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Green Energy & Environment 7 (2022) 3e15
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Review article

Recent progress on synthesis of ZIF-67-based materials and their application

to heterogeneous catalysis
Chongxiong Duan a,c, Yi Yu b,*, Han Hu a,*
a
State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, Institute of New Energy, China University of Petroleum (East China), Qingdao,
266580, China
b
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China
c
School of Materials Science and Hydrogen Engineering, Foshan University, Foshan, 528231, China
Received 6 October 2020; revised 18 December 2020; accepted 23 December 2020
Available online 29 December 2020

Abstract

In recent years, an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their
exceptionally high surface area, tunable porosity, and excellent thermal and chemical stabilities. This review summarizes the latest strategies of
synthesizing ZIF-67-based materials by exploring the prominent examples. Then, the recent progress in the applications of ZIF-67-based
materials in heterogeneous catalysis, including catalysis of the redox reactions, addition reactions, esterification reactions, Knoevenagel con-
densations, and hydrogenation–dehydrogenation reactions, has been elaborately discussed. Finally, we end this work by shedding some light on
the large-scale industrial production of ZIF-67-based materials and their applications in the future.
© 2020, Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communi-
cations Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Zeolitic imidazolate framework-67; Synthetic methods; Heterogeneous catalysis

1. Introduction active sites [5–7]. Based on the aforementioned advantages,

ZIFs have attracted extensive research interest in a variety of
Zeolitic imidazolate frameworks (ZIFs), constructed by fields, including gas storage [8], adsorption [9], drug delivery
tetrahedral metal cations M (M ¼ Zn or Co) and imidazolate [10], sensors [11], bioimaging [12], supercapacitors [13], and
ligands (Im), are a unique and intriguing subclass of porous catalysis [14,15].
metal–organic frameworks (MOFs) [1,2]. The structure of ZIF To date, more than 150 ZIFs have been reported, of which
contains M-Im-M angle (~145 ), which is similar to the Si–O– many ZIFs have received significant research and application
Si angle in conventional zeolites, thereby resulting in a zeolite interest [16,17]. The representative ZIF-67 (Co(Hmim)2,
type tetrahedral topology for a large number of ZIFs [3,4]. Hmim ¼ 2-methylimidazole) consists of cobalt ion (Co2þ) and
Compared with conventional zeolite/MOFs or their simple 2-methylimidazolate anions, and exhibits a cubic crystal
mixtures, ZIFs provide new scientific and technological op- symmetry with unit cell parameters of a ¼ b ¼ c ¼ 16.9589 Å
portunities by organically combining the respective benefits of [16,18]. Specifically, ZIF-67 has a high surface area
zeolites and MOFs, such as high surface area, permanent (SBET > 1700 m2 g1) that endows ZIF-67 with abundant
porosity, high thermal and chemical stability, and abundant active sites, and the presence of micropores (pore diameter:
~0.34 nm) is favorable for reactions due to their strong affinity
for guest molecules [19–21]. Moreover, the abundant coordi-
* Corresponding authors. nated unsaturated metal sites (CUSs) embedded in the ZIF-67
E-mail addresses: [email protected] (Y. Yu), [email protected]
(H. Hu).
framework have been proven to show excellent activity for

https://doi.org/10.1016/j.gee.2020.12.023
2468-0257/© 2020, Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co.,
Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
4 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15

many guest molecules, for example ammonia borane [22,23]. successfully synthesized nanosized ZIF-67 crystals in meth-
Moreover, the ZIF-67 derivatives, such as metal oxides and anol at the ambient temperature over a longer period (24 h).
metal/carbon composites, could bring some novel character- The products exhibited a more uniform and monodispersed
istics which are absent in the pristine ZIF-67 [24–26]. These morphology of rhombic dodecahedron, as shown in Fig. 1.
merits allow ZIF-67-based materials to operate under harsh However, the problems related to energy consumption and
catalytic conditions, making them highly suitable in numerous environmental pollution caused in the traditional synthesis
applications, including adsorption and separation [27], drug process should not be neglected, such as the heavy use of toxic
delivery [28], bioimaging [29], supercapacitors [30,31], and solvents [45,46]. With the proposition of green synthesis route,
catalysis [32]. the preparation of ZIFs in an energy-saving and environmen-
Recently, various approaches have been developed to syn- tally-friendly method is a novel tendency, such as the use of
thesize ZIF-67 and its derivatives with tunable morphology water as the solvent [47]. After the successfully synthesizing
and porosity, including the solvothermal method, surfactant- ZIF-8 in an aqueous phase at room temperature [5], the
assisted method, sol–gel method, microwave/ultrasound- organic solvents for the preparation of ZIF-67 have been
assisted method, etc. These methods not only synthesize high- gradually replaced with water [48]. To control the structural
quality ZIF-67 but it also can effectively adjust the crystal size and morphological of ZIF-67, the reaction conditions such as
and porosity of ZIF-67 by choosing the appropriate parameters the concentration of reactants, synthetic time, and pH have
(e.g., temperature or synthesis time) [21,33]. The versatile been investigated. For example, Zhang et al. [49] constructed a
synthesis strategies together with fascinating physical and novel zeolite imidazole salt framework (ZIF-L-Co), which had
chemical properties of ZIF-67 make it an ideal candidate for been proven to be the transient phase of ZIF-67 by the process
various applications such as volatile organic compounds of mixing Co(NO3)2 with Hmim in an aqueous media. The
(VOCs) adsorption [34], separation [35], supercapacitors [36], phase and morphology of the samples can be tuned by con-
and catalysis [37]. Recently, some comprehensive review ar- trolling the concentration or molar ratios of the reactants. As
ticles regarding the synthesis and application of ZIFs have shown in Fig. 2, when the Hmim/Co2þ molar ratio was
been published [38–41]. However, to the best of our knowl- increased from 8 to 24, the morphology transformed from the
edge, the advances of these materials in terms of their syn- leaf-like sheets to rod-like structures. By further increasing
thesis and application in heterogeneous catalysis are rarely this value from 32 to 48, the rough polyhedron smoothed, and
summarized. Therefore, a brief review that focuses on the obvious edges and corners appeared. The combination of
synthesis of ZIF-67-based materials and their applications in heating in vacuum or under water vapor-assisted environments
heterogeneous catalysis is highly desirable. In this review, we resulted in the crystallization of ZIF-67 to follow the solid
discuss various strategies for the preparation of ZIF-67-based transformation mechanism. More importantly, water media
materials including the solvothermal method, surfactant- played a dominant role in accelerating the transformation from
assisted method, sol–gel method, and microwave/ultrasound- ZIF-L-Co phase to ZIF-67. Furthermore, a lower Hmim/Co2þ
assisted method. We also discuss the applications of ZIF-67- molar ratio and higher concentration of reagents facilitated the
based materials in heterogeneous catalysis fields including crystallization of ZIF-L-Co. Subsequently, Civan et al. [50]
redox reactions, addition reaction, esterification, Knoevenagel constructed ZIF-67 crystal using Co(OAc)2∙4H2O and Hmim
condensation, and hydrogenation–dehydrogenation reactions. in the aqueous phase and then adjusted the pH of the etchant
solution to facilitate unprecedented structures of the crystals,
2. Synthesis strategies for ZIF-67-based materials such as truncated rhombic dodecahedra, cubes, tetrahedra, and
even hollow boxes without any loss of porosity. The etching
2.1. Solvothermal method solvent served to destroy part of the original three-dimensional
(3D) framework connected by cobalt ions and ligands, through
Solvothermal method is the most widely used technique for the process of sequentially protonating the ligands, dis-
the synthesis of ZIF-67. Typically, the reactants (including connecting the coordination bonds and then liberating Co2þ
cobalt sources and 2-methylimidazole (Hmim)) dissolved in ions.
solvents are heated between 50 and 200  C in autoclaves and
the crystals are obtained after 12–72 h. Three key processes, 2.2. Surfactant-assisted method
i.e. hydrolysis, coordination, and deprotonation are generally
involved [42], which makes it easy to precisely control the The surfactant-assisted method focused on the addition of
material properties by changing experimental conditions. For surfactants into the solution of precursors to promote their
example, Jayashree et al. [43] adopted Co(NO3)2$6H2O and dissolution and the dispersion of product particles [51,52].
Hmim to prepare ZIF-67 materials in two organic solvents, Furthermore, the morphology and structure of the samples can
dimethylformamide (DMF) and methanol for 4 h at 60  C, be regulated by controlling the types or amount of surfactants
separately. SEM and N2 adsorption–desorption tests demon- [53]. For example, a cobalt source can be mixed with an
strated that the solvent is a vital factor in the process of aqueous solution of Hmim containing cetyl-
crystallization as ZIF-67 prepared in methanol had micropo- trimethylammonium bromide (CTAB) to synthesize ZIF-67
rous structure whereas hierarchical structure appeared in the materials in a very short time (~5 min). In such a reaction,
products synthesized in DMF. Similarly, Qin et al. [44] CTAB can be used as a capping agent to adjust the particle
 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15 5

Fig. 1. The proposed synthesis process of the ZIF-67 material. Reprinted with permission from Ref. [44]. Copyright 2017 Elsevier.

size within 50–320 nm during the process of crystal formation micrometer-sized particles is derived from MOF precursors
[54]. In a recent report, Li et al. [55] immersed Fe2O3 nanorod cooperating with coagulants through hydrolysis and conden-
in the DMF containing a certain amount of poly- sation processes. Then, the gels with certain spatial structure
vinylpyrrolidone (PVP) followed by the introduction of Hmim form solid particles via a heat treatment [61]. For example,
and Co(NO3)2$6H2O, resulting in the formation of Fe2O3@- Yang et al. [62] developed a sol–gel process to fabricate 3D
ZIF-67 composites after the drying treatment at 80  C for 12 h rGO/ZIF-67 aerogel (reduced graphene oxide (GO)). As
(Fig. 3). In a typical procedure, PVP served as a dual-function shown in Fig. 5, the key is to mix ZIF precursor solutions with
additive: (i) a capping agent to modulate the size of products the as-prepared 3D rGO sequentially rather than simulta-
and (ii) a linker to enhance the affinity of Fe2O3 nanorods and neously. Based on the good adsorption performance of rGO
ZIF-67 via the coordination of Co2þ and pyrrolidone rings (C towards metal ions, cobalt ions were adsorbed on the surface
¼ O).
Surfactants can also function as a structure-directing agent
(SDA) to guide the construction of hierarchical channels in
MOFs [56–58]. Duan et al. [59] adopted three surfactants that
include tetrabutylammonium hydroxide (TBAOH), tetrapro-
pylammonium hydroxide (TPAOH), and tetraethylammonium
hydroxide (TEAOH) for the rapid preparation of hierarchically
porous ZIF-67 at ambient temperature and pressure. Experi-
mental and simulated tests demonstrated the growth mecha-
nism of hierarchical ZIF-67, as shown in Fig. 4. Specifically,
the surfactant served as a bifunctional modulator including
deprotonation agent and SDA to rapidly deprotonate Hmim,
promote the coordination with Co2þ, and then dominate the
formation of mesoporous and macroporous channels during
the growth of crystals. The hierarchical structure was achieved
after activating and drying processes. In addition, other sur-
factant, such as N,N-dimethyl-1, 2-ethanediamine, was also
successfully employed to introduce hierarchical pores into the
microporous ZIF-67 [34].

2.3. Sol–gel method

Sol–gel technology has emerged as an approach to control Fig. 2. SEM images of samples synthesized from various Hmim/Co molar
the molecular composition and frameworks at various length ratio: (a) 8, (b) 16, (c) 24, (d) 32, (e) 40 and (f) 48. Reprinted with permission
scales [60]. Typically, a colloidal suspension of sub from Ref. [49]. Copyright 2015 Royal Society of Chemistry.
6 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15

Fig. 3. Schematic of the fabrication procedure of Fe2O3@ZIF-67 composite. Reprinted with permission from Ref. [55]. Copyright 2019 Elsevier.

of rGO and subsequently coordinated with Hmim. The final the processes, which facilitate narrow size contribution of
3D rGO/ZIF-67 aerogel was obtained after freeze-drying. particles, enhance the phase purity and shorten the reaction
Subsequently, Xu et al. [63] fabricated a hierarchically time [64,65]. Niyaz et al. [66] proposed a facile and efficient
porous aerogel of Fe3O4/ZIF-67@WA (WA ¼ wood aerogel) ultrasound-assisted strategy to synthesize ZIF-67
via in-situ loading of magnetic Fe3O4/ZIF-67 materials into a @Fe3O4@ESM (ESM ¼ eggshell membrane) composite
lightweight natural WA. The synthesis mechanism is shown in (Fig. 7). The cobalt nitrate solution was sonicated and then
Fig. 6. Fe3O4 NPs (NP ¼ nanoparticle) were first treated with mixed with the pre-synthesized Fe3O4@ESM in water phase,
Co2þ solution containing PVP, and subsequently the Fe3O4 and then sonicated again in the Hmim solution. SEM image
NPs decorated with Co2þ were anchored in situ onto the showed the ZIF-67 crystals grown onto the highly interwoven
surface of the wood aerogel laminate. The strong hydrogen cross-linked protein fibers of ESM. The ultrasound-assisted
bond and electrostatic attraction because of the numerous technology improved the local turbulence/liquid microcircu-
oxygen-containing groups on the long chain of cellulose and lation in the reaction system and shortened the coordination
the presence of Hmim, ZIF-67 crystals grow on the wood time from 6 h (stirring method) to 3 h.
aerogel. However, the Fe3O4 or ZIF-67 NP are usually In addition, Tu et al. [67] proposed the use of a homemade
attached to the surface of WA rather than penetrating in the microwave-assisted synthesis device mainly including sample
interior of WA. chamber, microwave generator, time control and cooling sys-
tem, to prepare ZIF-67 in the mixture of ethanol and methanol.
2.4. Microwave/ultrasound-assisted method Microwave heating enables the ZIF precursor solution to serve
as a heat source rather than being conducted through the
In recent years, the synthesis of ZIF-67 via microwave or surface. Consequently, the instantaneous high temperature
ultrasound-assisted method has attracted increasing attention. lead to rapid growth kinetics and greatly shortened the
High local temperature and pressure can be produced during experimental time. It also afforded better control of the size

Fig. 4. Mechanism for the formation of hierarchically porous ZIF-67. Reprinted with permission from Ref. [59]. Copyright 2018 American Chemical Society.
 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15 7

Fig. 5. Synthesis scheme for the fabrication of 3D rGO/ZIF-67. Reprinted with permission from Ref. [62]. Copyright 2018 Elsevier.

and morphology of nanoparticles. Similarly, Febrian et al. [68] ensure the rapid crystallization of crystals, which may
first successfully used the one-step microwave-assisted strat- consume huge amounts of energy and increase the operating
egy to rapidly fabricated CoZn-ZIF-8 membrane with mixed and production costs [69].
metals (Zn2þ and Co2þ) and ligand (Hmim) in ~1.5 min within
a microwave oven with a power of ~100 W. This rapid and 2.5. Other methods
green technology can significantly promote the industrializa-
tion of ZIF-67 materials. However, additional energy input and In addition to the aforementioned techniques, some special
set-ups have to be provided during the synthesis so as to strategies for ZIF-67 preparation have been developed in

Fig. 6. Schematic of the preparation of Fe3O4/ZIF-67@WA aerogel. Reprinted with permission from Ref. [63]. Copyright 2019 Elsevier.
8 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15

recent years. For example, Cristina et al. [70] proposed a novel two-electrode electrochemical cell. The ZIF-67 coating was
and facile method called “accelerated aging” to prepare generated through the redox reaction on the electrodes acti-
microporous ZIF-67 using CoO and Hmim powders without vated by ion migration whose rate can be simply controlled by
continuous agitation, bulk solvent or high temperature. Under changing the voltage. This method could exclude the influence
the mild diffusion-control conditions, microporous ZIF-67 of anions (e.g., NO 
3 and Cl ) during synthesis, thus securing
materials can be fabricated by self-assembly of ligands and a continuous high-throughput production with low cost in a
cobalt oxide despite its high melting point. During the process, short time at ambient temperature and pressure.
the salt additives (Hþ donors) e.g. (NH4)2SO4 are key to Reverse micro emulsion provides an efficient means of
activating Hmim via acid-catalysis mechanism and further controlling the size and morphology of monodispersed crys-
promoting the coordination between CoO and activated tals. Sun et al. [74] first reported ZIF-67 fabricated by reverse
Hmim. In addition, the influence of relative humidity in the micro emulsion method (water in non-polar media) using
system was investigated. Results showed that a small increase CTAB as surfactant, 1-hexanol as co-surfactant and heptane as
in the relative humidity indeed contributed to significant in- oil phase at room temperature. The product owns small par-
creases in the yield and speeding up the reaction; however, the ticle size, uniform particle size distribution and good thermal
sample remained in a powder state. stability, and its specific surface area and pore volume are
The conversion from Co oxides to ZIF-67 was also studied much larger than ZIF-67 prepared in the aqueous media. The
by Krishtab et al. [71] adopting the chemical vapor deposition principle relied on the abundant nano-reactors (micelles),
(CVD) method for the integration of ultra-low-k MOF di- which acted as a platform for the reaction of metal ions and
electrics in on-chip by an interconnection based on two syn- ligands. Clearly the reaction was limited in the nano-reactors,
thetic routes (Fig. 8). Route A targeted the conformal oxide/ thus the dimension of micelles, which was demonstrated by
hydroxide layer previously deposited at the surface of the dynamic light scattering (DLS) test in the report, can control
metal lines to fill the trenches. While route B relied on se- the size of crystals.
lective conversion of metal oxide formed by controlled
oxidation, which was proved preferable because the CoOx 3. Application of ZIF-67-based materials in
precursor could conformally cover the metal lines to avoid the heterogeneous catalysis
impact on the leakage current between the capacitor forks.
Upon exposure to organic linker (Hmim) vapor, a metal oxide Unlike the homogeneous catalysts such as transition metal
precursor film is consumed and further nucleated and con- complexes and ionic liquids facing difficulties during the
verted into a porous MOF-CVD ZIF film. This strategy separation, purification, and recovery phase, the ZIF-67 as
enabled the controllable deposition of ZIF-67 film with uni- heterogeneous catalysts is free of these problems [75,76].
form thickness. More importantly, it facilitates the integration Moreover, the structural regulation of ZIF-67 crystals with
of MOFs in on-chip interconnects that rationally connects the molecular scale can be comprehended without sacrificing
rising MOF materials with the microelectronics manufactures catalytic activity [77,78]. For example, a new technique for
[72]. Besides, Du et al. [73] proposed another deposition improving catalytic activity of ZIF-67 was developed wherein
technique, electrochemical deposition, for the synthesis of different NPs (e.g., metal and metal oxide NPs) were loaded in
porous high-throughput ZIF-67. This formation mechanism ZIF-67 crystals, resulting in the NPs@ZIF-67 composites thus
focused on supplying Co(II) ions continuously by the anodic combining the merits of both NPs and ZIF-67 [79,80]. These
dissolution of Co metal rather than using Co2þ salts to the characteristics allow ZIF-67 guarantee to be one of the most
reaction media containing the ethanol solution of Hmim and functional materials for the heterogeneous catalysis regime in
the electrolyte (hexadecyl trimethyl ammonium bromide) in a the future chemical industry.

3.1. Catalysis of the redox reaction

Recent researches have demonstrated that ZIF-67 and its

derivatives have been identified as the ideal candidates for the
various catalytic redox reactions such as carbon dioxide (CO2)
conversion and benzyl aromatic hydrocarbons oxidation. For
the catalytic conversion of CO2, Wang et al. [81] reported the
use of ZIF-67 as heterogeneous catalyst and ruthenium-based
dye ([Ru(bpy)3]Cl2$6H2O) as photosensitizer for photochem-
ical reduction of CO2 to CO and H2 under facile reaction
conditions. The as-synthesized nanosized ZIF-67 crystals
exhibited excellent catalytic performances with yields of CO
and H2 as high as 37.4 and 13 mmol in 30 min, respectively,
which was higher than yields of other catalysts such as ZIF-8,
Fig. 7. Schematic of the synthesis of ZIF-67@Fe3O4@ESM. Reprinted with MIL-101, and UiO-66, [82–84]. The superior catalytic activity
permission from Ref. [66]. Copyright 2019 Elsevier. of ZIF-67 could be attributed to the electron-mediating
 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15 9

function of cobalt species [85,86]. Although the derivation of extra alkali, and noble metals, making it one of the most
carbon source of the generated CO was confirmed from CO2 desirable catalysts [16]. As shown in Fig. 10, the reaction
using 13CO2 isotropic experiments, the catalytic mechanism mechanism for chemo selective oxidation of benzylic C–H
remained unclear. bonds was proposed, wherein the tert-butoxy and tert-butyl-
Subsequently, Sun et al. [87] studied the influence of ZIF- hydroperoxide radicals were generated via a redox reaction
67 morphology on the catalytic performance of CO2. Results between ZIF-67 and tert-butyl hydroperoxide (TBHP).
indicated that the obtained ZIF-67 crystal with leaf-like shape Moreover, the oxidation reaction of benzyl aromatic hydro-
showed higher catalytic activity than that of ZIF-67 with carbons was subsequently distended to different reactants. In
rhombic dodecahedral morphology. Importantly, the reaction addition, Li et al. [90] also reported that ZIF-67 exhibited high
mechanism for photocatalytic reduction of CO2 into CO using conversion rate and selectivity for the oxidation of ethyl-
ZIF-67 as a cocatalyst was proposed. First, the [Ru(bpy)3]2þ benzene to acetophenone under mild conditions (373 K,
photosensitizer was stimulated and the formation of excited 0.3 MPa, and O2 for 9 h). Overall, although ZIF-67 as a
states of [Ru(bpy)3]2þ* (electron–hole pairs) under visible- catalyst exhibits a high catalytic performance, only few reports
light irradiation was observed. The formation of [ZIF-67_3]1 the standalone catalysis for the various redox reactions that are
and triethanolamine (TEOA) is caused following the charge served by ZIF-67.
separation of the resulting excited states of [Ru(bpy)3]2þ* at
the interface between [Ru(bpy)3]2þ and ZIF-67_3, and the 3.2. Catalysis of the addition reaction
formed light-induced electrons and holes that are subsequently
transferred to ZIF-67 catalyst (ZIF-67_3) and TEOA, respec- The cycloaddition of CO2 to epoxides is a typical addition
tively. The electrons stored in [ZIF-67_3], which are strongly reaction and is most studied in recent years [91]. To date,
adsorbed on the ZIF-67_3 catalytic sites of Co ions or those in many catalysts such as metal oxides, immobilized complexes,
strong interaction with 2-methyl imidazole, resulted in further zeolites, and MOFs have been widely used to catalyze this
migration to CO2 for the reduction of CO2 to CO. The H2 was reaction, wherein ZIF-67 is a potential catalyst because of its
derived from the reduction of the existing protons in the re- abundant active sites, and exceptional chemical and thermal
action system by the light-induced electrons, as shown in stability. For example, Park et al. [48] reported the use of ZIF-
Fig. 9. 67 to catalyze the cycloaddition of CO2 and epoxides forming
The catalytic oxidation of benzylic C–H bonds at eco- cyclic carbonates under solvent free and co-catalyst free
friendly conditions is highly desirable to synthesize high conditions. The conversion of more than 97% epichlorohydrin
value-added products [88]. Wang et al. [89] reported the use of (ECH) and the selectivity of more than 99% toward epichlo-
ZIF-67 as the catalyst and tert-butyl hydroperoxide as an rohydrin carbonate was higher in ZIF-67 than other ZIFs such
oxidant for the oxidation of 2,3-dihydro-1H-indene and eth- as ZIF-8, ZIF-68, and ZIF-90. Moreover, the as-synthesized
ylbenzene to 2,3-dihydro-1H-inden-1-one and acetophenone ZIF-67 catalyst has excellent reusability for the CO2-epoxide
with high catalytic activity and reaction yield. Furthermore, cycloaddition without any observable loss. The catalytic
the as-synthesized ZIF-67 catalyst can be reutilized at least six mechanism for the ZIF-67 mediated cyclic carbonate synthesis
times without the loss of conversion. Compared to other cat- was proposed based on the experimental and computational
alysts such as VO@g-C3N4, MnO2@wool, and rhenium (V) results. In addition, Verpoort et al. [92] also adopted ZIF-67 as
complexes, the use of ZIF-67 catalyst can avoid harsh reaction catalyst for the cycloaddition of CO2 to epoxides to afford
conditions such as high temperature, toxic organic solvents, cyclic carbonates, wherein the high conversion rate and

Fig. 8. Two synthetic routes of ZIF-67 via CVD process. Reprinted with permission from Ref. [71]. Copyright 2020 Springer.
10 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15

Visible light

TEOA+
(3-1) TEOA
[Ru(bpy)3]2+* (1)
Charge separation h+
(2) e-
(electron transfer) e-

[ZIF-67_3]- (3-2)

[ZIF-67_3)]-
(4) CO2 + 2H+ + 2e- CO + H2O H2 2H+ + 2e-

Fig. 9. A possible mechanism for photocatalytic reduction of CO2 into CO using ZIF-67 as a cocatalyst, and TEOA and [Ru(bpy)3]2þ as an electron donor and as a
photosensitizer, respectively. Reprinted with permission from Ref. [87]. Copyright 2018 Royal Society of Chemistry.

selectivity were achieved. As shown in Fig. 11, due to the As shown in Fig. 12b, the conversion of CO2 to cyclic car-
presence of both Lewis acid sites (Co(II) and Co(III) species) bonates onto Zn/Co-ZIF catalyst was 57%, higher than ZIF-8
and uncoordinated nitrogen atoms, ZIF-67 has polar pore walls (40%) and ZIF-67 (50%). The improved catalytic performance
which favor the binding and activation of the polar carbon– can be ascribed to the higher basic value of Zn/Co-ZIF than
oxygen bond of CO2 [93]. Compared with other ZIFs, the those of ZIF-8 and ZIF-67. However, the structure contains
ZIF-67 catalysts exhibit higher economic and environmental both Zn and Co in one cluster of Zn/Co-ZIF and their positions
efficiency for the conversion of CO2 to cyclic carbonates due are completely random and uncontrolled.
to their abundant Lewis acid sites.
Recently, the Zn-doped ZIF-67 has proved to have fasci- 3.3. Catalysis of the esterification reaction
nating physical and chemical properties and thus offers
excellent catalytic performance. For instance, Verpoort et al. The esterification reaction is an important type of reaction
[94] investigated a high nano-crystallinity dual metallic Zn/ that has been widely used in the field of organic synthesis.
Co-ZIF using a facile strategy (Fig. 12a). The resultant Zn/Co- However, there remains a huge challenge to finish the esteri-
ZIF possesses different physical properties in comparison to fication reaction under mild conditions [95]. To achieve this
ZIF-8 and ZIF-67 individually such as high surface area. target, Yu et al. [96] first reported the preparation of ethyl
Furthermore, compared with the original ZIF-8 or ZIF-67, the methyl carbonate (EMC) from diethyl carbonate and dimethyl
dual metallic Zn/Co-ZIF exhibited better catalytic perfor- carbonate using ZIF-67 as a catalyst. The yield of EMC
mance for the cycloaddition of CO2 with epichlorohydrin to reached up to 83.39%, which was higher than ZIF-8 catalyst
obtain cyclic chloropropene carbonate under mild conditions. (50.7%) due to the lager surface area of ZIF-67. In addition,

Ar R

t-BuOOH

t-BuOOH
t-BuOO
OOt-Bu O
Ar R R R
Colll ZIF-67 Coll Ar Ar
A B P
t-BuOH
t-BuOO
t-BuO
t-BuOOH
t-BuOH
R
Ar
t-BuOOH t-BuOH

Fig. 10. A plausible reaction mechanism for chemoselective oxidation of benzylic C–H bonds. Reprinted with permission from Ref. [89]. Copyright 2017 Elsevier.
 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15 11

Fig. 11. Possible mechanism for cycloaddition of CO2 to epoxide via using ZIF-67 catalyst. Reprinted with permission from Ref. [92]. Copyright 2016 Royal
Society of Chemistry.

compared to other heterogeneous catalysts, such as MCM-41, using a bottle-around-a-ship method. The resulting lipase@-
MgO, La2O3, and CeO2 [97], the ZIF-67 catalysts have been ZIF-67 composites exhibited excellent catalytic performance
proven effective under mild reaction conditions for the syn- for the transesterification of soybean oil to biodiesel in a
thesis of EMC with either low yields or high reaction tem- solvent-free medium (Fig. 13), and its initial activity can be
perature (> 180  C). kept after 6 cycles without a significant decrease owing to the
Enzymes are a high-effective bio-catalyst due to their enhanced stability (e.g., pH and thermal stability).
excellent properties such as chemo selectivity, stereo selec- In addition, some Co-based catalysts that derived from ZIF-
tivity and the mild reaction conditions [98]. Especially, the 67 materials also show excellent catalytic performance for the
encapsulation of enzyme into ZIF-67 to form composites can esterification reaction. For example, Li et al. [100] reported the
bring novel properties for catalyzing esterification reaction synthesis of Co-based catalysts by one-pot thermolysis of ZIF-
when compared to enzyme and ZIF-67 individually. For 67. The as-synthesized cobalt-based catalyst was used for
instance, Rafiei et al. [99] reported the immobilization of li- catalytic direct oxidation of alcohols to esters at mild condi-
pases (triacylglycerol-acyl-hydrolases, EC 3.1.1.3) into ZIF-67 tions without the assistance of any base additives. Moreover,

Fig. 12. (a) Single-crystal structure of the as-synthesized Zn/Co-ZIF; (b) and the conversion of CO2 to cyclic carbonates using different catalysts. Reprinted with
permission from Ref. [94]. Copyright 2017 Royal Society of Chemistry.
12 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15

as M-MOF-74 (M ¼ Cu, Zn, Co), ZIF-9, CoCl2, FeCl3, etc.

Furthermore, ZIF-67 catalysts could be conveniently reused
HN N many times for the condensation reaction without a noticeable
Co+2 + +
Lipase c deterioration in catalytic performance. Notably, the reaction
route between 2-nitroaniline and benzylamine to form 2-phe-
nylbenzimidazole was proposed based on GC–MS analysis. In
addition, ZIF-67 can also be used as the catalyst to catalyze
other condensation reactions with different reactants such as
benzylamine (4-methoxyphenyl)methanamine, and (2-chlor-
ophenyl)methanamine.
In addition, bimetallic ZIF (e.g., ZnCo-ZIF) have proven
effective for the Knoevenagel condensation reaction due to the
Fig. 13. Schematic of the preparation of the lipase@ZIF-67 and their appli- synergistic effect of two metals. For example, Verpoort et al.
cation for the transesterification of soybean oil to biodiesel. Reprinted with
[104] adopted the bimetallic ZnCo-ZIF (Zn@ZIF-67) to
permission from Ref. [99]. Copyright 2018 Elsevier.
catalyze the Knoevenagel condensation reaction between
the proposed esterification reaction features a broad substrate malononitrile and benzaldehyde derivatives (Fig. 14). The
scope for aromatic and aliphatic alcohols as well as diols such resulting Zn@ZIF-67 showed higher reaction rates and
as p-nitrobenzyl alcohol and 1,2-benzenedimethanol, which enhanced activities when compared to ZIF-67 and ZIF-8,
provides excellent yields of the target products with high which can be attributed to the synergistic effect of the two
selectivity. metals on the activation of the substrates [105]. Moreover, the
resulting Zn@ZIF-67 catalyst could be recycled up to at least
3.4. Catalysis of the knoevenagel condensation reaction 4 times without considerable loss of activity while maintaining
their crystalline structure.
Knoevenagel condensation of aldehydes with compounds
containing activated methylene groups is one of the most 3.5. Catalysis of the hydrogenation–dehydrogenation
useful and widely employed methods for C–C bond formation reaction
with a large number of applications such as the fine chemicals
synthesis [101]. Compared with traditional heterogeneous The hydrogenation–dehydrogenation reaction is one of the
catalysts, including mesoporous silica, zeolites, and metallic most important processes in the chemical and petroleum
oxide, ZIFs are promising catalysts for the Knoevenagel refining industries [106]. To date, enormous efforts have been
condensation due to their high surface area and abundant made to developing ZIF-67 and its derivatives that are capable
active sites [102]. Phan et al. [103] reported the use of ZIF-67 of catalyzing the hydrogenation–dehydrogenation reactions,
as the catalyst for the preparation of benzimidazoles via the but the use of pure ZIF-67 as catalyst hardly been reported
cascade redox condensation of 2-nitroanilines with benzyl- owing to its low stability [107]. However, the use of ZIF-67 as
amines without any other oxidizing or reducing agents. The a precursor to generate ZIF-67 derivative has showed excellent
ZIF-67-catalysis transformation would yield 97% of product, catalytic performance for the hydrogenation–dehydrogenation
which is higher than other MOFs and many conventional ho- reaction. For example, Lin et al. [108] reported the use of ZIF-
mogeneous catalysts under identical reaction conditions, such 67 as a template precursor to produce Co3O4 rhombic

O Knoevenagel condensation
N
H
N

Fig. 14. The as-synthesized Zn@ZIF-67 as catalysts for catalyzing the Knoevenagel condensation of benzaldehyde and malononitrile. Reprinted with permission
from Ref. [104]. Copyright 2017 Springer.
 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15 13

N + H
Co2+ + HN Na —
NaBH4
H B H
H

Co3O4NPs

Hydrolysis

Carbonization
calcination
ZIF-derived
ZIF-67 Co3O4 (ZIFCoO)

Fig. 15. Schematic of the preparation of ZIF-67-derived Co3O4 (ZIFCoO) and application in the H2 generation from NaBH4 hydrolysis. Reprinted with permission
from Ref. [108]. Copyright 2018 Elsevier.

dodecahedral (RD) granule. The resulting ZIF-derived Co3O4 of Ni3N–Co3N catalyst in the hydrogenation reaction can be
(ZIFCoO) can facilitate NaBH4 hydrolysis to generate a large attributed to its porous and sheet-like structure.
number of H2 at a high rate of 1825 mL min1 g1 (Fig. 15).
The value was higher than those of ZIF-67, and commercial 4. Conclusions and outlook
Co3O4 NPs, which can be attributed to the low activation
energy (Ea) of ZIFCoO (Ea ¼ 39.4 kJ mol1). However, the In summary, this review mainly focuses on the recent de-
catalytic mechanism of ZIFCoO for H2 generation from velopments of controlled synthesis of ZIF-67-based materials
NaBH4 hydrolysis has not been explored. as heterogeneous catalysts. As mentioned above, ZIF-67-based
Shen et al. [109] developed a facile and efficient method to materials possess high surface area and stability, and abundant
synthesize Co@Pd core–shell nanoparticles by using ZIF-67- active sites, which make it an attractive option to explore
derived Co NPs as the sacrificial template to reduce noble various synthesis methods and applications over the past
metal ions (Pb2þ) via a galvanic replacement reaction. The decade. However, a general, environment-friendly, and low-
resulting Co@Pd/NC exhibited an unprecedented high activity cost synthetic strategy of ZIF-67-based materials is of high
in the hydrogenation of nitrobenzene, yielding 98% conver- value to meet their large-scale production. Furthermore, the
sion after 45 min's reaction, which was more active in hy- premises for the commercial application of ZIF-67-based
drogenation than the pristine ZIF-67 and other MOFs materials in heterogeneous catalysis are that they can be
supporting noble NPs under identical conditions. Moreover, produced via a simple and low-cost approaches, which meets
the as-synthesized Co@Pd/NC has good recyclability and can the requirements of being economical and environment-
be used for the hydrogenation of various substituted nitro- friendly. Overall, the low-cost and large-scale production of
arenes. However, the better catalytic performance in the hy- high-quality ZIF-67 and its derivatives are a pre-requisite for
drogenation of nitrobenzene over Co@Pd/NC should be their widespread application in heterogeneous catalysis.
further explored. Subsequently, Li et al. [110] developed an Therefore, the following aspects should be considered or
effective strategy to synthesize a noble metal@MOF yolk– improved in the future to realize the industrial production and
shell composite via the spontaneous phase transformation of catalytic application of ZIF-67-based materials. (i) The novel
ZIF-67 under solvothermal conditions and enabled the synthetic methods should be explored for the scale up of ZIF-
encapsulation of Pd NPs within the cavities of ZIF-8. The 67-based materials where the concentrated attention should be
resulting Pd@H–Zn/Co-ZIF nanoreactor exhibited superior focused on economically viable strategies without expensive
activity (> 80% conversion of acetylene) and selectivity or toxic solvents. (ii) The majority of ZIF-67-based materials
(> 80%) for catalyzing semi-hydrogenation of acetylene. are microporous regime (pore diameter < 2 nm), which re-
Recently, Fu et al. [111] reported the formation of 2-D porous stricts their applications involving large molecules due to the
Ni3N–Co3N hybrids by controlling growth of ZIF-67 on steric-hindrance effect. Therefore, it is highly desirable to
Ni(OH)2 sheets followed by nitration. The as-synthesized 2-D synthesize hierarchically porous ZIF-67-based materials with
porous Ni3N–Co3N showed excellent performance in the micro-, meso-, and macropores to improve diffusion rate and
conversion of p-nitrophenol (PNP) into p-aminophenol (PAP), reduce mass transfer resistance. (iii) The stability of ZIF-67-
which was superior to some noble-metal based catalyst such as based materials should be solved if they are to be applied in
Ag-NP/C and Ag/TiO2. The outstanding catalytic performance industrial applications such as chemical, thermal, and
14 C. Duan et al. / Green Energy & Environment 7 (2022) 3–15

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[27] Y. Xue, P. Xiang, H. Wang, Y. Jiang, Y. Long, H. Lian, W. Shi, J. Mol.
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