number of linkers. Rather than
energy storage device for wearable computer applications. using the post-synthesis technique, hydrothermal or sol-
Overall, MOF/GO composites offer a versatile platform for vothermal synthesis, co-precipitation method and mixing
the development of smart supercapacitors with enhanced method routes are typically used to guarantee a stronger contact
performance, responsiveness, and versatility, opening up between two materials, offering a better control over the
exciting opportunities for advanced energy storage applications. composite's properties.
This combination exploits the excellent electrical conductivity Lastly, GO-based nanostructures have demonstrated their
and mechanical strength of GO along with the enormous distinctive qualities in MOF/GO composites for smart super-
surface area and tunable pore size of MOFs, resulting in capacitors, according to data that have been presented, which
a unique morphology with synergistic effects. The hybrid represent a signicant advancement beyond traditional energy
material enhances charge storage capacity, accelerates electron storage devices, with additional functionalities enabling them
transport, and ensures structural stability, making it ideal for to sense, adapt, and respond to changes in their environment or

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There are no conicts to declare.

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