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Metal-Organic Framework-Based Materials for Energy Conversion and

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Article  in  ACS Energy Letters · January 2020

DOI: 10.1021/acsenergylett.9b02625

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Review
http://pubs.acs.org/journal/aelccp

Metal−Organic Framework-Based Materials

for Energy Conversion and Storage
Tianjie Qiu, Zibin Liang, Wenhan Guo, Hassina Tabassum, Song Gao, and Ruqiang Zou*

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ABSTRACT: Metal−organic frameworks (MOFs) have emerged as

desirable cross-functional platforms for electrochemical and photo-
Downloaded via 72.228.165.227 on March 30, 2022 at 01:28:54 (UTC).

chemical energy conversion and storage (ECS) systems owing to their

highly ordered and tunable compositions and structures. In this Review,
we present engineering principles promoting the electro-/photochemical
performance of MOF-based materials for ECS by component design and
nanostructuring. Through the discussion of the engineering strategies of
pristine MOFs, MOF composites, and their derivatives for ECS, the
superiority and composition−structure−activity relationships of the
engineered MOF-based materials with advanced components and
nanostructures will be clarified. Finally, we provide a concluding
discussion on the challenges and direction of future development in
this emerging area of MOF-based materials for ECS.

W ith the dramatic depletion of fossil fuels along with

severe environmental problems, it is urgent to
develop sustainable energy conversion and storage
(ECS) technologies to power our future society.1,2 Energy
conversion systems based on photocatalysis and electro-
large overpotentials and sluggish kinetics, which consume
abundant extra energy. For practical applications such as water-
splitting devices and fuel cells in harsh operating conditions,
the short lifetime and high cost of the catalysts also greatly
hinder their widespread and large-scale applications.4 (3) For
catalysis are among the most clean and renewable ways to energy storage devices, the severe shuttle effect in LSBs,
mitigate the energy and environment problems. Photocatalysis sluggish oxygen redox reaction during recharging in MABs,
involving light harvesting, electron−hole separation, and uncontrolled formation of metal dendrites in metal (Li, Na,
surface redox processes can produce various high-reward and K) ion batteries, and large volume variation of the
molecules such as H2 and O2 by water splitting and electrode materials will result in low energy density, low rate
carbonaceous fuels by reduction of CO2.3 Electrocatalysis is capability, and poor cycling stability.5 To advance these
the key of many ECS systems such as water splitting, environmentally friendly energy conversion and storage
electrocatalytic reduction of N2 and CO2, fuel cells, and technologies, development of highly efficient and durable
metal−air batteries (MABs).4 Moreover, electrochemical catalysts and electrode materials with desirable electro- and
energy storage technologies such as supercapacitors (SCs),
photochemical properties becomes necessary. Appropriate
metal (Li, Na, and K) ion batteries, and lithium−sulfur
compositions and nanostructures of these materials are highly
batteries (LSBs) are promising to store energy in an
environmentally friendly way. These energy storage devices desirable to alleviate these issues. Diverse compositions can
enable the efficient reversible storage and release of electricity introduce multifunctionality into one system. Porous structure
for portable electronics, electric vehicles, and electric grids.5 and large surface area are promising to enable abundant and
However, there are still many challenges in these fields: (1) accessible exposed active sites. Transport distance of charge
Conventional photocatalysts always suffer from low light carriers to active sites can also be greatly shortened to suppress
utilization because of the insufficient light-harvesting units with the photocatalytic electron−hole recombination and facilitate
a narrow absorption region. A long carrier transport distance
always results in severe recombination phenomenon of Received: December 2, 2019
electron and hole with low photocatalytic efficiency. Accepted: January 8, 2020
Furthermore, complex photocatalysts synthesized in compli- Published: January 8, 2020
cated routes often possess low porosity, low exposed actives
sites, and poor stability.3 (2) Electrocatalysts generally possess

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsenergylett.9b02625

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kinetics owing to the porous designed structure. Hence, it is MOFs.9−12 In terms of structural superiorities, MOFs possess
highly desirable to conduct rational design for these materials inherently high porosity, which can achieve a high accessibility
to achieve high efficiency and durability in practical ECS of interior active species; accumulate the reactants; and
applications. facilitate the kinetics owing to the open channel, spatial
Of particular interest, metal−organic frameworks (MOFs) confinement, and host−guest interactions of the pore.13
have emerged as promising platforms to develop advanced Suitable pore size, pore shape, and pore surface environment
materials for efficient ECS systems.2,6−8 Compared with can be delicately designed to achieve the structural
conventional materials, MOFs offer various unique composi- superiorities by judicious selection of the metal sites and
tional and structural advantages by virtue of the highly ordered ligands.6,14 In addition, diverse MOF nanoarchitectures such as
and tunable metal nodes and organic linkers (Figure 1). Use of 0D nanoparticles, 1D nanorods, 2D nanosheets, and 3D
hierarchical structures with high porosity can be produced via
precise control of MOF growth by recrystallization, surface-
control, and size-confinement. Also, assembly of MOF crystals
into superstructures or template-guided growth of MOF-based
materials can further enrich their structural diversities. The
porous structures and large surface areas of the obtained
advanced MOF-based nanoarchitectures can offer advantages
of facile mass transport and high exposure of active sites for
efficient ECS.15−17
This Review focuses on rational component design and
nanostructuring of pristine MOFs, MOF composites, and their
derivatives for various ECS applications. We also discuss the
advances and challenges of these design strategies for practical
ECS systems. We hope this Review will provide guidance and
inspiration for future development of high-performance
electrode materials for efficient and durable ECS systems.
Component Design of Pristine MOFs. Component design of
pristine MOFs can be achieved by judicious selection and
modification of metal sites and organic ligands at an atomic
level. The physical and chemical properties of MOFs, including
electronic structures, electron−hole separation efficiency,
hydrophilicity, electrical conductivity, and stability, can be
modulated by component design, which are desirable
Figure 1. Merits of MOF-based materials for ECS applications.
advantages for high efficiency and durable ECS applica-
MOF-based materials with appropriate physical and chemical tions.18−21 For component design of metal sites, introduction
properties is promising to alleviate the above-mentioned issues of heterometallic doping, coordinatively unsaturated metal
of conventional catalysts and electrode materials in ECS sites (CUMSs), metal site defects, multiple valences of metal
systems. By component design and nanostructuring of MOF- centers, and external coordination ions is an efficient strategy
to improve the activity of pristine MOFs. For component
design of organic ligands, the commonly used strategies are
By component design and nanostruc- functional group modification, metal site adsorption, selection
turing of MOF-based materials, active of large π-conjugated organic ligands, and creation of organic
sites with both high activity and ligand defects (Figure 2).
Component Design of Metal Sites of Pristine MOFs for ECS.
desirable stability can be created for Metal ions in the skeletons of as-synthesized MOFs are
efficient and durable ECS. commonly coordinated by the organic ligands and solvent
molecules with low accessibility for reactants. For many MOFs,
based materials, active sites with both high activity and the removal of solvent molecules can create CUMSs, which
desirable stability can be created for efficient and durable ECS. can serve as electron-deficient Lewis acid centers to accept
In terms of component superiorities, diverse metal nodes and electrons from reactant molecules.9,10 For example, the
organic ligands can be used to construct MOFs with various coordinatively unsaturated Fe sites created by removal of
physical and chemical properties. The highly ordered arrange- terminal waters in MIL-101(Fe) could act as active centers to
ment of metal nodes and organic ligands results in uniform and accumulate and activate CO2 molecules during photocatalytic
abundant active sites with well-defined configurations.6 In reduction of CO2.29 In addition to removal of solvent
addition, MOFs can be facilely coupled with functional molecules, introduction of metal/ligand defects can also create
materials such as graphene, metal nanoparticles, and functional abundant CUMSs in pristine MOFs for ECS perform-
molecules to form multifunctional MOF composites. The ance.22,30−33 For example, missing organic linkers in ZIF-67
combined advantages of both MOFs and the incorporated created by plasma treatment can lead to a mesoporous
components as well as the induced synergistic effects can lead structure with numerous CUMSs for efficient OER.33
to improved photo/electrochemical performance of the MOF In addition to CUMSs, introduction of heterometallic ions is
composites. Furthermore, transformation of MOFs into another effective strategy to improve the performance of
various MOF-derived nanoarchitectures by chemical/thermal MOFs by optimizing the electronic structures of the active
treatments can also lead to novel properties over pristine metal sites. As an example, for heterometallic NiCo-MOF, the
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Figure 2. Schematic illustration of component design of pristine MOFs on metal sites and organic ligands. (a) Structural description of metal
nodes defects. Reprinted with permission from ref 22. Copyright 2014 Springer Nature Publishing Group. (b) MOFs with different
decorated ions like OH− and Cl− possessing various coupling ways for OER. Reprinted from ref 23. Copyright 2016 American Chemical
Society. (c) Crystal structure of heterometallic NiCo-MOFs and schematic representation of the electronic coupling between Co and Ni.
Reprinted with permission from ref 24. Copyright 2016 Springer Nature Publishing Group. (d) Introduction of missing linker defects to the
hexanuclear Zr cluster leads to more labile protons that can be subsequently replaced by Li ion. Reprinted from ref 25. Copyright 2019
American Chemical Society. (e) Various functional groups anchored on the ligands with great influence on the band gap of MOFs. Reprinted
from ref 26. Copyright 2015 American Chemical Society. (f) Incorporating metal complexes in MOFs. Reprinted with permission from ref
27. Copyright 2016 Wiley-VCH. (g) Molecular structure of conductive MOF with conjugated ligands and a space-filling diagram of idealized
MOF with electrolytes in the pores. Reprinted with permission from ref 28. Copyright 2017 Springer Nature Publishing Group.

coupling between Ni2+ and Co2+ could lead to a partial Efforts are also devoted to the development of MOFs with
electron transfer from Ni2+ to less filled Co2+ sites in 3d eg high-valence and multivalence metal sites for ECS.37 The
orbitals through the bridging oxygen of the ligands.24 This existence of high-valence metal sites can strengthen the
electron transfer could result in an optimized interaction coordination bond between the metal nodes and organic
between intermediates and the metal centers, which led to a linkers and improve the stability of MOFs during ECS
much higher electrochemical OER performance of the processes. Moreover, the multivalence metal sites can induce
heterometallic NiCo-MOF (250 mV at 10 mA cm−2) than long-range electron delocalization via strong overlap of the
monometallic Ni-MOF (321 mV at 10 mA cm−2) and Co- metal−ligand frontier orbitals, which can afford a long-range
MOF (371 mV at 10 mA cm−2) in 1 M KOH. Moreover, the network semiconductivity and enhance the electrical con-
electronic configurations of the active metal atoms and the ductivity of pristine MOFs.38,39 For instance, it was reported
adsorption energy of intermediates, which dominate electro- that the mixed-valence Fe3+/2+ in Fe-based MOF could
significantly facilitate interiron charge hopping and improve
chemical performance, could be tuned by heterometallic
charge mobility.40 Also, the mixed-valence Fe3+/2+ in Fe-based
doping.34 It was also demonstrated that the heterometallic
MOF could serve as active sites for fast Li-ion insertion and
ions can also modify the band gap of MOFs and promote the
desertion along with the change of the valence of Fe.37 In
electron−hole separation and light adsorption.35 Also, the addition, the multivalence metal sites in MOFs can also give
heterometallic ions could act as electron mediators to promote rise to semiconductivity with low band gap energy for desirable
the charge transfer from excited ligands to metal clusters. For photoresponse. For example, ((CuICuII2(DCTP) 2)NO 3·
example, doping Ti atoms in NH2−Uio-66 (Zr) with Ti partial 1.5DMF)n MOF demonstrated high photochemical perform-
substitution can induce an electron transfer from the Ti3+ to ance for water splitting by virtue of its multivalence Cu sites.41
Zr4+ through the oxo-bridge Ti3+−O−Zr4+,36 which led to the The low-valence CuI can be excited in the visible light region
formation of Zr3+ metal center with high photocatalytic CO2 and produce holes in the valence bands, while the CuII sites
reduction activity. The heterometallic MOF showed good served as the building blocks to stabilize the MOF structure.
selectivity and produced 5.8 mmol mol−1 HCOO− after 10 h Additionally, decoration of coordinative ions onto the metal
of irradiation, 1.7 times that observed over monometallic sites of MOFs is also an efficient strategy to optimize the
NH2−Uio-66(Zr) (3.4 mmol mol−1). performance of MOFs for ECS by modification of the reaction
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pathways. As an example, replacing the Cl− on the Co sites of electrical conductivity of the resultant MOFs for improved
the Co-based MOF by OH− ions could induce an intraframe- HER, ORR, and supercapacitor performance.20,28,50,51 The
work coupling pathway for enhanced OER performance.23 The conductive scaffolds constructed by judiciously selected
OH− ion-decorated Co-based MOF could thus achieve an conjugated ligands and metal sites will provide inspiring
overpotential of 292 mV at 10 mA cm−2 in 1 M KOH for OER, opportunities to develop pristine MOFs for efficient electro-
while Cl−-decorated MOF showed rather poor OER perform- chemical ECS systems.
ance. Component Design of MOF Composites for ECS. In many
Component Design of Organic Ligands of Pristine MOFs for cases, pristine MOFs cannot offer desirable performance to
ECS. Similar to metal nodes, the infinite diversities of organic meet the requirements of practical ECS applications because of
ligands also offer great opportunities to design and tune the the intrinsic deficiencies of conventional MOFs like poor
functionalities of pristine MOFs for ECS. Functionalization of conductivity and limited functionality. Recent efforts have
the ligands with functional groups can effectively regulate the demonstrated that combination of MOFs with functional
photo/electrochemical properties of pristine MOFs. For materials to form MOF composites can overcome the
example, introduction of electron-donating groups such as deficiencies of conventional MOFs while maintaining the
−NH2 and −SH into the organic ligands of MOFs can greatly original advantages of MOFs. Various functional materials,
improve light response in the visible region by regulating the including metal nanoparticles (MNPs), carbon nanotubes
band gap.26 In addition, the functional groups of organic (CNTs), reduced graphene oxide (rGO), porous supports,
ligands can also serve as active sites for ECS processes like Li molecule complexes, and conductive substrates, have been
storage. The COO− groups, nitrogen-containing groups, and coupled with MOFs to form MOF composites for enhanced
aromatic ring in the organic ligands of MOFs could serve as Li ECS applications (Figure 3).52 Generally, the introduced
insertion sites for Li storage.42−44 In addition, anchoring metal
atoms on the organic ligands like porphyrin-based ligands
could also significantly improve the activity of MOFs for ECS.
The anchored metal atoms can act as catalytically active sites
while the organic ligands can strongly stabilize the metal atoms
and prevent them from aggregation and inactivation.8 For
example, MOFs constructed by porphyrin-based ligands can
immobilize various active metal atoms such as Cu, Au, Fe, Pt,
and Ir into the porphyrin groups. The conjugated porphyrin-
based ligands and the immobilized metal atoms can synergisti-
cally enhance the activities of MOFs for CO2 reduction and
water splitting.45−47
In addition, construction of organic ligand defects also has
great influence on the performance of MOFs for ECS.
Modified charge-transfer pathways, abundant CUMSs, high
porosity, and enhanced electrical conductivity can be achieved
by defect design of the organic ligands for efficient and durable
ECS performance.22,31,48 It has been theoretically revealed that
the missing linkers in UiO-66 could lower the energy of
unoccupied d orbitals and optimize the charge-transfer
pathways.31 A moderate amount of organic linker defects
could improve the photocatalytic activity and facilitate
electron−hole separation.48 In addition, the ligand defects
could induce a lattice strain in pristine MOF rather than
Figure 3. Component design of MOF composites.
structural collapse for improved electrochemical activity. For
example, the ligand defects in NiFe MOF can not only result in
a swelling of the metal oxide interlayer spacing by weakening functional materials are combined with MOFs in two ways: (1)
the interlayer interaction but also transform the ORR/OER The functional materials are encapsulated inside MOF crystals.
reacting pathways into a fast 4e− process rather than low- (2) The functional materials serve as substrates to support
efficiency 2e− or 2e− + 2e− kinetics.49 Hence, the lattice- MOFs. In regard to the former way, MNPs, polyoxometalates
strained NiFe MOFs displayed high mass activities of 500 A (POMs), quantum dots (QDs), and metal complex molecules
gmetal−1 at a half-wave potential of 0.83 V for ORR and 2000 A are commonly encapsulated in MOFs to achieve an improved
gmetal−1 at an overpotential of 300 mV for OER, which were 2 ECS performance of the resultant MOF composites. These
orders of magnitude greater than that of original NiFe MOF encapsulated materials can serve as the active sites or
without organic defect-induced lattice strain. performance-enhancing auxiliaries while the MOF crystals
Moreover, for electrochemical ECS applications, conven- serve as supports to stabilize and confine these materials. In
tional MOFs always suffer from poor electrical conductivity. many cases, strong interactions and synergistic effects between
Efforts devoted to the development of conductive MOFs the encapsulated materials and MOFs contribute greatly to the
eventually led to MOFs constructed with conjugated organic ECS performance of the MOF composites.52,53 Taking
ligands such as 1,2,5,6,9,10-triphenylenehexathiol and photocatalytic hydrogen production as an example, Pt NPs
hexaiminobenzene. These conjugated ligands are highly encapsulated in MOFs could accept the generated photo-
delocalized and likely to form energy overlap with the adjacent electrons from MOFs under illumination and catalyze the
metal ions and ligands, which can significantly enhance the production of hydrogen with a rate of 381.2 μmol·g−1·h−1.48 In
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this case, Pt NPs acted as catalytically active sites while the conditions like OER conditions with high oxidizing potential
MOFs served as light adsorbents. Similarly, POMs with high will oxidize the nonredox active ligands and the metal nodes,
redox activity can be also encapsulated in MOFs for which will lead to structural collapse and conversion of MOFs
photochemical hydrogen generation.54,55 The incorporated into other phases (metal oxide/hydroxide).65,66 Hence,
POMs can serve as electron acceptors and active sites to boost construction of stable pristine MOFs and their composites is
the photocatalytic hydrogen generation performance. Also, highly desirable to fully exploit the superiorities of pristine
metal complexes such as [CoII(TPA)Cl][Cl] (TPA = tris(2- MOFs and their composites for ECS systems. It has been
pyridylmethyl)amine) incorporated in MOFs can accumulate reported that the stability of pristine MOFs can be effectively
the electrons from the photosensitive MOF and greatly enhanced by rational selection of high-valence Zr-based MOFs
improve the spatial charge separation for efficient H 2 with strong Zr−trioxobenzene bonds, nitrogen-containing
production.53 Apart from the roles as supports, MOFs can linkers, and buffer behaving ligands that feature both weak
also function as catalytic sites in MOF composites. For acidic and basic functional groups.64,67 Moreover, because of
example, Au NPs in MOFs could be excited to produce the elusive transformation of MOFs during ECS in a limited
plasma-induced hot-electrons to the catalytic active MOFs by surface region, which truly dominates the activity,68 confirming
incident light, which can lift the Fermi level of MOFs for water the true origin of the activity of MOFs is in high demand.
splitting.56 Upon light irradiation, these MOF composites Combination of surface-sensitive characterization technologies,
demonstrated more than 4-fold enhancement of the current such as in situ and ex situ high-resolution transmission electron
density (at −0.236 V) via the synergistic effect between Au and microscopy (TEM), Raman spectroscopy, synchrotron X-ray
active MOF than pure MOF. Also, QDs such as metal oxide, spectroscopy, and electrochemical and photochemical charac-
nitride, sulfide, and carbon nanodots have also been widely terizations, is an effective way to provide in-depth under-
encapsulated in active MOFs to enhance the photoresponse standing for the fabrication of customized pristine MOFs,
and electrical conductivity of MOF composites for ECS identify the exact active species, speculate on the possible
applications.57,58 For functional materials encapsulated inside mechanisms, and guide the development of stable MOFs for
MOF crystals, it is noted that the location and loading amount ECS.
of the functional materials should be carefully controlled in Component Design for MOF-Derived Materials for ECS.
order to maximize the utilization efficiency of the active sites. A Recently, MOFs and MOF composites were widely used as
uniform distribution of the guest functional materials inside the precursors to fabricate nanomaterials for ECS. The high
MOF crystals that could greatly shorten charge-transfer diversity of metal ions and organic linkers renders MOFs as
distance is highly desirable.59 ideal platforms to design and fabricate various functional
For MOFs supported by functional substrates, MOFs materials, including carbons, metal compounds, and their
generally serve as the main active species while the functional composites (Figure 4). These MOF-derived materials can not
substrates assist to disperse and stabilize the MOFs.60,61
Porous supports like mesoporous silica and carbon can be used
to support MOF particles in their accessible channels or pores
and avoid MOFs from aggregation and deactivation during
ECS processes. Also, the porous structures of the substrates
ensure high exposure of active species, fast mass transport,
desirable structural robustness, and good recyclability of the
MOF composites. For example, conductive CNTs and rGO
can not only strongly disperse MOF particles but also enhance
the mechanical stability and conductivity of MOFs by virtue of
the strong surface immobilization ability and high conductivity
of the substrates.11,62 The combination of MOFs and the
functional substrates can also benefit the charge separation
during photocatalysis via introduced interaction. For instance, Figure 4. Component design of MOF-derived materials.
ZIF-8 layer on TiO2 surface can lead to an efficient charge
separation by electron injection from ZIF-8 to TiO2 for only inherit the advantages of MOFs like high porosity and
efficient hydrogen generation under illumination.63 These high surface area but also offer opportunities to control and
MOF composites exhibited high photocatalytic quantum design the compositional/structural features by controlled
efficiencies of 50.89% at 380 nm and high hydrogen evolution conversion such as pyrolysis or ion-assisted solvothermal
rate up to 261.7 μmol g−1 h−1, which is 3.5 times higher than conversion processes of predesigned MOF precursors.4 By
that of the bare TiO2. virtue of the employment of advanced in situ characterization
Although extensive efforts have been devoted to fabricating technologies during the conversion processes for MOF
various MOFs and their composites, directly using them for precursors, the accurate conversion processes can be probed
electrochemical application is still in its infancy. The main and designed, which will offer guidance for the preparation of
reason lies in the poor stabilities of most MOFs and their specific MOF-derived materials. For example, in situ environ-
composites originating from two aspects during electro- mental TEM has monitored the transformation of noble metal
chemical processes. First, a large number of MOFs are nanoparticles (Pd, Pt, and Au) to thermally stable single atoms
unstable in aqueous acidic and basic solutions because of the (M-N4) in the MOF-derived carbon scaffolds in an inert
weak coordination bonds. The unstable MOFs will be atmosphere. Noble metal encapsulated in ZIF-8 would sinter
hydrolyzed into a protonated linker and a hydroxide (or to a larger one in high temperature, and then the enlarged NPs
water) ligated node in electrochemical acidic or basic aqueous would intensively collide with the substrate to gradually
conditions.64 Second, the strong electrochemical oxidation become smaller and finally obtain the single atoms.69 Likewise,
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in situ UV−vis spectra and in situ Raman spectra were also Besides carbon and metal compounds, conversion of MOFs/
developed to reveal the transforming processes of MOFs MOF composites into metal/carbon hybrid materials is an
during electrochemical OER, which indicated that Co(OH)2/ efficient way to fully utilize the organic−inorganic hybrid
CoOOH as the true active sites would be produced on the nature of MOFs. In the MOF-derived metal/carbon hybrids,
surface of ZIF-67.66 The MOF-templated method combined metal species (metal NPs, metal compounds, and atomically
with advanced technologies presents an advantageous way to dispersed metal sites) are uniformly dispersed onto the porous
design and fabricate functional nanomaterials compared with carbon substrates. The carbon scaffolds offer advantages of
traditional synthetic routes, which will bring in diverse desired high conductivity, large surface area, desirable robustness, and
MOF-derived carbon, metal compounds, and their composites hierarchical porous structure. Complicated multicomponent
for practical ECS devices with high efficiency and durability. metal−carbon nanostructures can also be fabricated from
For MOF-derived carbonaceous materials, doping heter- MOFs with incorporated guests or substrates for improved
oatoms into carbon is efficient to achieve high conductivity and photocatalytic and electrochemical performance.11,72,85 For
high affinity for adsorption of intermediates. The porous example, CoSe2@ B and N codoped carbon (CoSe2@BCN)
carbon skeletons with various doping atoms can be facilely can be obtained by pyrolysis and selenization of ZIF-67
obtained through pyrolysis of MOFs with judiciously selected encapsulated in BCN nanotube for high-performance Na
organic ligands and encapsulated additives under specific storage, which demonstrated a capacity of 580 mA h g−1 at
atmosphere such as NH3, H2S, and PH3 gases.70−72 The doped current density of 100 mA g−1 at the 100th cycle.86 The high
heteroatoms such as nitrogen, sulfur, boron, and phosphorus Na adsorption ability resulted from the synergistic effects
with different electronegativity and spin status from carbon between CoSe2 and porous BCN nanotubes while B−C and
atoms can induce a charge/spin redistribution and shorten the N−C bonds also provided additional Na adsorption for Na
band gap to promote electron-transfer and reinforce the storage. In addition, the porous BCN nanotubes are also vital
structure of the MOF-derived carbon materials.73 This has to confine and protect the CoSe2 during electrochemical cycles
been proven to be of utmost importance for improving the to ensure a high durability (almost 98% storage retention after
ECS activity of MOF-derived carbon. For example, doping 4000 cycles at large current density of 8000 mA g−1).
nitrogen into an MOF-derived carbon lattice could not only Modulation of the electronic structures of the active species
tune the charge density of adjacent carbon but also serve as the by controlling the compositions is also effective to engineer the
active sites for adsorption of OOH* in ORR and Li anchoring metal/carbon hybrids for ECS. For example, Ni NPs dispersed
in LIBs.74,75 Moreover, release of produced gas during on porous carbon obtained by pyrolysis of Ni-MOF in NH3
gas demonstrated only ordinary electrocatalytic HER perform-
pyrolysis of the ligands in MOF templates also helps to form
ance.87 However, nanoalloying Ni NPs with Ru via pyrolyzing
hierarchically porous structures as the released gas can
Ru-doped Ni-MOF could greatly enhance its electrochemical
generate force to expand pores and induce the structure
HER performance showing an overpotential of 32 mV at 10
evolution, which is beneficial to facilitate the kinetics of ECS
mA cm−2 in 1 M KOH.88 Design of MOF-derived metal/
applications. Also, selection of volatile metal nodes such as Zn
carbon hybrids for ECS also involves downsizing metal species,
can further improve the porosity of the obtained MOF-derived
which can lead to a high exposure of the active sites because of
carbon scaffolds.76 the increased exposed surface ratio. Atomically dispersed metal
In addition to carbon materials, various metal compounds sites (ADMS) can realize a maximum utilization and exposure
can also be obtained from MOFs by pyrolysis or solvothermal of the active metal centers. MOFs are excellent platforms to
conversion.4,10,77 These MOF-derived metal compounds afford ADMSs on porous carbon scaffolds owing to the
feature small particle size, high porosity, and high surface abundant anchoring sites like N, highly regular porosity, and
area, which can ensure high exposure of the active surface and ordered atom arrangements to ensure an atomically uniform
facilitated mass transfer for ECS. For example, yolk−shell dispersion of the metal species.89−91 Through pyrolysis of the
Co3O4 could be obtained by simple pyrolysis of ZIF-67 under MOF precursors with predoping or postsynthetic immobiliza-
air, and bubble-like CoS2 nanoprisms could be gained by tion of the targeted metal ions, ADMSs could be implanted on
sulfidation of MOFs.78,79 These MOF-derived metal com- MOF-derived porous carbons for high-performance ECS
pounds showed outstanding Li storage performance with high applications.91,92 For example, atomically dispersed MnN4
rate capability by virtue of their specific composition and moieties on porous carbon derived from Mn-doped ZIF-8
advanced nanostructures. Various metal compounds such as showed excellent ORR performance in acids with a half-wave
porous RuO2,10 CoSe2,77 and CoP80 have been fabricated from potential of 0.8 V.91 Besides, high loading amount of single-
MOFs by simple pyrolysis with high ECS activity. Complicated atom Zn up to 11.3 wt % could be also achieved by MOF-
metal compounds with multiple compositions and nanostruc- templated method, which would encourage more efforts to
tures could also be fabricated by using MOF composites as develop novel high-density ADMS catalysts from MOFs for
precursors. For example, Fe2O3@TiO2/Pt was fabricated by high-performance ECS.93
pyrolysis of the MIL-101/TiO2 composites as precursors, Nanostructuring MOF-Based Materials for ECS. Besides
followed by deposition of Pt NPs cocatalyst on the outside component design, nanostructuring MOF-based materials is
shell. By virtue of the synergistic effect between the multiple also important for ECS applications. Advanced nanostructures
compositions, Fe2O3@TiO2/Pt demonstrated a high photo- can increase the accessibility to active sites, facilitate mass and
chemical activity with a total of 30.0 μmol H2 per mg of charge carrier transfer, and ensure a high structural robustness,
material produced after 48 h under visible light.81 In other which are important factors that govern the activity and
cases, complex metal compounds like Co/(NiCo)Se2, ZnO/ durability of electrode materials for ECS. Different nanostruc-
NiO, and NiCoS/Ti3C2Tx were also fabricated from MOFs tures will exhibit vastly different performance even with the
and showed excellent photochemical and electrochemical same species.94 Hence, it is of vital importance to conduct
performance.82−84 rational structural design of MOF-based materials for ECS
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of the MOFs NPs. As an example, well-defined carbon

Advanced nanostructures can increase polyhedra decorated with Co NPs could be fabricated by
the accessibility to active sites, facilitate morphology-preserved pyrolysis of ZIF-67 polyhedra for ORR
mass and charge carrier transfer, and electrocatalysis.95 It exhibited enhanced ORR performance in
acidic solution with a half-wave potential of 0.71 V compared
ensure a high structural robustness, with the bulk counterparts owing to the well-defined 0D
which are important factors that morphology with high exposure of active species and desirable
govern the activity and durability of mass/electron transfer. Construction of porous hollow 0D
electrode materials for ECS. nanostructures can further increase the surface ratio of MOF-
based materials and provide more accessible active sites. The
hollow architectures could shorten the mass transport
applications. The structural design strategies for MOF-based
pathways, facilitate electrolyte infiltration with high perme-
materials mainly focus on the construction of 0D, 1D, 2D, and
ability, and mitigate volume expansion for ECS applications
3D nanostructures with high surface area, porosity, and
like Li-ion batteries.79 More complicated multishelled hollow
robustness, which can enable high exposure of active sites,
structures could further increase the hierarchical porosity and
fast mass/charge transport, and structural stability for efficient
possess more abundant active materials than single-shelled
ECS (Figure 5).
structures. Recently, multishelled hollow Mn/Fe-HIB-MOFs
were fabricated as excellent bifunctional electrode materials
with a half-wave potential of 0.883 V for ORR and an
overpotential of 280 mV@10 mA cm−2 for OER, which
demonstrated a record-breaking cycle life for zinc−air batteries
(600 h@25 mA cm−2).96 Owing to the advantages of low
density, large internal void, and robust structure, hollow/
multishelled architectures also demonstrate large potential for
flexible ECS devices. Tremendous MOF-derived single-shell
and multishelled nanoarchitectures have been fabricated
through controlled thermal/chemical conversion of pristine
MOFs and MOF composites for ECS.97,98 However, direct use
of single-shell/multishelled pristine MOFs and MOF compo-
sites for ECS is rarely reported, which deserves more attention.
In addition to nanostructuring of 0D MOF-based particles,
fabricating 1D MOF-based materials is also beneficial for ECS
reactions by virtue of the unique superiority of fast axial
electron transport, short pathways for ion diffusion, large
surface area, and fast strain relaxation in electrochemically
driven volume expansion and contraction. In addition, 1D
materials are promising to make up 3D networks for flexible
devices.99 It has been demonstrated that 1D pristine MOF
nanorods are suitable for ECS because of the inherent porous
structure and short ion transversal pathways with enhanced
diffusion kinetics. Several methods for the nanostructuring of
1D MOFs, including modulator-assisted recrystallization,
Figure 5. Schematic illustration of the nanostructured MOF-based
materials. template methods, and electrospinning technologies, are used
to prepare 1D MOF-based materials.100 Recently, a superlong
single-crystal MOF has been prepared through a recrystalliza-
For 0D MOF-based materials, the top-down approach by tion method with a length of 20−35 μm.15 By virtue of the
downsizing MOF particles to nanoscale is an effective method uniform and monodisperse morphology of the 1D superlong
to improve their ECS performance compared with the bulk MOF precursor, its derived 1D carbonaceous materials
counterparts. Use of deprotonation additives such as sodium composed of carbon nanofiber trunks and carbon nanotube
hydroxide and triethylamine during the synthetic process could branches demonstrated excellent electrocatalytic activity for
successfully lead to MOF NPs. It has been reported that 150 ORR and rechargeable Zn−air batteries with an initial open-
nm sized ZIF-8 could possess a mucher high discharge capacity circuit potential of 1.46 V and a maximum power density as
(733 mAh g−1) for LSBs than large ZIF-8 of 3 μm (491 mAh high as 220 mW cm−2 without degeneration in performance
g−1) because of the shortened diffusion length with high rate even after 400 cycles (133 h). Furthermore, fabricating 1D
capabilities and high utilization of sulfur. In addition, the small hollow and hierarchically holey MOF-based materials is more
pore aperture of ZIF-8 (3.4 Å) showed better confinement of desirable to further promote the ECS performance. The 1D
polysulfides (S8 ring: 6.9 Å) in the pores than MIL-53 with 1D hierarchical structures can significantly facilitate mass transport
channels (8.5 Å), which led to smaller capacity decay of 0.08% and expose more active sites of the inner space.101
per cycle of ZIF-8 than that of MIL-53(0.19%). Also, Construction of 2D MOF-based materials can also increase
functionalization of the pore surface with acidic environment the exposure of active sites by gaining large surface area ratios
would also enhance the capacity retention by affinity with the compared with bulk materials. The low thickness of 2D MOF-
polysulfide anions.14 Besides 0D MOFs, MOF-derived NPs based materials can also shorten the mass- and charge-transfer
could be obtained through morphology-preserved conversion pathways and enrich the active sites on the surface. Every
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active site of the 2D MOFs is highly accessible to the reagents predesigned core−shell Zn@Co-MOFs incorporated with Fe
with negligible diffusion limitations across the surface to ions to get 3D hydrangea-like superstructures of open carbon
internal pores.32 For instance, ultrathin NiCo-MOF with a cages interconnected by carbon nanotubes, which exhibited
thickness of several nanometers possessed higher percentage of superior electrocatalytic ORR and OER performances.107 In
CUMSs and faster electrocatalytic kinetics than bulk MOF for addition, direct pyrolysis of Zn-MOFs constructed with
enhanced OER performance with an overpotential of 250 mV energetic ligands (1H-1,2,3-triazole) could also generate
at 10 mA cm−2. The metal species of the ultrathin NiCo-MOF carbon foam with 3D hierarchical architectures, in which the
are inclined to be oxidized to the active high-valence state eruption of gases released from the decomposed energetic
because of the 2D configuration.24 Furthermore, the 2D MOFs ligands induced a pore expansion phenomenon and formed the
also facilitate the engineering of nanohybrids by loading 3D foam-like carbon networks.76 These examples show that
nanomaterials on the surface of the 2D MOF nanosheets or the introduction of additives or energetic ligands into the MOF
growing 2D MOFs on functional substrates.17 As an example, precursors could interestingly trigger a morphology evolution
Co-BDC MOF could grow on the surface of conductive from MOF NPs to 3D hierarchical structures.72 In addition,
Ti3C2Tx nanosheets via an interdiffusion reaction-assisted direct use of 3D MOFs as precursors can also lead to 3D
process. The resultant Co-BDC/Ti3C2Tx 2D nanostructure MOF-derived materials through a morphology-preserved
offered various advantages, such as highly porous structure, method. Preformed 3D hierarchical MOF superstructures,108
large surface area, rapid charge/ion transfer, and easy access of 1D/2D MOF arrays on various supports,4,109 and 3D
the electrolyte/reactant molecules, which resulted in excellent hierarchical MOF@templates11,110 have been successfully
OER performance to achieve 10 mA cm−2 at a potential of 1.64 utilized as precursors to generate 3D hierarchical MOF-
V, which is better than that of commercial IrO2 catalyst (1.69 derived structures. Their unique 3D hierarchically porous
V) in 0.1 M KOH solution.102 Through morphology-preserved structures offer the advantages of abundant active sites with
conversion of 2D MOFs or 2D MOF composites, MOF- high accessibility, fast mass/charge transport, and high
derived carbon, metal compounds, and metal−carbon structural stability, which endow them with desirable perform-
materials with 2D morphologies could be obtained for ECS. ance for practical ECS systems.
Furthermore, construction of holey 2D MOF-based materials Summary and Perspective. The development of efficient ECS
is more desirable, which can further enrich the exposed active systems greatly relies on the design and fabrication of advanced
sites and greatly promote fast mass transfer in the direction electrode materials. Efficient strategies for the component
perpendicular to the 2D plane. For example, 2D Co-MOF- design and nanostructuring of the electrode materials are in
derived cobalt sulfide holey nanosheets with hierarchical pores high demand to meet the requirements of practical ECS
displayed high reversible capacity, long-life cycling stability systems. By precise design and engineering of the components
with retention of 80% after 400 cycles, and exceptional rate and nanostructures, both high activity of each active site and
capacity for SIBs.103 high exposed number of the active sites can be achieved in one
For 0D, 1D, and 2D materials, the aggregation and electrode materials. This concept can be also applied to MOF-
restacking issues may lead to low permeability of electrolyte/ based materials, which emerge as a new kind of promising
reactant molecules and low accessibility of the interior active porous materials for ECS by virtue of the unique organic−
sites. Therefore, nanostructuring MOF-based materials with inorganic hybrid nature and porous structures of MOFs. MOFs
hierarchically porous 3D skeletons is more desirable for
practical ECS applications. Assembling 0D, 1D, and 2D MOF- MOFs also provide great opportunities
based building blocks across multiple length scales can as multifunctional platforms for design
successfully lead to hierarchically porous 3D MOF-based
materials. The formed hierarchically porous 3D MOF-based of active sites and nanostructures at an
materials are promising to meet the requirements of practical atomic level and model materials for
ECS devices such as fast kinetics, high efficiency, and high exploration of the underlying mecha-
durability.4,16,104 For example, 3D hierarchical Prussian blue nisms during electrocatalysis and pho-
superstructures were obtained by spontaneous assembly of
Prussian blue building NPs, and the hierarchical 3D structures tocatalysis.
with mesopores showed good capacitance and rate capability
for supercapacitors by virtue of the facilitated charge transfer also provide great opportunities as multifunctional platforms
and ion diffusion.105 In addition to 3D MOF superstructures, for design of active sites and nanostructures at an atomic level
rational spatial layout of MOF building blocks with well- and model materials for exploration of the underlying
defined shapes and uniform sizes on substrates could also lead mechanisms during electrocatalysis and photocatalysis. By
to an advanced 3D structure for ECS. For example, an ultrathin precise component design and nanostructuring of MOF-based
NiFe-MOF nanosheet array could be vertically grown on 3D materials, including pristine MOFs, MOF composites, and
Ni foam, which showed highly exposed active sites on the 2D MOF derivatives, advanced electrode materials with superior
surface, improved conductivity, excellent permeability, and fast electro-/photochemical properties can be obtained for efficient
kinetics for efficient electrochemical water splitting (a cell ECS applications.
voltage of 1.55 V@10 mA cm−2).106 Moreover, 3D hierarchical For pristine MOFs, the highly ordered atom arrangements
MOF-derived materials of nanohybrids (metal@carbon) can and regular pore structures provide great opportunities to
present higher conductivity, richer hierarchical pores, and correlate the structure−composition−activity relations and
better structural robustness for enhanced ECS. The methods achieve ideal active sites with both high activity and high
by skeleton expansion and coalesce processes during pyrolysis abundance. Given the high structural and compositional
of simple MOF NPs precursors could lead to 3D hierarchical diversity of pristine MOFs, engineering the metal nodes and
MOF-derived materials. A typical example is the pyrolysis of organic ligands can greatly modulate the activity of pristine
527 https://dx.doi.org/10.1021/acsenergylett.9b02625
ACS Energy Lett. 2020, 5, 520−532
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MOFs. The creation of CUMSs can provide dense active sites standing of MOF-based materials for the ECS processes, we
in MOFs. Generation of defects or nanostructuring MOFs with believe MOF-based materials with desirable photo/electro-
large surface ratios can effectively increase the number of chemical properties can be achieved for practical ECS devices.
CUMSs. To optimize the activity of pristine MOFs,
introduction of heterometallic doping and multiple valence
metal sites, incorporation of functional groups into organic
■ AUTHOR INFORMATION
Corresponding Author
ligands, adsorption of various ions on the metal nodes/organic
Ruqiang Zou − Beijing Key Laboratory for Theory and
ligands, and immobilization of conjugated organic ligands in
Technology of Advanced Battery Materials, Department of Materials
the skeletons are powerful strategies. These modulations are Science and Engineering, College of Engineering and Institute of Clean
fascinating to modulate the electronic structures, charge- Energy, Peking University, Beijing 100871, China; orcid.org/
transfer pathways, bonding energy of intermediates, con- 0000-0003-0456-4615; Email: rzou@pku.edu.cn
ductivity, photoresponse, and structure stability of pristine
MOFs. Other Authors
Combining functional components with MOFs to form Tianjie Qiu − Beijing Key Laboratory for Theory and
MOF composites can effectively overcome the drawbacks of Technology of Advanced Battery Materials, Department of Materials
individual components and gain multiple functionalities. Science and Engineering, College of Engineering and Institute of Clean
Incorporation of functional materials such as MNPs, quantum Energy, Peking University, Beijing 100871, China
dots, POMs, and other guest materials or loading MOFs on Zibin Liang − Beijing Key Laboratory for Theory and
functional supports can effectively enhance the properties of Technology of Advanced Battery Materials, Department of Materials
MOFs. The functional materials can introduce synergistic Science and Engineering, College of Engineering and Institute of Clean
effects with MOFs and provide opportunities to achieve Energy, Peking University, Beijing 100871, China
multifunctionality in a single material, which can maximize the Wenhan Guo − Beijing Key Laboratory for Theory and
potential of MOFs and functional materials for ECS. Technology of Advanced Battery Materials, Department of Materials
MOF derivatives have also attracted great attention by virtue Science and Engineering, College of Engineering and Institute of Clean
of their high activity and desirable stability for practical ECS Energy, Peking University, Beijing 100871, China
systems. The conversion of MOFs and MOF composites could Hassina Tabassum − Beijing Key Laboratory for Theory and
lead to MOF-derived carbon, metal compounds, and metal/ Technology of Advanced Battery Materials, Department of Materials
carbon hybrids. The component design of MOF-derived Science and Engineering, College of Engineering and Institute of Clean
materials shows great superiority for obtaining desirable Energy, Peking University, Beijing 100871, China
compositions and structures, by which heteroatom doping, Song Gao − Beijing Key Laboratory for Theory and Technology
multiple components, desirable synergistic effects, high of Advanced Battery Materials, Department of Materials Science and
structural robustness, and full utilization of active species can Engineering, College of Engineering and Institute of Clean Energy,
be achieved. Peking University, Beijing 100871, China
In addition to component design, it is also important to
Complete contact information is available at:
engineer MOF-based materials into porous 0D, 1D, 2D, and
https://pubs.acs.org/10.1021/acsenergylett.9b02625
3D nanostructures for ECS. Advanced nanostructures can
provide high structural robustness in harsh conditions, facile
Notes
accessibility of reactants toward active sites, and efficient
electron transport pathways. Nanostructures are especially The authors declare no competing financial interest.
important for practical industrial applications, where stacking Biographies
and pulverization always lead to slow mass transport and loss Tianjie Qiu is currently a Ph.D. candidate under the supervision of
of active materials. Thus, rational design of advanced Professor Ruqiang Zou at the College of Engineering, Peking
nanostructures is a key to extending the adaptability of University. He received his bachelor degree from College of
MOF-based materials for ECS. In particular, construction of Chemistry, Nankai University. His research interests focus on the
3D porous MOF-based hierarchical nanostructures with low- synthesis metal−organic framework-derived porous nanomaterials for
dimension building blocks is promising for future practical energy conversion applications.
ECS systems, which allows a relatively high mass loading, high Zibin Liang is currently a Ph.D. candidate under the supervision of
exposure of active sites, and fast mass/electron transport. Professor Ruqiang Zou at the College of Engineering, Peking
Despite the great progress achieved on MOF-based University. His research interest is the synthesis of functional
materials for ECS, there are still many challenges to be nanomaterials based on metal−organic frameworks for energy storage
addressed. The poor stability of pristine MOFs and MOF and conversion applications.
composites should be overcome to meet the requirements in
practical ECS devices, especially electrochemical ECS devices Wenhan Guo obtained his Ph.D. degree from Peking University and
where harsh electrolytes and potentials are applied. For MOF is currently a member of the Boya Postdoc Fellowship in the same
composites, the characterization and control of the interactions department. His research focuses on the rational design and synthesis
and synergistic effect between MOFs and the incorporated of porous nanomaterials and their applications in energy- and
components remains a challenge. For MOF-derived materials, environment-related electrochemical processes, typically electro-
the complexity of the conversion process from MOF chemical nitrogen and carbon dioxide reduction.
precursors to MOF-derived materials always results in Hassina Tabassum is currently a postdoctoral research fellow at the
uncontrollable structural and compositional evolution far College of Engineering, Peking University, China. She received her
from the targeted compositions and structures. Although Ph.D. degree from the College of Engineering, Peking University. Her
there is heavy mist of challenges, with the advent of more research interests include nanomaterials synthesis and their energy
advanced characterization technologies and in-depth under- storage and conversion applications.

528 https://dx.doi.org/10.1021/acsenergylett.9b02625
ACS Energy Lett. 2020, 5, 520−532
ACS Energy Letters http://pubs.acs.org/journal/aelccp Review

Song Gao is an assistant research fellow of the College of for sulfur storage in fast, long-cycle Li−S batteries. Energy Environ. Sci.
Engineering, Peking University, China. She received her Ph.D. from 2014, 7, 2715−2724.
Harbin Institute of Technology. Her research interest is the (15) Zou, L.; Hou, C. C.; Liu, Z.; Pang, H.; Xu, Q. Superlong Single-
fabrication of metal−organic framework-derived nanomaterials and Crystal Metal-Organic Framework Nanotubes. J. Am. Chem. Soc.
energy storage and conversion. 2018, 140, 15393−15401.
(16) Feng, L.; Li, J. L.; Day, G. S.; Lv, X. L.; Zhou, H. C.
Ruqiang Zou is a professor at the College of Engineering, Peking Temperature-Controlled Evolution of Nanoporous MOF Crystallites
University. He was awarded Changjiang Scholar for Young Scientist into Hierarchically Porous Superstructures. Chem. 2019, 5, 1265−
and the National Science Fund for Distinguished Young Scholars. His 1274.
research interests focus on the controllable preparation of nanoporous (17) Zhao, M.; Huang, Y.; Peng, Y.; Huang, Z.; Ma, Q.; Zhang, H.
materials for energy utilization and environmental remediation Two-dimensional metal-organic framework nanosheets: synthesis and
(http://www2.coe.pku.edu.cn/faculty/zouruqiang/Home.html). applications. Chem. Soc. Rev. 2018, 47, 6267−6295.
(18) Xiao, J. D.; Jiang, H. L. Metal-Organic Frameworks for

■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Photocatalysis and Photothermal Catalysis. Acc. Chem. Res. 2019, 52,
356−366.
(19) Li, J.; Huang, W.; Wang, M.; Xi, S.; Meng, J.; Zhao, K.; Jin, J.;
Xu, W.; Wang, Z.; Liu, X.; Chen, Q.; Xu, L.; Liao, X.; Jiang, Y.;
Science Foundation of China (51825201), the National Key Owusu, K. A.; Jiang, B.; Chen, C.; Fan, D.; Zhou, L.; Mai, L. Low-
Research and Development Program of China Crystalline Bimetallic Metal-Organic Framework Electrocatalysts with
(2017YFA0206701), National Program for Support of Top- Rich Active Sites for Oxygen Evolution. ACS Energy Lett. 2019, 4,
notch Young Professionals, and Changjiang Scholar Program. 285−292.

■
(20) Zhong, H.; Ly, K. H.; Wang, M.; Krupskaya, Y.; Han, X.;
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