Advanced Materials - 2021 - Zhang

Progress Report
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Designing MOF Nanoarchitectures for Electrochemical

Water Splitting
Ben Zhang, Yijuan Zheng, Tian Ma, Chengdong Yang, Yifei Peng, Zhihao Zhou,
Mi Zhou, Shuang Li,* Yinghan Wang,* and Chong Cheng*
carrier with an extremely high energy

Electrochemical water splitting has attracted significant attention as a key density (approximately 142 MJ kg−1) and
pathway for the development of renewable energy systems. Fabricating zero-carbon content, has been regarded
efficient electrocatalysts for these processes is intensely desired to as a promising clean fuel.[1,2] In this
reduce their overpotentials and facilitate practical applications. Recently, context, electrochemical water split-
ting, which converts electricity into stor-
metal–organic framework (MOF) nanoarchitectures featuring ultrahigh able hydrogen, is a viable and efficient
surface areas, tunable nanostructures, and excellent porosities have solution to mitigate severe energy short-
emerged as promising materials for the development of highly active ages and greenhouse gas emissions.[3]
catalysts for electrochemical water splitting. Herein, the most pivotal Among these strategies, hydrogen and
advances in recent research on engineering MOF nanoarchitectures for oxygen evolution reactions, which occur
on the cathode and anode, respectively, in
efficient electrochemical water splitting are presented. First, the design of
a water electrolyzer, are considered as two
catalytic centers for MOF-based/derived electrocatalysts is summarized critical half-reactions of the water-split-
and compared from the aspects of chemical composition optimization and ting process.[4] Theoretically, water split-
structural functionalization at the atomic and molecular levels. Subsequently, ting requires a thermodynamic Gibbs free
the fast-growing breakthroughs in catalytic activities, identification of highly energy (ΔG) of approximately 237.2 kJ mol−1,
active sites, and fundamental mechanisms are thoroughly discussed. Finally, corresponding to a standard potential (ΔE)
of 1.23 V versus a reversible hydrogen
a comprehensive commentary on the current primary challenges and future electrode (RHE), which allows the ther-
perspectives in water splitting and its commercialization for hydrogen modynamically uphill reaction to occur
production is provided. Hereby, new insights into the synthetic principles in the electrolyzer.[5] However, the unfa-
and electrocatalysis for designing MOF nanoarchitectures for the practical vorable thermodynamics and resulting
utilization of water splitting are offered, thus further promoting their future large overpotential are the main barriers
to the scalable implementation of water
prosperity for a wide range of applications.
electrolysis for hydrogen generation.[6,7]
Currently, noble metal-based electro-
1. Introduction catalysts exhibit the most efficient activity for water splitting,
particularly Pt-based hydrogen evolution reaction (HER) cata-
Considering the rise in the number of global energy crises lysts and Ir/Ru-based oxygen evolution reaction (OER) cata-
and environmental concerns, it is crucial to develop green lysts.[8,9] Nevertheless, the scarcity and high price of precious
and sustainable energy resources to substitute nonrenewable metals severely impede their widespread use in commercial
sources, such as fossil fuels. Hydrogen (H2), as an energy water-splitting applications. Taking these limitations into
B. Zhang, Y. J. Zheng, Dr. T. Ma, C. D. Yang, Y. F. Peng, Z. H. Zhou, Dr. T. Ma
Prof. Y. H. Wang, Prof. C. Cheng West China School of Medicine/West China Hospital
College of Polymer Science and Engineering Sichuan University
State Key Laboratory of Polymer Materials Engineering Chengdu 610041, China
Sichuan University Dr. M. Zhou
Chengdu 610065, China College of Biomass Science and Engineering
E-mail: [email protected]; [email protected] Sichuan University
Chengdu 610065, China
The ORCID identification number(s) for the author(s) of this article
Dr. S. Li
can be found under https://doi.org/10.1002/adma.202006042.
Functional Materials
Department of Chemistry
© 2021 The Authors. Advanced Materials published by Wiley-VCH Technische Universität Berlin
GmbH. This is an open access article under the terms of the C
reative Hardenbergstraße 40, 10623 Berlin, Germany
Commons Attribution-NonCommercial License, which permits use, E-mail: [email protected]
distribution and reproduction in any medium, provided the original work
is properly cited and is not used for commercial purposes. Prof. C. Cheng
Department of Chemistry and Biochemistry
Freie Universität Berlin
DOI: 10.1002/adma.202006042 Takustraße 3, 14195 Berlin, Germany
Adv. Mater. 2021, 33, 2006042 2006042 (1 of 37) © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH
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consideration, developing non-precious alternatives with excel- comprehensive review summarizing MOF-based/derived mate-
lent activity and durability is a challenging but essential task. rials with well-defined synthetic methods, chemical composi-
As a new class of highly porous materials, metal–organic tions, nanostructured morphologies, electrocatalytic activities,
frameworks (MOFs) consisting of organic ligands and metal and reaction mechanisms is urgently needed to provide strong
ions or clusters have high crystallinity and long-range order.[10,11] inspiration and direct future developments in engineering MOF-
Owing to the intrinsic features of large surface areas, adjust- based/derived electrocatalysts for water splitting.
able chemical components, tunable pore structures, and diverse Herein, this new progress report provides pivotal advances
topologies, a large number of MOFs have been employed for and commentaries on recent research on engineering MOF
electrochemical water splitting.[12–17] Moreover, the properties of nanoarchitectures for efficient electrochemical water splitting.
MOFs can be improved or modified by coupling various func- First, the design of catalytic centers for MOF-based/derived
tional materials, including polyoxometalates (POMs), metal electrocatalysts is summarized and compared from the aspects
compounds, carbon nanotubes (CNTs), and other conductive of synthetic strategy, chemical composition optimization, and
substrates to form guests@MOFs or MOF/substrates.[18–22] The structural functionalization at the atomic and molecular levels
superior electrochemical performance of water splitting can be (Scheme 1). Second, we focus on the electrocatalytic performance
achieved from the combined advantages of more active sites and of MOF-based/derived materials for the HER, OER, and bifunc-
enhanced conductivity through functionalization. Additionally, tional catalysts. In particular, significant attention has been paid
the MOF-based skeleton allows the rearrangement of the ele- to summarize the fast-growing breakthroughs on the catalytic
ments at the molecular and atomic levels during pyrolysis. Thus, activity, identification of the highly active sites, and fundamental
MOFs or MOF-based composites can act as templates for the syn- mechanisms of MOF-based/derived electrocatalysts with unprec-
thesis of MOF-derived porous, carbon-based nanomaterials, such edented water splitting performance. Finally, we provide a compre-
as metals, metal compounds, and single-atom catalysts (SACs), hensive commentary on the current primary challenges and future
under thermal treatments. The pyrolysis of MOFs with ordered perspectives on the design and commercialization of MOFs and
calcination modulates various characteristics, such as conduc- their derived electrocatalysts for water splitting. We believe that
tivity and porosity, surface area, stability, and catalytic activity; this progress report may offer new insights into the synthetic prin-
hence, such derivatives are highly interesting for water split- ciples and electrocatalysis in designing MOF nanoarchitectures for
ting.[23–30] Based on these guidelines, diverse MOF-based/derived practical utilization in water splitting, thus further promoting their
materials have been reported in the past five years. However, a future prosperity for a wide range of applications.
Scheme 1. Illustration for the design of MOF nanoarchitectures for electrochemical water splitting.
2. Design of MOF-Based/Derived MOFs while retaining the original character of the structure; 2)
Electrocatalytic Materials the real active sites and the catalytic mechanism are difficult to
identify.
2.1. MOF-Based Electrocatalytic Materials Structural Design of Organic Ligands in Pristine MOFs: Another
way to adjust the characteristics of MOFs for electrocatalysts is
Owing to their high surface areas, controllable porous structures, to modify the chemical composition of the organic ligands. It
and diverse active metal sites or organic linkers, MOF-based has been theoretically and experimentally studied that UiO-66
electrocatalytic materials have been extensively investigated can be functionalized with single- and dual-functionalized
in the field of water splitting. In this section, recent advanced linkers (OH, NH2, or SH).[36] Syzgantseva et al. studied and
synthetic strategies of MOF-based electrocatalytic materials summarized the impact of the functional groups and scaffolds
as promising electrocatalysts are discussed in the sequence of of ligands in MOFs.[37] The influence of F, Cl, Br, I, OH, SH,
pristine MOFs, guest-encapsulated MOFs (guests@MOFs), and CN, NH2, NO2, SO3H, PO3H2, and NMe2 in MIL-125 were
substrate-modified MOFs (MOF/substrates). studied systematically. Meanwhile, for UiO-66, F, Cl, Br, I, OH,
SH, CN, NH2, and NO2 were considered. The results implied
that the electron-donating groups would boost the energy of
2.1.1. Pristine MOFs the ligand-centered states, whereas the electron-withdrawing
groups could facilitate the opposite effect. With the increase in
Much attention has been paid to the selection and optimi- the degree of conjugation in the organic ligand, MOFs could
zation of metal sites and organic ligands at an atomic level, have fewer electrons localized on it. These observations support
which is considered a powerful strategy to regulate the elec- the idea that the component design of organic ligands could
trocatalysis behavior of pristine MOFs. The component design adjust the electron structure of MOFs, subsequently optimizing
could readily modulate the physical and chemical properties the catalytic performance. Nevertheless, little attention has
of MOFs, such as electron structures, conductivity, bonding been paid to the modification of organic ligands by introducing
energy of the intermediates, and stability. The commonly used functional groups in the field of electrocatalysis due to the com-
strategies to optimize the catalytic performance of pristine plex and varying effects of the side group.
MOFs are introducing multivalent metal sites and heterome- Structural defects may offer opportunities to tune and opti-
tallic doping, incorporating functional groups into organic mize the performance of electrocatalysts because of the modu-
ligands, adsorbing multiple ions onto the organic ligands or lation of the electronic and geometric structures. Recent work
metal nodes, and immobilizing conjugated organic ligands in on missing linker defects of the UiO-66-type framework unam-
the skeletons. biguously demonstrated that structural defects mostly affect the
Structural Design of Metal Nodes in Pristine MOFs: Some local node geometry and, therefore, offer an alternative route
monometallic MOFs, such as Co-MOFs,[31] Cu-MOFs,[32] and to node modification.[38] Furthermore, Zheng et al. applied a
Zr-MOFs,[33] have witnessed rapid and significant develop- NaBH4 treatment to modulate the defect concentration to opti-
ment in electrocatalysis. Moreover, bimetallic and trimetallic mize the electrochemical performance.[39] It has been revealed
sites have shown catalytic activity in the OER. Zhao et al. that the defects created in MOFs will lead to redistributed elec-
designed and synthesized NiCo bimetal–organic framework tronic configurations, which may provide defective conducting
nanosheets (NiCo-UMOFNs) that achieved extraordinary elec- channels, thus resulting in enhanced OER catalytic activity.
trocatalytic activity toward the OER under alkaline conditions Additionally, the coordinatively unsaturated sites associated
(Figure 1Aa–d).[34] Among the four catalysts mentioned, the with organic linker defects could serve as catalytic sites and
NiCo-UMOFNs achieved a very low overpotential of 250 mV enhance the intrinsic activity of the catalytic sites. For instance,
at 10 mA cm−2 and a low Tafel slope (42 mV dec−1) in an N2- the missing ligands of Co2(OH)2(C8H4O4) (CoBDC) modified
saturated 1 m KOH solution (Figure 1Ae,f). Subsequent density the local coordination geometry of Co2+ and generated unsat-
functional theory (DFT) studies confirm that the high electrocat- urated Co2+ sites, achieving remarkable OER catalytic activity
alytic activity is attributed to the coordinatively unsaturated metal with an extremely low overpotential of 241 mV at 100 mA cm−2
center and the coupling effect between Co and Ni. Zhang et al. with Ni foam as the substrate.[14] From the above examples,
reported the facile ambient temperature synthesis of a unique the defect engineering of MOFs with a controllable density of
trimetallic MOF nanofoam (Figure 1Ba) with controllable molar defects is generally followed by electron localization, lattice dis-
ratios.[35] The transmission electron microscopy (TEM) image of tortion, and bond breaking and reforming, resulting in a larger
the (Ni2Co1)1−xFex-MOF-NF and high-resolution TEM (HRTEM) number of active sites. Nonetheless, several significant chal-
analysis after the OER are illustrated in Figure 1Bb,c. The over- lenges still exist: 1) high densities of defects may reduce electro-
potential values needed for different molar ratios to achieve a conductivity, thereby reducing the electrocatalytic activity; 2) it
current density of 10 mA cm−2 in 1.0 m KOH are summarized in is difficult to define the actual reactive sites due to the various
Figure 1Bd, in which (Ni2Co1)0.925Fe0.075-MOF-NF has the lowest types of defects.
overpotential (257 mV). The component design of metal nodes
is a simple and efficient strategy to purposefully introduce cata-
lytically active metal nodes into MOFs for various types of elec- 2.1.2. Guests@MOFs
trocatalysis and take advantage of the synergistic effect between
the multi-metal elements. However, challenges still need to be In many cases, due to the inherent defects of MOFs, such as
addressed: 1) it is difficult to introduce multiple metal nodes into poor conductivity and inferior functionality, pristine MOFs
Figure 1. A) a) Crystal structure of NiCo-UMOFNs. b) TEM, c) energy-dispersive X-ray spectroscopy (EDS) mapping, and d) high-angle annular dark-
field scanning transmission electron microscopy (HAADF-STEM) images of NiCo-UMOFNs, showing metal atoms (pink), light elements (blue), and
background (green). e) Linear sweep voltammetry (LSV) curves and f) Tafel plots of various catalysts. A) Reproduced with permission.[34] Copyright
2016, Springer Nature. B) a) Synthesis process and b) TEM image of hierarchical (Ni2Co1)0.95Fe0.05-MOF-NF (NF:Ni foam) c) HRTEM analysis after the
OER. d) The overpotential of different molar ratios at 10 mA cm−2. B) Reproduced with permission.[35] Copyright 2019, Wiley-VCH.
could not provide an ideal performance to meet the needs of MOFs can be regarded as essential materials to introduce active
electrocatalysts for practical industrial applications. Owing to guest species, such as metal nanoparticles,[20,40] metal com-
their well-defined pore structures and various organic linkers, plexes,[41–43] and POMs,[44] through covalent or noncovalent
bonds (electrostatic, π–π interactions, host–guest interactions). achieving improved electrochemical HER performance under
In many cases, the synergistic effect between the guests and both acidic and alkaline conditions (Figure 2Aa,b). As shown
MOFs could also improve the catalytic activity. in Figure 2Ac, X-ray absorption fine structure (XAFS) analysis
The immobilization of precious metals with functional demonstrated the dominant metallic state of Pt, and the result
supports could be an effective strategy to acquire excellent electro- of the Fourier transformation of the extended XAFS (EXAFS)
catalysts because of the desirable dispersity and regulated inter- (Figure 2Ad) indicated the possible strong interaction in the
faces.[45,46] Rui et al. prepared a 2D Ni-MOF@Pt hybrid with Ni-MOF@Pt. The as-prepared Ni-MOF@Pt exhibited excellent
well-defined interfaces via in situ deposition of Pt nanoparticles,[20] electrocatalysis behavior in 1 m KOH with an overpotential of
Figure 2. A) a) Schematic illustration for the preparation of the 2D MOF@Pt heterostructure. b) HRTEM image of 2D MOF@Pt hybrid nanosheets.
c) XANES and d) Fourier transform-EXAFS (FT-EXAFS) profiles of Ni-MOF@Pt, pure Pt nanoparticles, and Pt foil for the Pt LIII-edge. e) LSV curves and
f) corresponding Tafel slopes in 1 m KOH. A) Reproduced with permission.[20] Copyright 2019, American Chemical Society. B) a) Schematic represen-
tations of the syntheses of ZIF-8, FSZ-8, and FSWZ-8. b,c) FESEM images of FSZ-8 (b) and FSWZ-8 (c). d) LSVs of FSWZ-8 and FSZ-8 in 0.1 m KCl.
B) Reproduced with permission.[49] Copyright 2020, American Chemical Society. C) a) 3D POM-encapsulated metal–organic nanotube. b) Diagram of POM
linkage mode in a 1D POM-encapsulated metal–organic nanotube. c) LSV curves of the catalysts. d) Cycling stability tests of the catalysts. HUST-200
(X = P) and HUST-201 (X = As). C) Reproduced with permission.[44] Copyright 2018, American Chemical Society.
102 mV at 10 mA cm−2, outperforming that of the commer- nanoparticles with enhanced OER performance and stability
cial Pt/C (Figure 2Ae–f). The strong PtO covalent bonds in via the in situ etching of Cu–Ni nanostructures.[52] TEM/STEM
Ni-MOF@Pt are believed to enable ideal interfacial interaction images and EDS mapping showed no significant changes in
and facilitate the electron transfer of the Pt nanoparticles. This the structure and element distribution after the electrochemical
interface engineering method provides a broad prospect for measurements. In particular, Ni-Cu@Cu-Ni-MOF presented the
developing new functional MOFs and other 2D nanocompos- lowest overpotential at a current density of 10 mA cm−2 and the
ites with great potential for water-splitting applications. smallest Tafel slope of 98 mV dec−1. Notably, for the strategy to
The incorporation of base metal complexes into MOFs introduce electrocatalytic nanomaterials into MOFs, the locality
has been investigated to enhance the catalytic properties. and loading number of the functional materials must be regu-
Lin et al. reported that UiO-67 doped with [Ru(tpy)(dcbpy) lated and controlled meticulously to ensure the maximum utility
OH2]2+ (tpy = 2,2′:6′,2′-terpyridine, dcbpy = 5,5′-dicarboxy- of the active sites. The uniform dispersion of the guest materials
2,2′-bipyridine) via coordination bonds for electrochemical inside the MOF nanocrystals could significantly shorten the
water oxidation achieved a high turnover frequency (TOF) and charge transfer distance and facilitate the catalytic reaction.
good electrochemical stability in a buffered solution (pH = 7).[47] In brief, loading functional materials inside MOFs is a prom-
Meanwhile, the strategy to incorporate metal complexes into ising strategy to yield heterogeneous catalysts with high activity
MOFs, such as porphyrins and phthalocyanines, could fur- and stability. The confined materials could serve as the active
ther improve the stability under the highly oxidative environ- sites and deliver outstanding catalytic functionality, and uniform
ment in OER catalysis, thus guaranteeing efficient and stable dispersion of the guest materials inside the MOF crystals could
catalytic performance. For instance, the Co-tetramethoxyphenyl significantly shorten the charge transfer distance and facilitate the
porphyrin has been incorporated into the cavity of ZIF-8 via catalytic reaction. However, because organic ligands can partition
host/guest interaction and functions as a high-performance the metal nodes of MOFs and guest nanoparticles, the interaction
bifunctional electrocatalyst for both the OER and oxygen reduc- between the encapsulated metal nanoparticles and MOFs is weak.
tion reaction (ORR). The strong interactions between the guest Strengthening the interaction between the host and guest (such as
molecule and ZIF-8 host ensure excellent structural and elec- the PtO and CuO covalent bonds mentioned above) is the key
trochemical stability.[48] to enhancing the structural stability and catalytic activity.
Recently, the metal–salen complex, one of the closest analogs
to metal porphyrin complexes, has also received increasing atten-
tion for OER catalysis. The Fe–salen complex and POM co-loaded 2.1.3. MOF/Substrates
ZIF-8 have been reported as electrocatalytically active OER mate-
rials. The synthesis of ZIF-8, [Fe(salen)(OH)]@ZIF-8 (FSZ-8), and Functional materials as substrates to support MOFs are another
([Fe(salen)(OH)]+H4[SiW12O40]·HCl)@ZIF-8 (FSWZ-8) is shown way of introducing functional materials into pristine MOFs.
in Figure 2Ba.[49] Figure 2Bb,c presents the field emission SEM Quite a few MOFs have been assembled onto various sub-
(FESEM) images of FSZ-8 and FSWZ-8, respectively. The LSV strates as building blocks; this not only endows more expo-
of FSWZ-8 and FSZ-8 (Figure 2Bd) demonstrates that FSWZ-8 sure to the active sites of the catalysts but also improves the
could achieve a higher water oxidation current than FSZ-8 under conductivity of the MOFs. For instance, Duan et al. prepared
the same potential, proving the benefits of the strong interactions ultrathin nanosheet arrays of 2D MOFs on various supports
between the co-encapsulated Fe–salen and POM. through a facile route of one-step chemical bath deposition,
POMs are highly soluble inorganic nanoclusters com- showing superior performance for the OER, HER, and overall
posed of polyanion clusters and counter cations, which can be water splitting.[53] An NiFe-MOF with the presence of Ni foam
immobilized in the pores of MOFs via covalent or noncovalent (NF) as substrates demonstrated the best OER performance in
bonds to serve as different kinds of active sites for many cata- a 0.1 m KOH electrolyte, achieving an overpotential of 240 mV
lytic reactions.[50,51] Mukhopadhyay et al. reported an efficient at 10 mA cm−2 and a small Tafel slope of 34 mV dec−1.
and robust OER catalyst in neutral pH through the encapsula- Recently, Cheng et al. reported a lattice-strained NiFe-MOF
tion of [CoW12O40]6− inside the pores of ZIF-8. Moreover, POM nanosheet array with foamed Ni as a substrate synthesized
(X2W18O62, X = P/As)-encapsulated metal–organic nanotubes, through a low-temperature hydrothermal approach, exhib-
[CuII6(pzta)6(bpy)3(X2W18O62)]·2H2O, were synthesized as iting excellent electrocatalytic performance as a bifunctional
shown in Figure 2Ca,b.[44] These two types of POM-encapsulated oxygen electrocatalyst.[54] The mechanism of lattice expansion
MOF with CuO covalent bonds show high activity and sta- of NiFe-MOF under ultraviolet light is shown in Figure 3Aa.
bility toward the HER under acidic conditions (Figure 2Cc,d). Ultraviolet treatment leads to the enlargement of the inter-
In particular, the best catalyst achieved a relatively low overpo- layer of the lattice-strained NiFe-MOF from 11.6 to 12.1 Å
tential of 131 mV to reach a current density of 10 mA cm−2. It (Figure 3Ab,c). Lattice-strained NiFe-MOFs exhibit extraordi-
has also been reported that POMs can migrate within MOFs nary OER and ORR activities, achieving comparable activity to
if induced by thermal treatment.[21] Additional investigation is RuO2 and Pt/C (Figure 3Ae). Notably, the 4.3%-MOF catalyst
required to insert other types of POMs to explore their effects shows mass activity of 2000 and 3100 A gmetal−1 at overpoten-
on the HER or OER catalytic activities. tials of 300 and 400 mV, respectively, which are significantly
Bimetallic alloys or core–shell nanoparticles on MOF sub- higher than those of commercial RuO2 and pristine NiFe-MOF
strates are promising catalysts because they typically pre- (Figure 3Af). The catalyst also exhibited superior Faradaic effi-
sent higher catalytic activity than their monometallic coun- ciency and desirable stability after 200 h of continuous OER
terparts. Ma et al. synthesized MOF-encapsulated bimetallic (Figure 3Ag). As illustrated in Figure 3Ad, the improvement
Figure 3. A) a) Schematic diagram of the crystal structure change of NiFe-MOF under ultraviolet light. b) HRTEM (top) and SEM (bottom) images of
the pristine and 4.3%-MOFs. Scale bars represent 5 nm for HRTEM and 200 nm for SEM. c) Ni K-edge FT-EXAFS spectra of lattice-strained NiFe-MOF.
d) Schematic representation of the electron exchange for the lattice-strained MOF. e) LSV curves and f) mass activity of the OER. g) OER stability for
RuO2 and the 4.3%-MOF and OER Faradaic efficiency of the 4.3%-MOF. h) OER catalytic mechanism of the lattice-strained MOFs. A) Reproduced with
permission.[54] Copyright 2019, Springer Nature. B) a) A schematic illustrating the synthetic procedures for NiCo-MOF/rGOAS. b,c) SEM images of
NiCo-MOF-coated Ni-mesh (b) and the nanoflocks of NiCo-MOF (c). d) HER LSV curves and e) Tafel plots in 0.1 m KOH. B) Reproduced with permis-
sion.[18] Copyright 2018, Royal Society of Chemistry.
in the OER and ORR catalytic performance of the NiFe-MOF the HER performance (Figure 3Bd,e). The physicochemical
may be ascribed to the change in the electron structure driven interactions between the rGOAS and NiCo-MOF, as well as its
by the tensile lattice strain. The OER catalytic mechanism dia- unique architecture, guarantee excellent electroconductivity,
gram in Figure 3Ah shows that NiFe-MOF undergoes a quick mass transport of the electrolyte, and high exposure of the
and efficient four-electron pathway for oxygen electrocatalysis, active sites, subsequently leading to a superior HER catalyst.
for either the ORR or OER, as the key intermediates superoxide Growing the MOF on the substrate can not only inherit the
*OOH species emerge on the high-valence Ni4+ active sites. advantages of pristine MOFs but also provide a flexible and
Khalid et al. reported a bimetallic NiCo-MOF that was effective strategy to increase the macro- or mesoporosity for
directly grown on Ni-mesh and wrapped by a graphene oxide mass transport and facilitate the exposure of active sites during
aerosol skeleton, providing a highly available active surface area electrocatalysis. Moreover, attaching MOFs to high-conductivity
and showing improved electrocatalytic activity for the HER in substrates may overcome the limited electrical conductivity of
an alkaline medium (Figure 3Ba).[18] Figure 3Bb,c shows that pristine MOFs. Nonetheless, MOF/substrates catalysts are still
NiCo-MOF was homogeneously grown on the Ni-mesh. The in their infancy, and some underdeveloped issues still need
catalytic performance apparently increased owing to the elec- to be resolved: 1) hybridization with substrates may block the
tronic coupling between NiCo-MOF and rGOAS and the Ni- intrinsic micropores of the MOFs, resulting in poor mass trans-
mesh substrate, ensuring a strong electron transfer within the port; 2) it is critical to design MOF/substrates catalysts with
composite. The LSV curves and Tafel values suggested that the enhanced stability in aqueous media, particularly in acidic and
rGOAS-covered nanoflocks led to a profound improvement in basic media.
In summary, pristine MOFs can theoretically be employed 2.2. MOF-Derived Electrocatalytic Materials
as electrocatalysts to maximize the electrocatalytic surface
area and precisely adjust the active sites straightforwardly by Since the research of MOF-5 calcined into carbons was first
the rational selection and modification of the organic ligands reported in 2008,[55] carbon-based materials derived from
and metal nodes. For example, incorporating nonbridging MOFs, featuring high conductivity and well-dispersed cata-
ligands into the MOF could significantly improve the elec- lytic sites, have been increasingly employed as highly efficient
trocatalytic performance. Converting bulk MOF crystals into electrocatalysts. During the pyrolysis of the MOF synthesis,
2D nanosheets could also enable a higher exposure of the the organic linkers are converted to a highly porous graphitic
active surface sites. Designing bimetallic MOFs may further carbon matrix, and the metal nodes transform into metal com-
optimize the electrocatalytic performance for water splitting pounds, alloys, or single-atom dopants in carbon materials.
because of the synergistic effect between the multi-metal Herein, the design strategies of MOF-derived carbon-based
elements. Nevertheless, the inferior conductivity, controver- catalysts are presented in detail.
sial stability, and generally poor activity of MOFs hinder the
extensive development of pristine MOFs for electrocatalysis.
Synthesizing the π-conjugated structure with transition metal 2.2.1. MOF-Derived Metal-Free Carbon Electrocatalysts
atoms and aromatic organic ligands as precursors could also
provide a promising pathway to achieve highly conductive Carbon materials with heteroatomic dopants (e.g., B, N, P, S,
MOF-based electrocatalysts. etc.) have drawn increasing attention because of their high
Furthermore, benefiting from the tunable pore structures of conductivity, erosion resistance, and excellent catalytic perfor-
the MOFs, functional nanomaterials, such as metal nanoparti- mance. Some reports have proved that metal-free carbon nano-
cles, metal complexes, and POMs, can be encapsulated inside materials can catalyze the OER[56,57] and HER.[58,59] Recently,
MOFs to form guest@MOFs. The resulting MOF nanocom- MOFs have been regarded as ideal templates for producing
posites can always achieve multifaceted catalytic activity or sig- carbon nanomaterials owing to their large surface area, high
nificantly improved conductivity. In many cases, the synergistic conductivity, and affordable price. Heteroatom-containing
and strong interactions between the guests and MOFs could MOFs can be employed as precursors to obtain metal-free
further enhance the catalytic performance. Meanwhile, the uni- carbon-based electrocatalysts by carbonization. Lei et al. dem-
form dispersion of the guest materials inside the MOF crystals onstrated that MOF-derived N- and O-doped carbon materials
could improve the stability of the catalysts. For MOF/substrates, could be utilized for the electrochemical splitting of water. This
the functional materials serve as substrates that generally con- bifunctional catalyst was prepared by calcinating the ZIF-8 pre-
tribute to the dispersion and stability of the MOFs and may also cursor, followed by the electrochemical activation of the cata-
improve the electrical conductivity in many cases. lytic sites (Figure 4a).[60] As revealed by energy-dispersive X-ray
Figure 4. a) Schematic of the fabricated carbon electrocatalysts. b) EDX elemental maps of ZIF-8-C6. c) HER and d) OER LSV polarization curves.
e) Photograph of the electrolyzer using ZIF-8-C6 as the HER electrocatalyst and ZIF-8-C4 as the OER electrocatalyst. a–e) Reproduced with permission.[60]
Copyright 2018, Royal Society of Chemistry.
spectroscopy (EDX), N and O were uniformly dispersed and sites (Ru-HPC, Ru-decorated hierarchically porous carbon)
anchored in the MOF-derived porous carbon matrix (Figure 4b). with bimetallic CuRu-MOFs serving as templates for highly
The excellent electrocatalysis behavior could be attributed to efficient hydrogen evolution (Figure 5Aa,b).[70] As revealed by
the modulated N- and O-containing surface groups caused by X-ray diffraction (XRD) patterns (Figure 5Ae), the less active Cu
the electrochemical activation (Figure 4c–e). The carbonaceous species of CuRu-C were etched by an FeCl3 solution to achieve
materials with heteroatomic dopants can also be synthesized by Ru-HPC. Meanwhile, the results of Brunauer–Emmett–Teller
the calcination of MOFs with a highly porous nature and con- (BET) surface areas and TEM images revealed that abundant
trollable nanostructures under certain atmospheres, like NH3, meso- and macropores were generated in situ (Figure 5Ac,d).
H2S, and PH3 gases.[23,61,62] For instance, Liu et al. reported Remarkably, Ru-HPC presented desirable catalytic activity for
an efficient trifunctional electrocatalyst with N- and P-doping the HER, outperforming the commercial Pt/C by achieving a
synthesized by the calcination of MOF precursors under a PH3 current density of 25 mA cm−2 at an overpotential of 22.7 mV
atmosphere.[63] (Figure 5Af).
For the synthesis of heteroatom-doped carbons with organic Metal alloy nanomaterials, including FeNi,[82,83]
ligands containing heteroatoms as precursors, heteroatom FeCo, [84–86] [87] [88,89]
IrCo, and CoNi alloys, can also be obtained
doping will be more uniform, but the design of appropriate from MOFs by pyrolysis for application in the field of electrocat-
precursors is more complex. Using certain gas environments alysts. Recently, Zhang et al. reported FeCo bimetallic N-doped
(e.g., NH3, H2S, and PH3) as an external heteroatom source is porous carbons (FeCo-C/N) obtained from the calcination of
a feasible and straightforward strategy, but the dispersion of yolk–shell-structured ZIFs.[84] The obtained FeCo-C/N exhibited
the heteroatoms is relatively poor. To date, MOF-derived carbon excellent ORR performance and good OER activity because of its
materials for electrochemical water splitting have rarely been unique structural and compositional features. Xu et al. reported
reported, which may be caused by the limited intrinsic electro- a self-template approach to preparing open carbon cages with
catalytic of these metal-free sites. It is still a great challenge to a hydrangea-like superstructure by the morphology-controlled
design MOF-derived metal-free carbon materials with excellent thermal transformation of core@shell MOFs.[85] The direct calci-
electrochemical water splitting performance. nation of core@shell Zn@Co-MOFs could be used to construct
well-defined open-wall carbon cages. However, the introduction
of guest Fe3+ ions into the Zn@Co-MOF precursor will lead to
2.2.2. Metal- and Alloy-Doped Carbon Electrocatalysts the self-assembly of open carbon cages into a hydrangea-like 3D
superstructure connected by CNTs, which are grown in situ on
In recent years, metals and alloy nanoparticles supported by the Fe–Co alloy nanoparticles formed during the calcination of
heteroatom-doped carbon materials have become a thriving Fe-doped Zn@Co-MOFs. The as-prepared composite exhibits
topic for designing highly efficient electrocatalysts.[64,65] excellent performance as an air cathode catalyst in a Zn–air bat-
Through the pyrolysis of MOFs in the presence of carbon or tery owing to its unique superstructure.
external reductive agents, metal ions around organic ligands Xiong et al. reported a group of optimized bimetallic
(e.g., Co, Ni, and Fe ions) could be reduced in situ to metal or MOF-derived Co–Fe alloys trapped within the carbon nanocom-
alloy nanoparticles encapsulated in a heteroatom-doped carbon posites via a combination of the typical self-assembly of MOFs
frame, which exhibits excellent catalytic performance and sta- and a guest–host method.[86] Among them, Zn6Co has been
bility owing to its highly adjustable metal composition and proven to be a compositionally optimal precursor for synthe-
robust carbon structure.[66–71] As representatives of MOFs, there sizing bimetallic nanoparticle-carbon composite materials with
are many reports about zeolite imidazole frameworks (ZIFs) the incorporation of external Fe (Figure 5Ba,b). As revealed by
as precursors to prepare metal-nitrogen-carbon electrocata- STEM and EDX spectroscopy (Figure 5Bc–f), Co0.9Fe0.1 bime-
lysts,[24,72–81] for instance, the porous cage structure of N-doped tallic nanoparticles, with a uniform distribution of Co and Fe
carbon nanotubes (NCNTs) synthesized via the simple pyrolysis and a Co/Fe ratio of 9:1, were uniformly dispersed and anchored
of polyhedral ZIF-67 particles.[72] Thus, enhanced electrocata- in the MOF-derived porous carbon matrix. The resulting nano-
lytic performance and durability for the ORR and OER were composite exhibited excellent stability after 30 000 cycles in
observed, which were mainly attributed to the synergistic effect alkaline solution due to its compositional and structural integ-
between the N dopants and restricted Co nanoparticles in the rity (Figure 5Bg).
CNTs, the NCNTs structure, and the rugged porous cage struc-
ture. Li et al. developed a series of Co/Zn bimetallic zeolitic
imidazolate frameworks (BMZIF) that served as precursors to 2.2.3. Metal-Compound-Doped Carbon Electrocatalysts
synthesize porous carbon nanomaterials loaded with Co nano-
particles (Co@NC-x/y) and exhibited exceedingly high activity Monometallic-Compound-Doped Carbon Electrocatalysts: Mono-
for bifunctional oxygen electrocatalysis.[73] Recently, Wang et al. metallic compounds, including metal carbides,[90,91] oxides,[92,93]
reported a 2D dual-metal (Co/Zn), leaf-like ZIF-pyrolysis rou- nitrides,[94] phosphides,[25,95–100] and chalcogenides,[101–103] can
tine for scalable preparation to encapsulate Co nanoparticles be directly synthesized from the pyrolysis of MOFs. Recently,
within N-doped CNTs.[74] The resultant Co-N-CNTs were shown by making use of the unique characteristics of highly and uni-
to be excellent bifunctional air electrodes for primary and formly dispersed metal nodes and the suitable thermostability
rechargeable Zn–air batteries. Noble-metal electrocatalysts can of MOFs, Deng et al. reported an efficient Bi2O3@C catalyst,
also be synthesized using MOFs as precursors. Qiu et al. synthe- which was prepared by an oxidation treatment after the carbon-
sized Ru-based electrocatalysts that exposed massive Ru active ization of Bi-based MOFs.[93]
Figure 5. A) a) Schematic diagram of the approach to form Ru-HPC. b) SEM and c) TEM images of the Ru-HPC. Inset: ultrafine Ru nanoparticles.
d) The N2 adsorption/desorption isotherms of Ru-HPC and CuRu-C. Inset shows the corresponding pore size distributions for Ru-HPC and CuRu-C.
e) XRD patterns of Ru-HPC and Ru-C. f) HER polarization curves of the catalysts in 1 m KOH solution. A) Reproduced with permission.[70] Copyright
2019, Elsevier Ltd. B) a,b) SEM images of pyrolyzed BMOF_Zn6Co (a) and Zn6Co_Fe (b). c) STEM image and the corresponding EELS elemental maps
of Co (red), Fe (green), and the composite map (Co vs Fe). d) Low-magnification STEM image of BMOF. e) Atomic-scale STEM image of a Co0.9Fe0.1
nanoparticle with five subregions on the [110] zone axis. Inset: the corresponding Fourier transform with five pairs of {111} diffraction spots. f) STEM-
EDX spectrum with Fe Kα and Co Kα,β edges. g) EDX patterns of BMOF before and after 30 000 cycles. B) Reproduced with permission.[86] Copyright
2019, American Chemical Society.
In addition to the optimal pyrolysis time and temperature, particles can be synthesized. Lou et al. reported the facile syn-
suitable ligands play a critical role in forming metal compounds. thesis of biphasic carbide nanocrystals composed of MC and
For example, Cu3P/CNS composites were directly prepared by M2C (M = Mo or W) confined in porous N-doped carbon dodec-
annealing the MOPF, whose ligand contained the P atom.[98] ahedrons (PNCDs) by annealing functional ZIF-8 containing
However, additional heteroatom-containing sources are usually molybdate or tungstate, as illustrated in Figure 6Ba.[90] The
necessary to prepare metal phosphides, nitrides, and chalcoge- TEM images (Figure 6Bb,c) and XRD pattern (Figure 6Bd) show
nides. Kang et al. fabricated 3D and mesoporous Co3N@AN-C the presence of ultrafine nanocrystals for MoC-Mo2C. Further-
nanocubes (NCs) using in situ nitridation and calcination pro- more, the strong coupling interactions between MC and M2C
cesses under an N2 (200 sccm)/NH3 (10–100 sccm) atmosphere afford favorable sites for both water dissociation and hydrogen
via a Prussian blue analog (PBA) of Co3[Co(CN)6]2 NC precur- desorption, which endows dual-phased carbide nanocrystals
sors (Figure 6Aa,b).[94] The TEM images (Figure 6Ac,d) and with much better catalytic activity than that of the single-phase
X-ray photoelectron spectroscopy (XPS) profiles (Figure 6Ae) MC or M2C (Figure 6Be–g).
illustrate the successful formation of mesoporous Co3N@AN-C Multiple-Metal-Compound-Doped Carbon Electrocatalysts:
NCs, which demonstrate excellent OER activity (Figure 6Af). MOF-derived bimetallic compounds may exhibit superior cat-
By pyrolyzing the MOFs with external precursors to provide alytic activities compared to their monometallic counterparts
metal ions, a carbon matrix with encapsulated metal compound due to the strong synergistic effects that overcome the sluggish
Figure 6. A) a) Schematic diagram of the synthesis process for Co3N@AN-C NCs. b) SEM images of Co3[Co(CN)6]2 PBA. c) Normal- and d) high-
magnification TEM images of Co3N@AN-C NCs (inset image is the fast Fourier transform patterns). e) Co 2p XPS profiles of the Co3N@AN-C NCs.
f) IR-corrected OER LSV recorded in 1 m KOH solution. A) Reproduced with permission.[94] Copyright 2019, Tsinghua University Press/Springer Nature.
B) a) Schematic illustration of the MC-M2C/PNCDs. b) TEM and c) HRTEM images of MoC-Mo2C/PNCDs. d) XRD patterns of MoC-Mo2C/PNCDs.
e) LSV curves. f) Comparison of onset overpotential and the overpotentials at 10 and 100 mA cm−2, and g) Tafel slopes of MoC/PNCDs, MoC-Mo2C/
PNCDs, and Mo2C/PNCDs (insets: histograms of exchange current density). B) Reproduced with permission.[90] Copyright 2019, Wiley-VCH.
kinetics of multiple electron transfer processes. Directly employed CoMo-MOF as the precursor to synthesize a mag-
annealing bimetallic MOF precursors is a common approach netically functionalized Co2Mo3O8@NC-800 consisting of
to prepare bimetallic compounds.[104–109] Lou et al. designed highly crystallized Co2Mo3O8 and ultrathin N-rich carbon via
Ni-doped FeP/C hollow nanorods with Ni–Fe bimetallic an NaCl-assisted pyrolysis strategy (Figure 7Aa).[109] According
MIL-88A as the template and phytic acid as the etching agent to the XRD results, Co2Mo3O8@NC-800 presents a hexagonal
and phosphorus source.[105] The optimized hollow nanorods crystal structure with the space group P63mc (Figure 7Ab).
obtained via the pyrolysis process exhibited pH-universal HER The successful formation of Co2Mo3O8 with high crystal-
activity. XPS and DFT calculations attributed the efficiency to linity was confirmed by atomic-scale STEM (Figure 7Ac,d).
the synergistic modulation of the active components and the Besides, the magnetic and theoretical calculation results
structural and electronic properties. Recently, Ouyang et al. reveal that Co2Mo3O8 with Td Co2+ (high spin, t23e4) atoms as
Figure 7. A) a) Illustration of fabricated Co2Mo3O8@NC. b) Refined XRD profile of Co2Mo3O8@NC-800. c,d) HAADF-STEM images of Co2Mo3O8@
NC-800. Inset of (d): corresponding FFT pattern for Co2Mo3O8. e) Computed free energy diagram of Co2Mo3O8 with Td Co2+ as the active adsorption
sites at U = 0.00 V. f) LSV curves in 1.0 m KOH. A) Reproduced with permission.[109] Copyright 2020, Wiley-VCH. B) a) Schematic representation of the
preparation process and b) aberration-corrected HAADF-STEM image for RuIrOx nanonet-cages. Scale bar: 10 nm. c) Normalized Ru K-edge and d) Ir
L3-edge XANES spectra of RuIrOx were measured at different electrode potentials during the HER process in an alkaline medium. e) ECSA of different
catalysts. f) Comparison of the ratios of an effective surface between the loaded nanoparticle and the 3D open nanonet-cage structures. B) Reproduced
under the terms of the CC-BY Creative Commons Attribution 4.0 International License (https://creativecommons.org/licences/by/4.0).[114] Copyright
2019, The Authors, published by Springer Nature.
the active sites are beneficial to the rate-determining step to operando XAS results confirmed that ZnO could be etched in
form *OOH, consequently enhancing the OER performance situ during the HER process, while the provided RuIr alloy
(Figure 7Ae,f ). acted as the active sites (Figure 7Bc,d). The DEH method
A solvothermal reaction is a facile synthesis strategy for might significantly enhance the electrochemically active sur-
introducing metal ions into the precursor, which is further face area (ECSA) by providing a porous nanocage with a large
converted to multimetallic, compound-doped carbons through number of exposed active sites and the 3D availability of sub-
a post-annealing process.[26,110–115] Li et al. reported a novel strate molecules, as shown in Figure 7Be,f. Recently, Guo et al.
dispersing-etching-holing (DEH) approach to fabricate the reported a new strongly coupled NiCoN/C hybrid nanocage.[115]
3D open nanonet-cage electrocatalyst (Figure 7Ba,b).[114] The First, ZIF-67 and Ni(NO3)2 were used to synthesize NiCo LDH
nanoboxes via a chemical etching method under sonication. SACs via thermal treatment.[125,126] Li et al. developed a simple
Then, the nanoboxes were chemically converted into strongly method to create atomic-dispersed Fe–N4 active sites embedded
coupled NiCoN/C hybrid nanocages by a low-temperature into carbon phases, which are synthesized by the carboniza-
thermal ammonolysis treatment. The mass activity of the cata- tion of ZIF-8 precursors (Figure 8a).[125] Benefiting from this
lyst in the 1.0 m KOH electrolyte was 0.204 mA µg−1 at an over- method, researchers can fine-tune the Fe–N4 site structure and
potential of 200 mV. density while maintaining the carbon matrix and N doping.
Furthermore, through the pyrolysis of MOF precursors, Upon pyrolysis and etching, SACs can be obtained using
complex metal compounds with multiple nanostructures and bimetallic MOFs as the precursor.[127–130] For a facile adsorp-
compositions can be obtained.[116–122] Liang et al. synthesized tion strategy, engineering the structure and composition of the
bifunctional Co-NC@Mo2C complex catalysts that showed excel- carbon substrates is typically recognized as the focus of future
lent catalytic performance for overall water splitting with a low research.
cell voltage of 1.685 V at 10 mA cm−2.[119] The superior HER and A single-atom Ni electrocatalyst was designed using bime-
OER performance could be ascribed to the synergistic effects tallic MgNi-MOF-74 as a precursor (Figure 8b).[127] It is worth
of Mo2C and Co-NC. Remarkably, the coating structure of noting that the spatial distance of adjacent Ni atoms can be
Mo2C not only protects the electrolyte erosion of Co nanopar- extended by introducing Mg2+ ions into MgNi-MOF-74. The
ticles but also provides more catalytic sites. A recently reported N coordination numbers of single-atom Ni catalysts could be
Ru-modified Co-based electrocatalyst, which was anchored in an adjusted and controlled by regulating the pyrolysis tempera-
N-doped carbon (NC) matrix and presented a rationally designed ture. The pyrolysis-etching strategy is regarded as one of the
Mott−Schottky heterostructure (RuO2/Co3O4-RuCo@NC), most facile strategies. However, low metal loading resulting
achieved outstanding activity and stability for overall water split- from the activation process and a limited number of precursors
ting under strongly acidic conditions.[121] RuO2/Co3O4-RuCo@ are the disadvantages of the strategy.
NC was synthesized via a three-step process: pyrolysis of Another commonly used strategy for synthesizing SACs is
Co-MOF, galvanic replacement reaction between Co and Ru, the MOF-assisted host–guest strategy.[27,131–139] Typically, the
and controlled partial oxidation. Notably, the composite with extra metal precursor was encapsulated in the cavity or skeleton
rich metal–semiconductor interfaces obtained by partial oxida- of the MOF, and the pyrolysis process was performed to obtain
tion could promote the charge-transfer process; thus, the cata- the SACs. Recently, Xiong et al. reported single-atom dispersed
lytic performance would be further improved. Rh embedded on N-doped carbon (SA-Rh/CN) with favorable
In brief, for the design of MOF-derived metal-based elec- electrocatalytic performance. ZIF-8 with molecular-scale cavities
trocatalysts, choosing the appropriate MOF precursors is a was used as a precursor for the substrate to disperse and anchor
commonly adopted strategy. For instance, directly annealing Rh(acac)3 because the size of Rh(acac)3 (9.36 Å) is between that
bimetallic MOF precursors is a common approach to prepare of the large holes (diameter of 11.6 Å) and small pores (diameter
bimetallic compounds. The advantages of this strategy are that of 3.4 Å) of ZIF-8. Thus, Rh(acac)3 could be immobilized within
it is simple to adjust the proportion of the metal elements, and the molecular cages of ZIF-8 (denoted Rh/ZIF-8), which was
the resulting catalysts can be evenly dispersed on the carbon reduced in situ to synthesize SA-Rh/CN by pyrolysis (Figure 8c).
substrates, resulting in excellent catalytic performance. Manip- The spatial distribution and structure of the Rh species were
ulating the conversion conditions and the introduction of addi- elucidated by AC HAADF-STEM images and XAFS spectros-
tional precursors can also be employed to regulate the chemical copy (Figure 8d–f). The host–guest strategy could effectively
composition of MOF-derived metal-based electrocatalysts. This restrain the migration of the metal species during calcination.
strategy is applied widely, but it is difficult to adjust the ratio Nevertheless, mononuclear, metal-based guests with appropriate
of the components accurately. Indeed, these strategies are used sizes below those of the MOF pores should be considered.
simultaneously in many cases to obtain excellent electrocata- Recently, Fan et al. synthesized Ni-based SACs (A-Ni-C) with
lytic activity and stability. graphitized carbon materials.[140] The A-Ni-C was produced
by the carbonization of a Ni-MOF, followed by HCl etching
and electrochemical activation (Figure 9Aa). The presence of
2.2.4. Metal-Based Single-Atom Catalysts single Ni atoms was elucidated by HAADF STEM imaging
and XRD (Figure 9Ab,c). The A-Ni-C electrocatalysts exhib-
With high catalytic activity, selectivity, and maximum metal ited significantly improved HER performance after electro-
atom utilization efficiency, single-atom catalysts (SACs) have chemical activation, which could remove the Ni nanoparticles
drawn considerable attention in the field of catalysis. However, protected by graphitic carbons and create single-atom Ni sites
under realistic reaction conditions, the isolated atoms can easily (Figure 9Ad). Moreover, the host is crucial to the design of
migrate and aggregate into nanoparticles, owing to the high SACs because it influences the space and electronic environ-
surface energy of the monatomic catalysts. To overcome this ment of the metal center.[141]
problem, MOFs have become promising precursors to develop Besides the carbon frameworks, a variety of metal crys-
SACs owing to their porous structures and precisely designable tals doped with single-metal sites have also been identified
components. The direct pyrolysis of MOFs is a facile strategy to as promising SACs for electrochemical water splitting.[142,143]
synthesize SACs.[123,124] Recently, other strategies have also been Recently, Lou et al. reported a series of metal-atom-doped Co3O4
reported. nanosheets for efficient OER using MOF precursors.[143] These
MOF-derived N-doped carbon is an effective scaffold for novel electrocatalysts were fabricated by a cooperative etching-
the adsorption of metal ions and the subsequent formation of coordination-reorganization approach with ZIF-67 nanoplates.
Figure 8. a) Schematic diagram of the model systems constructed by adsorbing Fe onto N-doped carbon. b) Diagram illustrating the fabrication
of NiSA-Nx-C catalysts. c) Schematic image illustrating the synthesis of SA-Rh/CN. d) AC-HAADF-STEM image and corresponding Z-contrast anal-
ysis. e) FT-EXAFS spectra of SA-Rh/CN and reference samples. f) Experimental Rh K-edge XANES spectra of SA-Rh/CN and reference samples.
a) Reproduced with permission.[125] Copyright 2019, Wiley-VCH. b) Reproduced with permission.[127] Copyright 2019, Wiley-VCH. c–f) Reproduced with
permission.[138] Copyright 2020, The Authors, published by Springer Nature.
Remarkably, the Fe-doped Co3O4 nanosheets exhibited superior catalytic activities of MOF-derived SACs in both the HER and
OER activity with an overpotential of 262 mV at 10 mA cm−2, OER. For instance, DFT calculations have been extensively used to
which is comparable to that of commercialized noble-metal OER investigate the coordination environment of catalysts and reaction
catalysts. mechanisms and to analyze and design the active sites for electro-
Significant progress has been achieved toward the design of chemical reactions. Mohajeri et al. investigated a single transition
SACs for electrochemical catalysis, as summarized in Table 1, metal from 3d atoms (TM/B36, TM = Sc–Zn) with finite-sized B
including SACs from MOF precursors. However, a relatively clusters, B36, as the substrate.[144] Among the mentioned catalysts,
limited number of these MOF-derived SACs have been applied Ni/B36 was recognized as the most efficient OER electrocatalyst,
to electrochemical water splitting, especially in OER catalysis. which could be attributed to the appropriate binding strengths of
Because of the advantages afforded by the use of SACs for scalable various adsorbates (Figure 9Ba,b). The Ti/B36 electrode showed
production and electrochemical reactions, we believe that much the highest activity for the HER electrocatalyst owing to the lowest
more effort is needed to enhance further the current intrinsic ΔG*H (0.12 eV) (Figure 9Bc).
Figure 9. A) a) Schematic image illustrating the synthetic route of A-Ni-C. b) HAADF-STEM image of A-Ni-C. c) XRD patterns and d) LSV curves of
A-Ni-C and reference samples. A) Reproduced under the terms of the CC-BY Creative Commons Attribution 4.0 International License (https://crea-
tivecommons.org/licenses/by/4.0).[140] Copyright 2016, The Authors, published by Springer Nature. B) a) Reaction-free energy profile for the OER of
Ni/B36. b) Activity trends for the OER. c) Free energy profile for the HER at TM-sites of TM/B36 systems. B) Reproduced with permission.[144] Copyright
2019, American Chemical Society.
In brief, we put forward a summarization of the composition usually employed for the synthesis of MOF-derived SACs, and
and structural design of MOF-derived carbon-based electrocata- the regulation of pore size and guest matching has a substan-
lysts. MOF-derived carbon materials with heteroatomic dopants tial effect on the successful preparation of SACs. The SACs
(e.g., B, N, P, S, etc.) have drawn increasing attention because can also be obtained using bimetallic MOFs as the precursor
of their high conductivity, erosion resistance, and excellent through a pyrolysis-etching strategy, which is relatively simple
catalytic performance. The improvement of the electrocatalysis but is limited by the formation of a bimetallic MOF precursor.
behavior is due to charge accumulation and spin polarization Furthermore, to control the chemical composition of MOF
caused by heteroatom doping. We believe that carbon sub- derivatives, choosing appropriate MOF precursors is a com-
strates with nonmetallic heteroatomic dopants can be consid- monly adopted strategy. Manipulating the conversion con-
ered when designing the MOF-derived electrocatalysts. For ditions and introducing additional precursors can also be
metal-based-material-doped carbons derived from MOFs for employed to regulate the chemical composition of the elec-
electrochemical water splitting, more attention should be paid trocatalysts. Indeed, these strategies are used simultaneously
to the chemical and structural composition in the design pro- in many cases to obtain excellent electrocatalytic activity and
cess. For instance, more Mo- and W-based materials have been stability.
widely used to catalyze HER.
Besides the metal oxides and hydroxides commonly
employed as OER catalysts, other types of metal compounds 3. Recent Advancements of MOF-Based/Derived
(e.g., phosphides, nitrides, and chalcogenides) exhibit out-
Electrocatalysts for Water Splitting
standing HER performance. A limited number of studies on
MOF-derived SACs for electrochemical water splitting have 3.1. Catalysts for the Hydrogen Evolution Reaction
been reported. When the adsorption–calcination method is
applied to the design of SACs, the calcination temperature Hydrogen is a promising green energy source as a substitute
should be carefully considered. The host–guest strategy is for traditional fossil fuel energy. The HER is a key half-reaction
Table 1. Summary of the synthesized MOF precursors and metal catalytic centers of currently reported MOF-derived SACs.
Metal element MOFs Metal centers Metal content Ref.

Fe Cd-MOF Fe–N4 [27]
Mn Mn-BTC Mn–N3O1 [123]
Bi Bi-MOF Bi–N4 [124]
Fe ZIF-8 Fe–N4 1.12 wt% [125]
Ni ZIF-8 Ni–Nx–C [126]
Ni PPy@MgNi-MOF-74 NiSA–N2–C 0.90 wt% [127]
Co ZnCo-ZIFs Co–Nx 1.70 wt% [128]
Co Bimetallic Zn/Co ZIF Co–N2 0.25 wt% [129]
Fe Fe20-PCN-222 Fe–Nx 1.76 wt% [130]
Ru ZIF-8 Ru–N 0.18 wt% [131]
W UiO-66-NH2@WCl6 W1–N1–C3 1.21 wt% [132]
Ru UiO-66 Ru@Zr32O63 and Ru/NC2 0.10 wt% [133]
Fe, Co FeCo-ZIF-8 Fe-N4, Co–N4 0.26 wt% (Fe), 1.06 wt% (Co) [135]
Ru ZIF-8 Ru–N4 0.42 wt% [136]
Fe Fe/ZIF-8@SiOx Fe–Nx 0.11 wt% [137]
Rh ZIF-8 Rh–N4 0.92 wt% [138]
Ir, Rh, Pt, Pd ZIF-8 PM–N4 (PM = Ir, Rh, Pd, Pt) 1.20–4.50 wt% [139]
Ni Ni-MOF Ni–N–C 1.5 wt% [140]
Mn, Fe, Co, Ni, Cu ZIF-8 M–Nx(M = Mn, Fe, Co, Ni, and Cu) [145]
Co ZIF-8 Co–N4 0.70 wt% [146]
of electrochemical water splitting, which is an efficient strategy 1,3,5-triaminobenzene-2,4,6-trithiol, hexaaminobenzene,

for converting electricity into storable hydrogen. The HER reac- and benzenehexathiolate) as precursors.[17,149–152] Recently,
tion proceeds as follows hexaiminohexaazatrinaphthalene (HAHATN), an analog of
hexaazatriphenylene (HATN), was fabricated as an organic
2H+ + 2e − → H2 E 0 = 0 V versus RHE (1) ligand to prepare different bimetallic conductive MOFs with
in-plane mesoporous structures (2.7 nm) (Figure 10Aa,b).[17]
The evaluation parameters for the HER include the onset The obtained Ni3(Ni3∙HAHAT)2 bimetallic, conductive MOFs
potential, the value of the potential at a current density of exhibited outstanding HER catalytic activity, achieving a rather
10 mA cm−2 (the overpotential η10), and the Tafel slope, low overpotential of 115 mV at 10 mA cm−2 in an alkaline
among others. To concisely describe these concepts, the medium (Figure 10Ac). The DFT calculations suggest that the
overpotential (η) is a measurement of the additional poten- Ni–N2 groups have a stronger ability to absorb and bond pro-
tial needed above the thermodynamic potential (E0) required tons, which can remarkably enhance the HER performance
for an electrocatalytic reaction at a certain current density. of Ni3(Ni3∙HAHATN)2 compared to that of the traditional
The Tafel slope is a parameter of kinetic measurement, Ni3(HITP)2 conductive MOF (Figure 10Ad–f).
which describes the relationship between the overpotential Recent research has revealed that combining MOFs with
and the base 10 logarithm of the current density. A lower functional materials is an effective strategy to synthesize MOF
Tafel slope reflects better HER kinetics. During the HER composites, which can not only overcome the deficiencies of tra-
process, hydrogen intermediates (H*) are adsorbed onto the ditional MOFs, such as poor conductivity and limited function-
catalytic sites, so the hydrogen adsorption energy is crucial ality but also inherit their strengths.[153] In addition, numerous
for the sensible selection of active HER catalysts. According investigations have demonstrated that 2D MOFs could be utilized
to the HER mechanism, the active site with an H* adsorp- as promising electrocatalytic materials because of their intrinsic
tion free energy (ΔGH*) of 0 could achieve the best HER advantages, such as fast mass and electron transfer, tunable struc-
activity.[4,5] tures, and more exposed active sites.[8,20] In one study, novel 2D
MOFs have been extensively utilized as preferred het- Co-BDC/MoS2 hybrid nanosheets (Figure 10Ba) were designed
erogeneous catalysts for the HER because of their large sur- and fabricated as efficient electrocatalysts for alkaline HER via
face area and controllable structure.[1,147,148] In particular, a simple sonication-assisted solution strategy.[154] As shown in
the conductive MOFs exhibit significantly more electron Figure 10Bb, the introduction of Co-BDC in the Co-BDC/MoS2
transfer than traditional MOFs. Generally, to improve the resulted in a partial phase transfer from 2H-MoS2 to 1T-MoS2,
intrinsic electrical conductivity, one strategy is to synthe- which contributes significantly to enhanced HER activity. The
size a π-conjugated structure with transition metal atoms Co-BDC/MoS2 required a lower overpotential at −10 mA cm−2,
(Ni, Cu, and Co) and aromatic organic ligands (such as lower Tafel slope, and lower charge-transfer resistance than bare
Figure 10. A) a) TEM image of Ni3(Ni3∙HAHATN)2 nanosheets. b) The optimization structure of the Ni3(Ni3∙HAHATN)2 slab. c) Polarization curves
of the Ni3(HITP)2 and Ni3(Ni3∙HAHATN)2 samples toward the HER. d) PDOS of an Ni atom in Ni–N2 and Ni–N4 of the Ni3(Ni3∙HAHATN)2 slab.
e) Free-energy diagrams for the HER at different catalytic sites. f) The H2 adsorption slabs of Ni3(Ni3∙HAHATN)2 at the Ni–N2 and Ni–N4 sites.
A) Reproduced under the terms of the CC-BY Creative Commons Attribution 4.0 International license (https://creativecommons/licenses/by/4.0).[17]
Copyright 2020, The Authors, published by Wiley-VCH. B) a) HAADF-STEM image of Co-BDC/MoS2 hybrid nanosheets. b) Raman spectra of MoS2
and Co-BDC/MoS2. c) HER LSV curves of Co-BDC, MoS2, Co-BDC/MoS2, and Pt-C in 1.0 m KOH. d) HER mechanism of the Co-BDC/MoS2 hybrid
nanosheets in an alkaline electrolyte. e) Tafel plots and f) Nyquist plots of Co-BDC/MoS2 and corresponding counterparts. B) Reproduced with permis-
sion.[154] Copyright 2019, Wiley-VCH.
Co-BDC and MoS2 in 1 m KOH (Figure 10Bc,e,f). More impor- air compressor.[18] The obtained composites showed enhanced
tantly, a well-designed Co-BDC/MoS2 interface is highly desirable electrocatalytic behavior for the HER and excellent stability in the
for the alkaline HER. As shown in Figure 10Bd, Co-BDC facili- alkaline electrolyte compared to the pristine nanoflocks. Moreover,
tates the kinetics of the rate-determining water dissociation step coupling MOFs with conductive materials, such as acetylene black
of the alkaline HER, while modified MoS2 is beneficial for the (AB), have been reported to enhance the HER catalytic properties
subsequent H2-generation step. The high conductivity of sub- efficiently.[19,155] For instance, Li et al. designed and fabricated a
strates such as CNTs and rGO can be used to support MOF par- series of composites containing [Co1.5(TTAB)0.5(4,4′-bipy)(H2O)]
ticles and improve the mechanical stability of pristine MOFs.[8,18] (CTGU-9) and AB, which demonstrated a distinct electrocata-
Khalid et al. reported nanoflocks of a bimetallic organic frame- lytic activity for the HER with an overpotential of 128 mV at
work (NiCo-MOF), which was grown on a Ni mesh and covered 10 mA cm−2, a small Tafel slope of 87 mV dec−1, and excellent
with a graphene oxide aerosol skeleton by utilizing a nebulizer long-term stability of no less than 21 h.[19]
In situ synthesis of hybrid catalysts combining metal com- (Figure 11Ae). Feng et al. fabricated porous, rodlike Co–Ni
pounds and MOFs for the HER has been considered as an bimetal nitrides (CoxNiyN) as high-efficiency HER electrocata-
ideal strategy to enhance further the HER activity owing to the lysts in all pH environments through nitridation from a bime-
strong interaction of the MOF-based composites.[2,156] Recently, tallic MOF-74 precursor.[168] The obtained CoxNiyN presents
Liu et al. synthesized CoP-doped MOF-based electrocatalysts several advantages, such as large specific surface area, abun-
for the pH-universal HER via a controllable partial phosphori- dant mesoporous structure, and perfect active site dispersion,
zation strategy.[156] The CoP/Co-MOF hybrid also showed excel- resulting in enhanced HER catalytic activity.
lent electrocatalytic activity for the HER with overpotentials of In recent years, MOF-derived SACs have been explored
27, 49, and 34 mV at a current density of 10 mA cm−2 in 0.5 m as promising electrocatalysts.[132,170,171] Chen et al. designed
H2SO4, 1 m phosphate buffer solution (PBS, pH 7.0), and 1 m and synthesized a W-SAC, with W atoms immobilized on a
KOH, respectively. The results of DFT calculations and experi- N-doped carbon substrate derived from a MOF for HER appli-
ments show that the MOF-based HER electrocatalysts not only cations.[132] WCl5/UiO-66-NH2 was annealed at 950 °C and then
possess the optimal adsorption energy of H2O (ΔGH2O*) and treated with a hydrofluoric acid solution to etch the zirconic
hydrogen (ΔGH*) but also take advantage of the well-defined oxide (Figure 11Ba). HAADF-STEM and XAFS analyses reveal
channel structure of MOFs. Huang et al. introduced a facile in the uniform dispersion of the W atoms (Figure 11Bb,c). The
situ sulfurization strategy to synthesize a hybrid catalyst con- W-SAC exhibited a small overpotential of 85 mV at 10 mA cm−2
taining good conductive Fe3S4 ultrasmall nanosheets attached and a low Tafel slope of 53 mV dec−1 in a 0.1 m KOH solution
on the surface of 3D MIL-53(Fe) for the HER under acidic (Figure 11Bd,e). DFT calculations suggested that the ΔGH*
solutions.[2] The Fe3S4/MIL-53(Fe) hybrid catalysts maintain of the W-SAC approached the ideal value of zero, which is
the advantages and overcome the deficiencies of the indi- closely related to the HER activity of the catalyst (Figure 11Bf).
vidual components, which contributes to the remarkable HER Recently, Li et al. reported novel synthesis tactics utilizing an
performance. in situ phosphatizing of triphenylphosphine embedded within
Recently, transition metal compounds and composites MOFs to obtain an atomic Co1-P1N3 interfacial structure, where
derived from MOF precursors, featuring their well-defined one single Co atom is coordinated with one P atom and three
structure and large surface area, have been applied as excellent N atoms (denoted as Co-SA/P-in-situ).[170] In the acid solu-
electrocatalysts. With MOFs as precursors, Ni-based catalysts, tion, the as-prepared Co-SA/P-in-situ exhibited excellent HER
such as Ni2P,[118,157,158] Ni/NiO,[159,160] NiSe,[161] and NiFeP,[105,162] activity with an overpotential of 98 mV at 10 mA cm−2 and a
have been widely used to catalyze the HER.[105,118,140,157–164] For Tafel slope of 47 mV dec−1, which are better values than those
instance, Jiao et al. designed and fabricated a Ni/NiO nanopar- of the catalyst with the Co–N4 interfacial structure. Moreover, in
ticle with subtle lattice distortions using Ni-MOF as the pre- situ XAFS analysis and DFT calculations supported the expla-
cursor and template.[160] Notably, the incorporation of Ni3+ in nation that the enhanced HER performance was ascribed to the
Ni/NiO heterostructures led to a subtle atomic rearrangement bond-length-extended, high-valence Co1-P1N3 atomic interface
and exposed more electrochemically active reaction sites, which structure. The most recently reported MOF-based/derived elec-
promoted HER activity with a rather low overpotential of 41 mV trocatalysts with different substrate that are favorable for the
at 10 mA cm−2. Recently, Lou et al. reported a simple method HER are systematically summarized in Table 2.
to prepare Ni-doped FeP/C hollow nanorods with adjustable
aspect ratios by the etching and coordination reaction between
MOFs and phytic acid followed by a pyrolysis process.[105] The 3.2. Catalysts for the Oxygen Evolution Reaction
obtained Ni-doped FeP/C hollow nanorods show outstanding
electrocatalytic activity and robust stability in solutions for the The OER, with an equilibrium potential of 1.229 V versus
HER over a full range of pH values because of their abundant RHE, is vital for several energy-related applications, including
active sites and the shortening of the diffusion distance for both rechargeable metal–air batteries and water electrolysis.[174] The
mass and electron transport. The overpotential at 10 mA cm−2 reaction equation for the OER is as follows
of the Ni-doped FeP/C hollow nanorods was only 72, 117, and
95 mV in acidic, neutral, and alkaline media, respectively. H2O → O2 + 4H+ + 4e − E0 = 1.229 V vs RHE (2)
Moreover, the DFT-calculated electronic structures indicate that
Ni doping can further improve charge transfer. The parameters commonly utilized to assess the activity of
Co-based catalysts derived from MOFs, such as CoSe2,[165] OER electrocatalysts include the onset potential, η10, and the
CoP,[100,166] CoPS,[167] IrCo nanoalloys,[87] CoxNiyN,[168] CoFeP,[107] Tafel slope, which resemble those of HER electrocatalysts. The
and CoNiP,[169] have also been widely reported to facilitate the OER is a complicated 4-electron process, in which the oxygen
HER. Jiang et al. designed a one-step annealing strategy for intermediates are adsorbed onto the active sites. In order to fur-
Ir-doped MOFs to prepare IrCo nanoalloys coated with N-doped ther optimize the durability of earth-abundant transition-metal-
graphene shells (IrCo@NC) (Figure 11Aa,b).[87] The as-prepared based OER catalysts, and to improve the kinetics, the OER is usu-
IrCo@NC shows excellent catalytic activity for the HER with ally carried out under extremely alkaline environments (pH = 13
an exceedingly low Tafel slope of 23 mV dec−1 and an over- or 14). More details of the MOF-based/derived materials for OER
potential of only 24 mV at a current density of 10 mA cm−2 electrocatalysis are discussed in the subsequent sections.
under acidic conditions (Figure 11Ac,d). The remarkable HER Recent studies have shown that Co-,[13,175,176] Mn-,[177]
activity is even more outstanding than that of commercial Pt/C Ni-,[178,179] and Fe-based MOFs[180,181] with enhanced elec-
catalysts, which results from the significantly reduced ΔGH* trocatalytic activity have been widely investigated as novel
Figure 11. A) a) Schematic illustrating the preparation of IrCo@NC hybrid. b) TEM image of IrCo@NC-500. c) HER polarization curves and d) Tafel
plot of IrCo@NC-500 and counterparts. e) ΔGH* of the IrCo@NC-500 and counterparts. A) Reproduced with permission.[87] Copyright 2018, Wiley-VCH.
B) a) Illustration of the formation of W-SAC. b) HAADF-STEM image of the W-SAC. c) k3-weight FT-EXAFS curves of the W-SAC and the references
at W L3-edge. d) HER polarization curves, e) Tafel plots, and f) ΔGH* of the W-SAC and counterparts. B) Reproduced with permission.[132] Copyright
2018, Wiley-VCH.
materials for the OER owing to their tunable structures, well- of the coordinatively unsaturated metal sites of Co-MOF-74 with
defined pores, and high specific surface areas. For instance, a distinctly improved OER activity and no damage to the integ-
Zhang et al. prepared an Fe-MOF nanosheet array on Ni foam rity of its phase.[176] The hydrogen-plasma-engraved Co-MOF-74
(Fe-MOF/NF) by the hydrothermal treatment, which showed exhibited superior OER activity in a 0.1 m KOH electrolyte with
outstanding electrocatalytic performance for the OER with an a relatively low overpotential of 337 mV at 15 mA cm−2, a high
overpotential of approximately 240 mV at 50 mA cm−2 and TOF of 0.0219 s−1, and large mass activity of 54.3 A g−1.
a relatively low Tafel slope of 72 mV dec−1 in 1.0 m KOH.[181] However, most MOFs bear intrinsic, low electronic conduc-
Moreover, Fe-MOF/NF showed robust long-term electrochem- tivity, limited active sites, and poor chemical stability, which are
ical stability with its catalytic activity being maintained for no the major barriers that hinder their electrocatalytic application
less than 30 h. Recently, Jiang et al. employed a microwave- for the OER. Therefore, many efficient strategies have been
induced plasma engraving strategy to achieve a fine regulation reported to strengthen the OER catalytic performance of MOFs.
Table 2. HER performances of MOF-based/-derived electrochemical catalysts (GCE: glassy carbon electrode; CC: carbon cloth; CFP: carbon fiber
paper; FTO: fluorine-doped tin oxide).
Catalyst Substrate Electrolyte Overpotential [mV] at 10 mA cm−2 Tafel slope [mV dec−1] Mass loading [mg cm−2]
MOF-based catalysts
Fe3S4 (52.1 wt%)/MIL-53[2] GCE 0.1 m NaClO4 92 60 0.610
Gr (4 wt%) and Co-MOF[8] GCE 0.5 m H2SO4 125 91 0.283
Ni3(Ni3∙HAHATN)2[17] GCE 0.1 m KOH 115 ≈46 0.112
NiCo-MOF/rGOAS[18] GCE 0.1 m KOH 210 73
AB&CTGU-9 (3: 4)[19] GCE 0.5 m H2SO4 128 87 0.070
[20]
2D Ni-MOF@Pt NSs GCE 0.5 m H2SO4 43 30 0.250
GCE 1 m KOH 102 88 0.250
AB and CTGU-5 (1:4)[147] GCE 0.5 m H2SO4 44 45 0.140
[149]
Cu-BHT NP GCE 0.5 m H2SO4 450 95 0.084
CoBHT[151] GCE pH 1.3 H2SO4 185 88
NiBHT[151] GCE pH 1.3 H2SO4 331 67
FeBHT[151] GCE pH 1.3 H2SO4 173 119
2D Co-BDC/MoS2[154] GCE 1 m KOH 248 86 0.160
Cu.BTC, 1.7 wt% AB[155] GCE 0.5 m H2SO4 208 80 0.280
CoP/Co-MOF[156] CC 1 m PBS 49 63 5.000
CC 1 m KOH 34 56 5.000
CC 0.5 m H2SO4 27 43 5.000
MOF-derived catalysts
IrCo@NC-500[87] GCE 0.5 m H2SO4 24 23 0.285
GCE 1 m KOH 45 80 0.285
[100]
CoP/NCNWs CFP 0.5 m H2SO4 95 50 1.000
CFP 1 m KOH 154 59 1.000
NFP/C-3[105] CFP 0.5 m H2SO4 72 54 0.390
CFP 1 m PBS 117 70 0.390
CFP 1 m KOH 95 72 0.390
Co-Fe-P NTs[107] GCE 0.1 m KOH 86 66 0.285
GCE 1 m PBS 138 138 0.285
GCE 0.5 m H2SO4 66 72 0.285
Ni2P/Ni@C[118] GCE 0.5 m H2SO4 149 ≈61 0.354
W1N1C3 SAC[132] GCE 0.1 m KOH 85 53 0.204
A-Ni–C[140] GCE 0.5 m H2SO4 34 41 0.283
Ni2P/C[157] GCE 0.5 m H2SO4 198 ≈113 0.566
NHPBAP[158] GCE 0.5 m H2SO4 70 52 0.285
GCE 1 m KOH 121 67 0.285
Ni/NiO@C/GR-t-w[159] GCE 0.5 m H2SO4 108 44 0.205
Ni/NiO-400[160] CC 1 m KOH 41 59 1.000
NiSe@NC-600[161] GCE 0.5 m H2SO4 123 ≈53 0.350
GCE 1 m KOH 250 ≈55 0.350
GCE 1 m PBS 300 ≈66 0.350
NiFeP nanorods[162] GCE 1 m KOH 178 69 0.071
[163]
Ni/C-1 GCE 1 m KOH 40 77 0.500
Ni@NC-rGO[164] GCE 1 m KOH 218 ≈99 1.400
CoSe2@NC-NR/CNT[165] GCE 0.5 m H2SO4 ≈50 1.300
CoP/Mo2C-NC[166] GCE 0.5 m H2SO4 55.7 49 0.453
GCE 1 m KOH 67.2 66 0.453
Table 2. Continued.
CoPS/N-C[167] GCE 0.5 m H2SO4 80 68 0.170
GCE 1 m KOH 148 78 0.170
Co2Ni1N[168] GCE 1 m KOH ≈102 ≈60 0.240
GCE 0.5 m H2SO4 92 ≈55 0.240
GCE 1 m PBS ≈153 ≈90 0.240
CoNiP nanoboxes[169] GCE 1 m KOH 138 65 0.517
Co-SA/P[170] GCE 0.5 m H2SO4 98 47 0.102
Co-SAC[171] GCE 0.5 m H2SO4 260 80 0.500
Py-ZIF[171] GCE 0.5 m H2SO4 260 84 0.500
MoS-CoS-Zn[172] GCE 0.5 m H2SO4 ≈73 ≈38 0.250
[173]
CoSx-(0.2-0.02)-12 FTO 1 m PBS 168 76
For instance, incorporating nonbridging ligands into the MOF fabricate well-defined, ultrathin CoNi-MOF nanosheet arrays
could significantly improve OER performance.[14,182] Converting (CoNi-MOFNA), which could be employed as a highly active
bulk MOF crystals into 2D nanosheets could expose more active OER electrode.[183] The catalysts achieved an extremely low
surface sites.[15,183–186] Additionally, multimetallic MOFs present overpotential of 215 mV at a current density of 10 mA cm−2,
a significant improvement in catalytic activity due to the syner- and its mass activity was 14 times that of commercial RuO2.
gistic effect between different metal sites.[35,187–194] Furthermore, Besides, the current density of CoNi-MOFNA showed no sig-
MOF-involved hybridization, such as Ni-BDC/Ni(OH)2,[195] nificant degradation even after 300 h of continuous electrolysis.
CoFeOx/Co-MOF,[16] and POM@ZIF-8,[196] have also been Pang et al. reported a new method for preparing single-layer
reported to accelerate the OER.[16,21,195–198] These explorations metal–organic nanosheets from 3D layered-pillared MOFs by
have promoted the further development of MOF-based OER capping solvent molecules prepared with sonication in a solvent
electrocatalysts. over a comparatively short period (30 min).[15] The as-obtained
Theoretical calculations suggest that the electron structure of single-layer metal–organic nanosheets exhibited higher OER
MOFs can be regulated by introducing missing linkers, which activity than other heterogeneous catalysts.
enhances the OER activity of the MOF.[14] Inspired by this, Multimetallic MOFs, such as CoFe-,[187,190,192] NiCu-,[188]
Xue et al. reported a universal strategy to introduce different FeNi-,[189,191,193] NiCo-,[194] and NiCoFe-based MOFs,[35] have
missing linkers, such as carboxyferrocene (Fc), to regulate the been reported with the enhanced catalytic performance for the
electronic structure of layered-pillared MOF Co2(OH)2(C8H4O4) OER relative to their monometallic counterparts. For example,
(CoBDC) (Figure 12Aa–c). The calculated density of states Sun et al. proposed a self-templating approach to growing NiFe-
(DOS) of CoBDC and CoBDC-Fc revealed that new electronic based MOF nanosheets, such as MIL-53(FeNi)/NF, on foamed
states near the Fermi level were generated after introducing nickel in situ using a one-step solvothermal synthesis.[193]
missing linkers, demonstrating that the CoBDC-Fc has a more An overpotential of 233 mV at 10 mA cm−2, mass activity of
conductive structure (Figure 12Ad). The conductive structure 19.02 A g−1, Tafel slope of 31.3 mV dec−1, and desirable stability
plays a critical role in improving the OER activity by intro- was obtained for MIL-53(FeNi)/NF in 1 m KOH electrolyte,
ducing missing linkers into the MOF, which could reduce demonstrating the superior OER performance of MIL-53(Ni).
the energy barrier (Figure 12Ae). The self-supported CoBDC The encapsulation of the Fe species into MIL-53 could readily
nanoarrays with missing linkers of Fc and NF serving as sub- facilitate the modulation of the electronic structure, facilitate
strate (CoBDC-Fc-NF) exhibited remarkable OER activity with electron transport, and increase the number of active electro-
an ultralow overpotential of 241 mV at 100 mA cm−2 and a chemical areas to improve the catalytic performance.
small Tafel slope of 51 mV dec−1 (Figure 12Af,g). More recently, MOF-based hybrids have also been reported to accelerate the
Ji et al. proposed a facile linker scission strategy to induce OER. In a recent study, 2D Ni-BDC/Ni(OH)2 hybrid nanosheets
lattice strain in MOF catalysts by partially replacing binary were fabricated by a simple sonication-assisted solution route.[195]
carboxylic acids with monocarboxylic acids.[182] The strained Ni-BDC/Ni(OH)2 showed excellent activity, desirable kinetics, and
NiFe-MOFs with 6% lattice expansion showed excellent activity long-term stability for the OER. Because of the strong electronic
for the OER in an alkaline electrolyte with a low overpotential interactions between Ni(OH)2 and Ni-BDC, the electron struc-
of 230 mV at a current density of 10 mA cm−2 and a small Tafel ture of Ni(OH)2 was fine-tuned. As a result, Ni(OH)2 with higher
slope of 86.6 mV dec−1. oxidation states could be obtained; thus, the OER catalytic per-
A 2D sheet-like nanostructure could facilitate not only mass formance could be further improved. Notably, the OER current
or electron transfer but also enable higher exposure of the active density of Ni-BDC/Ni(OH)2 was 82.5 mA cm−2 at 1.6 V versus
catalytic sites of unsaturated coordinated metal atoms, which RHE, outperforming the benchmark commercial Ir/C catalyst by
remarkably enhances their intrinsic OER activity. Huang et al. up to three times. Ultrafine CoFeOx nanoparticles were immobi-
developed a typical self-dissociation-assembly method to lized in the lattice of a poly[Co2(benzimidazole)4] (PCB) layer. The
Figure 12. A) a) Schematic illustrating the modulation of the electron structure of MOFs by introducing missing linkers. b,c) SEM images of CoBDCNF
(b) and CoBDC-Fc-NF (c); inset: the corresponding TEM images. d) Calculated DOS of CoBDC and CoBDC-Fc in DFT calculations. e) Free energy
diagrams toward the OER on CoBDC and CoBDC-Fc. f) OER LSV plots in 1 m KOH. g) Tafel plots of different catalysts. A) Reproduced under the terms
of the CC-BY Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0).[14] Copyright 2019, The Authors,
published by Springer Nature. B) a) Schematic representation of the approach to fabricate M-PCBN. b) TEM images of M-PCBN. The inset shows the
Tyndall effect of M-PCBN under laser irradiation. c) Comparison of the OER performance for all working electrodes. d) Chronoamperometry testing
and e) Tafel plots for different catalysts. f) Calculated the free energy diagram of the OER on i-Co-Co, i-Co-Fe, and p-CoN4 at the equilibrium potential
(1.23 V). The dashed lines represent the potential-limiting steps. B) Reproduced with permission.[16] Copyright 2020, American Chemical Society.
metal-oxide-nanoparticle-embedded PCB (M-PCB) bulk micro- Over the past few years, MOF-derived transition metal (Fe, Ni,
crystals were further exfoliated into a layered heterostructure to Co, Mo, Cu, etc.)-based compounds, including oxides,[113,199–202]
obtain monolayered M-PCB nanosheets (M-PCBN) by ultrasoni- hydroxides,[203] phosphides,[104,204] selenides,[205] nitrides,[94]
cation (Figure 12Ba).[16] The TEM image reveals the formation of borates, and chalcogenides,[103,206,207] have been employed exten-
M-PCBN with an ultrathin heterogeneous nanosheet structure sively as electrocatalysts for the OER. Among these, Co-based
(Figure 12Bb). Structural characterization and analysis suggested transition metal oxides and (oxy)hydroxides, particularly cobalt-
a changed 3d electronic configuration and a higher valence for based polymetallic compounds,[112,208–213] are prominent owing to
the interfacial Co sites between the metal oxide nanoparticle and their unique 3d electronic configurations. Zhou et al. reported a
monolayered MOF, resulting in an enhanced OER activity, which facile strategy in which layered 2D MOFs were used as precur-
was consistent with the theoretical calculations and electrochem- sors to fabricate metal oxide/carbon (MOx/C, M = Co, Ni, and
istry measurements (Figure 12Bc–f). Electrochemical tests indi- Cu) nanosheet arrays for the OER.[202] Owing to the enhanced
cated the excellent OER activity and durability of the M-PCBN conductivity and higher exposure of the active sites, these
with an overpotential of 232 mV at 10 mA cm−2 and a Tafel slope MOx/C arrays showed excellent electrocatalytic performance
of 32 mV dec−1. and good stability. In particular, Co3O4/CBDC exhibited ultralow
Figure 13. A) a) Schematic illustration of the route to synthesize Co3O4/Co-Fe oxide DSNBs. b) FESEM images of ZIF-67/Co-Fe PBA YSNCs (inset
is the corresponding TEM image). c) HAADF-STEM and elemental mapping images of a Co3O4/Co-Fe oxide DSNB. d) LSV curves and e) Tafel plots
of different electrocatalysts. f) LSV curves were obtained after continuous CV sweeps at 5 mV s−1 after the stability test. A) Reproduced with permis-
sion.[213] Copyright 2018, Wiley-VCH. B) a) TEM image of an individual HXP@NC800 nanoplate (inset is the corresponding HXP image). b) LSV curves,
c) corresponding Tafel plots, and d) chronoamperometry curve of HXP@NC800 measured on graphite foil. B) Reproduced with permission.[218]
Copyright 2020, American Chemical Society. C) a) Illustration of the preparation approach of the hybrid nanostructure CeOx/CoS. b,c) TEM images for
CoS (b) and for 14.6% CeOx/CoS (c). d) LSV curves and e) Tafel plots of various catalysts for the OER. f) Chronopotentiometric curves of water electrolysis
for CoS and 14.6% CeOx/CoS. C) Reproduced with permission.[223] Copyright 2018, Wiley-VCH.
overpotentials of 208 mV at a current density of 10 mA cm−2. PBA yolk–shell nanocubes (YSNCs) (Figure 13Ab). Co3O4/
Lou et al. fabricated unique Co3O4/Co-Fe oxide double-shelled Co-Fe DSNBs were synthesized by a subsequent annealing treat-
nanoboxes (DSNBs) by a successive anion-exchange and ment (Figure 13Ac). The as-obtained hybrids exhibited superior
pyrolysis strategy (Figure 13Aa).[213] In the first step, an anion- electrocatalytic activity and stability for the OER compared to
exchange process between the ZIF-67 NCs and [Fe(CN)6]3− ions Co-Fe oxides and Co3O4 single-shelled nanoboxes owing to their
was performed to transform the ZIF-67 NCs into ZIF-67/Co-Fe structural and compositional advantages (Figure 13Ad–f).
Many researchers have also found that MOFs can act Co(OH)2 (D-U-Co(OH)2) nanoarray under room temperature
as attractive templates or precursors to prepare porous for the OER by in situ etching of a Co-MOF (ZIF-L-Co).[226]
carbon-encapsulated metal (M@C) materials via a pyrolysis Here, the remarkable OER performances of recently reported
method.[79,214–220] The M@C materials retain not only the large MOF-based/derived electrocatalysts are summarized (Table 3).
surface area of their parental MOFs but also show excellent
conductivity and catalytic activity. Meanwhile, the metal nodes
around organic ligands can be reduced in situ to single atomic 3.3. Bifunctional Electrochemical Catalysts (HER + OER)
sites[221] or bimetal alloy[82,88,89,222] cores encapsulated in a
heteroatom-doped carbon frame after pyrolysis under an inert Electrochemical water splitting consists of two half-reactions:
gas atmosphere. The resulting materials possess a unique elec- the HER occurs at the cathode and the OER occurs at the
tronic effect and extra synergistic effect, resulting in the accel- anode. The cell voltage to afford a specific current density (gen-
eration of the catalytic reaction kinetics for the OER. Recently, erally 10 mA cm−2) in an electrolysis cell is generally applied to
Lin et al. reported a topology-guided synthetic procedure for a assess the HER/OER bifunctional performance of the electro-
novel 2D Ni-based MOF hexagonal nanoplate (HXP).[218] Under catalyst. In this section, MOF-based/derived catalytic materials
the inhibition and modulation of pyridine in the substitution- with activities for both OER and HER will be discussed.
suppression process, the morphology could be changed from A small number of MOF-based materials have emerged as
hexagonal nanorods (HXR) to nanodisks (HXD) and nanoplates electrocatalysts for water splitting, mainly due to their low elec-
with controllable thickness by regulating the amount of pyri- trical conductivity and stability.[12,227,228] 2D MOFs have been
dine. Moreover, a subsequent calcination process transformed demonstrated to have enhanced conductivity and more expo-
the nanoplates into nitrogen-doped Ni@carbon nanocomposites sure to active sites. For instance, Duan et al. developed a 2D
(Figure 13Ba), which showed a low overpotential of 307 mV at a bimetallic MOF on conductive substrates for high-efficiency
current density of 10 mA cm−2, Tafel slope as low as 48 mV dec−1, water electrolysis via a dissolution–crystallization process.[53]
and satisfactory durability in the OER (Figure 13Bb–d). Bu et al. Recently, Xu et al. reported another 2D MOF-based cata-
developed a versatile, ultrafast microwave-assisted chemical lyst (ultrathin Ni-ZIF/Ni-B NSs with massive crystalline–
vapor deposition (CVD)-like route to synthesize a variety of uni- amorphous phase interfaces), which was derived from Ni-ZIF
formly dispersed mono- or few-layer N-doped graphene shell nanorods through a facile and room-temperature boroniza-
immobilized metal nanocrystals (M@NC) within 10 s using tion strategy.[229] Remarkably, the Ni-ZIF/Ni-B@NF required an
MOFs on graphene as the precursors in the presence of carbon extremely low cell voltage of 1.54 V for overall water splitting
cloth (CC).[82] Among the M@NCs, the as-synthesized FeNi@ to achieve a current density of 10 mA cm−2. By hybridizing the
NC/graphene exhibited the best electrocatalytic activity toward 2D Ni-MOF and noble Pt nanocrystals into one heterostructure,
the OER with the lowest overpotential (261 mV) at 10 mA cm−2 an interfacial-bond-induced charge transfer takes place and
in 1 m KOH, the smallest Tafel slope of 40 mV dec−1, and robust electronically optimizes the active sites further to modify inter-
stability for no less than 120 h. mediate adsorption (Figure 14Aa), providing significant elec-
Studies have demonstrated that MOF-derived materials trocatalysis behavior.[230] The aberration-corrected TEM image
without high-temperature treatment were also employed as reveals the interfacial structures of the Pt-NC/Ni-MOF at the
OER catalysts. For instance, Xu et al. proposed a new hybrid atomic scale (Figure 14Ab). The positive shift of A1 and A2 is
nanostructure CeOx/CoS consisting of hollow CoS derived from attributed to the electronic state transition from low-energy Ni
ZIF-67, which was decorated with CeOx nanoparticles grown in 2p3/2 to high-energy Ni 3d, optimizing the adsorption of OH*
situ (Figure 13Ca).[223] The TEM images of the precursor CoS (Figure 14Ac). The as-prepared Pt-NC/Ni-MOF presented out-
and 14.6% CeOx/CoS are displayed in Figure 13Cb,c, respec- standing electrocatalytic performance for both the HER and
tively. The obtained CeOx/CoS hybrid exhibited outstanding OER (Figure 14Ae) and outstanding stability toward the HER
OER performance by regulating the surface electron states and (Figure 14Ad).
producing defective sites, which is related to the increase in the Lu et al. synthesized a Ni- and Fe-based bimetallic MOF on
Co2+/Co3+ molar ratio and defect number. Additionally, the dep- a conducting Ni foam, NFN-MOF/NF, which is an efficient and
osition of CeOx in situ on the surface of the CoS hollow struc- stable electrocatalyst with double function for water splitting
tures can avoid the corrosion of CoS. As expected, the CeOx/CoS (Figure 14Ba).[231] These NFN-MOF/NF materials are nanosheets
exhibited a low overpotential of 269 mV at 10 mA cm−2, a low with thicknesses of approximately 15 nm and are bundled into
Tafel slope of 50 mV dec−1, and significant operational stability micrometer-sized clusters (Figure 14Bb). The NFN-MOF/NF
in an alkaline electrolyte (Figure 13Cd–f). Hollow (Ni, Co)Se2 catalyst can provide a current density of 10 mA cm−2 at a low
arrays immobilized on flexible CC originating from cobalt- cell voltage of 1.56 V, which is better than the performance of
MOF via an ion-exchange/etching reaction, and following sol- the Pt-C/NF//IrO2/NF couple, the accepted benchmark cata-
vothermal selenization exhibited excellent OER performance, lysts (Figure 14Bc). The Tafel slope of 143 mV dec−1 obtained
as reported by Song et al.[224] Similarly, Li et al. successfully syn- for the NFN-MOF/NF//NFN-MOF/NF couple is also consider-
thesized a hierarchical hollow (Co, Ni)Se2@NiFe layered double ably lower than that of the benchmark couple (160 mV dec−1)
hydroxide (LDH) nanocage originating from ZIF-67 for efficient (Figure 14Bd). Moreover, the NFN-MOF/NF catalysts possess
OER with a facile ion-exchanged method and then decorated remarkable durability, presenting negligible chronopotenti-
the nanocage with NiFe LDH to enhance the electrocatalytic ometry decay of 7.8% at 500 mA cm−2 after 30 h (Figure 14Be).
kinetics further.[225] Qiu et al. reported a universal and straight- Recently, Lu et al. further developed well-blended Fe- and
forward approach to preparing a boundary defect-rich, ultrathin Ni-MOFs[232] and modulated Fe-rich FeNi(BDC)(DMF,F) and
Table 3. OER performance of MOF-based/derived catalysts (NF: Ni foam; CP: carbon paper).
MOF-based catalysts
CoBDC-Fc-NF[14] NF 1 m KOH 178 51 2.000
M-PCBN[16] CC 1 m KOH 232 32 0.928
Co-MOF NS/CC[175] CC 1 m KOH η20 = 330 ≈107 7.195
Co-MOF-74[176] GCE 0.1 m KOH η15 = 337 0.396
Mn(TCNQ)2[177] Copper foam 1 m KOH η20 = 306 166 3.100
Ni MOF (BTC)[178] CP 1 m KOH 346 64 0.480
Ni-MOF NSs[179] NF 1 m KOH 320 123 4.500
Fe(TCNQ)2 [180]
Fe 1 m KOH 340 110 0.490
Fe-MOF[181] NF 1 m KOH η50 = 370 72 5.900
LS-6%-NiFe-MOFs[182] GCE 1 m KOH 230 ≈87 0.343
CoNi-MOFNA[183] 1 m KOH 215 ≈52
2D Co–MOF NSs[184] GCE 1 m KOH 263 74 0.250
Fe:2D-Co-NS@Ni[185] GCE 0.1 m KOH 211 46 0.210
NiPc-MOF[186] FTO 1 m KOH 74 ≈0.008
Co0.6Fe0.4-MOF-74[187] GCE 1 m KOH 280 56
NiCu-MOF NSs[188] NF 1 m KOH η100 = 290 ≈107 4.200
NNU-22[189] CC 0.1 m KOH 376 ≈77
A2.7B-MOF-FeCo1.6[190] GCE 1 m KOH 288 39 0.350
NiFe-MOF-74[191] NF 1 m KOH 223 ≈72 1.000
CoFe-MOF[192] GCE 1 m KOH 263 44 0.212
MIL-53(FeNi)/NF[193] NF 1 m KOH η50 = 233 ≈31 2.630
CTGU-10c2[194] 1 m KOH 240 58
2D Ni-BDC/Ni(OH)2[195] GCE 1 m KOH 320 41 0.159
POM@ZIF-8[196] GCE 0.1 m Na2SO4 η1 = 784.19 ≈784 0.057
Fe-MOFs@Ni-MOFs[197] Carbon Paper 1 m KOH 275 ≈57 1.000
Ni-MOF@Fe-MOF[198] GCE 1 m KOH 256 82 0.200
CoNC-CNF-1000[79] GCE 0.1 m KOH 450 94 0.132
FeNi@NC/RGO[82] GCE 1 m KOH 261 40 0.510
CoDNi-N/C p[89] GCE 0.1 m KOH 360 72 0.300
Co9S8/NSCNFs-850[103] GCE 1 m KOH 302 54 0.212
Fe1Co2-P/C[104] GCE 1 m KOH 362 ≈50 0.170
ZnCo-Fe-20[112] GCE 1 m KOH 176 ≈69 0.255
Mg-RuO2 (350)[113] GCE 0.5 m H2SO4 228 ≈49
Cu@CuO–C[199] Carbon fiber cloth 1 m KOH 340 156 1.100
M-Co3O4[200] NF 1 m KOH 230 74
Co@Co3O4[201] GCE 1 m KOH 333 69 0.204
Co3O4/CBDC[202] 1 m KOH 208 ≈50
CoTFBDC/EG_250[203] GCE 1 m KOH ≈40 0.100
CNTs@NiCoP/C[204] GCE 1 m KOH 297 ≈57 0.354
Co-Fe-P-Se/NC[205] GCE 1 m KOH 270 42 0.350
Co9S8@CT-800[206] GCE 0.1 m KOH 390 72 0.200
NiCoS/Ti3C2Tx[207] GCE 1 m KOH 365 ≈58 0.210
Co3O4/CoMoO4-50[209] GCE 1 m KOH 318 63 0.255
MoO2-Co2Mo3O8@C NRs[210] GCE 1 m KOH 320 88 0.200
NiCo@NiCoO2/C PMRAs[212] CFC 1 m KOH η20 = 366 ≈84 3.200
Table 3. Continued.
[213]
Co3O4/Co-Fe oxide DSNBs GCE 1 m KOH 297 61 0.255
Co–Nx/C NRA[214] GCE 6 m KOH 300 ≈62 0.510
MnO@Co-N/C[215] GCE 0.1 m KOH 450 112 0.255
[216] GCE 0.1 m KOH 400 89 0.255
Co–N/PC@CNT
CoTIB-C/G[217] GCE 0.1 m KOH 509 ≈165 0.400
HXP@NC800[218] GCE 1 m KOH 307 48 0.200
[220]
P-Co-NC-4 GCE 1 m KOH 315 ≈76 0.400
CoSAs@CNTs[221] GCE 0.1 m KOH 410 85 0.300
CeOx/CoS[223] GCE 1 m KOH 269 50 0.200
[224]
(Ni,Co)Se2/CC CC 1 m KOH 256 74
Co(OH)2 (D-U-Co(OH)2)[226] GCE 1 m KOH 223 131 0.620
Figure 14. A) a) H* and OH* adsorption energy comparison and b) morphology of the Pt-NC/Ni-MOF. c) Synchrotron-based XANES Ni L3 edge spectra of
the materials investigated. d) Durability test by recording LSV curves. e) CV curves for Pt-NC/Ni-MOF. A) Reproduced with permission.[230] Copyright 2019,
Elsevier Ltd. B) a) Schematic illustration of the synthetic process of NFN-MOF/NF. b) SEM image of NFN-MOF/NF. c) LSV curves and d) corresponding
Tafel plots for couples with different components. e) Stability test of NFN-MOF/NF. B) Reproduced with permission.[231] Copyright 2018, Wiley-VCH.
Ni-rich FeNi(BDC)(F),[233] grown in situ on NF, to obtain MOF/ DFT calculations and a series of experiments to systemati-
NF composite electrodes, which showed remarkable electro- cally analyze and evaluate the effect of phosphorization and
catalytic activity for water splitting as well as outstanding dura- Fe doping (Figure 15Ac,d). The results show that while phos-
bility at a high current density. phorization is more beneficial for the OER than the HER, Fe
In recent years, to reduce the overpotential (η) resulting doping is not only able to tune the micromorphology of the
from the OER on the anode and the HER on the cathode, a catalyst but also modulate the electronic structure, synergis-
wide variety of MOF-derived carbon-based materials have been tically resulting in enhanced HER and OER. Consequently,
thoroughly explored (e.g., noble metals,[70] non-noble metals/ the hybrid displayed outstanding electrocatalytic performance
alloys,[64,65,76,234–236] metal carbides,[237] oxides,[238] chalcoge- for overall water splitting with a cell voltage of 1.66 V at
nides,[239–241] phosphides,[242–252] etc.[253–255]). Among them, 500 mA cm−2, which is far better than the standard electrode
transition metal phosphides (Fe2P,[243] CoP,[246] Ni2P,[251,252] couple consisting of Pt/C and RuO2 (Figure 15Ae). Cao et al.
etc.) are promising for overall water splitting because of designed a 3D bifunctional porous Fe-CoP electrocatalyst
their remarkable activity, excellent stability, and low fabrica- formed by directly growing a Co-Fe PBA on Ni foam with fur-
tion cost. In particular, bimetallic phosphides can further ther phosphorization, showing excellent performance toward
enhance the electrocatalytic activity by adjusting the atomic large current density OER and overall water splitting.[250] The
coordination and electronic structure.[242,245,247–250] Recently, obtained Fe-CoP/NF catalyst with meso- and macropores pre-
Sun et al. reported that an Fe-doped Ni(BDC) MOF (BDC = 1, sented high electrocatalytic efficiency and excellent stability for
4-benzenedicarboxylate) was utilized as the precursor to syn- the OER and HER, reaching a current density of 10 mA cm−2
thesize Fe-doped Ni2P/C toward highly efficient water splitting with a rather low cell voltage of 1.49 V in 1.0 m KOH, which
(Figure 15Aa).[249] As shown in Figure 15Ab, Fe-doped Ni2P far outperforms that of the electrolyzer with IrO2-Pt/C as the
nanoparticles were encapsulated in the CNTs after the phos- electrode couple. Notably, the catalyst showed remarkable
phorization process. More importantly, Sun et al. employed electrocatalytic performance for the OER and provided high
Figure 15. A) a) Schematic illustration of Fe-doped Ni2P/C catalyst preparation. b) TEM image of Fe2-Ni2P/C. c) Free-energy diagrams of the interme-
diates on different modeled surfaces for the OER. d) ΔGH* for the HER. Inset: Volcano plot depicting the HER overpotentials as a function of ΔGH*.
e) Polarization curves of overall water splitting in a water electrolyzer. A) Reproduced with permission.[249] Copyright 2019, American Chemical Society.
B) a) Schematic illustration of the synthetic procedure for NG-NiFe@MoC2. b) HRTEM image of NG-NiFe@MoC2. c) LSV of water electrolysis with
non-noble NG-NiFe@MoC2 and a noble couple of Pt/C//RuO2 in 1 m KOH condition. Inset: stability testing of the electrolyzer at 10 mA cm−2. B) Repro-
duced with permission.[256] Copyright 2018, Elsevier Ltd.
current densities of 500 and 1000 mA cm−2, only requiring Water electrolysis is the main application of HER/OER
ultralow overpotentials of 295 and 428 mV, respectively, to sat- bifunctional catalysts, which can effectively optimize the energy
isfy the rigorous criteria for practical industrial applications. utilization of the water electrolyzer. The cell voltage to afford
In recent times, a versatile strategy for designing high- a particular current density (generally 10 mA cm−2) in an elec-
performance electrocatalysts has been to controllably introduce two trolysis cell is commonly applied to estimate the activity of an
different metal species into a single nanostructure, namely Co-NC@ HER/OER bifunctional electrocatalyst. A large variety of MOF-
Mo2C,[119] Co3O4-RuCo@NC,[121] NG-NiFe@MoC2,[256] Co/Co9S8@ based materials and MOF-derived carbon-based materials
NSOC,[122] NiO/Co3O4,[120] Co@Ir/NC,[257] Ni2P/CoN-PCP,[258] (e.g., metal NPs, metal carbides, phosphides, and complicated
among others,[92,259–264] to further facilitate and accelerate the acti- metal compounds) have been explored for efficient water split-
vation process of the reactants. For instance, Hu et al. synthesized ting (Figure 16e,f). The MOF-based/derived catalyst with a cell
MoC2-doped NiFe alloy nanoparticles (NPs) embedded within sev- voltage of less than 1.6 V at 10 mA cm−2 can be regarded as an
eral-layer-thick N-doped graphene (NG-NiFe@MoC2) using one-step excellent catalyst for water splitting.
calcination of hybrid precursors composed of PVP-encapsu-
lating NiFe-PBA and grafted Mo6+ cations (Figure 15Ba).[256] The
HRTEM image of NG-NiFe@MoC2 (Figure 15Bb) demonstrated 4. Conclusions and Perspectives
that the majority of NPs were embedded within several layers
of the graphene shell. An NG-NiFe@MoC2-based water electro- We have reviewed pivotal advances and provided commentary
lyzer required a potential of 1.53 V to reach a current density of on recent research on engineering MOF nanoarchitectures for
10 mA cm−2 in 1.0 m KOH with impressive durability of 10 h, efficient electrochemical water splitting. Benefiting from the
exceeding the noble Pt/C//RuO2-based electrolyzer (Figure 15Bc). large surface area, adjustable chemical components, tunable
Recently, Du et al.[122] proposed a facile route to fabricate Co/ pore structure, controllable topology, and well-defined surface
Co9S8 nanoparticles incorporated into an N, S, and O ternary- functionality, various MOF-based/derived materials with excel-
doped carbon support with a Co-based MOF (Co-NSOMOF) as lent water splitting performance have been developed. A range of
a single precursor. The optimized Co/Co9S8@NSOC exhibited new synthetic strategies for chemical composition optimization
impressive performance for overall water splitting, resulting from and structural functionalization to improve the electrocatalytic
the synergistic effects and protection of the ternary-doped carbon performance of catalytic sites are highlighted herein, especially
shell, requiring a rather low cell voltage of 1.56 V at 10 mA cm−2. at the molecular and atomic scales and for tailored nanoarchi-
The electrochemical performances of recent MOF-based/derived tectures and configurations. Meanwhile, the fast-growing break-
catalysts for water splitting considered in this review are listed in throughs in catalytic activity, identification of highly active sites,
Table 4. fundamental mechanisms, and recent designs of electrolyzers
To briefly conclude, MOF-based/derived materials exhibit a to promote the commercialization of electrochemical hydrogen
prospect of widespread application as water-splitting electro- production are also fully discussed and summarized. Although
catalysts. For the HER under alkaline conditions, the reacting abundant efforts have been devoted to this newly emerging area,
species are H2O or OH−, which possess much lower conversion and rapid and promising progress has been achieved in recent
kinetics to H* than the conversion from H+ to H* under acidic years, there are several challenges for the future engineering
conditions. As a result, the HER performance under acidic con- of high-efficiency and durable MOF-based/derived electrocata-
ditions is generally superior to that under alkaline conditions, lysts for water splitting. The general comments are summarized
as identified with the works reviewed above. In contrast to the below.
OER electrocatalysts, Mo- and W-based materials have been
widely used to catalyze the HER. Rather than metal oxides and 1) For MOF-based materials, poor electron conductivity is the
hydroxides commonly employed as OER catalysts, other types biggest obstacle for electrochemical applications and needs
of metal compounds (e.g., phosphides, nitrides, and chalco- to be further enhanced by adjusting the chemical properties
genides) exhibit outstanding HER performance. As shown in and structure of the ligands to increase the electron trans-
Figure 16a,b, a MOF-based/derived catalyst with an overpoten- port and electrocatalytic reaction rate, especially for pristine
tial of 150 mV at a current density of 10 mA cm−2 can be consid- MOFs. In addition to the poor conductivity, the controversial
ered as an excellent catalyst for the HER. stability should also be overcome to satisfy the requirements
Various kinds of MOF-based electrocatalysts with remarkable of actual water splitting. The characterization and regulation
OER electrocatalysis behavior have been reported (Figure 16c). of the synergistic effects between the functional components
Apart from the catalytic performance, electrocatalysts for the and MOFs remain challenges for guest@MOF and MOFs/
OER need excellent stability under harsh alkaline environments. substrates.
Thus, for MOF-derived OER catalysts, a high extent of graphiti- 2) The high cost of ligands, harsh synthetic conditions, and lim-
zation of the carbon substrate and the existence of metal-based ited synthetic strategies comprise the major impediment to
constituents are favored. Moreover, a limited number of studies the large-scale preparation of MOFs, which is crucial for the
on MOF-derived SACs for water oxidation have been reported, development of cost-effective water splitting electrocatalysts.
resulting from the SACs migrating and aggregating into NPs 3) For MOF-derived materials, high-temperature calcination usu-
under harsh reaction conditions. Figure 16d shows, through ally causes severe structural damage and the collapse of porous
appropriate design of the composition and structure, some frameworks, which hamper the rationally controlled design of
MOF-derived electrocatalysts can attain high OER activity with MOF derivatives and decrease the accessibility of catalytic cent-
an overpotential of no more than 300 mV at 10 mA cm−2. ers and their intrinsic electrocatalytic performance.
Table 4. Overall water splitting performances of MOF-based/derived electrochemical catalysts.
Catalyst HER overpotential [mV] at 10 mA cm−2 OER overpotential [mV] at 10 mA cm−2 Cell voltage [V] at 10 mA cm−2 Electrolyte
MOF-based catalysts
Fe2M-MOF[12] 221 (Zn) 339 (Co) 0.1 m KOH
NiFe-MOF[53] 134 240 1.550 0.1 m KOH
PBAs@PANI[227] 170 330 1.730 1.0 m KOH
Ni-ZIF/Ni-B@NF[229] 67 234 1.540 1.0 m KOH
Fe2Ni-MIL-88B/NF[231] 87 240 1.560 1.0 m KOH
MFN-MOFs(2:1)/NF[232] 79 235 1.495 1.0 m KOH
Co/NBC-900[65] 117 302 1.680 1.0 m KOH
Co@N-CS/N-HCP@CC[76] 66 248 1.545 1.0 m KOH
Co-NC@Mo2C[119] 99 347 1.685 1.0 m KOH
NiO/Co3O4 NCMC[120] ≈169 290 1.630 1.0 m KOH
RuO2/Co3O4-RuCo@NC[121] 141 247 1.660 0.5 m H2SO4
Co/Co9S8@NSOC- 800[122] 216 373 1.560 1.0 m KOH
[234]
Co-NCNTFs//NF 140 230 1.620 1.0 m KOH
CNT network[235] 133 286 1.690 1.0 m KOH
Co0.75Fe0.25-NC[236] 202 303 1.680 1.0 m KOH
PMo/ZIF-67-6-6N[237] 83 295 1.0 m KOH
CoS2[240] 196 298 1.650 1.0 m KOH
FeNiP/NCH[242] 216 250 1.590 1.0 m KOH
NiCoFeP/C[244] 149 270 1.600 1.0 m KOH
Mn-CoP NSs[245] 195 290 1.0 m KOH
CoP/NCNHP[246] 115 310 1.640 1.0 m KOH
CC-NC-NiFeP[247] 94 145 1.540 1.0 m KOH
[248]
Fe-CoP HTPAs 98 230 1.590 1.0 m KOH
Fe-CoP/NF[250] 78 190 1.490 1.0 m KOH
Ni2P-NPCM-900-2[251] 125 255 1.620 1.0 m KOH
Ni2P/rGO[252] 142 260 1.610 1.0 m KOH
Ru-CoNi@NC-2[253] 268 240 1.0 m KOH
Co2P/Mo2C/Mo3Co3C@C[254] 182 362 1.740 1.0 m KOH
CoPS@NPS-C (4 wt%)[255] 191 320 1.620 1.0 m KOH
NG-NiFe@MoC2-2[256] 150 320 1.530 1.0 m KOH
Co@Ir/NC-10%[257] 121 280 1.0 m KOH
Ni2P/CoN–PCP[258] 94 270 1.580 1.0 m KOH
Co-MOF/H2[260] 30 312 1.619 1.0 m KOH
Co3ZnC/Co-NCCP[261] 188 295 1.650 1.0 m KOH
Co9S8−NSC@Mo2C[262] 89 293 1.610 1.0 m KOH
Ni@Ru/CNS-10%[263] ≈20 356 1.612 1.0 m KOH
Co–Mo2N[264] 76 302 1.576 1.0 m KOH
4) Although other single-atom electrocatalytic systems have been and thorough mechanistic studies are urgently needed to
used in applications for the HER and OER, MOF-derived guide the future rational synthesis of MOF-based/derived
SACs with efficient catalytic activity and stability for water electrocatalysts with well-defined catalytic structures and du-
splitting are rarely reported. Considering the maximum rable activity.
atom-utilization efficiency and low cost, the development of 6) For the industrialization of water splitting, numerous chal-
MOF-derived SACs is urgently required for water electrolysis. lenges still exist, such as the formation of explosive H2/O2
5) Research on the synthetic mechanisms and characteriza- gas mixtures and reactive oxygen species, the limited HER
tions of intrinsic active sites for MOF-based/derived electro- rate due to the more sluggish kinetics of the OER, as well as
catalysts are still in the initial stage. More comprehensive the lack of cost-efficient H2 storage and transport systems.
Figure 16. Summary and comparison of activity for water splitting. a,b) MOF-based/derived electrocatalysts for the HER in 0.5 m H2SO4 (a) and 1 m KOH
(b). c) MOF-based and d) MOF-derived electrocatalysts for the OER in 1 m KOH. e) MOF-based and f) MOF-derived electrocatalysts for overall water
splitting in 1 m KOH.
To address the above challenges, some strategies and per- in the frameworks evaporate, causing the formation of ad-
spectives are detailed below. ditional porous structures for the MOF-derived materials.
3) Under reaction conditions for water splitting, carbons are
1) Numerous efficient and versatile strategies have been usually not chemically or thermodynamically stable; thus, a
proven to strengthen the electrocatalytic activity of pristine carbon matrix with a high level of graphitization is preferred
MOFs. For instance, incorporating nonbridging ligands into to maintain the high conductivity of the catalysts.
the MOF could significantly improve the electrocatalytic 4) With the advances in characterization techniques (e.g., XAFS,
performance. Synthesizing the π-conjugated structure HAADF-STEM, and Raman spectroscopy) and theoretical
with transition metal atoms and aromatic organic ligands calculations, systematic studies will provide a new perspective
as precursors could enhance the conductivity. Converting to identify the intrinsic catalytic active sites and many new
bulk MOF crystals into 2D nanosheets could also enable possibilities for the rational design and performance break-
the higher exposure of the active surface sites. Designing throughs in state-of-the-art water-splitting electrocatalysts.
bimetallic MOFs may further optimize the electrocatalytic 5) Low-cost and high-performance non-precious electrocatalysts
performance for water splitting because of the synergis- for overall water splitting are urgently needed to promote
tic effect between the multi-metal element. Furthermore, the development of affordable water-splitting electrolyzers,
MOFs could be combined with various functional materials thus accelerating future industrialization. Meanwhile, new
(e.g., metal NPs, molecule complexes, and graphene) to techniques to fabricate electrodes or electrolyzers are
achieve more exposure of the active catalytic sites, thus required for the rational assembly of water splitting devices
significantly improving the conductivity for the resulting for scalable and safe production or utilization of hydrogen.
MOF composites. For instance, decoupled water electrolyzers have recently
2) Solvothermal reactions with extra salt solutions and the syn- been developed to separate the HER and OER processes to
thesis of bimetallic MOFs are commonly employed strate- avoid the formation of explosive H2/O2 gas mixtures, which is
gies to introduce the second metal component into MOFs, usually achieved by redox mediators (Figure 17a). Due to the
followed by pyrolysis, to realize heteroatom doping, more lack of cost-efficient hydrogen storage and transport systems,
accessible active sites, well-controlled nanostructures, well- tandem water electrolysis has been developed; as shown in
designed synergistic effects, and robust structural stability. Figure 17b, the produced hydrogen can be converted in situ
During the calcination process, the low-boiling-point metals to valuable chemicals (e.g., NH3, CH4, etc.).[265]
Figure 17. a) Decoupled water electrolyzer system. b) Tandem water electrolyzer system. a,b) Reproduced with permission.[265] Copyright 2018, Amer-
ican Chemical Society. c) The chemical structures of the AEM electrolytes. TMA: trimethyl ammonium functionalized polystyrenes. HTMA-DAPP:
hexamethyl trimethyl ammonium-functionalized Diels–Alder polyphenylene. d) AEM electrolyzer performance that equipped with the HTMA-DAPP.
c,d) Reproduced with permission.[266] Copyright 2020, Springer Nature.
6) Low-temperature water electrolyzer systems can use either and 2019YFA0110601), National Natural Science Foundation of China
a proton exchange membrane (PEM) or alkaline anion ex- (Nos. 82071938, 82001824, 51903178, 81971622, 51803134, and 51703141),
change membrane (AEM) as the electrolyte. Nevertheless, the Science and Technology Project of Sichuan Province (Nos.
2020YFH0087, 2020YJ0055, 2019YFS0219, and 18YYJC1417), Special
the high capital cost of the cell stack and the large noble Funds for Prevention and Control of COVID-19 of Sichuan University
metal loading amount required for the electrodes are nota- (2020scunCoV-YJ-20005) and SKLFPM, Donghua University (YJ202005),
ble disadvantages for the PEM-based electrolyzer. It has been and the Post-Doctor Research Project, West China Hospital, Sichuan
found that alkaline AEM electrolysis can offer the possibility University (No. 2018HXBH077). C.C. acknowledges the support of the State
of replacing the PEM-based electrolyzer, including the pos- Key Laboratory of Polymer Materials Engineering (No. sklpme2019-2-03),
sible use of noble metal-free catalysts, without significant Fundamental Research Funds for the Central Universities, Thousand
Youth Talents Plan, and Alexander von Humboldt Fellowship. The authors
loss of catalytic performance. For instance, Li et al. recently
thank their laboratory members for their generous help, and gratefully
reported several quaternized polystyrene electrode binders, acknowledge Dr. Chao He for the analytical support, Sichuan University.
which show excellent activity for the HER and OER in AEM Open access funding enabled and organized by Projekt DEAL.
electrolyzers.[266] The electrolyzer of the NiFe-anode-catalyzed
device showed excellent operational performance compara-
ble to that of a state-of-the-art PEM electrolyzer using noble Conflict of Interest
metals (Figure 17c,d). The authors declare no conflict of interest.
In summary, from a practical standpoint, the development Keywords

of low-cost and high-efficiency electrocatalysts is crucial to
electrocatalytic nanostructures and electrocatalysts, hydrogen evolution
address the challenges, both in water splitting and other energy
reaction, metal–organic frameworks, oxygen evolution reaction, water
devices, for overcoming the ever-growing energy crisis and splitting
environmental concerns. We hope that this review will advance
the rapid exploration of MOF-based/derived electrocatalysts Received: September 4, 2020
for water splitting. Furthermore, we anticipate that, with the Revised: October 18, 2020
development of inexpensive and efficient electrocatalysts, a new Published online: March 22, 2021
technological revolution will take place in the field of electro-
chemical hydrogen production in the not-too-distant future.
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Ben Zhang is currently a Master’s student at the College of Polymer Science and Engineering,
Sichuan University. His research interest is synthesizing metal–organic-framework-based catalytic
materials for energy storage and conversion applications.
Yijuan Zheng is currently a Master’s student at the College of Polymer Science and Engineering,
Sichuan University. Her research interest is synthesizing functional nanomaterials related to
electrocatalysis in energy conversion.
Shuang Li received her Master’s degree at Shanghai Jiao Tong University. During her Master’s
period, she took part in the ERC grant 2DMATER at the Max Planck Institute for Polymer
Research in Mainz, Germany in 2013. Then, she became a research scholar from 2014 at the
University of Michigan, Ann Arbor. From 2015, she was doing her Ph.D. research studies in the
group of Prof. Arne Thomas at Technische Universität Berlin. Now, she is doing her independent
postdoctoral research at Technische Universität Berlin on the synthesis of metal–organic-
precursor-based materials for electrocatalytic electrodes and devices.
Yinghan Wang is a full professor in the Department of Polymer Science at Sichuan University.
He received his B.Eng. from East China University of Science and Technology, his M.Eng. from
Sichuan University, his Ph.D. from Tokyo Institute of Technology. He joined JSR Corporation and
DIC Corporation as a research fellow. His main research interests include functional membrane
materials, fuel-cell proton-exchange membranes, polyimide liquid-crystal alignment materials,
polymer-dispersed liquid crystals, high-performance composite materials, and energy-storage and
electrocatalytic materials.
Chong Cheng is currently a full professor in the Department of Polymer Science at Sichuan
University. He obtained his B.Sc. and Ph.D. from Sichuan University. After a research stay at the
University of Michigan, Ann Arbor, USA, he joined the Freie Universität Berlin as an AvH research
fellow. His current scientific interests include fabricating advanced low-dimensional materials for
nanomedicines (antibacterial, virus inhibition, anti-tumor), stem cell scaffolds, electrocatalysts,
and energy-related applications, especially the cutting-edge applications of coordination polymers
and metal–organic frameworks.

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Progress Report

Designing MOF Nanoarchitectures for Electrochemical

carrier with an extremely high energy

Metal element MOFs Metal centers Metal content Ref.

of electrochemical water splitting, which is an efficient strategy 1,3,5-triaminobenzene-2,4,6-trithiol, hexaaminobenzene,

Table 4. Overall water splitting performances of MOF-based/derived electrochemical catalysts.

In summary, from a practical standpoint, the development Keywords

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