Review
Hydrogen Evolution Reactions
Metal–Organic Framework Based Catalysts for Hydrogen
Evolution
Bingjun Zhu, Ruqiang Zou,* and Qiang Xu*
Highly efficient hydrogen evolution reactions (HERs) will determine the
mass distributions of hydrogen-powered clean technologies in the future.
Metal–organic frameworks (MOFs) are emerging as a class of crystalline
porous materials. Along with their derivatives, MOFs have recently been
under intense study for their applications in various hydrogen production
techniques. MOF-based materials possess unique advantages, such as
high specific surface area, crystalline porous structure, diverse and tunable
chemical components, which offer attractive functionalities in catalyzing
hydrogen evolution processes, by lowering reaction potentials, and speeding
up reaction rates. Considering the rapid increase in research interest in
hydrogen evolution in the last several years, this review aims to summarize
recent advances in MOF-associated hydrogen evolution research, including
electrocatalytic, photocatalytic, and chemocatalytic HER. Particular attention
is paid to the design and utilization of postsynthetic modification of MOFs,
MOF-supported catalysts, and MOF derivatives for highly efficient HER. The
opportunities and challenges for MOF-based materials in a hydrogen-powered
clean future are also discussed.
1. Introduction
Environment and energy are two unshakable foundation stones
for the survival of mankind. Although state-of-the-art tech-
niques (such as carbon capture,[1] wind,[2] and solar power[3,4])
are under studies to remediate the problems of environmental
pollution and energy shortage, the development of modern
Dr. B. Zhu, Prof. R. Zou
Beijing Key Laboratory for Theory and Technology of Advanced Battery
Materials
Department of Materials Science and Engineering
College of Engineering
Peking University
Beijing 100871, China
E-mail: rzou@pku.edu.cn
Prof. Q. Xu
AIST-Kyoto University Chemical Energy Materials Open Innovation
Laboratory (ChEM-OIL)
Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
E-mail: q.xu@aist.go.jp
Prof. Q. Xu
School of Chemistry and Chemical Engineering
Yangzhou University
Yangzhou, Jiangsu 225009, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201801193.
DOI: 10.1002/aenm.201801193
Adv. Energy Mater. 2018, 1801193 1801193  (1 of 33)
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society is still heavily relying on chemical
fuels. Therefore, the essential and realistic
approaches to environmental and energy
issues remain to be the exploration of
clean and sustainable energy sources, in
order to meet the ever-increasing energy
demand. Thanks to its high energy
density and environmental friendliness,
hydrogen fuel comes into play as a much-
anticipated new energy carrier, which is
under intensive studies in the academic
field.[4] Furthermore, we are already in
the new era witnessing the transforma-
tion of hydrogen-powered technologies
from science fictions to realities. UK is
already in the process of replacing their
traditional diesel-powered double decker
buses with the hydrogen-powered version,
which aims to phase out the former by
2018.[5] China announced its world’s first
hydrogen-powered tram, which was put
into business service in the latter half of
2017.[6] Mercedes-Benz had even started its
development of personal hydrogen-powered car, and Toyota had
commercialized its hydrogen fuel-cell car branded “Mirai.”[7,8]
However, one critical issue remains to be the conflict between
the hydrogen production efficiency and the demand for the
mass distribution of hydrogen-powered technologies.
Current industrial hydrogen production methods include
coal gasification (followed by water–gas shift reaction), steam
reforming, cryogenic distillation, and water splitting.[9] Coal
gasification and steam reforming utilize the reaction between
conventional fossil fuels and water to produce syngas (pri-
marily CO and H2) or CO2 and H2 mixture. However, both
reactions require high temperatures (can be over 1000 °C) and
pressures, which is an energy intensive process and has strict
requirements on infrastructures.[10] The reaction products also
need to be further separated to obtain relatively high-concen-
tration of hydrogen. Cryogenic distillation takes the advantage
of difference in gas boiling points, which can be applied to
separate hydrogen from other gas components in the former
two hydrogen production methods. However, cryogenic distil-
lation is also an energy intensive process for low-temperature
gas liquification. In comparison, hydrogen evolution reaction
(HER) through water splitting is much-favored because of the
following three prominent advantages: 1) Water splitting can be
carried out at room temperature and ambient pressure, which
is less restricted by infrastructure requirements. 2) Oxygen and
hydrogen can be produced separately or selectively, which elim-
inate the need for gas separation. 3) Both the hydrogen source
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(H2O) and products (O2 and H2) are environmentally preferred,

which truly fulfills the concept of clean technology.[11] Despite Bingjun Zhu is currently a
the abovementioned superiorities, in the case of electrocatalytic postdoctoral research fellow
water splitting, high electric power consumption is the key at the College of Engineering,
obstacle for the utilization of water electrolysis for mass Peking University, China. He
hydrogen production. More specifically, the fundamental causes received his Ph.D. degree
for high electric power consumption are the relatively high from the Department of
electric potential to initialize HER and low H2 production rate. Chemistry, University College
On the one hand, electrocatalysts can be introduced to lower London, UK, and his Master
reaction potential and speed up reaction rate, and therefore, the of Engineering degree from
overall electric power consumption is reduced. On the other the School of Engineering
hand, photocatalytic HER is an alternative option, since solar and Materials Science,
irradiation can be regarded as a “free” natural energy resource. Queen Mary, University of
Theoretically, light irradiation around 1000 nm wavelength can London, UK, and his Bachelor of Engineering degree from
be used to activate photocatalytic water splitting with the assis- the School of Engineering and Materials Science, Beihang
tance of photocatalysts, since the standard Gibbs free energy for University, China. His research interests include metal–
the water splitting reaction is 1.23 eV (i.e., activation energy). organic frameworks, biomass, polymers, and their deriva-
However, it sets an extremely strict requirement, because the tives for energy and environmental applications.
catalyst’s bandgap must be exactly 1.23 eV. In addition, the
edges of its conduction and valence bands must locate exactly at Ruqiang Zou is currently a
the redox potentials of H+/H2 (0 V vs normal hydrogen electrode professor of Materials Science
(NHE)) and O2/H2O (1.23 V versus NHE), respectively.[12] In and Engineering at the
practice, ultraviolet (UV) or visible light are frequently applied College of Engineering, Peking
in photocatalysis-related studies.[13] Furthermore, chemocata- University, China. He received
lytic HER is an alternative option, where hydrogen is generated his Ph.D. from Kobe University
through chemocatalytic decomposition of hydrogen precursors, and the National Institute of
such as ammonia borane, hydrazine monohydrate, and sodium Advanced Industrial Science
borohydride.[14] Precious metals, such as platinum, iridium, and Technology (AIST),
and ruthenium, are frequently used as catalysts for HER.[15] Japan. After graduating from
Particularly, in the case of electrocatalytic HER, commercially Kobe University in 2008, he
available 20% Pt/C is usually applied as the benchmark catalyst, was awarded a Director’s
where most research objectives are to match and surpass its Postdoc Fellowship at Los Alamos National Laboratory
performance. However, significant issues of expensiveness in the United States. His research interests focus on the
and relatively low stability limit their applications in practice. controllable preparation of nanoporous materials for green
As a result, materials scientists have been considering nonpre- energy utilization. He proposes to construct hierarchically
cious metal catalysts as alternative options, such as transitional porous materials for single-molecule adsorption, and extend
metal oxides, sulfides, and nitrides.[16] However, their perfor- their potential applications in hydrogen storage, carbon
mances are far from approaching those of precious metal-based capture, and energy storage materials.
catalysts, due to low porosity or limited flexibility in material
design. On this occasion, metal–organic frameworks-based Qiang Xu received his Ph.D.
(MOFs) catalysts stand out as a distinguished candidate for in Physical Chemistry in
highly efficient HER, including electrocatalytic, photocatalytic, 1994 from Osaka University,
and chemocatalytic HER, as illustrated in Figure 1.[17] Japan. He is the Director
Along with the research on MOF-based catalysts for HER, of AIST-Kyoto University
there are various types of porous materials under intensive Chemical Energy Materials
studies at the same time, including zeolitic,[18] polymeric,[19,20] Open Innovation Laboratory
carbonaceous,[21] and composite[22] materials. They share the (ChEM-OIL), Prime Senior
common merit of well-developed porosities with high specific Researcher of the National
surface area and large pore volumes, which is the key advantage Institute of Advanced
for their applications in HER. In addition, external modifica- Industrial Science and
tions, such as loading active nanoparticles[23,24] and grafting sur- Technology (AIST, Japan),
face functional species,[25,26] can be applied to further enhance Distinguished Professor of Yangzhou University, Adjunct
the activities of the catalysts. However, when compared with Professor at Kobe University and at Kyoto University, and
other types of porous catalysts, the attractions of MOF-based a Distinguished Honorary Professor at The Hong Kong
materials in catalytic HER are reflected in their unique char- Polytechnic University. His research interests include the
acteristics, including their adjustable crystalline porous frame- chemistry of nanostructured materials and their appli-
works and tunable chemical constituents and structures, which cations, especially for energy. He is a member of the
originates from the diverse combinations of metal centers European Academy of Sciences (EURASC).
and organic ligands. In addition, Figure 1 shows that another

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Figure 1.  A schematic flow chart shows how MOF-based catalysts can be used for different hydrogen evolution reactions. Apart from their pristine
forms, MOFs can also be utilized in the forms of supporting frameworks and precursor materials for electrocatalytic, photocatalytic, and chemocatalytic
hydrogen evolution reactions.
distinguishing feature of MOFs is their flexibility. Similar
to other porous catalysts, MOFs can be either used in their
pristine forms,[27] or be applied as supporting frameworks to
disperse, immobilize, or even isolate extrinsic catalytically active
species, owing to their well-developed and tailorable porous
networks.[28–31] Frequently, the combination of catalytically
active nanoparticles and frameworks can introduce surprising
synergistic effects, which leads to much improved performance
than that of either host or guest material. However, MOFs
can also be used as precursors to synthesize a variety of metal
compounds or metal/carbon composites with intentionally
designed elemental compositions and structures.[17,32] These
three forms of MOF-based catalysts raise the potential to syn-
thesize a great number of MOF-based catalysts for different
HER types. In recent years, there is an explosive development
of hydrogen-powered technologies in industries and a consider-
able number of published articles on MOF-based catalysts for
HER. Although MOF-based materials were comprehensively
reviewed for their designs, characteristics, syntheses, and appli-
cations in electrocatalysis[12,33,34] and photocatalysis.[35–37] For
example, in 2015, Meyer et al. published a perspective article
that focuses on MOFs for photocatalytic water splitting, which
offered a comprehensive review on the fundamentals and
advances of MOFs for water oxidation and reduction reactions.
Later in 2016, Mahmood et al. presented a progress report on
MOF-based nanomaterials for electrocatalysis, which demon-
strates the applications of MOFs in all kinds of electrochemical
applications, including electrocatalytic HER. In 2017, Wang
et al. delivered a complete review of MOFs for all kinds of
energy applications, including CO2 reduction, fuel cells, Li-ion
batteries, chemical storage, as well as HER/water splitting.[34]
However, rare review went into an in-depth summary of MOF-
based materials for catalyzing HER, covering pristine MOFs,
MOF supports, and MOF derivatives for electrocatalytic, photo­
catalytic, and chemocatalytic HER. Herein, this review aims to
summarize recent advances in MOF-based materials for the
above three hydrogen evolution reactions with the in-depth
discussion of their material processing and mechanisms for
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enhanced performance. This review also proposes prospects for
opportunities and challenges of MOF-based catalysts for mass
hydrogen production in the future.
2. Merits of MOFs for Catalysis
MOFs are a family of crystalline porous materials, which are
constructed by metal ion/cluster centers and coordinated
organic linkers.[38] Thanks to the unique characteristics of
MOFs, they have attracted great attention in a wide range of
applications in energy conversion, including oxygen reduction
reactions (ORR),[39–41] oxygen evolution reactions (OER),[42–44]
metal–air/O2 batteries,[45–47] CO2 reductions,[48] as well as
catalytic HER. Figure 2 uses zeolitic imidazolate framework
(ZIF)-67 as an example to show how each characteristic of
MOFs can be utilized as an advantage in catalysis.
2.1. Ultrahigh Porosities for Accessible Active Sites
The specific surface area of MOFs can range from 1000 to over
6000 m2 g−1, thanks to their tailorable porous structures, which
play a significant role in enhancing the catalytic HER process.[49]
First, large surface area and pore volume ensure sufficient con-
tact between the electrolyte (or reactant solution) and the surface
of the catalyst, which essentially improves catalytic performance
by exposing more active sites for the catalytic reactions to take
place. In particular, when synergy occurs between guest spe-
cies and host MOFs, well-distributed nanoparticles may further
strengthen the synergistic effect because of enlarged interface
between the guest and the host. Moreover, a well-developed hier-
archically porous network can further promote the diffusion of
electrolyte, shorten the transport distant for reactants to move
from the solution to the surface of a catalyst, and thus lower
the kinetic barrier for an efficient catalytic reactions, as demon-
strated by recently published works on MOF-derived catalysts
with hierarchically porous structures.[44,50–52] More importantly,
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Figure 2.  Key merits of MOFs as catalysts for HER (ZIF-67 is used here as an example, green ball: pore space; purple: Co; yellow: nitrogen; grey: carbon).
the ordered porous structures of MOFs make target-driven
designs, repeatable syntheses, and systematic studies on cata-
lytic mechanisms a controllable work.
When MOFs are utilized as supports or precursors,
MOF-based composites or derivatives may inherit the porous
structures of pristine MOFs, however, with reduced specific
surface areas and pore volumes. In the case of MOF deriva-
tives, the reduced porosity results from the collapse of
crystalline porous structure, which is caused by the breaking of
coordination bonds and the removal of noncarbon elements at
high temperatures. When MOFs are used as supports, it is a
consequence of pore occupation or blocking by guest particles.
In this case, the decrement in porosity is usually determined
by the sizes and dispersity of guest particles. However, reduced
porosities are not necessary detrimental to the performance
of MOF derivatives. On the one hand, thermal treatments on
MOFs usually aim to obtain MOF derivatives with specific
chemical contents and structures, such as metal oxides, metal
carbides, metal nitrides, metal sulfides, and metal/carbon
composites. Yan et al. synthesized nickel–cobalt bimetallic
phosphide nanotubes derived from their bimetallic MOF-74-
CoxNiy precursor for electrocatalytic water splitting. The spe-
cific surface area of the pristine MOF was greatly reduced from
1100 to 55.6 m2 g−1 after oxidation and phosphorization.[53]
Yan et al. obtained hierarchical titania by pyrolyzing Ti-MOF
Material from Institut Lavoisier (MIL)-125-NH2(Ti) in air, which
is further loaded with palladium for photocatalytic HER. The
specific surface area drops from 947.9 m2 g−1 for the pristine
MOF to 86.8 m2 g−1 for the 1.5% Pd/TiO2 after pyrolysis and Pd
loading.[54] On the other hand, the encapsulation of guest mole­
cules targets to introduce more catalytic active sites to the pris-
tine MOFs or to promote synergistic effects between the guest
molecules and host materials. Hao et al. reported the introduc-
tion of MoS2 quantum dots and graphene into UiO-66-NH2, a
Zr-containing MOF for photo­catalytic HER. The pristine MOF
possesses a specific surface area of 712.3 m2 g−1. This value
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drops to 457.24 m2 g−1 after the loading of MoS2 (5.0 wt%) and
graphene.[55] Zhen et al. developed Ni nanoparticles (9.7 wt%)
loaded MOF-5 for the same application. In this case, due to
highly dispersed nanoparticles, the corresponding specific sur-
face area is only slightly reduced from 2973 to 2961 m2 g−1.[56]
MOF composites and derivatives in all the abovementioned
examples exhibit significantly better performance in catalyzing
HER when compared with those of their corresponding sup-
ports and precursors.
2.2. Tunable Catalytical Metal Active Sites
The diversity of MOF-based materials originates from vastly pos-
sible combinations of metal ion/cluster nodes and coordinating
organic linkers. In terms of metal nodes, catalytic active metal
elements can be purposely selected to construct MOF-based
materials for different types of catalytic HER. For examples,
Qin et al. developed ultrastable polymolybdate-based MOFs,
Mo-containing NENU-500 and NENU-501, for electrocatalytic
HER. Both MOFs consist of Mo-based polyoxometalate (POM)
nodes ε-PMoV8MoVI4O36(OH)4Zn4, which possess encouraging
redox activity. The combination of redox-active POM nodes
and MOF porous structures leads to excellent and stable HER
catalytic performance.[57] Garcia and co-workers first reported
Zr-containing MOFs UiO-66 for photocatalytic HER under UV
irradiation.[58] Besides the merits of considerable porosity and
excellent stability in water, the photocatalytic HER capability of
UiO-66 is attributed to their semiconducting behaviors, which
arises from the semiconducting characteristics of their oxidized
constructive units Zr6O32 as photocatalytic active sites.
As mentioned previously, MOFs can also be used as pre-
cursors to produce various metal compounds and metal/
carbon composites. In this case, the choice of metal node is
mainly based on the formation of final products after thermal
treatments. ZIF-67 is a Co-based MOF, which consists of cobalt
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ion center and 2-methylimidazole linkers.[59] It is one of the
most frequently studied MOF precursors for the syntheses of
metal oxides, phosphides, sulfides, and metal-doped carbon
composites. For instance, Yilmaz et al. proposed an in situ trans-
formation method to convert ZIF-67 into bimetallic (Ni and Co)
layered double hydroxide embedded cobalt sulfide for electro-
catalytic HER. It is processed by thermal annealing and hydro-
thermal reactions with thioacetamide and nickel nitrate hexa-
hydrate.[60] Enhanced electrocatalytic performance is associated
with the embedment of Co9S8 between layered double hydrox-
ides. You et al. reported the derivation of CoP and Co2P nano-
particles in N-doped carbon composites from ZIF-67 through
direct carbonization followed by phosphorization for electrocat-
alytic water splitting.[61] In this case, ZIF-67 plays multiple roles
in improving the catalytic performance of its carbon derivative.
Cobalt atoms from the pristine ZIF-67 remain in the resulting
carbon products as the active sites for HER catalysis. The pris-
tine ZIF-67 also plays the role of template to direct the forma-
tion of carbon matrix. Meng et al. carried out one-step seleniza-
tion of ZIF-67 into nitrogen- and Co/Se-doped carbon for the
same application.[62] Similar to You’s work, ZIF-67 is applied as
both precursor and template, which leads to a porous carbon
network with encapsulated Co0.85Se nanocrystals. It should be
noted that, in both cases, the carbonization process has signifi-
cant impacts on the catalytic performance of the resulting MOF
derivatives. Generally speaking, apart from porous structures
inherited from MOF precursors, a catalyst can benefit from
the carbonization process through improved electric conduc-
tivity.[17] Furthermore, the strategy of carbonization can achieve
intended functional chemical structures with synergistic effects
between metallic and carbonaceous components. For example,
in the work of Meng et al., the MOF carbonization intended to
obtain the “metal–nitrogen–carbon (M–N–C)” structure, which
is the coordination of cobalt cations through nitrogen func-
tional groups from N-derived carbon.[62] The M–N–C structure
usually results in the charge redistribution at the metallic sites,
rendering them more catalytically active. In addition, in some
cases, the carbonization of MOFs may lead to the formation
of metal–carbon core–shell structures.[63,64] In this case, the
carbon shell can protect the encapsulated metal nanoparticles
from external corrosion or further agglomeration, which helps
to enhance the stability of a catalyst.
It can be concluded from the above examples that, for both
pristine MOFs and MOF-derived catalysts, metal nodes are the
key to determine their catalytic capabilities in HER. In addition,
when porous network is preserved in the form of carbon
matrix after thermal treatment of MOFs, the resulting metal
dopants may work synergistically with the carbon matrix, which
can effectively improve the catalytic performance of MOF
derivatives when compared with those of the pristine MOFs.
2.3. Functionalizable Organic Linkers
Diverse and tunable chemical constituents are a key merit of
MOF-based materials. This is reflected as vast combinations
of metal nodes and organic linkers. On the one hand, organic
ligands play the role of “skeletons” to link metal nodes, which are
critical for the formation of porous networks of MOFs, as demon-
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strated by the structure of ZIF-67 in Figure 2. On the other hand,
organic linkers can also be the source of carbon when MOF pre-
cursors are thermally treated in inert gas atmospheres (such as
N2 and Ar), which is directly associated with the formation of
metal-doped carbon network. More importantly, they raise the
possibility of introducing nonmetallic active sites in both pristine
MOFs and MOF derivatives, such as O, N, P, and S, which can
further enhance the material’s catalytic performance in HER.
Liang et al. developed a Ni- and Co-based bimetallic MOF for
the subsequent synthesis of Ni2P–CoP bimetallic phosphides for
electrocatalytic water splitting. In this case, benzenedicarboxylic
acid is applied as the organic ligand to link Ni and Co atoms.[65]
Sun et al. reported a gadolinium-based MOF [Gd2(abtc)(H2O)
(OH)2]·2H2O (H4abtc = 3,3′,5,5′-azobenzene tetracarboxylic
acid) for photocatalytic HER.[66] The choice of azo-carboxylic acid
is attributed to its dye-like characteristics, which aims to intro-
duce a light harvesting unit into MOFs and thus improves the
overall catalytic performance. It is aforementioned that UiO-66
is frequently utilized for photocatalytic HER. However, the reac-
tion can only be activated under UV irradiation. By modifying its
organic linkers with amino groups, that is, UiO-66-NH2, the cor-
responding light absorption spectra can be extended to the visible
light range.[58] Zhang and co-workers demonstrated the assembly
of Co-based MOF with S-containing ligand thiophene-2,5-di-
carboxylate (tdc) and nitrogen-containing 4,4′-bipyridine (bpy)
ligand, which is simultaneously loaded on graphene oxide (GO)
sheets.[67] The pyrolysis of this precursor leads to core–shell Co/
Co9S8 structure anchored on S,N codoped graphene sheets,
which is then applied for electrocatalytic water splitting.
3. MOFs for HER
It is aforementioned that researches on MOFs for HER pri-
marily focus on the following three techniques: electrocatalytic,
photocatalytic, and chemocatalytic HER. Pristine MOFs, MOF
supports, and MOF derivatives can be utilized as catalysts in
the abovementioned hydrogen production methods. The fun-
damentals, characterizations, and catalytic performance of
specific MOF-based catalysts for different HER techniques are
presented and summarized in the following subsections.
3.1. MOFs for Electrocatalytic HER
As illustrated in Figure 3, electrocatalytic HER is usually real-
ized by applying electrical current through an aqueous electro-
lyte to produce O2 on the anode side through OER and H2 on
the cathode side through HER. Although studies on electro-
catalytic HER mainly focus on the half reaction at the cathode
side, in the case of research on overall water splitting, the per-
formance of MOF-based catalysts in both HER and OER needs
to be evaluated.
3.1.1. Electrocatalytic HER
Fundamentals and Characterizations: Electrocatalytic HER is
the half reaction of water electrolysis, which takes place at the
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Figure 3.  An illustration of a water electrolyzer for electrocatalytic HER/
water splitting.
side of cathodes, where MOF-based catalysts can be utilized
to modify electrodes and lower their hydrogen adsorption
free energies. Electrocatalytic HER can be carried out in both
acidic (usually 0.5 m H2SO4) and alkaline (usually 1 m KOH)
electrolytes. However, the catalytic reactions follow different
mechanisms. On the one hand, in an acidic solution, the
reaction follows the combination of protons from the electro-
lyte and electrons from the electrode surface, which is referred
as Volmer pathway.[68] Then, hydrogen molecule is produced
by the further combination of the existing hydrogen atom with
the adjacent one (referred as Tafel pathway), or with another
proton from electrolyte and an electron from the electrode
surface (referred as Heyrovsky pathway). On the other hand, in
an alkaline solution, because the protons are absent in electro-
lytes, the catalytic reaction starts from the dissociation of water
(Vomer pathway). Then, hydrogen molecules are generated by
following Tafel or Heyrovsky pathway as well. The additional
water dissociation step indicates that, for the same catalyst, its
performance in an alkaline electrolyte is very likely worse than
that in an acidic solution.[68] However, the unique characteris-
tics of MOFs still arise the opportunities for MOF-based cata-
lysts to surpass the performance of benchmarking catalyst 20%
Pt/C in both acid and alkaline electrolytes.
The electrocatalytic performance of MOF-based catalysts in
HER is usually carried out by the method of rotating disk elec-
trode in a three-electrode configuration (working, counter, and
reference electrodes), where the catalysts are deposited on the
surface of a glassy carbon electrode. Onset potential, overpoten-
tial, and Tafel slope are the key parameters that can be derived
from linear sweep voltammetry (LSV) polarization curves for
determining a catalyst’s performance. The former two reflect
the thermodynamic barrier to initiate HER catalysis, while the
latter can be used for the analysis of reaction kinetics. However,
due to the ambiguity in the definition of onset potential for
HER, the overpotential at the current density of 10 mA cm−2 is
widely accepted for the performance comparison.
Furthermore, Tafel slope is regarded as an important param-
eter to analyze the rate-determining step in HER (namely,
Volmer, Tafel, and Heyrovsky steps), where its value can be
used to evaluate how fast the electric current responses to
the applied potential. However, a key assumption here is the
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constant surface coverage of the intermediate species. In
practice, the coverages of the intermediate species are very
likely different with varied potentials. In 2015, Shinagawa et al.
published their study on Tafel slope, which demonstrated that
a Tafel slope of 120 mV dec−1 for HER cannot simply be attrib-
uted to the Volmer step. The same slope was also observed for
the Heyrovsky step with the condition of the high coverage of
adsorbed hydrogen.[69] Therefore, Tafel slope is both potential-
and coverage-dependent and thus the rate-determining step
cannot be simply determined by Tafel slope.
Moreover, the stability of the catalyst is measured by cyclic
voltammetry (CV), chronoamperometry, or chronopotentiom-
etry. Although quantitative test results are preferred in the form
of “percentage drop,” most published works tend to use qualita-
tive terms to describe the stabilities of the catalysts, only with
reference to the number of CV cycles or the duration of the test.
In addition, the influence of the reaction at the anode side
(counter electrode) may not be neglected in some circum-
stances.[70] First, the reaction at the anode side may depend on
the material of the counter electrode. For example, when Pt
is used as the counter electrode, OER can occur at the anode
side with the company of partial oxidation and dissolution of
Pt in the electrolyte. The redeposition of Pt on the cathode side
(working electrode) can lead to a delusively improved HER
activity. Second, in the case when OER occurs at the anode
side, proton reduction at the cathode side is a 2-electron pro-
cess, while OER at the anode side is a 4-electron process. To
compensate the charges at the cathode side, OER at the anode
should occur as fast as the proton reduction at the cathode.
Therefore, when compared with working electrodes in practice,
counter electrodes (such as platinum sheet or graphite rod)
with larger area (i.e., larger catalytically active surface) are used
to achieve this goal. The reaction rate at the anode side is able
to catch up with that at the cathode side if the cathode current
density is relatively low. In this case, the influence of the reac-
tion at the counter electrode may be neglected. However, when
the cathode current density is too large, the reaction rate at the
anode side may reach its upper limit, which is unable to match
that at the cathode side. In this case, the anode reaction deter-
mines the overall reaction rate and thus needs to be taken into
consideration.[70]
The performance of recently reported MOF-based catalysts
for electrocatalytic HER is presented in the following subsec-
tions and summarized in Table 1.
Pristine MOFs: When designing a pristine MOF cata-
lyst for electrocatalytic HER, the choice of metal nodes and
organic linkers is mainly based on their catalytic activities
and framework formation. Qin et al. developed an ultrast-
able polymolybdate-based MOF electrocatalysts NENU-500
and NENU-501 (NENU = Northeast Normal University).[57]
NENU-500 and NENU-501 compose of Mo-based POM nodes
ε-PMoV8MoVI4O36(OH)4Zn4 and ε-PMoV8MoVI4O37(OH)3Zn4
(Zn-ε-Keggin), respectively. They are also connected with dif-
ferent organic linkers. In the case of NENU-500, it is BTB (ben-
zene tribenzoate) to form [TBA]3[ε-PMoV8MoVI4O36(OH)4Zn4]
[BTB]4/3·xGuest (TBA = tetrabutylammonium) (Figure 4A).
For NENU-501, it is BPT (1,1′-biphenyl]-3,4′,5-tricarboxylate)
to form [TBA]3[ε-PMoV8MoVI4O37(OH)3Zn4][BPT] (Figure 4B).
Their electrocatalytic HER activities primarily originate from
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Table 1.  Summary of MOF-based catalysts for electrocatalytic HER in recent publications.

Sample ID Electrolyte Overpotentiala) [mV] Tafel slope [mV dec−1] Stability testsb) Ref.
NENU-500 0.5 m H2SO4 237 96 2000 cycles [57]
NENU-501 0.5 m H2SO4 397 137 2000 cycles [57]
THAT-Co 0.5 m H2SO4 283 71 300 cycles and 4 h [71]
CTGU-5 0.5 m H2SO4 388 125 N/A [72]
CTGU-6 0.5 m H2SO4 425 176 N/A [72]
AB&CTGU-5 0.5 m H2SO4 44 45 96 h [72]
NU-1000_Ni–S 0.1 m HCl 238 120 2h [73]
UiO-66-NH2-Mo-5 0.5 m H2SO4 200 59 5000 cycles and 7h [76]
MoCx 0.5 m H2SO4 142 53 10 h [77]
1 m KOH 151 59
S-600 0.5 m H2SO4 262 74 10 000 cycles and 10 h [78]
NiS 1 m KOH 94 139 16 h [79]
C/LDH/S 1 m KOH 142 62 60 h [60]
CoPd@NC 0.5 m H2SO4 80 31 10 h [98]
NiFe-NGT-800 0.5 m H2SO4 150 mV at 63.4 3000 cycles [95]
18 mA cm−2
MoS2/3D-NPC 0.5 m H2SO4 210 51 1000 cycles [102]
Co–N–GA 0.5 m H2SO4 46 33 5000 cycles [99]
1 m KOH 232 102
1 m PBS 299 159
Co/N–C 1 m KOH 103 N/A 11 h [100]
FexP@NPC 0.5 m H2SO4 227 81 1000 cycles and 11 h [88]
Mo2C/C 1 m KOH 165 63.6 20 h [89]
MoC@GS(700) 0.5 m H2SO4 124 43 3000 cycles and 10 h [103]
1 m KOH 77 50
Fe3C/Mo2C@NPGC 0.5 m H2SO4 98 45.2 10 h [90]
Ni-0.2NH3 1 m KOH 88 mV at 71 12 h [96]
20 mA cm−2
Ni2P 0.5 m H2SO4 172 62 200 cycles and 6 h [53]
NiS2 HMSs 1 m KOH 219 157 19 h [93]
Ni2P polyhedron 0.5 m H2SO4 158 73 2000 cycles [92]
HC800 1 m KOH 123 83 2h [94]
NiMo2C@C 0.5 m H2SO4 169 100 10 h [97]
1 m KOH 181 84
Co0.59Fe0.41P 0.5 m H2SO4 72 52 1000 cycles and 20 h [101]
1 m KOH 92 72
CoPN-C-400 0.5 m H2SO4 91 42 1000 cycles [80]
Co/(NiCo)Se2 0.5 m H2SO4 200 mV at 17.5 mA cm−2 39.8 1000 cycles [82]
CoP CPH 0.5 m H2SO4 133 51 1000 cycles [83]
CoSe2@DC 0.5 m H2SO4 132 82 1000 cycles and 20 h [84]
Co@NCNTs-800 0.5 m H2SO4 280 95.9 1000 cycles and 10 h [86]
1 m KOH 240 83
CoP NRAs 0.5 m H2SO4 181 69 1000 cycles and 10 h [81]
Co@N–C-600 0.5 m H2SO4 339 119 200 cycles and 6 h [87]
MOF-CoSe2 0.5 m H2SO4 330 mV at 80 mA cm−2 42 2000 cycles and 20 h [85]

is measured at 10 mA cm−2; b)Due to qualitative descriptions of stability test results in most published works, only the duration of the chronoamperometric
a)Overpotential

(or chronopotentiometric) test and the number of CV cycles are summarized in this table.

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Figure 4.  Structures and HER performance of NENU-500 and NENU-501. A) NENU-500 (each BTB3− is connected with 3 Zn-ε-Keggin units) and
B) NENU-501 (each BPT3− is connected with 3 dimeric Zn-ε-Keggin units). Their corresponding C) HER LSV polarization curves and D) Tafel plots in
comparison with other MOF catalysts. Reproduced with permission.[57] Copyright 2015, American Chemical Society.

their POM units and Mo element. However, the choice of
Mo-based POM units is further based on the consideration
of the tetrahedral arrangement of Zn cations for the construction
of 3D MOF structure. As a result, the combination of both merits
of POMs (redox activity) and MOFs (extendable porous frame-
work) leads to comparatively excellent and stable HER perfor-
mance. In 0.5 m H2SO4 electrolyte, NENU-500 exhibits an over-
potential of 237 mV at the current density of 10 mA cm−2 and a
Tafel slope of 96 mV dec−1, while those of NENU-501 are 392 mV
and 137 mV dec−1, respectively (Figure 4C,D). The catalytic per-
formance of NENU-500 approaches that of commercial Pt/C
(52 mV and 30 mV dec−1). The author concluded that the better
catalytic performance of NENU-500 is a result of its open pore
network with a Brunauer–Emmett–Teller (BET) surface area of
195 m2 g−1, where NENU-501 is essentially nonporous due to the
occupation of pore space by TBA cations. In addition, NENU-500
shows no apparent drop in performance after 2000 CV cycles.
Dong and co-workers reported the utilization of the 2D
Co-based MOF THAT-Co for electrocatalytic HER.[71] THAT-
Co consists of Co centers, 2,3,6,7,10,11-triphenylenehexathiol
(THT), and 2,3,6,7,10,11-triphenylenehexamine (THA) as the
coordinating ligands. The interesting feature of this MOF cata-
lyst is the incorporation of HER catalytic active metal complexes
CoS2N2, CoS4, and CoN4 into the 2D framework through metal
dithiolene–diamine coordination. The 2D structure of THAT-Co
realizes the molecular distribution of metal complex and leads
to more exposed active sites. Furthermore, the immobilization
of metal complexes can improve the stability of the catalyst.
In 0.5 m H2SO4 electrolyte, THAT-Co exhibits an overpotential
of 283 mV at the current density of 10 mA cm−2 and a Tafel
slope of 71 mV dec−1. THAT-Co also shows 12 mV increase
in overpotential to reach 10 mA cm−2 and 34 mV increase in
overpotential after 4 h operating at 10 mA cm−2, which demon-
strates its stable performance in HER.
Another representative pristine MOF for electrocatalytic HER
is reported by Wu et al.[72] They demonstrated two polymorphic
Co-based MOFs CTGU-5 and CTGU-6 (CTGU = China Three
Gorges University). Both MOFs composed of cobalt centers,
naphthalene-1,4-dicarboxylic acid (L), 1,4-bis(imidazole)
butane (bib) as the coordinating ligands. However, the differ-
ence between these two MOFs is the coordination mode with
water molecules, where H2O is coordinated with the cobalt

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center in CTGU-5 (CoL(bib)(H2O)), while H2O is connected
with the framework through hydrogen bonds in CTGU-6
([CoL(bib)]·H2O). The difference in coordination modes
leads to a layered structure for CTGU-5 and a 3D framework
for CTGU-6. In 0.5 m H2SO4 electrolyte, HER electrocata-
lytic characterizations show that the overpotentials and Tafel
slopes of CTGU-5 and CTGU-6 are 388 and 425 mV, 125 and
176 mV dec−1, respectively. The better performance of CTGU-5
is attributed to the layered structure and thus more open access
to the catalytic active Co sites. The performance of CTGU-5 is
significantly improved by the addition of cocatalyst acetylene
black (AB). The composite of AB&CTGU-5 (with the mixture
ratio of 1:4) shows an overpotential of 44 mV at 10 mA cm−2 and
a Tafel slope of 45 mV dec−1 with a stable performance for 96 h
in the chronoamperometric test under 255 mV overpotential.
It can be concluded that the choice of metal nodes is the
key to the electrocatalytic activities of pristine MOF catalysts
in HER. However, the choice of organic linkers is also critical
because of their significant influences on the final coordina-
tion structures and porous networks, which subsequently
influences the electrocatalytic performance of the corre-
sponding MOF catalyst.
MOFs as Supports: The choice of MOFs as supports is usu-
ally based on the appreciation of their high specific surface area
and pore volume for highly dispersed and exposed catalytically
active sites. However, synergistic effects may occur between
MOF supports and supported catalysts, which may intrigue cer-
tain surprising mechanisms.
Hod et al. reported the application of MOF NU-1000 (NU =
Northwestern University) as scaffolds for the electrodeposi-
tion of Ni–S for electrocatalytic HER (Ni–S as a hybrid material
containing Ni and S, not the compound NiS).[73] NU-1000 is a
mesoporous MOF, which is made up of hexa-Zr oxo/hydroxo/
aquo (Zr6(µ3–O)4(µ3–OH)4(OH)4(OH2)4) as metal nodes and
TBAPy4− (1,3,6,8-tetrakis(p-benzoic-acid)pyrene) as organic
linkers. It can be grown on the fluorine-doped tin oxide (FTO) sub-
strate to form rod-like crystal structures (as shown in Figure 5).
Besides its well-developed porous structure, the choice of
NU-1000 is also based on its high resistance to hydrolysis and
chemical stability.[74,75] Initially, the authors aimed to deposit
Ni–S on the MOF framework, in order to enlarge the catalyti-
cally active area of Ni–S. However, realistically, Ni–S is deposited
at the bottom of the MOF rods as thin film. In 0.1 m HCl elec-
trolyte, the Ni–S deposited NU-1000 exhibits an overpotential of
238 mV and a Tafel slope of 120 mV dec−1. It also shows a good
stability for 2 h under the operating current density of 10 mA
cm−2. The authors proposed that the enhanced HER catalytic
performance (when compared with pristine NU-1000 and Ni–S)
may be associated with synergy between Ni–S and the aquo- and
hydroxo-groups on the Zr6 based nodes, which may facilitate the
local proton activity in terms of short-range proton delivery and
long-range proton transport. This proposal is indirectly proved
by replacing the original aquo- and hydroxo-­ terminals with
benzoate ligands. The electrocatalytic performance of benzoate-
modified NU-1000_Ni–S is apparently reduced when compared
with that of the original NU-1000_Ni–S (Figure 5E,F).
A similar phenomenon was observed by Dai et al. in their
work on the utilization of UiO-66-NH2 as a supporting informa-
tion to anchor molybdenum polysulfide (MoSx).[76] The loading
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of MoSx is simply carried out by the addition of (NH4)2MoS4
during the solvothermal synthesis of UiO-66-NH2. The
catalyst shows an overpotential of 200 mV (10 mA cm−2) and
a Tafel slope of 59 mV dec−1. Both repeated CV (5000 cycles)
and chronoamperometric (under 200 mV for 7 h) tests dem-
onstrate the stable performance of the catalyst. Interestingly,
besides large surface area, highly dispersed active sites, and fast
electron transport, the authors attribute the excellence of their
catalyst to a similar mechanism of previously discussed Ni–S
deposited NU-1000, that is, improved local proton delivery. In
this case, the authors propose that Zr-based MOF UiO-66-NH2
can also modify the immediate environment of sulfide-based
catalysts for enhanced HER catalytic performance due to its
proton conductive nature.
MOF Derivatives: Compared with the applications of pristine
MOFs and MOFs as supports, relatively more attentions are
focused on the utilization of MOFs as precursors to produce
a wide range of metal-based catalysts with specific designed
chemical components and structures.
Wu et al. demonstrated the synthesis of a porous molyb-
denum carbide nano-octahedron from a Cu-based MOF
(HKUST-1, Cu3(BTC)2(H2O)3, HKUST = Hong Kong University
of Science and Technology, BTC = benzene-1,3,5-tricarboxylate)
with guest polyoxometalate units (H3PMo12O40) located in
the porous network of the MOF.[77] This MOF precursor
is designated as NENU-5 ([Cu2(BTC)4/3(H2O)2]6[H3PMo12
O40]). Direct pyrolysis of NENU-5 in N2 gas flow leads to the
formation of molybdenum carbide (MoCx) and elemental Cu
embedded in amorphous carbon matrix, where Cu is removed
by FeCl3 solution, leaving MoCx nano-octahedrons for elec-
trocatalytic HER (as shown in Figure 6A). The electrocatalytic
performance of MoCx in HER is tested in both acidic and
alkaline electrolytes. In 0.5 m H2SO4, it requires an overpoten-
tial of 142 mV to reach the current density of 10 mA cm−2 and
the corresponding Tafel slope is 53 mV dec−1 (Figure 6B,C).
In 1 m KOH, those two values are 151 mV and 59 mV dec−1,
respectively (Figure 6E,F). NENU-5 does not just play the role
of precursor but also confines the growth of MoCx and thus
obtains uniformly distributed and nanosized crystals embedded
in amorphous carbon matrix. The amorphous carbon matrix
further provides extra protection for the embedded nanocrys-
tals. Therefore, the catalyst also exhibits excellent stabilities in
both acidic and alkaline electrolytes.
Yang et al. reported the derivation of FeCo alloy nanopar-
ticles encapsulated nitrogen-doped graphene layers from a
bimetallic MOF precursor Fe3[Co(CN)6]2 (Sample ID: S-600).[78]
Fe3[Co(CN)6]2 consists of Fe and Co as bimetallic nodes and
cyanides (CN−) as organic linkers. Therefore, Fe3[Co(CN)6]2
is rich in both catalytic active metal and nitrogen elements,
which leads to the formation of FeCo alloy nanoparticles and
high nitrogen content (8.2 at%) in its annealing products. In
0.5 m H2SO4, the catalyst shows an overpotential of 262 to reach
10 mA cm−2 and a Tafel plot of 74 mV dec−1. It also exhibits
excellent stabilities after 10 000 CV cycles and 10 h chrono-
amperometric test under 300 mV overpotential. The excellent
performance of their catalyst can be attributed to the following
features based on their computational analysis: 1) nitrogen
dopants in graphene provide additional hydrogen adsorp-
tion sites and effectively lower the free energy for hydrogen
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Figure 5.  The electrodeposition of Ni–S on NU-1000. A) The initial plan is to deposit Ni–S on the surface of the MOF (blue arrow). However, Ni–S
is deposited at the bottom as a flat layer (dark green arrow). B) The crystal structure of NU-1000 shows its hexa-Zr nodes and TBAPy4− linkers.
C) A SEM image of NU-1000_Ni–S from the top of FTO substrate shows the rod-like crystals of NU-1000 (scale bar: 1 µm). D) A cross-sectional SEM
image shows Ni–S thin film at the bottom of NU-1000 rod crystals (scale bar, 2 µm). E) Original Zr6 based node (with aquo- and hydroxo-groups) and
benzoate-modified Zr6 based node. F) HER LSV polarization curves of original and benzoate-modified NU-1000_Ni–S. Reproduced with permission.[73]
Copyright 2015, Nature Publishing Group.

adsorption (ΔGH) when compared with that of pure graphene.
2) The incorporation of Fe atoms into Co clusters (Co4) alters
CoCo bond length and introduces new FeCo and FeFe
bond lengths, which can be tailored to achieve optimized ΔGH
as well. 3) The synergistic effect between metal and nitrogen-
doped graphene can also improve the material’s catalytic perfor-
mance through enhanced charge transfer from metal clusters to
the graphene side. 4) The encapsulation of alloy nanoparticles
by graphene shells can further protect the nanoparticles from
corrosion and thus improve the stability of the catalyst.
Besides synergistic effects and chemical compositions,
the use of MOFs as precursors can also deliver “pleasant
surprise” in structural transformation. Yu et al. presented
the utilization of bimetallic Ni–Co Prussian blue analogue
(PBA) nanocubes (Ni3[Co(CN)6]2·12H2O) as the precursor to
produce nickel sulfide (NiS) nanoframes.[79] The synthesis
follows the anion exchange reaction between Ni–Co PBA and
Na2S, where the reaction products are NiS and Na3[Co(CN)6].
As illustrated in Figure 7A, the exchange reaction is
preferably initiated at the edges of the original MOF due to

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Figure 6.  The synthesis of porous MoCx nano-octahedrons. A) The 3-step material synthesis procedure: a) Synthesis of NENU-5 and encapsulation
of POM units; b) Thermal annealing to form MoCx-Cu nano-octahedrons; c) FeCl3 etching to remove Cu. The HER LSV polarization curves and the
corresponding Tafel plots of MoCx in B,C) 0.5 m H2SO4 and D,E) 1 m KOH, respectively. Reproduced with permission.[77] Copyright 2015, Nature Pub-
lishing Group.

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Figure 7.  The transformation of NiS nanoframes from Ni–Co PBA nanocubes. A) An illustration of the NiS nanoframe formation by the exchange
reaction with Na2S. B–E) SEM images of the transformation process. F) LSV polarization curves of NiS nanoframes with different sizes and G) their
corresponding Tafel plots. Reproduced with permission.[79] Copyright 2015, Wiley-VCH.

the existence of more defects when compared with the com-
paratively smoother surface. Then, the etching moves from
the edges to the less-corroded middle surface. This structure-
induced reaction results in the transformation of MOF nano-
cubes to NiS nanoframes. The obtained NiS nanoframes
(100 nm) show an excellent electrocatalytic performance in
1 m KOH with an overpotential of 94 mV at 10 mA cm−2 and
a Tafel slope of 139 mV dec−1 (as shown in Figure 7F,G). The
corresponding chronoamperometric test shows only 8% cur-
rent drop after 16 h operation under 115 mV overpotential.
Besides the HER catalytic activity of NiS, the superior per-
formance of the catalyst is mainly associated with the 3D
frame-like hollow structure, thanks to its large electrolyte–
electrode contact area and robust building structure.
ZIF-67, a Co-based MOF with 2-methylimidazole as organic
linkers, is one of the most popular MOF precursor for electrocat-
alytic HER. It was mentioned in the section of MOF character-
istics that Yilmaz et al. proposed the synthesis of NiCo layered
double hydroxide embedded Co9S8 from ZIF-67 (sample ID: C/
LDH/S).[60] In 1 m KOH electrolyte, the catalyst demonstrates a
remarkable overpotential of 142 mV to reach 10 mA cm−2 and a
small Tafel slope of 62 mV dec−1. The chronoamperometric test
shows no apparent current drop for 60 h under the constant
potential corresponding to 20 mA cm−2, indicating its superior
stability.[60] The conductivity and hydrogen adsorption on the
catalyst are enhanced through bimetallic heterosulfides–hydrox-
ides system and the formation of hollow structure. Besides the
work of Yilmaz et al., CoP/N-doped carbon composites,[61,80,81]
CoSe2/(NiCo)Se2 hollow nanocubes,[82] porous CoP con-
cave polyhedron,[83] CoSe2 embedded carbon nanotubes,[84]
N-doped carbon,[85] Co@N-doped carbon nanotubes,[86] and
nickel phosphides[87] are also reported as catalysts derived from
ZIF-67.
Apart from the above-discussed cases, there is an explosive
number of MOF-derived catalysts reported for electrocatalytic
HER in the last several years (particularly in 2016 and 2017).
MIL-101-NH2,[88] MIL-53,[89] MOF-100,[90] MOF-199,[91]
[92] [87,93,94] [95–97]
MOF-74, Ni-BTC, and other Ni-, Co-,[98–101]
[97]
Mo-, Al-based [102,103]
monometallic and bimetallic MOFs are
reported as precursors for the synthesis of various catalysts
with specifically designed chemical components and struc-
tures. It can be concluded in Table 1 that the performances of
reported MOF-based catalysts vary significantly from each other
in terms of overpotentials and Tafel slopes. This can be attrib-
uted to diverse metallic and nonmetallic active species in these
MOF-based catalysts. However, those with the same metallic
and nonmetallic elements still exhibit great difference in
performance, which are usually explained by varied dispersities

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and uniformities of active sites in those catalysts and evidenced
by high-resolution transmission electron microscope (TEM)
images. However, it is necessary to highlight a common issue,
that is, the lack of preconditions for reported electrocatalytic
HER performance, which may result in potential discrepancies
between different research articles in Table 1. For example, it
is aforementioned that Tafel slope is a potential- and coverage-
dependent parameter, where the information about interme-
diate coverage is frequently not discussed, resulting in the mis-
interpretation of the rate-determining step in a specific case of
electrocatalytic HER. Another frequently omitted precondition
is the information about iR compensation. Since iR compensa-
tion is very likely to influence the shapes of polarization curves,
the missing information makes the performance parameters
(including overpotentials and Tafel slopes) not comparable
between different research articles. Particularly, it may cause
discrepancy when authors claim their samples demonstrate
the best performance to date when other samples from litera-
ture are used for comparison. Very recently in February 2018,
this issue was particularly stressed in the perspective article of
Anantharaj et al. as well.[104] The same attention should be paid
to the case of photocatalytic and chemocatalytic HER (Tables 3
and 4), where the test preconditions (such as the use of cocata-
lysts, reaction temperatures, and pH values) must be clarified
to avoid any discrepancies when comparing the results from
different reports.
3.1.2. Overall Water Splitting
Fundamentals and Characterizations: Besides recent advances in
MOFs for electrocatalytic HER, there is fast growing interest
in the electrocatalytic performances of MOF-based catalysts in
overall water splitting. HER is a half reaction of water elec-
trolysis at the cathode side, while the other half is OER, which
takes place at the anode side. Differing from the published
work on solo HER, studies on overall electrocatalytic water
splitting investigate the performance of the same MOF-based
catalyst in both HER and OER. OER is the process where
water is oxidized into O2. Similar to electrocatalytic HER, onset
potential, overpotential at 10 mA cm−2, Tafel slope, and stability
are the key parameters to determine the catalytic performance
of MOF-based catalyst as well, which can also be obtained by
LSV, CV, chronoamperometry, and chronopotentiometry in
both acidic and alkaline electrolytes. Furthermore, some elec-
trocatalytic water splitting associated work also investigates
the overall water splitting performance by the assembly of a
water electrolyzer in the form of two-electrode configuration.
The performance of the electrolyzer is evaluated in terms of
cell voltage and stability. According to literature survey, cur-
rent published works for electrocatalytic water splitting mainly
focus on pristine MOFs and MOF derivatives. In addition,
when MOFs are applied as precursors, in some cases, they also
play the role of supports and templates either to encapsulate
other catalytic active species or to direct the structural forma-
tion of the resulting derivatives. The performance of recently
reported MOF-based catalysts for electrocatalytic water splitting
is presented in the following subsections and summarized in
Table 2.
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Pristine MOFs: Duan et al. reported 2D ultrathin bimetallic
NiFe-MOF nanosheet arrays (Ni0.8Fe0.2(C12H6O4)(H2O)4) for
electrocatalytic water splitting.[105] The synthesis is carried out
on different substrates with nickel acetate and iron nitrates as
metal sources and 2,6-naphthalenedicarboxylic acid dipotas-
sium as organic linkers. The substrate candidates include nickel
foam, stainless-steel mesh, and glassy carbon. The synthesis
procedure and the resulting MOF structure are illustrated in
Figure 8C. The NiFe-MOF, which is grown on the nickel foam,
presents the best electrocatalytic performance in 0.1 m KOH
electrolyte. In the HER test, NiFe-MOF demonstrates an over-
potential of 134 mV to reach the current density of 10 mA cm−2
(Figure 8D), and a stable performance under overpotential
of 200 mV after 2000 s. In the OER test, it shows an overpo-
tential of 240 mV, a Tafel slope of 34 mV dec−1 (Figure 8E), a
stable performance after 1000 CV cycles, and a chronoamper-
ometric test under the overpotential of 190 mV for 20 000 s,
which surpass those of commercial benchmark catalyst IrO2
(overpotential: 320 mV; Tafel slope: 46 mV dec−1). In order to
test the overall electrocatalytic water splitting capability of the
catalyst, the authors also assembled a two-electrode water elec-
trolyzer by using NiFe-MOF at both anode and cathode sides.
It takes a cell voltage of 1.55 V to deliver a current density of
10 mA cm−2 (Figure 8F). Its stable performance is also dem-
onstrated by chronoamperometric test at 1.5 V for 20 h. The
authors proposed that the oxidation of NiO6 in NiFe-MOF into
NiO6/NiOOH leads to the catalyst’s excellent performance in
OER, because NiO6/NiOOH is the active site to promote the
formation of oxygen molecules. The existence of Fe in this
bimetallic system can introduce additional structural vacancies,
which further improves the performance of NiFe-MOF. In the
meantime, its performance in HER benefits from the forma-
tion of Ni/NiO6 interface, where the NiO6 sites attract OH− due
to locally positively charged Ni2+ and hydrogen is preferentially
adsorbed on the Ni sites. Besides the above enhancements, the
improved performance of overall water splitting is ascribed
to the highly exposed metal active sites and the high conduc-
tivity, which can be attributed to the 2D nanosheet structure of
NiFe-MOF. Moreover, the direct growth of the catalyst on nickel
foam avoids the necessity for the use of insulating binders to
produce electrode. The use of nickel foam as the substrate also
enhances the catalytic performance by improved mass trans-
port of the electrolyte and diffusion of the products due to its
well-developed macroporous structure (Figure 8A,B).
Jahan et al. demonstrated a Cu-based MOF–GO composite
and its application as a trifunctional catalyst for ORR, OER,
and HER.[106] The Cu-MOF/GO composite is synthesized
through a solvothermal reaction, involving GO, copper nitrate
trihydrate as the source of metal, 1,4-benzenedicarboxylic acid
and triethylenediamine as organic linkers. In 0.5 m H2SO4,
the as-synthesized MOF/GO composite exhibits a potential of
−0.209 V versus RHE at the current density of 30 mA cm−2
and a Tafel slope of 84 mV dec−1 in HER, while 1.34 V versus
RHE at 2 mA cm−2 and 64 mV dec−1 are obtained in the OER
test, respectively. These parameters are comparable to those of
20% Pt/C benchmarking catalyst in HER (−0.058 V vs RHE and
30 mV dec−1) and OER (1.43 V vs RHE and 61 mV dec−1) at
the same current densities, respectively. It can be noted that the
authors did not use 10 mA cm−2 as the benchmarking current
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Table 2.  Summary of MOF-based catalysts for electrocatalytic water splitting in recent publications.

Sample ID Electrolyte HER OER Electrolyzer Ref.

Overpotentiala) Tafel slope Stability Overpotential Tafel slope Stability Cell voltagec) Stability
[mV] [mV dec−1] testsb) [mV] [mV dec−1] tests [V] tests
NiFe-MOF array 0.1 m KOH 134 N/A 2000 s 240 34 1000 1.55 20 h [105]
cycles and
20 000 s
8 wt% 0.5 m H2SO4 −0.209 V versus 84 N/A 1.34 V versus 64 N/A N/A N/A [106]
GO–Cu-MOF RHE at RHE at
30 mA cm−2 2 mA cm−2
Ni/CoO@CoNC 1 m KOH 190 98 3000 cycles 309 53 3000 N/A N/A [107]
and 20 h cycles and
20 h
3D-CNTA 1 m KOH 185 135 3000 cycles 360 89 3000 1.68 10 h [108]
and 40░000 s cycles and
40░000 s
Co-P/NC 1 m KOH 154 51 1000 cycles 319 52 1000 2. 0 V 24 h [61]
cycles at
165 mA cm−2
Co@NC/NF 0.1 m KOH 240 126.8 50 h 390 125 50 h N/A N/A [115]
CoP/rGO-400 1 m KOH 150 38 3000 cycles 340 66 3000 N/A N/A [109]
and 22 h cycles and
22 h
(Ni,Co) 1 m KOH 87 65 36 h 245 70 36 h 1.58 20 h [51]
Se2/C-HRD
Co0.85Se@NC 1 m KOH 230 125 10 h 320 75 1000 1.76 35 h [62]
cycles and
12 h
Co–Ni–Se/C/NF 1 m KOH 90 81 2000 cycles 275 mV at 63 2000 1.6 100 h [111]
and 24 h 30 mA cm−2 cycles and
24 h
Co-NC/CNT-800 1 m KOH 203 125 1000 cycles 314 78 1000 1.625 24 h [116]
and 30 000 s cycles and
30 000 s
Ni1Co4S@C-800 0.5 m H2SO4 247 for N/A 1000 cycles 280 mV for 64 1000 N/A N/A [114]
and and 0.1 m Ni1Co4S@C-800 Ni1Co4S@C-1000 cycles
Ni1Co4S@C-1000 KOH in 0.5 m H2SO4 in OER in 0.1 m
KOH
CoSe2/CF 1 m KOH 95 52 5000 cycles 297 41 5000 1.63 30 h [112]
and 20 h cycles and
20 h
CoP3 CPs 1 m KOH 124 88 3000 cycles 343 76 3000 N/A N/A [110]
and 24 h cycles and
12 h
Zn0.1Co0.9Se2 0.5 m H2SO4 140 49.9 5000 cycles 340 43.2 5000 N/A N/A [113]
for HER and 30 h cycles and
30 h
1 m KOH for
OER
Co@NCNT 0.5 m H2SO4 210 93 20 000 s 429 116 N/A N/A N/A [117]
for HER
1 m KOH for
OER
MSZIF-900 0.5 m H2SO4 233 N/A 100 000 s 337 N/A 20 000 s N/A N/A [50]
for HER
1 m KOH for
OER

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Table 2. Continued.

Sample ID Electrolyte HER OER Electrolyzer Ref.

Overpotentiala) Tafel slope Stability Overpotential Tafel slope Stability Cell voltagec) Stability
[mV] [mV dec−1] testsb) [mV] [mV dec−1] tests [V] tests
Ni3ZnC0.7-550 1 m KOH 93 48 24 h 320 52 24 h 1.65 24 h [125]
RuO2/Co3O4 1 m KOH 89 91 10 000 305 69 10 000 N/A N/A [118]
cycles and cycles and
40 000 s 10 h
CoS2 NTA/CC 1 m KOH 193 88 20 h 276 81 20 h 1.67 20 h [119]
FeNi@NC for 1 m KOH 77 mV at 20 mA 68 10 h 300 47.7 10 h N/A N/A [121]
OER, Ni@NC for cm−2
HER
Co4Ni1P 1 m KOH 129 52 3000 cycles 245 61 3000 1.59 50 h [53]
and 20 h cycles and
20 h
NiFe-Se/C 1 m KOH 160 94 20 h 240 73 20 h 1.68 20 h [126]
Ni@NC-800 1 m KOH 205 160 1000 cycles 280 45 1000 N/A N/A [123]
and 10 h cycles and
10 h
Ni2P−CoP@CM 0.5 m H2SO4 105 64 N/A 320 69 N/A N/A N/A [65]
Ni@graphene 1 m KOH 240 120 10 h 370 66 10 h N/A N/A [124]
Co/Co9S8@ 0.1 m KOH 350 mV at 96.1 1000 cycles 290 80.2 1000 1.58 V N/A [67]
SNGS-1000 20 mA cm−2 cycles (20 mA
cm−2)
Co–P@NC-800 0.5 m H2SO4 98 74 12 h 370 79 3h N/A N/A [120]
for HER
1 m KOH for
OER
NGO/Ni7S6 0.1 m KOH 370 145.5 10 h 380 45 16 h N/A N/A [122]
for OER
1 m KOH for
HER

Overpotential is measured at 10 mA cm−2; b)Due to qualitative description of stability test results in most published work, only the duration of the chronoamperometric
a)

(or chronopotentiometric) test and the number of CV cycles are summarized in this table; c)A current density of 10 mA cm−2 is delivered by the reported cell voltage.

density for the comparison of the sample performance, which
is possibly due to the early year of publication (2013). The over-
potential at 10 mA cm−2 was later widely accepted and reported
for the comparison of experimental results from different
literature.
MOF Derivatives: Similar to the case of electrocatalytic HER,
ZIF-67 demonstrates its popularity in electrocatalytic water
splitting as well. Cai et al. reported the self-templated growth
of CoO@N-doped carbon composite (Ni@CoO@CoNC) by the
fabrication of a well-aligned rod-like CoO/ZIF-67 hybrid arrays
on nickel foam (Ni@CoO@ZIF-67).[107] The synthesis proce-
dure and nanoarray formation are depicted in Figure 9A. In this
way, the as-synthesized catalyst can be directly used as a self-
supporting electrode. As mentioned previously, MOF-based cat-
alysts are usually deposited on the surface of a conductive glassy
carbon electrode for the catalytic measurement. Therefore, the
loss of catalyst may occur due to the continuous bursting of
hydrogen and oxygen gases in HER and OER, respectively. The
utilization of Ni@CoO@ZIF-67 as a self-templating precursor
eliminates the abovementioned problem. The uniformly well-
aligned rod-like nanostructure ensures a smooth diffusion of
the electrolyte through the space around those nanorods, which
renders a sufficient contact between the electrolyte and the
electrode. This further exposes more active sites and promotes
fast electron transportation for improved electrocatalytic per-
formance. Benefiting from the above advantages, in 1 m KOH
electrolyte, Ni@CoO@CoNC shows an overpotential of 190 mV
at 10 mA cm−2 and a Tafel slope of 98 mV dec−1 in HER, while
those parameters are 309 mV and 53 mV dec−1 in OER, respec-
tively (as shown in Figure 9B–E). More importantly, thanks to
its self-supporting structure, the catalyst exhibits a superior sta-
bility in both HER (190 mV) and OER (309 mV) in 3000 CV
cycles and 20 h chronoamperometry tests.
Besides nanorod, another common form of MOF-derived
catalysts is nanoparticle. Wang and et al. synthesized an
actiniae-like carbon nanotube assembly (3D-CNTA) as a catalyst
for electrocatalytic water splitting, which is also derived from
ZIF-67.[108] The synthesis was carried out by mixing ZIF-67
with melamine followed by the pyrolysis of the mixture, which
leads to a 3D carbon nanotube assembly with Co@N-doped

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Table 3.  Summary of MOF-based catalysts for photocatalytic HER in recent publications.

Sample ID Irradiation Condition Solvent Cocatalyst H2 evolution rate Stability testsb) Ref.
Al-ATA-Ni MOF UV–Vis water N/A −1 N/A [131]
7 °C 36 µmol h
pH = 5 (30 mg catalyst)
[Gd2Cu5(OH)2 UV RT a) 10 vol% methanol solution N/A 2050.4 µmol 3 cycles: 2050.4, [133]
(pydc)6(H2O)8]∙I8 h−1 g−1 2107.7, and
1973.9 µmol
h−1 g−1
[Ni2(PymS)4]n White LED RT 15 vol% TEA% N/A TOF: up to TON in 4 cycles: [134]
pH = 10 2 × 10−3 m FI 10.6 h−1 2.5, 2.5, 2.2, and
2.0 (1 h)
UG-50 Visible pH = 4 0.1 m L-ascorbic acid aqueous solution 0.5 wt% Pt 14.11 µmol h−1 No distinct [136]
(10 mg catalyst) decrease after
24 h usage
Ag(1.5)/Gd-MOF UV–Vis RT 40 vol% TEOA aqueous solution 1.5 wt% Ag 10.6 µmol h−1 N/A [66]
(50 mg catalyst)
AlTCS-1 Visible RT 20 vol% TEOA aqueous solution N/A 50 µmol g−1 h−1 N/A [141]
pH = 11
CPM-2-NH2 UV N/A 25 vol% methanol aqueous solution 1 wt% Pt 2.0 µmol h−1 N/A [142]
(100 mg)
TEA@ NH2-MIL-125 Visible 40 °C 23.5 mL acetonitrile N/A 26.47 µmol in N/A [140]
0.5 mL water 18 h
Pt/NH2-UiO-66(Zr/ Visible N/A 16 vol% TEOA acetonitrile solution N/A 3.5 mmol mol−1 N/A [138]
Ti)-120-16 in 9 h
UiO-66/CdS/1%RGO Visible N/A 0.1 m Na2S and 0.1 m Na2SO3 aqueous 1 wt% Pt 105 µmol h−1 N/A [137]
solution
UiO-66-NH2 Mono (370 nm) 38 °C 25 vol% methanol aqueous solution N/A Quantum yield: N/A [58]
3.5%
Ni4P2@MOF-1a Visible pH = 1.2 10% methanol solution N/A TON: 1746 (72 h) TONs in 3 cycles: [143]
346, 329, and 297
(20 h)
CdS/MIL-101(10) Visible RT 10 vol% lactic acid aqueous solution 0.5 wt% Pt 75.5 mmol h−1 Stable in 3 cycles [130]
gcds−1
CdS@ ZAVCl UV N/A 7.5 vol% ethanol aqueous solution 0.5 wt% Pt 500–510 µmol N/A [144]
h−1 g−1
Visible 398–418 µmol Stable in 12 cycles
h−1 g−1
Ni/MIL-101 Visible N/A 5 mL deionized water N/A TOF: 3238 h−1 Stable in 3 cycles [151]
40 µL 0.5 m ammonia borane
NiMo@MIL-101 Visible pH = 11 10 vol% TEOA aqueous solution N/A 740.2 µmol h−1 Stable in 4 cycles [152]
70 mg Eosin Y as photosensitizer (50 mg)
Pt@UiO-66-NH2 Visible RT 18 mL acetonitrile N/A 257.38 µmol Stable in 4 cycles [145]
0.2 mL deionized water h−1 g−1
2 mL TEOA
Pt@2 Visible N/A 2 mL THF N/A TON: 1620 in 6 h TON: 1620, 1500, [153]
0.1 mL deionized water 990, and 1380 in 4
0.1 mL TEA cycles
0.04–0.05 µmol Ir-phosphor
POM@UiO Visible pH = 1.8 10% methanol aqueous solution N/A 699 µmol h−1 g−1 Stable in 3 cycles [154]
Ni@MOF-5 Visible pH = 11 10 vol% TEOA, 0.1 mol L−1
Na2SO4 N/A 30.22 mmol Slightly reduced in [56]
aqueous solution h−1 g−1[Ni] 4 cycles
10CFBM Visible N/A 10 vol% TEOA aqueous solution 3 wt% Pt 1.123 mmol Stable in 4 cycles [156]
h−1 g−1
PNPMOF Visible pH = 4.5 0.2 m ascorbic acid aqueous solution N/A TON: 66 (with Stable in 3 cycles [158]
respect to Pt in
6 h)

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Table 3. Continued.

Sample ID Irradiation Condition Solvent Cocatalyst H2 evolution rate Stability testsb) Ref.
UiO-66- [FeFe] Blue LED pH = 5 1 m acetate buffer N/A ≈3.5 µmol from N/A [146]
(dcbdt)(CO)6 (740 nm) 100 × 10−3 m ascorbic acid 0.59 µmol catalyst
0.5 × 10−3 m [Ru(bpy)3]2+ in 150 min
ErB-sensitized Visible pH = 4 0.1 m L-ascorbic acid 0.5 wt% Pt 4.6 µmol 80% remains after [147]
Pt-UiO-66 h−1 (10 mg) 3 cycles
rGO/MOF/ Visible pH = 9 15 vol% TEOA aqueous solution N/A 339 µmol in 5 h N/A [148]
Co–Mo–S 20 mg Eosin Y as photosensitizer (10 mg)
RhB/Pt@ Visible pH = 7 10 vol% TEOA aqueous solution N/A 116.0 µmol Stable in 3 cycles [149]
UiO-66(Zr)-100 h−1 g−1
Pt@UiO-66-NH2 Visible pH = 7 20 vol% methanol aqueous solution N/A 1528 µmol Stable in 3 cycles [150]
h−1 gMOF−1
5 wt%MoS2/ Visible pH = 7 10 vol% TEOA aqueous solution N/A 62.12 µmol Unstable in [55]
UiO-66-NH2/G 28 mg Eosin Y as photosensitizer h−1 (30 mg) 4 cycles due to
unstable Eosin
Y dye
Ru–Pt@UiO-67 Visible RT 0.1 m acetate buffer N/A 0.5 µmoL in 5 h N/A [155]
pH = 5 67 mg EDTA-2Na as electron donor
(ethylenediaminetetraacetic acid
disodium salt)
[FeFe]@ZrPF Visible pH = 5 1 m acetate buffer, 20 × 10−3 m ascorbic N/A 3.5 mmol in 2 h N/A [159]
acid aqueous solution (2 × 10−6 m cata-
lyst in reaction
solution)
Pt–Zn3P2–CoP Visible N/A 10 vol% of methanol aqueous solution N/A 9.15 mmol h−1 g−1 Stable in 5 cycles [161]
Cu2O@C3N Visible RT 0.01 m EDTA aqueous solution N/A 5.9 µmol in 9 h Stable in 3 cycles [163]
(25 mg)
NC-PA UV–Vis RT 15 vol% methanol aqueous solution N/A 7 mmol N/A [165]
pH = 7 h−1 g−1
MoS2@TiO2 Visible pH = 11 25 vol% acetone, N/A 10 046 µmol Stable in 3 cycles [166]
7.5 vol% TEOA aqueous solution h−1 g−1
5 mg fluorescein as photosensitizer
Ni2P/CdS Visible pH = 2 20 vol % aqueous lactic acid solution N/A 33 480 µmol Stable in 5 cycles [167]
h−1 g−1
Cu/CuO@TiO2 UV–Vis RT 15 vol% methanol aqueous solution N/A 286 mmol Slightly decreased [168]
h−1 g−1 after 3 cycles
CdS-YS Visible RT 0.1 m Na2S + 0.1 m Na2SO3 aqueous N/A 3051.4 µmol Stable in 4 cycles [169]
pH = 10.8 solution h−1 g−1
HP-CdS Visible N/A 0.1 m Na2S + 0.1 m Na2SO3 aqueous N/A 350.1 µmol Stable in 4 cycles [52]
solution h−1 g−1
1 wt% Cu/ TiO2-400 UV N/A 5 vol% glycerol aqueous solution N/A 15.13 mmol Stable in 4 cycles [170]
h−1 g−1
1.5% Pd/TiO2 UV N/A 20 vol% methanol aqueous solution N/A 979.7 µmol h−1 N/A [54]
(20 mg)
Visible 112.7 µmol Stable in 3 cycles
h−1 (20 mg)
MoS2–ZnS Visible N/A 15 vol% TEOA aqueous solution N/A 411 µmol N/A [171]
Eosin Y as photosensitizer h−1 g−1
ZNG-1000 Visible N/A 10 vol% TEOA aqueous solution 3 wt% Pt 18.5 µmol h−1 Stable in 12 h [172]
(50 mg)
CoZC0.5 Visible N/A 0.35 m Na2S + 0.25 m N/A 17.36 mmol h−1 Stable in 30 h [173]
Na2SO3 aqueous solution g−1

a)RT = room temperature. Test conditions are summarized according to available information in literature; b)The
catalyst is recycled and used for repeated tests with
refreshed solutions.

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Figure 8.  NiFe-MOF on Ni foam. A) A photograph of NiFe-MOF on the Ni foam electrode and B) the SEM image (scale bar: 100 nm) of its macroporous
network. C) The synthesis procedure of NiFe-MOF array on Ni Foam. LSV polarization curves of NiFe-MOF array, Ni-MOF array, bulk NiFe-MOF, and
commercial benchmarking IrO2 in D) HER, E) OER, and F) water electrolyzer in 0.1 m KOH (the inset shows both cathode for H2 evolution and anode
for O2 evolution in the water electrolyzer). Reproduced with permission.[105] Copyright 2016, Nature Publishing Group.

carbon core–shell particles on the tips of the nanotubes (see
Figure 10). This unique structure formation enhances the
catalytic performance based on the same reasons in the pre-
vious example, that is, efficient electrolyte diffusion and con-
tact, more exposed active sites, and faster electron transporta-
tion. In 1 m KOH, the optimized sample 3D-CNTA presents
an overpotential of 185 mV at 10 mA cm−2 and a Tafel slope
of 135 mV dec−1 in HER, and those in OER are 360 mV and
89 mV dec−1, respectively. The authors also assembled a water
electrolyzer by coating 3D-CNTA on Ni foams as both anode
and cathode. The water electrolyzer shows a cell voltage of
1.68 V to reach 10 mA cm−2. Moreover, 3D-CNTA shows excel-
lent stabilities in both HER and OER in 3000 CV cycles and
40 000 s chronoamperometric tests under 360 mV for OER and
185 mV for HER. The water electrolyzer also exhibits stable
performance under the operating cell voltage 1.68 V for 10 h.
Besides the above two examples, there are also reported works
on ZIF-67-derived CoPx/carbon composites,[61,109,110] CoSex/
carbon composites,[51,62,111–113] CoSx/carbon composites,[114]
cobalt-doped carbon nanotubes,[115–117] and other Co-doped
carbon matrices.[50] Their corresponding performance param-
eters are summarized in Table 2.
Apart from ZIF-67, other Co-based MOFs,[67,118–120] ZIF-8,[121]
MOF-74,[53,122] Ni2(bdc)2ted (bdc = 1,4-benzenedicarboxylic acid;
ted = triethylenediamine),[123] other Ni-based MOFs[124] and bime-
tallic MOFs (such as NiZn-MOF (ted as organic linkers),[125] NiFe-
MOF (bdc as organic linkers),[126] NiCo-MOF (bdc as organic
linkers)[65]) are demonstrated as effective precursors for the fab-
rication of various interesting metal compounds and metal/
carbon composites for electrocatalytic water splitting. Table 2

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Figure 9.  The synthesis of Co/N-doped porous carbon array. A) A schematic of the growth of ZIF-67 on CoO and Ni foam followed by pyrolysis to obtain
Co/N-doped porous carbon array (Ni@CoO@CoNC). HER LSV polarization curves and Tafel plots of Ni@CoO@CoNC for B,C) HER and D,E) OER
in 1 m KOH. Reproduced with permission.[107] Copyright 2017, Elsevier Ltd.

summarizes recently reported MOF-based catalysts for electro-
catalytic water splitting, which demonstrates growing attractions
on this research topic. However, the performance data in Table 2
reveal that the “bifunctional” performance of a MOF-based cata-
lyst for electrocatalytic water splitting is more likely a compromise
between its performances in HER and OER. The performance
of a MOF-based catalyst in both half reactions can be enhanced
through universal approaches, such as enlarged surface area
and enriched active sites. However, a “true bifunctional” catalyst
should achieve optimized performances in both half reactions.
This requires combined efforts from theoretical and experimental
studies to explore the possibilities to enhance the bifunctionality
of a MOF-based catalyst by following distinct mechanisms for
HER and OER, respectively. Table 2 demonstrates that the design
of bimetallic MOFs is the most applied approach to the intended
bifunctional activity (particularly the combination of Ni and Co).
However, rather than the abovementioned universal approaches,
it is still a challenge to unravel the underlying mechanisms to
demonstrate how bimetallic components may distinctively influ-
ence each half reaction by following different mechanisms.
To sum up, MOF-based catalysts have been intensively
studied for their performances in both electrocatalytic HER
and overall water splitting, where latest reported catalysts are
constantly refreshing the records with faster reaction kinetics
and lower overpotentials to achieve larger current densities. Up
to date, although MOF-based catalysts are utilized in different
ways (pristine MOFs, supporting frameworks, and precursors),
they share common approaches to enhanced performance,
which are the development of highly porous framework, the
uniform dispersion of nanosized active sites, and the promo-
tion of synergistic effects between active components. Despite
the ever-improving performance, the fundamental mechanisms
for enhanced activity in terms of charge transfer and redistri-
bution are not fully clarified at the moment. It requires both

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Figure 10.  The synthesis of 3D actiniae-like carbon nanotube from ZIF-67 for electrocatalytic water splitting. A) A flow chart of the synthesis procedure
of 3D actiniae-like carbon nanotube assembly (3D-CNTA). B) A schematic of pyrolyzed ZIF-67 without and with low or high melamine content, which
significantly influences the fabrication of nanotubes. C) SEM images of 3D-CNTA from low to high magnification (from left to right). Digital photos of
actiniae and synapse (left and right) are used to compare with the bulk structure and tip of 3D-CNTA, respectively. Reproduced with permission.[108]
Copyright 2017, Elsevier Ltd.

contributions from experimental and computational studies
on different MOF-based catalysts. The understanding of the
underlying mechanisms is particularly important in the case of
overall water splitting, because it makes the targeted design of
a “true bifunctional” catalyst a possible work. In this way, rather
than the abovementioned common approaches, the bifunc-
tionality can be obtained in a single catalyst through distinct
mechanisms to enhance its performance in HER and OER,
respectively. The diversity and flexibility of MOFs offer great
advantages for researchers to achieve this goal.
3.2. MOFs for Photocatalytic HER
3.2.1. Fundamentals and Characterizations
Similar to electrocatalytic HER, photocatalytic HER composes
of two half reactions as well. For example, when water is
used as a hydrogen precursor, it is reduced and oxidized into
hydrogen and oxygen by photoexcited electrons and holes,
which are generated by charge separation in semiconducting
catalysts (as illustrated in Figure 11). In this case, UV, visible
light, or UV–Vis (UV + Visible light) irradiations are applied to
activate the water splitting reaction instead of electric currents,
where solar light is a comparatively more environmentally
friendly source of energy. Moreover, due to rapid recombination
of charged pairs, in most cases, it is difficult to achieve efficient
hydrogen evolution through proton reduction by photocatalysts.
Therefore, sacrificial electron donors (SEDs) are applied in this
case.[127]
SEDs can take part in photocatalytic hydrogen evolu-
tion by following reductive and/or oxidative quenching
mechanisms.[128,129] In a typical 4-component photochem-
ical system (photosensitizer/electron relay/SED/catalyst),
the photosensitizer (PS) can absorb light irradiation and
become photoexcited (PS*). Then, the excited PS* can either

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Figure 11.  An illustration of photocatalytic HER by charge separation in
semiconducting catalysts.
be oxidized by the electron relay (ER) to form PS+ (oxidative
quenching mechanism), or reduced by SED to generate PS−
(reductive quenching mechanism). On the one hand, in the
case of oxidative quenching pathway, PS+ can further react
with SED to regenerate PS. On the other hand, in the case of
reductive quenching pathway, PS− can further react with ER to
achieve the same goal. At the end, the catalyst and reduced ER−
can take part in the proton reduction reaction to generate H2
through electron transfer between them and water. In addition,
in a 3-component photochemical system (PS/SED/catalyst),
SED takes part in the photocatalytic hydrogen evolution by fol-
lowing a simpler reductive quenching mechanism, where the
catalyst and PS can directly promote the proton reduction reac-
tion without ER.[128,129]
Ultrahigh surface area, well-developed pore networks, tun-
able chemical constituents and structures are common advan-
tages of MOF-based materials for catalytic applications. In the
specific case of photocatalytic HER, the crystalline porous net-
works of MOFs do not just shorten the transport distance of
charge carriers from electrolytes to their surface active sites,
but also avoid the structural defects, which are the potential
recombination centers for electron–hole pairs. The existence
of recombination centers can lower the overall photo­catalytic
efficiency. The photocatalytic capabilities of MOF-based cata-
lysts arise from their semiconductor-like behaviors. Semi-
conducting MOFs can be obtained by targeted selections of
semiconducting metal nodes. MOFs can also be utilized as
precursors to produce semiconducting metal compounds
with intended chemical compositions or structures for photo­
catalytic HER. Furthermore, MOFs can be applied as sup-
ports to load photo­sensitizing or photocatalytic active species
to either expand the range of the absorbed wavelengths or to
achieve highly dispersed active sites for improved hydrogen
evolution efficiencies. UiO-66/UiO-66-NH2 and MIL-101/
MIL-101-NH2 are the most widely applied MOFs for photo-
catalytic HER. The choice of both MOFs is primarily based
on their structural stabilities in water and photosensitizing
properties,[58,130] which are apparent advantages for photocata-
lytic HER in aqueous solutions. The grafting of amino groups
onto the frameworks is to expand the absorbed wavelength to
the visible light range (λ > ≈400 nm) due to auxochromic and
bathochromic shifts.[58]
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The measurement of photocatalytic HER is usually carried
out in aqueous solutions, which are suspended with catalysts,
possibly accompanied with cocatalysts, photosensitizers, and
electron donors. The addition of cocatalysts (such as Pt) is to fur-
ther improve the hydrogen evolution rate, while photosensitizers
(sometimes catalysts themselves) can expand the light absorption
band. The suspensions are then irradiated with UV or visible
light to activate HER, where the generated H2 gases are quanti-
fied by gas chromatography in most studies. The photocatalytic
performance of MOF-based catalysts is usually reported in terms
of hydrogen evolution rate, that is, the amount of evolved H2
per unit time. Turnover number (TON) and turnover frequency
(TOF) are also reported in some publications for the perfor-
mance comparison. The stability is evaluated by the amount of
evolved hydrogen in multiple cycles of photocatalytic reactions
with recycled catalysts and refreshed sacrificial electron donors.
3.2.2. Pristine MOFs
An et al. reported the synthesis of an Al-based MOF with the
coordination of Ni2+ to the amino groups in the pores of MOF
(Al-ATA-Ni MOF) for photocatalytic water splitting.[131] The
Al-based MOF Al-ATA is made up of AlO4(OH)2 octahedra
and 2-aminoterephthalates (ATA2−) as organic linkers. Al-ATA
has been studied by the same authors for its photocatalytic
oxygen evolution capability before.[132] The incorporation of
Ni2+ into the framework further grants Al-ATA-Ni the capability
of photocatalytic HER for overall water splitting (as shown in
Figure 12A,B). Through Tengs blue color reaction and electron
paramagnetic resonance spectra, the authors proved that Ni2+ is
reduced to Ni+ under UV–Vis irradiation, where Ni+ acts as the
active sites for photocatalysis. The material synthesis follows a
simple solvothermal reaction with aluminum nitrate nonahy-
drate and 2-aminoterephthalic acid in dimethylformamide
(DMF). The Ni-coordinated Al-ATA is then prepared by mixing
and stirring nickel nitrate hexahydrate and Al-ATA in water.
The photocatalytic reaction is carried out by the suspension of
the Al-ATA-Ni in water with UV–Vis irradiation from the top of
the reaction vessel. 30 mg catalyst suspension in 30 mL water
exhibits a hydrogen evolution rate of 36 µmol h−1 and an O2
evolution rate of 155 µmol h−1. The authors compared photocat-
alytic H2 and O2 evolutions from both Al-ATA with and without
Ni2+ coordination (as shown in Figure 12C,D). It clearly shows
that the coordination of Ni2+ is the key to enhanced photocata-
lytic performance. Particularly, in the case of H2 evolution,
Al-ATA without Ni2+ coordination shows no catalytic perfor-
mance at all.
Hu et al. presented a series of MOFs, which were constructed
with 3d–4f compounds ([Ln2Cu5(OH)2(pydc)6(H2O)8]∙I8; Ln =
Sm, Eu, Gd, or Tb; pydc = pyridine-2,5-dicarboxylate).[133] The
material synthesis also follows the solvothermal reaction with
Ln2O3, H2pydc, copper nitrate hexahydrate, and iodine mole­
cules in water. The photocatalytic reaction is carried out by
the suspension of the catalyst in 10% methanol aqueous
solution, where methanol plays the role of sacrificial elec-
tron donor. The UV irradiation is used in this work to activate
HER. The best performed catalyst is the Eu-based MOF, which
shows a hydrogen evolution rate of 2262.8 µmol h−1 g−1. The
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Figure 12.  The structure and photocatalytic HER performance of Al-ATA MOF. A) An illustration of Ni coordination with Al-ATA MOF (Al: blue; Ni:
green; O: red; N: light blue; C: black; OH: purple). B) Photocatalytic H2 and O2 evolution catalyzed by Al-ATA-Ni (black and red) and Al-ATA (green and
purple) in an aqueous solution with pH value about 5. Comparison of photocatalytic C) O2 and D) H2 evolutions between Al-ATA without and with Ni
coordination. Reproduced with permission.[131] Copyright 2017, Wiley-VCH.

authors also carried out the stability test on the Gd-based MOF
[Gd2Cu5(OH)2(pydc)6(H2O)8]∙I8. Its hydrogen evolution rate in
the first cycle was determined to be 2050.4 µmol h−1 g−1, while
2107.7 and 1973.9 µmol h−1 g−1 were detected in the second and
the third cycles, which demonstrates a stable performance in the
first three cycles. However, this value dropped significantly after
three cycles and the total evolved H2 in 15 h was 3066 µmol.
Feng et al. demonstrated a 2D layered Ni-based MOF
[Ni2(PymS)4]n (PymS = pyrimidine-2-thio) for photocatalytic
HER under white-light-diode light-emitting diode (LED).[134]
This MOF consists of binuclear [2Ni2S] nodes and pyrimidine-
2-thiol as organic linkers. Due to the structural similarity with
the active sites in [NiFe]-hydrogenase,[135] the binuclear Ni
nodes grant Ni2(PymS)4]n the capability of photocatalytic HER.
Furthermore, the 2D structure of the catalyst promotes the
exposure of the Ni active nodes. The photocatalytic HER test
is conducted in the triethylamine (TEA) aqueous solution with
added fluorescein (FI), where TEA is used as the electron donor
and FI plays the role of photosensitizer. The authors tested
their sample under different conditions, and the optimized
performance was reported in terms of TOF (up to 10.6 h−1). It
was achieved with 15 µmol catalyst and 2 × 10−3 m FI in 15%
TEA aqueous solution of pH = 10 (adjusted by concentrated
HCl). The catalyst also shows a gradual decrease in its perfor-
mance, as the corresponding TON is reduced from 2.5 to 2.0 in
four cycles with refreshed TEA and FI in each cycle, due to Ni
leaching.
Apart from the abovementioned work, other photocatalytic
MOFs are also published in the literature, including UiO-66 and
UiO-66-NH2,[58,136–138] Pt modified-MOF-253,[139] MIL-125-NH2,[140]
[Gd(abtc)(H2O)2(OH)2]·2H2O (abtc = 3,3′,5,5′-azobenzene tetracar-
boxylate),[66] AlTCS-1 (Al3(OH)3(HTCS)2, TCS = tetrakis(4-oxycar-
bonylphenyl)silane),[141] CPM-2-NH2 ([N(CH3)2]3[In3(aip)3(bpdc)3;
aip = 5-aminoisophthalate; bpdc = 4,4′-biphenyldicarboxylate).[142]
3.2.3. MOFs as Supports
In photocatalysis, when MOFs are utilized as supports, they
may function as both photosensitizers and photocatalysts at the
same time. For example, Kong et al. demonstrated the synthesis
of a POM encapsulated [Ir(ppy)2(bpy)]+-derived UiO-MOF

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(designated Ni4P2@MOF-1a) (Ni4P2  = Ni4(H2O)2(PW9O34)2]10−;
ppy = 2-phenylpyridine; bpy = 2,2′-bipyridine; MOF = UiO =
[Zr6(µ3-O)4(µ3-OH)4(L1)6](CO2CF3)6; L1 = [Ir(ppy)2(bpy)]+-derived
carboxylate).[143] In this work, the UiO-MOF is used as both
photo­sensitizer and porous support to encapsulate POM units,
due to its large tetrahedral and octahedral cavities. The photocat-
alytic HER measurement is carried out by the suspension of the
catalyst in 10 vol% methanol aqueous solution. The pH value of
the solution is adjusted to 1.2 by 6 m HCl. A 400 nm cut-off filter
is applied at the light source, which removes the influence of UV
irradiation. Catalytic performance is reported in terms of TON,
where it is 1476 for Ni4P2@MOF-1a in 72 h under visible light
irradiation. The catalyst also exhibits a relatively stable perfor-
mance in three cycles with only slightly reduced TON from 346
to 329 and 297 (20 h), respectively. The performance lost is very
likely due to the leaching of Ir into the solution. The excellence
of Ni4P2@MOF-1a originates from the synergistic functions of
POM units as electron acceptors and UiO-MOFs as photosen-
sitizers, where the excited state of the photosensitizers can be
quenched oxidatively by the electron acceptors. The proxi­mity of
Ni4P2 to the photosensitizer facilitates a facile electron transfer
pathway, leading to an efficient photocatalytic process.
He et al. reported the photocatalytic performance of a CdS
nanoparticles embedded MIL-101 (Cr3F(H2O)2O[BDC]3∙nH2O,
BDC = terephthalate).[130] The CdS embedded MOF is obtained
by the solvothermal reaction of cadmium acetate dihydrate
and MIL-101 in dimethylsulfoxide. The photocatalytic meas-
urement is carried out by the suspension of 10 vol% lactic acid
aqueous solution with 0.5 wt% Pt as cocatalyst and under vis-
ible light irradiation. The authors reported the performance
in terms of H2 evolved per gram of CdS, which is 75.5 mmol
h−1 gCdS−1. The corresponding stability test shows stable per-
formance in the first three cycles. However, the amount of
evolved H2 starts to show apparent drop in the fourth cycle.
The well-developed porous network of MIL-101 leads to the
well-dispersed CdS nanoparticles, which provides a consid-
erable number of both active absorption and catalytic active
sites. More importantly, due to the photosensitizing property
of MIL-101, its application as a supporting information pro-
vides an additional electron transfer path from excited MIL-
101 to CdS and then to the Pt cocatalyst for the reduction of
protons to hydrogen molecules, other than direct light absorp-
tion by CdS. This additional pathway can help to increase elec-
tron transfer efficiency and thus further enhance the catalyst’s
performance.
Another photocatalytic work on CdS quantum dots embedded
MOF is published by Saha et al.[144] As illustrated in Figure 13A,
the innovative feature of this work is the conversion of a CdS
incubated low-molecular-weight Zn-based metallohydrogel
(CdS@ZAVA) into CdS embedded MOF (CdS@ZAVCl). The
ZAVA gel is synthesized from zinc acetate dihydrate (ZA) and
organic ligands (VA; L-3-methyl-2-(pyridine-4-yl-methylamino)-
butanoic acid and sodium acetate). Then, the CdS@ZAVCl is
crystallized from CdS@ZAVA by the addition of sodium chlo-
ride (NaCl) to the metallohydrogel. The hydrogen evolution rate
of CdS@ZAVCl is measured under UV and visible light irradia-
tion, respectively, where the catalyst is suspended in 7.5 vol%
ethanol aqueous solution (ethanol as the electron donor) and
0.5 wt% Pt as cocatalyst. Under UV irradiation, the catalyst
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exhibits a hydrogen evolution rate of 500–510 µmol h−1 g−1,
while that under visible light is 398–418 µmol h−1 g−1. More
exceptional is that the catalyst shows a stable performance in
12 cycles (Figure 13C), considering most reported catalysts
show decreased performance after 3 cycles. The photocatalytic
performance of CdS@ZAVCl heavily relies on the mechanism
of electron transfer between CdS quantum dots and ZAVCl
MOF. The CdS quantum dots are mainly responsible for the
irradiation absorption and generation of electron–hole pairs.
Then, the electrons from CdS are transferred to the conduction
band of ZAVCl MOF and stabilized on its surface, leading to an
efficient charge separation. The additional Pt cocatalyst plays a
role of electron sink, which extracts electrons from the MOF
surface for the H2 generation by proton reduction (Figure 13B).
The above three examples demonstrate the utilization of
MOF as supports to load photosensitive or photocatalytic
active species in their porous networks through cation coor-
dination, physical mixing, or “one-pot synthesis” strategy.
Besides other UiO-66/UiO-66-NH2[55,145–150] and MIL-101/
MIL-101-NH2[151,152] associated work, the photocatalytic per-
formances of MOF-supported catalysts, including UiO-type
MOFs,[153–155] MOF-5,[56] MIL-125-NH2,[156,157] MIL-53-NH2,[158]
Zr-porphyrin-based MOF (ZrPF),[159] and NU-1000[160] are also
summarized in Table 3.
3.2.4. MOF Derivatives
The fabrication of MOF-derived catalysts usually targets to
generate heterojunctions with tunable band structures to facili-
tate effective pathways for charge separation and transporta-
tion. Because MOF-derived materials may inherit chemical
constituents and structural characteristics from their precur-
sors, crystalline porous bimetallic MOF precursors are par-
ticularly attractive to achieve this goal. Lan et al. reported
the derivation of a porous Pt-doped heterojunction catalyst
(Pt–Zn3P2–CoP) from a ZnCo–ZIF for photocatalytic HER.[161]
ZnCo–ZIF is a bimetallic MOF, which consists of Zn and Co
nodes and MeIM (1-methylimidazole) as organic linkers. The
Pt-doped heterojunction Pt–Zn3P2–CoP is achieved by the
phosphorization of ZnCo–ZIF followed by in situ photore-
duction with H6PtCl6. The catalyst is tested in a 10 vol% of
methanol aqueous solution for its photocatalytic performance.
It exhibits a hydrogen evolution rate of 9.15 mmol h−1 g−1
under visible light irradiation. The catalyst is recycled 5 times
for the repeated tests and demonstrates stable performance in
5 cycles. The good stability of the catalyst is attributed to the
strong electron coupling in the heterojunction and the stable
skeleton for the doped Pt nanoparticles. The author proposed
that the photocatalytic capability stems from the synergistic
functions of the metal components in the heterojunction,
which involves the electron–hole pair generation and transfer
within Zn3P2 and CoP, and electron trapping at the Pt active
sites. It can be expected that HER may occur at both Zn3P2–
CoP and Pt sites, due to the existence of photoexcited electrons.
However, it can also be anticipated that the reaction rate at the
Pt site is much faster than that at the Zn3P2–CoP sites because
of the role of Pt as “electron void.” The author also synthesized
another two types of heterojunctions, Pt–ZnO–Co3O4 and
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Figure 13.  The transformation from gels to MOFs. A) A schematic illustration of the transformation from CdS@ZAVA gel to CdS@ZAVCl-MOF and
the crystal structure of the MOF (blue lines: gel fiber; red dots: CdS quantum dots; light red rectangle: CdS@ZAVCl MOF). B) The mechanism of
photocatalytic HER by CdS@ZAVCl-MOF with cocatalyst Pt. C) The 12-cycle stability test of CdS@ZAVCl-MOF in 7.5 vol% ethanol solution and 0.5 wt%
Pt as cocatalyst. Reproduced with permission.[144] Copyright 2014, American Chemical Society.

Pt–ZnS–CoS. However, due to comparatively narrower band-
gaps (1.23 and 1.73 eV, respectively) and lower impedances of
Zn3P2 and CoP, Pt–Zn3P2–CoP shows much better catalytic
performance than those of Pt–ZnO–Co3O4 and Pt–ZnS–CoS
(7.80 and 8.21 mmol h−1 g−1, respectively). Besides the bime-
tallic MOF approach, high performance photocatalysts can also
be obtained by cation-exchanged monometallic MOFs. A repre-
sentative example was published by Chen et al., where hollow
Zn0.6Cd0.4S dodecahedral cages were synthesized by the sulfuri-
zation of ZIF-8 to obtain ZnS, followed by the cation exchange
reaction with Cd(CH3COO)2. The key feature of Zn0.6Cd0.4S
is its hollow cage structure, which is inherited from ZIF-8.
The cage structure benefits the photocatalytic performance by
means of multiple reflections within the cage, more exposed
active sites on both sides of the shell and reduced transporta-
tion distance for charge carriers.[162]
Besides bimetallic heterojunctions, porous metal/carbon com-
posites are another type of photocatalysts derived from MOFs
with promising photocatalytic performance. Noncrystalline
carbon structures and nonmetallic heteroatoms from organic
linkers are capable of introducing defects in the resulting carbon
derivatives after thermal treatments. Jayaramulu et al. presented
a mesoporous cuprous oxide/nitrogen-doped graphitic carbon
nanocomposite (Cu2O@C3N) derived from a urea-modified
Cu-based MOF Cu3(BTC)2 (HKUST-1) through direct pyrolysis
(see Figure 14A).[163] The photocatalytic measurement is carried
out in a 0.01 m ethylenediaminetetraacetic acid (EDTA) aqueous
solution (EDTA as electron donor) under visible light. The sus-
pension of 25 mg catalyst exhibits 5.9 µmol evolved H2 in 9 h,
where its performance is maintained in 3 cycles (Figure 14B).
The origin of the photocatalytic performance is similar to the
above-discussed example, that is, enhanced light absorption
and electron–hole separation with suppressed charge carrier
recombination. These improvements are mainly ascribed to the
relatively small bandgap of the composite (1.97 eV) to absorb
more visible light, and the facile electron transfer through the
Cu2O–carbon interface to avoid charge recombination. Particu-
larly, Cu3(BTC)2 acts as both precursor and template for the
formation of the resulting mesoporous graphite carbon, which
is critical to the uniformly distributed Cu2O nanoparticles in the

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Figure 14.  Mesoporous cuprous oxide/nitrogen-doped graphitic carbon nanocomposite. A) A schematic of urea modification of HKUST-1 and thermal
treatment to obtain mesoporous cuprous oxide/nitrogen-doped graphitic carbon nanocomposite (Cu2O@C3N). B) Photocatalytic H2 evolution by
Cu2O@C3N in 3 cycles (in the first cycle, red lines: Cu2O@C3N; blue lines: g-C3N4; green line: Cu2O; black line: activated carbon). C,D) SEM images
of Cu2O@C3N show the morphology of the carbon composite under different magnifications. E) A TEM image of Cu2O@C3N shows cuprous oxide
nanoparticles embedded in carbon. Reproduced with permission.[163] Copyright 2016, Royal Society of Chemistry.

final carbon matrix (as shown in Figure 14E). In addition, the
use of urea as the source of nitrogen introduces heteroatoms
and thus structural defects in the carbon matrix, which may be
another reason for the enhanced performance. Recently in 2018,
Yao et al. adopted a similar approach to synthesize maghemite–
carbonaceous composites from Fe-MIL-88 with the addition of
GO. In this case, Fe-MIL-88 also plays both roles of maghemite
precursor and template to guide the growth of uniformly distrib-
uted ferrite octahedra on reduced GO (rGO) nanosheets during
thermal treatment. As a result, on the one hand, rGO nanosheets
alter the composite thermodynamically more favorable for pho-
tocatalytic HER when compared with pristine maghemite and
rGO, due to the elevated energy level of conduction band. On
the other hand, the efficient charge separation and transporta-
tion are promoted by the sufficient contact between maghemite
and rGO.[164]
Another MOF-derived heterojunction work is reported by Bala
et al.[165] A Co3O4/TiO2 heterojunction (NC-PA) is derived from

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a Co-based MOF, which consists of cobalt nodes and methylene
bis(3,5-dimethylpyrazole) with pamoic acid as organic linkers.
The catalyst is tested in 15 vol% methanol aqueous solution
under UV–Vis irradiation. It demonstrates a hydrogen evolution
rate of 7 mmol h−1 g−1 with only 2 wt% Co content. No hydrogen
molecule is produced when visible light is applied. The photo-
catalytic HER follows a similar route of photoexcited electron–
hole separation and transfer to the conduction band of n-type
TiO2 and the valance band of p-type Co3O4, respectively, where
electrons at the TiO2 side take part in the reduction of water to
produce H2. However, the authors also proposed that Co3O4
may also play the role of cocatalyst when attached on the surface
of TiO2, which captures the electrons from TiO2. In this case,
hydrogen evolution takes place at the Co3O4 side.
Apart from the abovementioned works, Table 3 summarizes
other recently published MOF-derived catalysts for photocata-
lytic HER, including MoS2@TiO2 nanohybrid,[166] Ni2P/CdS
composite,[167] Cu/CuO@TiO2 nanocomposites,[168] yolk–shell
CdS microcubes,[169] porous CdS,[52] Cu–Cu2O nanoparticles,[170]
Pd-decorated TiO2,[54] MoS2 nanosheets,[171] N-doped graphitic
carbon,[172] and Co–Zn–Cd–S nanocrystals.[173] It can also be
noticed in Table 3 that quite a few studies still require the use of Pt
as the cocatalyst for prominent photocatalytic HER performance,
which weakens the practicability of reported catalysts in reality.
Therefore, a practical objective could be the development of highly
efficient MOF-based photocatalysts without the need for precious
metal cocatalysts. In addition, although the published works tend
to claim their samples demonstrate excellent stabilities, Table 3
indicates that the stable performances of reported MOF-based
catalysts can only be maintained in 3–4 cycles. In this case, the
corresponding mechanism analysis is the key to the targeted
design of highly stable MOF photocatalysts. Similar to the case of
electrocatalysts, the instable performance may be a consequence
of damaged catalyst or agglomerated active species.[33] However,
a photocatalyst may suffer from additional photodegradation,
which is caused by the partial oxidation/reduction of the catalyst,
due to photogenerated charges. The organic ligands in pristine
MOFs are susceptible to photodegradation, which may result in
the breakdown of the framework.[35]
In summary, MOF-based catalysts for photocatalytic HER
share some common advantages with those for electrocatalytic
HER, such as high surface area for more exposed and uniformly
distributed active sites. However, for photocatalytic HER, the
facilitation of bandgap and heterojunction interface is the key to
improve the photocatalytic performance. Therefore, the merit of
tunable chemical structures can be utilized to adjust the semicon-
ducting properties of MOF-based catalysts for optimized photo­
catalytic performance. In this case, MOF-based catalysts do not
just play the role of promising candidates for efficient photocata-
lytic HER but also a controllable solution to synthesize adjustable
catalysts for photocatalytic HER under varied conditions.
3.3. MOFs for Chemocatalytic HER
3.3.1. Fundamentals and Characterizations
Differing from electrocatalytic and photocatalytic HER,
chemocatalytic HER is based on the catalytic hydrolysis or
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decomposition of hydrogen precursors, such as ammonia
borane (NH3∙BH3), sodium borohydride (NaBH4), formic
acid (HCOOH), and hydrous hydrazine (N2H4∙H2O), due to
their high hydrogen contents. Besides hydrogen molecules,
the hydrolysis of ammonia borane or NaBH4 produces ammo-
nium or sodium and metaborate ions, while the decomposi-
tion of N2H4∙H2O produces nitrogen (N2). In the field of
chemocatalytic HER, rare research directly uses MOFs as
catalysts in hydrolysis reactions. However, recently, quite a few
studies report the applications of MOFs as supports and pre-
cursors to obtain metal nanoparticles with ultrasmall sizes and
high dispersity for chemocatalytic HER, thanks to the crystal-
line porous networks and tailorable chemical components of
MOFs.
A typical chemocatalytic HER follows the suspension
of catalysts in distilled water or alkaline solutions (usually
NaOH). The hydrolysis reaction is initiated by the injection of
aqueous solutions of hydrogen precursors. Similar to photo­
catalysis, the evolved hydrogen can also be measured by gas
chromatography or water displacement in a gas burette. In
addition, the performance of the catalyst is also often evalu-
ated by hydrogen evolution rate, TON, and TOF. The recy-
clability of the catalyst is determined by injecting hydrogen
precursor solution again after the completion of the reaction
in the previous cycle. The catalytic performance of MOF-
based catalysts in the following sub-sections is summarized
in Table 4.
3.3.2. MOFs as Supports
Zhu et al. demonstrated the immobilization of AuNi alloy nan-
oparticles on a Cr-based MOF MIL-101 (Cr3F(H2O)2O[(O2C)
C6H4(CO2)]3·nH2O); n  ≈ 25) for the chemocatalytic HER
from NH3∙BH3.[174] The choice of MIL-101 is based on the
consideration of its large specific surface area, pore volume,
and stability in air and water, which are apparently pre-
ferred for dehydrogenation reactions in aqueous solutions.
The sizes of pore windows in MIL-101 range from 1.2 to
1.6 nm, which are beneficial for the diffusion of Au and Ni
precursors (HAuCl4 and NiCl2 in this case). The catalyst is
synthesized through a double solvents method (DSM: water
and n-hexane) and concentration-controlled strategy (CCR,
overwhelming reduction route), which influence the size and
location of AuNi nanoparticles (as shown in Figure 15A). The
catalytic hydrolysis of ammonia borane is conducted by the
suspension of the catalyst in distilled water and the injection
of 1 mol L−1 NH3∙BH3 solution. The evolved amount of H2 is
measured by the water displacement in a gas burette, where
the hydrogen evolution rate is reported in terms of TOF
(66.2 min−1). This performance is better than those of its
monometallic counterparts Au@MIL-101 and Ni@MIL-101
(Figure 15B). The catalyst is also recycled and shows stable
performance in five cycles. The excellent performance of
the catalyst can be associated with the uniformly distributed
nanosized AuNi nanoparticles, which is a result of confined
growth of AuNi nanoparticles within the pores of MIL-101
to avoid particle agglomeration (as demonstrated in its TEM
image in Figure 15C). In addition, the confinement effect
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Table 4.  Summary of MOF-based catalysts for chemocatalytic HER in recent publications.

Sample ID H2 precursor Condition Solvent H2 production rateb) Stability testsc) Ref.

AuNi@MIL-101_a Ammonia borane RTa) Water TOF: 66.2 min−1 Stable in 5 cycles [174]
Au0.28Pd0.47Co0.25/ Formic acid 25 °C Formic acid and sodium TOF: 347 h−1 Significant decrease [175]
MIL-101–NH2 formate aqueous solu- after 9 cycles
tion (1:1 v/v)
NiPt@MIL-101 Hydrazine monohydrate 25 °C 80 mg NaOH TOF: 65.2 h−1 Slight decrease after 5 [176]
4 mL water cycles
CuCo/MIL-101 Ammonia borane RT Aqueous solution of TOF: 51.7 min−1 Stable in 5 cycles [178]
NH3·BH3 (1.71 mmol)
and NaBH4
(0.068 mmol)
FeCo/MIL-101 TOF: 50.8 min−1
NiCo/MIL-101 TOF: 44.3 min−1
CuCo/MIL-101 Ammonia borane RT Water TOF: 19.6 min−1 Stable in 5 cycles [179]
Ni0.9Pt0.1/MIL-101 Hydrazine borane RT 0.5 m NaOH aqueous −1 Slight decrease after 20 [180]
TOF: 1515 h
solution cycles
Ni0.8Pt0.2/MIL-101–NH2 Hydrazine monohydrate 25 °C 80 mg NaOH TOF: 114.3 h−1 Decrease in 4 cycles [183]
4 mL water
Ni64Pt36/MIL-96 Hydrazine monohydrate 50 °C 80 mg NaOH TOF: 90 h−1 Stable in 4 cycles [184]
4 mL water
(Ni3Pt7)0.5–(MnOx)0.5/ Hydrazine monohydrate 25 °C 0.5 m NaOH aqueous TOF: 120 h−1 Stable in 5 cycles [185]
NPC-900 solution
50 °C TOF: 706 h−1
Co-Co3O4@C-II Sodium borohydride RT 1 g NaOH in 20 mL 5260 mL min−1 gCo−1 Stable in 6 cycles [64]
water
Co@carbon–rGO Sodium borohydride RT 5 wt% NaOH aqueous 5560 mL min−1 gCo−1 Stable in 5 cycles [186]
solution
MCS Sodium borohydride 30 °C 1 m NaOH aqueous 247 mL min−1 (MCS = Stable in 10 cycles [187]
solution 50 mg) (>90%)

a)RT = room temperature. Information is summarized in the table according to given reaction conditions from literature; b)The value of turnover frequency (TOF) is
reported as the molar amount of H2 per molar catalyst per unit time; c)The catalyst is recycled and used for repeated tests with refreshed solutions.

can also lead to an enhanced stability at catalytic active sites
by protecting nanoparticles from leaching and aggregation
during operation.
A similar work is carried out by Cheng et al. on the
AuPdCo immobilized MIL-101-NH2 for chemocatalytic HER
from formic acid.[175] The chemocatalytic measurement is con-
ducted by the injection of formic acid and sodium formate
aqueous solution into a flask contained with the catalyst. The
catalyst exhibits a TOF value of 347 h−1 at 25 °C. The catalytic
mechanism is closely related with the confinement of AuPdCo
nanoparticles and the amino group functionalization of MIL-
101. The coexistence of amino groups (NH2), AuPdCo
nanoparticles, and formic acids leads to the formation of
coordination intermediate H2NH+–CoAuPd–OOCH−, which
undergoes hydride elimination to generate CO2 and a metal
hydride H2NH+–CoAuPd–H−. Finally, hydrogen molecules
are produced through the desorption of H+ and H− from the
metal hydride. It should be particularly noted that equal molar
amounts of H2 and CO2 are generated through the decompo-
sition of formic acid, which indicates it requires an additional
step to separate them if pure hydrogen production is taken
into consideration. The stability test suggests that the catalytic
performance decreases in the following two circumstances: 1)
after the conversion of 80% formic acid due to reduced con-
centration of hydrogen precursor; 2) after multiple cycles of
operation (9 cycles in this case) due to the agglomeration of
AuPdCo particles. Based on the same consideration, Cao et al.
also uses MIL-101 to immobilize NiPt nanoparticles insides its
pores for the dehydrogenation of hydrazine monohydrate.[176]
The catalytic measurement is conducted by the injection of
hydrazine monohydrate into an alkaline solution of NaOH.
The authors tested the hydrogen evolution rate at both 25 and
50 °C, in which the results are 65.2 and 375.1 h−1, in terms of
TOF, respectively. The catalyst also demonstrates only slight
decrease in performance after 5 cycles of operation.
Similarly, thanks to the superior confinement function of
MIL-101, there are other reports on the utilization of MIL-101
and MIL-101-NH2 as supporting frameworks for AuPd,[177]
CuCo,[178,179] FeCo,[178] NiCo,[178] NiPt,[180,181] and Pt[182] nano-
particles. MIL-96[183] and ZIF-8[184] are also presented in the
literature as supporting frameworks for NiPt nanoparticles for
chemocatalytic HER.

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the porous carbon framework, in order to

Figure 15.  AuNi nanoparticles immobilized in MIL-101. A) A schematic shows the immobiliza- core–shell structure. The improved catalytic
tion of AuNi nanoparticles in MIL-101 through a double-solvent method (DSM) and a concentra-
tion-controlled reduction strategy (CCR). B) The hydrogen evolution plot of AuNi@MIL-101_a
and comparison with those of mono-metallically loaded MOFs Au@MIL-101 and Ni@MIL-101.
C) A TEM image of AuNi@MIL-101_a shows metal nanoparticles are well-distributed in the
MOF. Reproduced with permission.[174] Copyright 2013, American Chemical Society.
3.3.3. MOF Derivatives
Xia et al. reported a catalyst with NiPt–MnOx supported on
N-doped carbon, which was derived from a Zn-based MOF
ZIF-7 ((Ni3Pt7)0.5–(MnOx)0.5/NPC-900) for chemocatalytic
HER from hydrazine monohydrate.[185] Similar to the case of
MOF supported catalysts, the catalytic performance is initi-
ated by the injection of hydrazine monohydrate to the catalyst
in a flask filled with 0.5 m NaOH aqueous solution. The addi-
tion of NaOH is associated with the decomposition mecha-
nisms of hydrazine monohydrate without (route a) and with
(route b) the presence of NaOH, as explained in Figure 16A.
The function of NaOH is to suppress the formation of N2H5+
in aqueous solution, which is unfavorable for the generation
of H2 at later steps. The authors tested the catalytic perfor-
mance of NiPt–MnOx supported N-doped carbon with different
MnOx loadings and Ni/Pt molar ratios. The optimized result
is achieved with the molar ratios of MnOx/NiPt = 1/1and Ni/
Pt = 3/7 (Figure 16B,C), which present TOFs of 120 and 706
at room temperature and 50 °C, respectively. The stability
tests show stable catalytic activity in 5 cycles of operation. In
this work, ZIF-7 plays both the roles of carbon precursor and
porous template, where its 900 °C calcined product NPC-
900 (NPC = nitrogen-doped porous carbon) partially inherits
the porous structure of its precursor. Therefore, instead of the
pristine MOF, ZIF-7 derivative NPC-900 is utilized to confine
the growth of metal nanoparticles and immobilize them in
achieve ultrafine and uniformly dispersive
catalytic active sites, that is, NiPt–MnOx in
this case. While NiPt is the main active site
for the decomposition of hydrazine monohy-
drate, porous NPC-900 can also enhance the
adsorption of hydrazine monohydrate for the
subsequent reaction. The addition of MnOx
further modifies the charge transfer within
the catalyst, which leads to more trans-
ferred electrons at Ni and Pt sites and thus
improves the catalytic performance.
ZIF-67 was utilized by Liu et al. to produce
Co-doped carbon composite (Co-Co3O4@C-
II) for chemocatalytic HER from sodium
borohydride (NaBH4).[64] The catalyst is
tested in the NaOH aqueous solution (1 g
in 20 mL) at room temperature, where it
shows a hydrogen evolution rate of 5260 mL
min−1 gCo−1 and maintains a stable perfor-
mance in 6 cycles. Its catalytic performance
is better than that of pure Co-Co3O4 catalyst.
Co-Co3O4@C-II is synthesized by wrapping
ZIF-67 with glucose polymer and followed
by pyrolysis in N2 and oxidation in air, which
leads to the formation of Co-doped carbon
performance can be attributed to the syn-
ergistic effect between Co-Co3O4 core and
carbon shell. The carbon coating isolates
Co-Co3O4 nanoparticles and protects them
from agglomeration and leaching. The high
surface area and porous structure of carbon
shell inherited from ZIF-67 also brings more active sites and
smoother mass transfer. The Co-Co3O4 active sites are respon-
sible for the formation of Co-Co3O4–borates intermediate
during the decomposition reaction of NaBH4.
There are other Co-based catalysts derived from ZIF-67,
such as Co@carbon–rGO composite[186] and magnetic carbon
sponge (MCS).[187] They are synthesized for chemocatalytic
HER from NaBH4.
On the one hand, based on the examples in Table 4, it can
be concluded that MOFs mainly play the roles of supporting
substrates and precursors for chemocatalytic HER. In other
words, at the current stage of research, the functions of MOFs
are primarily the structural directing agents and sources of
metals. To the best of our knowledge, there is rare report on the
use of pristine MOFs as catalysts in chemocatalytic HER. There-
fore, the development of chemocatalytically active MOFs for
hydrogen evolution is certainly an interesting and challenging
work to be explored in the future. On the other hand, similar
to the case of MOFs for photocatalytic HER, Table 4 shows that
the stability tests in most earlier works are limited in a few
cycles, which is most likely due to apparently decreased per-
formance and frequently attributed to the aggregation of cata-
lytically active nanoparticles.[175,187] Furthermore, many earlier
published works prefer ambiguous qualitative terms (such as
“no apparent drop” and “little loss”) over quantitative descrip-
tions about the results of stability tests. Therefore, apart from

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www.advancedsciencenews.com www.advenergymat.de

Figure 16. NiPt–MnOx supported on N-doped carbon derived from ZIF-7. A) An illustration of the decomposition mechanism of hydrazine on
(Ni3Pt7)0.5–(MnOx)0.5/NPC-900 without (route a) and with (route b) NaOH in aqueous solutions. B) Catalytic performance of (Ni5Pt5)1-y–(MnOx)y/
NPC-900 with different compositions of MnOx (i.e., with different values of y). C) Catalytic performance of (NiPt)0.5–(MnOx)0.5/NPC-900 with different
Ni/Pt molar ratios. Test condition: 0.5 m NaOH at 50 °C. Reproduced with permission.[185] Copyright 2016, Royal Society of Chemistry.

the continuous efforts to improve the stabilities of MOF-based spacecrafts in Figure 17). In the view of both energy efficiency
catalysts, the quantitative reports of performance changes (such and environmental protection, photocatalytic HER is the first
as “in percentage”) are necessary for the comparison of cata-
lysts from different research works.

4. Prospects for MOFs-Based Catalysts in Future

Mass Hydrogen Production
As indicated in the section of introduction, hydrogen-powered
technologies have already reached the stage of demonstration,
particularly in the fields of vehicles and transportation, due to
the promising development of fuel cell techniques. It can be
anticipated that both hydrogen production volume and rate are
going to be the primary limitations for the large-scale applica-
tions of hydrogen-powered technologies. Due to low output
rates by current hydrogen production methods, it is inevitable
for the above-summarized electrocatalytic, photocatalytic, and
chemocatalytic techniques to play a more significant role in
future mass hydrogen production or even replace the conven-
tional methods. Considering the need for chemical storage
and portability, chemocatalytic HER may be more suitable for Figure 17. Prospects for MOF-catalyzed hydrogen production tech-
niques. Photocatalytic and electrocatalytic HER may be more applicable
small-scale and portable devices (such as light vehicles and
in stationary and transport applications, while chemocatalytic HER may
computers in Figure 17) in daily lives, while electrocatalytic be more suitable for civil utilizations. The design of MOF-based cata-
and photocatalytic HER are more adaptive in large-scale sta- lysts should take specific conditions in the practical applications into
tionary and transport applications (such as power plants and consideration.

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www.advancedsciencenews.com
choice, due to the sustainability and environmental friendli-
ness of its participating components, including energy input
(sunlight), reactant (water), and product (hydrogen). However,
it can be expected that the selection of location for photocata-
lytic HER is restricted by local insolation intensities, weathers,
and temperatures. In comparison, electrocatalytic HER is more
flexible, as its energy input is electricity. However, it also raises
the issue of power consumption. The utilization of electricity
output during the off-peak period may be a win–win solution
for both hydrogen production and power grid operation.
MOF-based catalysts have demonstrated their superiori-
ties in hydrogen production when compared with many other
types of materials. However, cost-effectiveness and yield are
still the key issues, since most reported MOF-based catalysts
are still synthesized through lab-scale solvothermal reactions.
According to the prices on Sigma-Aldrich (January 2018), the
price for 10 wt% Pt/C is $21.7 per gram (10 g pack; no price
available for 20 wt% but it may be doubled).[188] This price can
be compared with those of other available MOFs on Sigma-
Aldrich, including HKUST-1 ($35.3 per gram),[189] ZIF-8 ($37.8
per gram),[190] Fe-BTC ($21.1 per gram),[191] and MOF-177
($33.8 per gram).[192] Based on the above information, it can
be concluded that current MOF prices are not very competi-
tive when compared with that of Pt/C catalyst. The cost for the
modification and processing on pristine MOFs can be expected
to further raise the cost of MOF-derived catalysts. However, at
the current stage of research, there is lack of studies on the
influence of scale-up production on the product yield and cata-
lytic performance. Therefore, corresponding work is encour-
aged to be carried out to fill up this gap.
Apart from cost-effectiveness and environmental friendli-
ness, safety, stability, weight, and product forms are also impor-
tant parameters to be considered. For example, safety is an
important factor in all above-mentioned hydrogen production
techniques. However, when it comes to civilian use, toxicity,
corrosiveness, and explosiveness are particularly critical for the
acceptance by general public. Therefore, in the case of MOF-
based chemocatalytic catalysts, the explorations of nontoxic
and noncorrosive metal and organic components are possible
studies to make MOF-based catalysts more adaptive and com-
petitive in this respect. The density of the catalyst is another
important factor when portability is taken into consideration
for some civilian applications, since lightweight is always pre-
ferred. In stationary applications, long-term stability, recycla-
bility, resistance to corrosion, humidity, and acidic and basic
environments are more likely to be assessed because they are
directly related with productivity and economic benefit.
5. Conclusions
With the pressing issues of energy depletion and environ-
mental pollution, it is inevitable for industries to be developed
toward the new era of clean technologies. Hydrogen-powered
technology is the most anticipated, which has even reached its
early stage demonstration and distribution. However, the pri-
mary issue is the cost-effective mass production of hydrogen
fuels. Thanks to the well-developed crystalline porous struc-
ture, vast combinations of chemical components and tailorable
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www.advenergymat.de
structures, MOF-based materials are a family of ideal catalysts,
which are under intensive studies for electrocatalytic, photocat-
alytic, and chemocatalytic HER. In this case, MOF-based mate-
rials can be utilized in different forms: 1) pristine MOFs with
catalytically active metal nodes and organic linkers; 2) MOFs as
supports for catalytically active species (such as nanoparticles,
charged ions, dyes); 3) MOF-derived compounds or composites
with specifically designed chemical structures and components.
No matter which forms of MOF-based catalysts are presented,
their syntheses and modifications always aim: 1) to introduce
catalytic active species or interfaces to the systems; 2) to con-
fine the growth of metal nanoparticles and expose uniformly
dispersed catalytically active sites; 3) to promote synergistic
functions between catalytically active species or between com-
pounds and supporting frameworks.
On the one hand, with the above considerations in mind,
researchers may continue to look into the mechanisms behind
the thermodynamics and kinetics for the formation of MOFs
and their derivatives, which is essential to achieve atomically
dispersed catalytically active sites. The other alternative rou-
tine is continuing to explore vast combinations of catalytically
active species through MOF syntheses and derivations, to
excavate the potential of interfaces and synergistic effects for
further improved catalytic performance. On the other hand, in
order to keep pace with the fast-developing hydrogen-powered
technologies, it is a pressing demand to demonstrate reliable
and cost-effective methods for the mass production of MOF-
based catalysts at the industrial scale, which is imperative for
MOF-based catalysts to secure their dominant role in future
hydrogen production. A more promising way to achieve this
goal is the stepwise scale-up of MOF synthesis and the corre-
sponding analysis of its influence on the production rate and
product performance.
In any event, both MOF-based catalysts and hydrogen pro-
duction have drawn a bright picture for the development of
clean technologies and will continue to demonstrate their sig-
nificant contributions to a hydrogen-powered future.
Acknowledgements
This work was financially supported by the Natural Science Foundation
of China (Grant No. 51772008), the National Key Research and
Development Program of China (Grant No. 2017YFA0206701), and
the National Program for Support of Top-notch Young Professionals,
Changjiang Scholar Program.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
chemocatalysis, electrocatalysis, hydrogen evolution reactions, metal–
organic frameworks, photocatalysis
Received: April 19, 2018
Revised: May 25, 2018
Published online:
© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
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