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Vacancy-engineered catalysts for water

Cite this: CrystEngComm, 2020, 22,
electrolysis
1500
Songa Choi, † Yeji Park, † Heesu Yang, † Haneul Jin,
Gracita M. Tomboc and Kwangyeol Lee *
Published on 07 January 2020. Downloaded on 5/21/2020 9:33:22 AM.

The development of electrochemical energy conversion and storage technologies is pivotal to the full-
fledged utilization of renewable energy sources. The successful commercial application of water electroly-
sis to produce hydrogen gas, in particular, requires highly active electrocatalysts that can operate for
prolonged periods. However, the high activity and high durability of electrocatalysts are often mutually ex-
clusive. Recent studies have demonstrated that vacancy engineering might effectively modulate the
Received 27th November 2019, electronic structures of catalysts, which can lead to high catalytic activity. Furthermore, it has been shown
Accepted 4th January 2020
that vacancies are closely related to catalyst stability under operational conditions. To understand the ben-
efits of vacancies in the catalyst structures, we discuss the recent advances in the development of
DOI: 10.1039/c9ce01883b
vacancy-engineered catalysts for water electrolysis. In addition, we discuss the present limitations in this
rsc.li/crystengcomm nascent field and provide directions for valuable future research.

1. Introduction process. However, the large operational potential window for

the main water splitting reactions—hydrogen evolution reac-
With the rapid consumption of fossil fuels and the associated tion (HER) and oxygen evolution reaction (OER)—signifi-
serious environmental problems, the global demand for sus- cantly hinders the commercialization of the water electrolysis
tainable energy production from carbon-neutral fuels has in- system. Catalysts play a vital role in efficient energy conver-
creased continuously in the past decades. The production of sions by decreasing the electrical energy usage during water
hydrogen via electrochemical water splitting is considered electrolysis. Therefore, the development of active and durable
one of the most promising energy sources due to the high en- catalytic materials for both HER and OER is an essential
ergy density of hydrogen and the pollutant-free production requirement for the advancement of water electrolysis
technology.
Department of Chemistry and Research Institute for National Sciences, Korea
Efficient catalysts require optimized surface physico-
University, Seoul 02841, Republic of Korea. E-mail: [email protected] chemical properties for facile adsorption and desorption of
† These authors contributed equally to this work. intermediates. Recently, vacancy engineering on the catalyst

Dr. Haneul Jin (Front line), Heesu Yang, Songa Choi, Yeji Park, and Dr.
Gracita M. Tomboc (back line: from left to right) are currently working
in inorganic chemistry under the supervision of Prof. Kwangyeol Lee at
the Department of Chemistry, Korea University (South Korea). H. Yang
has been working on synthesis of nanoscale materials and their applica-
tions toward water splitting reaction. S. Choi is involved in designing
noble metal-based functional nanomaterials for energy conversion/stor-
age and CO2 conversion. Y. Park is interested in the design of hetero-
nanostructured catalysts and the development of functional nano-
materials for energy conversion. Dr. G. M. Tomboc is focused on ad-
vanced materials processing of ideal electrode materials for electro-
chemical energy storage system applications such as supercapacitor and
Haneul Jin water splitting process. Dr. H. Jin is interested in the development of
synthetic methods for phase-controlled nano-catalysts and investigation
of water splitting reaction mechanism on the heterogeneous catalyst surfaces.

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surfaces has emerged as an effective strategy to enhance the electrochemical water splitting.3 Therefore, understanding
HER and OER performances by controlling the surface the relationship between the vacancy and electrocatalytic per-
electronic and atomic structures. The modification of the sur- formance is important for the rational design of a high-
face electronic structure adjusts the adsorption energy of the performance catalyst toward electrochemical HER and OER
intermediates (e.g., *H for HER; *OH, *OOH for OER) on (Scheme 1). In this section, we discuss the beneficial effects
the catalyst surface and promotes charge transfer at the of vacant sites on the electrocatalytic performance toward wa-
interface between the electrolyte and the electrodes.1,2 The ter splitting.
coordination-unsaturated structure derived from vacancy en-
gineering generates catalytically active sites for water electrol-
ysis on the catalyst surface. However, the development of 2.1. Formation of low-coordination sites
vacancy-engineered catalysts for electrochemical water split- Low-coordinated sites serve as active sites on catalysts to pro-
ting is only in its infancy. mote catalytic reactions4 owing to the high density of their
In this review, we provide a brief overview of the vacancy dangling bonds, namely coordinatively unsaturated sites
engineering of electrocatalysts for water-splitting reactions, (CUSs), which are highly reactive. For instance, micro-
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focusing on the nature of the vacant sites on the catalysts kinetics mode-based density-functional theory (DFT) calcula-
and their effect on the water-splitting reaction. First, we de- tions demonstrated that low-coordinated gold atoms at the
scribe the three aspects of vacancy engineering that affect corners and edges of nanoparticles act as active sites in a CO
catalytic performances: (1) formation of low-coordination oxidation reaction.5 Similarly, vacant sites can lower the coor-
sites, (2) reaction kinetics control, and (3) modulation of dination number (CN) of the adjacent sites and modulate the
electronic structures. Thereafter, we summarize the perfor- local electronic structures. Sun et al. demonstrated that the
mance of vacancy-engineered catalysts in their applications ultrathin Co3O4 structure offers a considerably large fraction
toward HER and OER. Finally, we discuss the current limita- of coordinatively unsaturated surface atoms that serve as ac-
tions of vacancy-engineered catalysts and the future research tive sites to facilitate the OER.6 As shown in Fig. 1A, the ad-
directions for the development of high-performance vacancy- sorption energy of H2O molecules on Co3+ atoms was opti-
engineered catalysts for the electrochemical water-splitting mized by the gradual decrease in their CNs from 6 to 3,
process. thereby indicating that a low CN could lead to high catalytic
activity for the OER. For porous Co3O4 thin sheets, the pres-
ence of numerous pores decreased the CN of Co3+ atoms to 4
2. The effects of catalyst vacancies on or even up to 3, and the thickness of half a unit cell enabled
electrochemical water splitting them to expose all the Co3+ atoms on their surfaces, thereby
demonstrating that all the Co3+ atoms could function as ac-
The formation of the vacancies on an electrocatalyst can ef- tive sites to catalyze the water oxidation reactions. Further-
fectively modulate the local atomic structure, which creates a more, the CUSs formed by S-vacancies on the edges of MoS2
low-coordinated local geometry, and changes the electron were demonstrated as active catalytic sites and were consid-
configuration, thereby leading to an increase in the number ered key descriptors to evaluate the catalytic activity of MoS2-
of active sites, surface energy, and electron transfer, which based materials.7–9 When the S-vacancies are introduced,
are crucial for the efficient performance of catalysts in new bands appear in the gap near the Fermi level, thereby in-
dicating that these states are localized around the S-vacancy
Professor Kwangyeol Lee (born in (Fig. 1B). Additionally, the bands move closer to the Fermi
1971) obtained his Ph.D. degree level and increase the number of gap states with increasing
(1997) in Chemistry from the S-vacancies (Fig. 1C), thereby leading to an increase in the ac-
University of Illinois at Urbana– tive site density and improvement of the HER catalytic perfor-
Champaign. After fulfilling his mance. Furthermore, the electronic structure of MoS2 was
military obligation, he joined Ko- highly dependent on the coordination of the Mo metal and
rea University in 2003 as a its d-electrons. A semiconducting behavior and metallic con-
Chemistry faculty member, before ductivity can be observed when the non-bonding d-orbitals
being appointed professor. He is are fully and partially occupied, respectively.10 In addition,
the recipient of the 2009 Wiley- the high exposure of the edges of MoS2 nanosheets with un-
KCS Young Scholar Award and saturated coordination and dangling bonds is crucial for
2019 Excellent Research Award their application in catalysis, electronics, and sensors, which
Kwangyeol Lee (KCS Inorganic Chemistry Divi- require the involvement of a highly active surface.
sion). His current interests lie in Chen et al. designed a pseudo-cubic SrCo0.9Ir0.1O3−δ perov-
the development of synthesis methods for nanoscale materials, ap- skite that exhibits in situ formed vacancies during electro-
plications of nanomaterials in biomedical fields, and development chemical cycling.11 During the electrochemical treatment
of nanotechnologies to support the environment by creating sus- within the potential range of 1.0–1.7 V at a scan rate of 10
tainable energy sources. mV s−1 in 0.1 M HClO4, Sr and Co were leached out, and a

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Scheme 1 Illustration of the strategies for enhancing the performance

of electrocatalytic water splitting via vacancy engineering.

surface reconstruction occurred, as shown in Fig. 1D. Then,

Fig. 1 (A) Calculated adsorption energy for the H2O molecules on Co3+
the SrCo0.9Ir0.1O3−δ perovskites contained a higher number of sites with different CNs (left), and crystal structure showing the different
oxygen vacancies in the lattice than in its initial pseudo-cubic CNs for surface and pore-surrounding Co3+ atoms. Reproduced with
structure. X-ray absorption spectroscopy (XAS) analysis re- permission from ref. 6. Copyright 2014 Royal Society of Chemistry. (B)
vealed that compared to the case in IrO2, the valence state of Kohn–Sham orbitals (red) are localized around the S-vacancies in MoS2
(left) and colored contour plot of surface energy per unit cell γ (with re-
Ir in SrCo0.9Ir0.1O3−δ slightly shifted toward >4+. Assuming
spect to the bulk MoS2) as a function of the S-vacancy and uniaxial
that the valence state of Ir is 5+, the δ (oxygen non-stoichiom- strain (right). Color bar represents the value of γ. (C) Band structure with
etry) in SrCo0.9Ir0.1O3−δ can reach a minimum value, which in- increasing S-vacancy concentrations (calculated using the full 4 × 4 unit
dicates that a high number of oxygen vacancies must exist in cell). Reproduced with permission from ref. 9. Copyright 2016 Nature
SrCo0.9Ir0.1O3−δ and that both Co and Ir must be highly un- Publishing Group. (D) Schematic illustrating the surface reconstruction
over the SrCo0.9Ir0.1O3−δ surface. Reproduced with permission from
der-coordinated. To support this assumption, Fourier trans-
ref. 11. Copyright 2019 Nature Publishing Group.
formed (FT) extended X-ray absorption fine structure (EXAFS)
spectra at the Ir LIII-edge were recorded to demonstrate that
the Ir in SrCo0.9Ir0.1O3−δ is highly under-coordinated with a
CN of ∼4.9 and that the under-coordinated IrOx octahedron cules in alkaline media (or H3O+ in acidic media), which
considerably improved the catalytic activity toward the OER. lowered the HER energy barrier. The HER process was facili-
tated by the cooperation between Mo5+ and oxygen vacancies
that led to the promotion of H2O adsorption and H–H bond
2.2. Optimizing the adsorption energy of intermediates formation on two adjacently adsorbed Hads and H2Oads spe-
Both HER and OER mechanisms consist of multi-step reac- cies, as shown in Fig. 2A. Under an alkaline condition, a fast
tions such as adsorption, reduction/oxidation, and desorp- charge-transfer process was the only effective method of
tion processes;12,13 their catalytic surfaces require suitable obtaining OH− during the reduction and formation of
surface energies at each step.14 Luo et al. showed that the adsorbed H2Oads and Hads species and the release of H2. Ad-
vacancy-induced hydrogen binding energy optimization in ditionally, Mo5+ ions donate electrons to become Mo6+ and
mesoporous MoO3−x could exhibit excellent HER activity un- then accept electrons to transform back to Mo5+. Similarly,
der both acidic and alkaline conditions.15 DFT calculation re- Cheng et al. demonstrated that 2D Cr2CO2, modified with a
vealed that the oxygen vacancies close to Mo5+ served as transition metal and with engineered carbon vacancy, could
electron acceptors and favored the adsorption of water mole- improve the HER performance.16 The formation of carbon

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vacancies (VC) in 2D Cr2CO2 can be a natural phenomenon the CO oxidation, they determined which oxygen atom in IrOx
because the calculated formation energy of VC decreased as (OI− or OII−) may serve as the active species for the OER. They
the percentage of VC increased. Additionally, when the con- found that bulk OI− species are more electrophilic than their
centration of VC reached up to 25%, the ΔGH* of VC-Cr2CO2 bulk OII− counterparts, as they were weakly bound to IrOx.
was very close to the ΔGH* value obtained for the perfect The reactivity of the OI− species was suspected to play a criti-
CrCO2. This suggests that VC-Cr2CO2 could provide an opti- cal role in the OER when reacted with OH/H2O to form the
mal reaction kinetics toward HER. OOH intermediate because the electrophilic OI− species in
On the contrary, it is imperative to control the reaction ki- amorphous IrIII/IV oxyhydroxide could be susceptible to nucle-
netics for the OER because of the multi-electrons (4e−) partici- ophilic attacks. In line with this, Nong et al. reported that Ni
pating in this process.14,17,18 The rate-determining step (RDS) leaching during catalyst activation at high potential could
of the OER may vary depending on the O-adsorption/desorp- lead to the formation of Ir lattice vacancies and numerous
tion on the catalyst surface. This implies that the formation d-band holes in the formed IrOx shell in IrNi alloy nano-
of OOH is the RDS on a weak O-adsorbate and vice versa.12,19 particles.21 The oxygen ligands adjacent to the lattice vacan-
Thus, the optimization of the bond strength between the in- cies were suggested to possess an electrophilic character that
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termediates and catalyst is crucial to facilitate the OER pro- initiates the formation of O–O bonds and weakens the kinetic
cess. Additionally, the nucleophilic attack of adsorbed oxygen barrier during the OER, eventually resulting in high activity.
by water/hydroxide has been proposed to describe the mecha- Meanwhile, Lee et al. investigated the transition metal
nism of O–O bond formation during the OER. Pfeifer et al. re- (TM) vacancies (VM) formed during the simultaneous incorpo-
vealed that the electrophilic oxygen species adsorbed on the ration of Ni and Fe metals into the same crystal structure.22
surface and in the subsurface of amorphous Ir were indis- The different preferential oxidation states (2+ for Ni and 3+
pensable for the high activity of hydrated amorphous IrIII/IV for Fe) would cause the VM to achieve charge neutrality with
oxyhydroxide (IrOx), compared to crystalline IrO2.20 During oxygen; the addition of Fe3+ into a NiO matrix resulted in the
formation of NiFe-VM-O. As shown in Fig. 2B, this vacancy
formation altered the bond strengths of adjacent Ni–O and
Ni–TM, which improved the catalytic activity of the modified
catalyst as compared to its original state, NiO. In terms of
electronic structure modification of the active site, the energy
of O-adsorption in NiFe-VM-O was lower than that in NiO ow-
ing to its flexible geometric distortions that can accommo-
date adsorbates easily.

2.3. Improving charge transfer

Most metal oxides have lower electrical conductivity than
metals, resulting in lower electrochemical efficiency. Oxygen
vacancy-engineered catalysts have been suggested to overcome
the low electrical conductivity problem of transition metal
oxides.23–25 Wang et al. reported that reduced mesoporous
Co3O4 nanowires (NWs) with abundant oxygen vacancies have
lower charge-transfer resistance than the pristine Co3O4 NWs.26
The total density of states (TDOSs) and the projected DOSs
(PDOSs) calculation showed that the oxygen vacancies in Co3O4
NWs induced new defect states within the bandgap (Fig. 3A).
The electron occupancy of the gap state was classified into three
different states of occupied electrons, namely empty, occupied
by one electron, or by two electrons, denoted as VO2+, VO+, VO,
respectively. According to the calculated formation energy
(Fig. 3B), VO2+ has the lowest formation energy for all the values
Fig. 2 (A) Proposed reaction pathway, and the energy barrier profiles
of the Fermi level in the bandgap, indicating that the oxygen va-
of mesoporous MoO3−x in 0.1 M KOH. Reproduced with permission cancy is most likely formed as VO2+. When the two electrons are
from ref. 15. Copyright 2016 Wiley-VCH. (B) Free energy diagrams of excited, the formation energy of VO2+ is about 1 eV. These calcu-
NiFe-VM-O at 0 V (black line) and 1.23 V (blue line). Red dashed lines lated values suggested that the reduced Co3O4 NWs can easily
correspond to the free energies of the ideal catalyst with 0 V
produce the oxygen vacancies with two positive charges (VO2+),
overpotential. Top views of each reaction step are presented. Each
color indicates Ni (gray), Fe (brass yellow), and O (red). Reproduced
and the two electrons are delocalized near the oxygen vacancy
with permission from ref. 22. Copyright 2019 American Chemical and are easily excited into the conduction band, thus leading to
Society. enhanced electrocatalytic performance. Likewise, other metal

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Fig. 3 (A) TDOS and PDOS of pristine Co3O4 and reduced Co3O4 with oxygen vacancies. (B) Calculated formation energies for the reduced
Co3O4. VO2+, VO+, and VO, denote that the gap state is empty, occupied by one electron, and occupied by two electrons, respectively. Reproduced
with permission from ref. 26. Copyright 2014 Wiley-VCH. (C) TDOS and PDOS for Co3O4 and Co-defected Co3−xO4. (D) Optimized cell structures
and the corresponding charge density mapping of normal Co3O4 and Co-defected Co3−xO4. (E) Optimized structures of water adsorbed at Co on
the (111) surface (top and side views) of Co3O4 (left) and Co3−xO4 (right). (F) Electrochemical impedance spectroscopy (EIS) (inset: EIS fitting model;
electrolyte resistance RS, charge-transfer resistance Rct, capacitive reactance Cd). Reproduced with permission from ref. 3. Copyright 2018 Ameri-
can Chemical Society.

oxides such as NiO nanorods (NRs) also showed great HER ac- function with neighboring O atoms compared to those of the
tivities owing to the vacancy-induced electronic structural modi- pristine Co3O4 (Fig. 3D). The charge density of Co3−xO4 in-
fication.1 Zhao et al. reported the synthesis of ultrathin NiFe- creased around the conduction band edge to form a more dis-
layered double hydroxide (NiFe LDH-UF) nanosheets containing persive electronic structure than that of pristine Co3O4, which
multi-vacancies, such as metal and oxygen vacancies, which en- resulted in a fast carrier transport for the OER. Moreover, the
hanced their electronic conduction and HER reaction kinetics.27 deformation charge densities of adsorbed H2O on Co3O4 and
DFT calculations revealed the effect of multi-vacancies (VO, VNi, Co3−xO4 revealed that the Co-defective surface is more benefi-
and VFe) on the electronic structure of the NiFe LDH ultrafine cial for the adsorption and desorption of water. When H2O
nanosheets. While the monolayer and multi-layered LDH had molecules were adsorbed onto the surface of the Co3−xO4 cata-
noticeable band gaps, their calculated DOSs showed that there lyst, one H atom from the adsorbed water of Co3−xO4 showed
is no noticeable band gap around the Fermi level in the LDH- relatively strong interaction with Os (surface O of Co3−xO4),
UF. This demonstrates the semi-metal-like character of the which resulted in the extension of the H–OH bond length of
modified material, which can result in the enhancement of the the adsorbed water to 1.014 Å, compared to 0.986 Å for normal
electrical conductivity. Additionally, LDH-UF showed a lower Co3O4. This result indicated that the Co-defective structure has
charge-transfer resistance during electrochemical tests, com- the ability to facilitate the adsorption/desorption of intermedi-
pared with the LDH-bulk and LDH-monolayer, supporting the ates and to improve the electronic conductivity, thus being
claimed excellent electrical conductivity. highly favorable toward water splitting (Fig. 3E and F).
Similar to anion vacancies, cation vacancies can promote
the charge transfer by modifying the electronic structures of
the catalysts. Zhang et al. demonstrated that Co deficient 3. Classification of vacancy-engineered
Co3−xO4, with structural distortion and electronic delocaliza- nanostructures and their catalytic per-
tion, enhanced the rate of carrier transport to participate in
OER.3 As the Co vacancies in Co3O4 are formed, the DOS for formances in HER and OER
the occupied states from ca. 0.50 eV above the Fermi level in- 3.1. Anion vacancy
creased and then showed a very small energy gap (Fig. 3C). The
electronic structures of Co3−xO4 showed a considerable charge Among various forms of vacancies, anion vacancies are the
depletion, with more overlap areas of the electron wave- most commonly used to improve catalytic performance

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because they are easily formed and can often generate an NiFe–OOH, which may be associated with the presence of oxy-
ideal Fermi level for water splitting reaction.9,26,28,29 gen vacancies. Furthermore, to gauge the oxygen vacancy den-
Oxygen evolution reaction. The oxygen vacancies in the sity, they fitted O 1s XPS spectra, which contains information
metal oxides that have been intensively investigated as cata- of (1) lattice oxygen (530.1 eV), (2) oxygen loss in the material
lysts for the OER alter the physicochemical properties of ma- (531.7 eV), and (3) adsorbed oxygen throughout the surface
terials such as atomic and electronic structures. (533.2 eV). The density of oxygen vacancy can be quantified
As mentioned in a previous section, low-coordination roughly by the ratio of (2) to (1), and the density of NiFe with
metal atoms are identified as the active sites of metal-oxide oxygen vacancies was 7.0, which is twice as high as that of the
catalysts for water-splitting reaction.30 Bao et al. synthesized pristine one (3.2). NiFe with numerous vacancies exhibited
oxygen-vacancy-rich NiCo nanosheets (NiCo-r) and compared enhanced OER current density (240 mA cm−2) at an
the results with bulk NiCo and oxygen-vacancy-poor NiCo overpotential of 270 mV from pristine NiFe (100 mA cm−2).
nanosheets (NiCo-p).28 The O 1s X-ray photoelectron spectro- Ling et al. synthesized single-crystal cobalt oxide nanorods
scopy (XPS) spectra of the three materials exhibited a peak at with exposed vacancy-rich pyramidal nano-facets.32 The
531.2 eV, with NiCo-r showing the highest intensity, which O-vacancy formation was identified by the O 1s XPS spectra
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may be correlated to its low oxygen coordination and the of single-crystal (SC) CoO nanorods (NRs) (Fig. 4C). The peak
high number of oxygen vacancies present compared to those at the middle binding energy (II) at 531.5 eV was attributed
in the others (Fig. 4A). The NiCo-r nanosheets showed en- to the oxygen vacant sites with relatively low oxygen coordina-
hanced activity toward the OER (320 mV at 10 mA cm−2) than tion. The large area of peak II revealed that the SC CoO NRs
oxygen-vacancy-poor or bulk catalysts. This result was consis- contain numerous O-vacancies on the surface. Moreover, the
tent with DFT calculation, which revealed that NiCo2O4 with peak at ∼536.0 eV of the O–K edge XANES spectra was associ-
oxygen vacancies has lower adsorption energy for H2O (−0.75 ated with O deficiency, resulting in the presence of abundant
eV) compared to the perfect surface (−0.41 eV) (Fig. 4B). O-vacancies on the surface of SC CoO NRs (Fig. 4D). This 1D
Asnavandi et al. reported that the NiFe (oxy)hydroxides SC CoO NRs exhibited an overpotential of 0.33 V (vs. RHE) in
with surface oxygen vacancies achieve enhanced OER perfor- the OER. They explained that the conductivity of the metal
mance.31 X-ray absorption near edge structure (XANES) spec- oxides was further improved by creating O-vacancies on {111}
tra displayed the relatively low oxidation states of Ni and Fe in facet and increasing the carrier concentration. Projected

Fig. 4 (A) The O 1s XPS spectra of the NiCo2O4 nanosheets. (B) Schematic illustration of the adsorption of H2O molecules onto the NiCo2O4
structure and the partial charge density of NiCo2O4 with oxygen vacancies. Reproduced with permission from ref. 28. Copyright 2015 Wiley-VCH.
(C) O 1s XPS spectra of SC CoO NRs. (D) O–K edge XANES spectra of SC CoO NRs and reference CoO. (E) The projected density of states (PDOSs)
on pristine CoO and CoO with O-vacancies. Reproduced with permission from ref. 32. Copyright 2016 Nature Publishing Group.

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density of states (PDOS) on pristine CoO and CoO with calculation (Fig. 5C). MoS2 and MoS without defect sites have
O-vacancies was determined to examine the electronic struc- relatively large ΔG values (2.06 eV and ∼−0.6 eV), which were
ture, which correlated the formed O-vacancies in the bandgap reduced to almost 0 eV upon the formation of defect sites.
of CoO to the observed strong adsorption of intermediates on However, an increase in the number of defect sites led to
the vacant sites and high electronic conductivity (Fig. 4E). larger ΔG; thus, the catalytic activity was further improved by
Hydrogen evolution reaction. In addition to the beneficial controlling the number of defect sites.
role of oxygen vacancy in the OER, a recent study on sulfur The placement of strain in the catalyst structure has
vacancies revealed the significance of S-vacancies in the en- been effective in optimizing the adsorption energy of the
hancement of the HER performance. Lu et al. created sulfur catalytic surface.34 Li et al. combined the sulfur vacancy
vacancies on molybdenum sulfide (MoS1.7) using hydrogen with strain effect to optimize the basal plane of monolayer
plasma, and obtained an overpotential of 143 mV at −10 mA 2H–MoS2 (Fig. 5D).9 Catalysts with various amount of vacan-
cm−2 under acidic condition, which is lower compared to that cies (0.00–25.00%) were analyzed by DFT calculations to un-
of untreated catalysts (MoS3.1, 206 mV) (Fig. 5A).33 They derstand the HER activity dependence on the vacancy
explained that the enhancement of the HER activity was due (Fig. 5E). The calculation results verified that the free energy
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to an increased active site density. The S 2p XPS spectra (ΔGH) related to hydrogen adsorption varied depending on
displayed peaks at binding energies (B.Es) of 163.5 eV and the number of removed sulfur atoms. The free energy of
162.3 eV, assigned to S2−, and B.Es of 164.6 eV and 163.4 eV pure 2H–MoS2 was about 2 eV, but it reduced to almost
indexed to S22− (Fig. 5B). While the peak intensities of Mo, in- 0 eV at 12.50% of sulfur vacancy. Li et al. concluded that
cluding MoIV species (B.E at 232.6 eV for Mo 3d3/2 and B.E at ΔGH might be reduced to 0 eV by applying the appropriate
229.5 eV for Mo 3d5/2) did not show any changes, the normal- amount of strain in each case. The HER activity was mea-
ized intensities of S2− and S22− in S 2p spectra showed a con- sured with respect to the sulfur vacancy and strain-control
siderable decrease, which may be due to the numerous sulfur in the catalyst (Fig. 5F). The modified catalyst with 12.5%
vacancies induced in the material. To evaluate the catalytic S-vacancies and 1.35 ± 0.15% strain exhibited an
properties of the modified material, the group designed sev- overpotential of 170 mV at −10 mA cm−2 in HER, which was
eral models by changing the number of the sulfur vacancies smaller than that of the catalyst modified with only
on the MoS2 lattice (4 × 4) and carried out a first-principles S-vacancy (250 mV at −10 mA cm−2) or with only strain.

Fig. 5 (A) HER polarization curves for Pt foil, Pt/CC, MoS3.1, and MoS1.7 in 0.5 M H2SO4 solution. (B) The Mo 3d and S 2p XPS spectra of the
pristine MoSx and plasma MoSx. (C) The free energy with different defective levels of MoS2. Reproduced with permission from ref. 33. Copyright
2016 Wiley-VCH. (D) Schematic of the top (upper panel) and side (lower panel) views of MoS2 with strained S-vacancies on the basal plane. (E) Free
energy versus the reaction coordinate of HER for the S-vacancy range of 0–25%. (F) LSV curves for Au substrate, Pt electrode, as-transferred MoS2
(strain: 0% and S-vacancy: 0%), strained MoS2 without S-vacancies (S-MoS2, strain: 1.35 ± 0.15% and S-vacancy: 0%), unstrained MoS2 with
S-vacancies (V-MoS2, strain: 0% and S-vacancy: 12.5 ± 2.5%), and strained MoS2 with S-vacancies (SV-MoS2, strain: 1.35 ± 0.15% and S-vacancy:
12.5 ± 2.5%). Reproduced with permission from ref. 9. Copyright 2016 Nature Publishing Group.

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3.2. Cation vacancy

Oxygen evolution reaction. To enhance the OER catalytic
activity, Suntivich et al. suggested the importance of catalysts
with cation eg occupancy close to unity.35 Cubic CoSe2 with
an optimal eg filling showed great potential as an excellent
catalyst. However, owing to its limited active sites, it exhibits
unsatisfactory catalytic activity. Liu et al. introduced Co va-
cancy (VCo) to modify the structure of CoSe2 nanosheets with
the aim of improving the OER activity (Fig. 6A).36 The XPS
spectra demonstrated the evident existence of the Co 2p sat-
ellite peak, which correlated to the antibonding orbital of Co
and Se, and thus, the presence of VCo (Fig. 6B). Additionally,
X-ray absorption fine structure (XAFS) and its corresponding
FT k 3ijχ(k)] functions in R space detected a significantly differ-
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ent atomic sequence between the modified and bulk cata-

lysts. As compared to the bulk catalyst (2.12 Å), the ultrathin
CoSe2 nanosheet showed a smaller R (Co–Se coordination
value, 2.08 Å) and lower intensity peak. These changes were
correlated to the reduced length of the bond between Co and
Se, and the lowered CN, respectively. Through DFT calcula-
tions (Fig. 6C), adsorption energies of −0.63 eV and −0.85 eV
were calculated for Co and VCo, respectively, which were
larger than that of the bulk catalyst with an adsorption en-
ergy of −0.38 eV. Ultrathin CoSe2 nanosheets with numerous
VCo, which acted as active sites, exhibited a low overpotential
of 0.32 V at 10 mA cm−2 for the OER.
Hydrogen evolution reaction. Kwong et al. reported an en-
hanced HER activity using the Fe-vacancy-rich FeP (Vc-FeP)
nanoparticulate film that was prepared by leaching out Mg
dopant.37 DFT calculation revealed that the material has an Fig. 6 (A) Schematic illustration of the formation of Co vacancies in
CoSe2 ultrathin nanosheets. (B) The XPS Co 2p of CoSe2 ultrathin
ideal hydrogen adsorption energy of 0.02 eV (Fig. 6D). The
nanosheets. (C) Geometries and binding energies of H2O molecules on
HER activity of Vc-FeP exhibited improvement under both al- Co sites and vacancies for bulk CoSe2 (left) and ultrathin nanosheet
kaline and acidic conditions, compared to pristine FeP or CoSe2 (right). Reproduced with permission from ref. 36. Copyright
FeP replaced by Mg (Mg–FeP) (Fig. 6E), with overpotentials of 2014 American Chemical Society. (D) Free energy diagram of FeP, Mg-
108 and 65 mV at −10 mA cm2, respectively; it showed great FeP, and Vc-FeP (111) surfaces. (E) Polarization curves for the HER ac-
tivity of Vc-FeP in 0.5 M H2SO4 (inset: HER activity in 1 M KOH). (F) The
stability even after 1 day in 1 M KOH, and 7 days in 0.5 M
CP tests of Vc-FeP in 0.5 M H2SO4 (inset: stability test on Vc-FeP
H2SO4 (Fig. 6F). The X-ray diffraction (XRD) analysis performed in 1 M KOH). (G) XRD data for FeP and Vc-FeP. The refer-
displayed a broadened peak width and reduced lattice spac- ence patterns of (a) orthorhombic FeP, (b) γ-Fe2O3, and (c) α-Fe2O3
ings (Fig. 6G), with respect to the FeP film, which were corre- also are shown. Reproduced with permission from ref. 37. Copyright
lated to the successful formation of Fe vacant sites.38 2017 Wiley-VCH.
Likewise, Liu et al. utilized the appropriate hydrogen ad-
sorption energy of the cation vacancies in five-fold twinned
PtPdRuTe anisotropic structures (v-Pd3Pt29Ru62Te6 AS).39 The Oxygen evolution reaction. Zhou et al. generated multiple
v-Pd3Pt29Ru62Te6 AS exhibited a low overpotential of 39 mV in types of vacancies of Co, Fe, and O (Fig. 7A).40 The variation
0.5 M H2SO4 and 22 mV in 1.0 M KOH to achieve current in the electronic structures of CoFe layered double hydrox-
densities of −10 mA cm−2. They demonstrated that the activity ides (LDHs) and modified-CoFe LDHs via chemical etching
of v-Pd3Pt29Ru62Te6 AS results from rapid charge transport (E-CoFe LDHs) was characterized by XAFS, wherein obvious
and a substantial amount of exposed surface area of the an- peak intensity changes were shown. Extended XANES oscilla-
isotropic structure. The catalysts were stable for 30 h with a tion functions revealed that the coordination environment of
current density of −10 mA cm−2. the metal atoms in the E-CoFe LDHs varied in favor of the
electrochemical activity. A modified catalyst with multiple va-
cancies delivered a lower overpotential of 300 mV at 10 mA
3.3. Multi-vacancies cm−2 compared to that delivered by pristine CoFe LDHs
A combination of the anion and cation vacancies often pro- (Fig. 7B). Additionally, the fitted Nyquist plot of E-CoFe LDH
duces synergy for the enhanced electrochemical activity for catalyst demonstrated a smaller charge-transfer resistance for
water-splitting reaction. water oxidation as compared to the pristine one (Fig. 7C).

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Similarly, Wang et al. proved that the CoFe LDH nano- The electrocatalytic OER and HER performances of various
sheets with multiple types of vacancies could promote the in- catalysts and their vacancy types are described in Table 1.
trinsic activity in the OER.41 Furthermore, the ultrathin LDH In addition, Fig. 8 summarizes the performance of
nanosheets through Ar plasma etching (CoFe LDHs-Ar) recently reported vacancy-engineered electrocatalysts. The
resulted in the formation of multiple vacancies, including O, overpotentials are plotted against the types of vacancies to
Co, and Fe vacancies. While the presence of oxygen vacancies provide a visual illustration for the effective vacancy types to-
facilitates the adsorption of intermediates such as OH*, O*, ward the water-splitting reaction.
and OOH*, cationic vacancies cause the effective distribu- In general, the vacancies are classified into three types,
tions of electrons and orbitals by adjusting the atomic envi- namely anion vacancies, cation vacancies, and multi-vacan-
ronment of Co. With a potential increase in the valence state cies. Anion vacancies are more easily formed, and oxygen va-
from Co2+ to Co3+, Co3+ with the higher valence state has a cancies are commonly observed with formed oxide-based
low coordination, resulting in increased catalytic activity. electrocatalysts for both the OER and HER. In contrast, the
CoFe LDHs-Ar with multiple vacancies showed low formation of the cation vacancy is considerably challenging
overpotentials of 266 mV at 10 mA cm−2 and 313 mV at a rela- due to the high formation energy required, compared to the
tively high current density of 50 mA cm−2 compared to that case with the anion vacancy.39 As compared to the electro-
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of CoFe LDHs (321 mV and 409 mV, respectively). catalysts without vacancies, the cation vacancy-engineered
Hydrogen evolution reaction. Yuan et al. introduced O electrocatalysts remarkably lowered the overpotentials, and
and metal vacancies to LDH materials via the calcination thus showed improved activity toward the OER and HER, as
process (Fig. 7D).42 XRD data showed that the vacancy- shown in Fig. 8, owing to their diverse chemical states that
containing NiFe LDH (v-NiFe LDH) has a noticeable broad are conducive for the optimization of intermediate B.Es For
peak, thus confirming the defect structure. The pair distri- the HER, the cation vacancy-controlled catalysts performed
bution function peaks associated with M–O and M–M were much better than the anion vacancy-engineered catalysts,
2.05 and 3.10 Å, respectively. They both displayed lowered with ∼50 mV lower overpotentials.
peaks in v-NiFe LDH, which indicate that O and M vacan- Multi-vacancies with both cation and anion vacancies
cies were formed. Furthermore, the bandgap energy of showed the synergistic effects of cation and anion vacancies
v-NiFe version was calculated as 2.16 eV, which is lower toward enhancing the performances of the electrocatalysts.
than that of the pristine version (2.85 eV). The presence of The presence of anion vacancies can effectively modulate the
vacancies in v-NiFe LDH lowered the CN of Ni–OOH, which electronic structures, tune the adsorption energies of inter-
helped decrease the overpotential from 246 mV to 87 mV at mediates, and improve the electrical conductivity.41 The pres-
−10 mA cm−2 (Fig. 7E). The fitted Nyquist plots showed that ence of cation/metal vacancies can increase the valence state
the charge-transfer resistance (Rct) of v-NiFe LDH (3.17 Ω) of nearby metal centers, which can also improve the reaction
was lower than that of the pristine NiFe LDH (6.99 Ω) kinetics due to the increased surface area with a low CN of
(Fig. 7F), which may be related to the improved electro- the catalytic active sites.42 However, the examples for multi-
conductivity. vacancies are very limited, thus calling for a great synthetic

Fig. 7 (A) Schematic illustration of E-CoFe LDHs after HNO3 etching. (B) OER performance of CoFe LDHs and E-CoFe LDHs in 1.0 M KOH. (C)
Nyquist plots at an overpotential of 270 mV. Reproduced with permission from ref. 40. Copyright 2017 Royal Society of Chemistry. (D) Schematic
illustration of defective NiFe LDH. (E) HER performance of v-NiFe LDH at a neutral pH. (F) Nyquist plots of pristine NiFe LDH and v-NiFe LDH nano-
sheets in 1.0 M PBS electrolyte. Reproduced with permission from ref. 42. Copyright 2019 American Chemical Society.

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Table 1 Summary of vacancy-engineered electrocatalysts for the OER and HER

Overpotential Tafel slope

Catalyst Vacancy type Application Electrolyte [mV@10 mA cm−2] [mV dec−1] Ref.
−2
SrCo0.9Ir0.1O3−δ Anion vacancy OER 0.1 M HClO4 250 mV@1 mA cm — 11
IrNiOx Anion vacancy OER 0.05 M H2SO4 280 [email protected] mA gIr−1 — 21
NiCo2O4 nanosheets Anion vacancy OER 1 M KOH 320 mV 30 28
Reduced NiFe Anion vacancy OER 1 M KOH 270 mV 40 31
CoO nanorods Anion vacancy OER 1 M KOH 330 mV 44 32
Reduced Co3O4 NWs Anion vacancy OER 1 M KOH 420 [email protected] mA cm−2 72 26
Fe1Co1-ONS Anion vacancy OER 0.1 M KOH 308 mV 36.8 60
CoOX(−4 h) nanoplates Anion vacancy OER 1 M KOH 306 mV 67 61
Plasma-engraved Co3O4 nanosheets Anion vacancy OER 0.1 M KOH 300 mV 68 62
YCRO-0.25 Anion vacancy OER 0.5 M H2SO4 275 mV 40.3 63
Amorphous MoS1.7 Anion vacancy HER 0.5 M H2SO4 143 mV 39.5 33
MoS2 basal plane Anion vacancy HER 0.5 M H2SO4 170 mV 60 9
NiO NRs-m-Ov Anion vacancy HER 1 M KOH 110 mV 100 1
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Mesoporous MoO3−x Anion vacancy HER 0.1 M KOH 138 mV 56 15

MoS2−xNy/rGO Anion vacancy HER 0.5 M H2SO4 217 mV 48 64
NiFe-VM-O Cation vacancy OER 1 M NaOH 371 mV 28 22
Co3−xO4 Cation vacancy OER 1 M KOH 268 mV 38.2 3
CoSe2 nanosheets Cation vacancy OER 0.1 M KOH 320 mV 44 36
NiFe LDHs-VNi nanosheets Cation vacancy OER 1 M KOH 229 mV 62.9 65
SnCoFe-Ar Cation vacancy OER 1 M KOH 300 mV 42.3 66
FeP Cation vacancy HER 1 M KOH 108 mV 62 37
FeP Cation vacancy HER 0.5 M H2SO4 65 mV 49 37
PtPdRuTe AS Cation vacancy HER 1 M KOH 22 mV 22 39
Pt/np-Co0.85Se Cation vacancy HER 1 M PBS 55 mV 35 67
NiAlδP Cation vacancy HER 0.5 M H2SO4 35 mV 38 59
OER 0.5 M H2SO4 256 mV 76 59
δ-FeOOH NSs/NF Cation vacancy HER 1 M KOH 108 mV 68 43
OER 1 M KOH 265 mV 36 43
CoFe LDHs-Ar nanosheets Multi vacancy OER 1 M KOH 266 mV 37.85 41
E-CoFe LDHs Multi vacancy OER 1 M KOH 300 mV 41 40
NiFe-LDH nanosheets Multi vacancy OER 1 M KOH 254 mV 32 27
H2O-Plasma exfoliated CoFe LDH Multi vacancy OER 1 M KOH 290 mV 36 68
NiFe LDHs Multi vacancy HER 1 M PBS 87 mV 46.3 42

effort to the controlled formation of multi-vacancies in cata- improved charge transfer in the catalyst structure. Some va-
lytic materials. cancy engineered catalysts with the high concentration of ox-
For practical applications of the electrocatalysts, their sta- ygen vacant sites have shown a superior stability toward
bility, the intrinsic property dependent on the material OER, because the oxygen-vacant sites can form direct O–O
phases, should be attained.43 Vacancy engineering of electro- bonds in the OER process, not necessitating significant reor-
catalysts might provide solutions to the catalyst stability is- ganization of atoms within the catalysts.29 Vacancy of other
sues via optimized adsorption energy of intermediates and anions such as sulfur anions can also boost the catalyst sta-
bility; porous nanosheets of Co3S4 with abundant sulfur va-
cancies showed excellent stability toward the HER even at
the high negative potentials.44 Catalysts with sulfur vacan-
cies, having more electrons, showed lower adsorption energy
of H2O, compared to other catalysts with no vacancy, accel-
erating electron/mass transfer and thus enhancing the
stability.
However, excessive vacancies in the catalysts could also
induce adverse effects on structural stability and
electronic conductivity.45,46 Also, the issues for structural
degradation and dissolution through vacant sites are far
from being resolved. Therefore, the establishment of rela-
tionships between the catalytic stability and the number
and nature of vacancies of the catalysts remains an im-
Fig. 8 Trend of the performance of recent vacancy-engineered portant task in accomplishing the catalyst stability toward
electrocatalysts. water splitting.

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4. Future perspectives be conducted. Moreover, several studies have proven that

multi (anion and cation) vacancies within one material can
The rapid growth of interest in engineering vacancy-rich have synergistic effects to accelerate the water electrolysis
electrocatalysts is a response to the increasing demand for process. In this context, the engineering of multi-vacancies
highly efficient electrocatalysts. In this review, we aimed at pro- with various catalytic materials is direly required for enhanc-
viding an overview of the recent studies on vacancy-engineered ing electrochemical water-splitting reactions.
catalysts for electrochemical HER and OER, regardless of metal
types. These engineering vacancies in electrocatalysts could
4.2. Development of a novel vacancy from noble metal-based
lead to the exposure of active sites through CUSs, optimization
electrocatalysts
of adsorption energy for intermediates, and improvement of
electrical conductivity. Based on these features from vacancy- The development of noble metal vacancies is also necessary. In
engineered electrocatalysts, we could categorize the types of va- acidic OER/HER, noble metals such as Ir, Ru, and Pt have been
cancies into anion, cation, and multi-vacancies. Despite the sig- greatly utilized because of their excellent intrinsic perfor-
nificant achievements in vacancy engineering toward water mances for electrolysis. Although the dissolution rates of noble
splitting in this review, the synthetic methodologies for the metals during electrochemical catalysis are lower than those of
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controlled formation of different vacancy types are severely un- non-noble metals, a small amount of noble metals can still be
derdeveloped. Therefore, continuous efforts on understanding traced in the electrolyzers.11,48 Although such dissolution can
the relationship between vacancy formation and catalytic per- initiate defects in the electrocatalysts with noble metal vacan-
formance are necessary to rationally design vacancy-optimized cies, these vacancies could not be finely controlled. The forma-
electrocatalysts. Some representative future perspectives are tion of well-defined noble metal vacancies can lead to the great
schematically shown in Fig. 9. modification of metal coordination, which can provide addi-
tional active sites and improve the electrocatalytic performance
4.1. Beyond anion vacancy engineering: importance of cation of water splitting in both acidic and alkaline media using a rel-
and multi-vacancy atively small amount of noble metals. Thus, further studies on
noble metal-based vacancies are required.
The most remarkable challenges for vacancy engineering are
the limited methods to induce cation vacancies because the
formation energy of metal/cation vacancy is quite higher than 4.3. Constructing the stability of vacancy-engineered
that of anion vacancy.47 However, as discussed in Table 1 and electrocatalysts
Fig. 8, the cation or metal vacancy-engineered catalysts could Very few studies have been conducted to understand the rela-
largely improve the catalytic activity for both OER and HER. tionship between the formation of vacancies and catalyst stabil-
This is because the excess electrons can facilitate the modula- ity. Because the vacancies in the structures can lead to geomet-
tion of the electronic structure on the catalyst surface. There- rical and electronic distortions,49 a weaker bonding of the
fore, additional research to create metal/cation vacancies to lattice in defective structures compared to that in crystalline
generate OER and HER active sites on the atomic level should ones might be induced, which would lead to the formation of

Fig. 9 Illustration of future perspectives for enhancing the performance of electrocatalytic water splitting via vacancy engineering.

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metastable structures and accelerate the degradation of catalyst Furthermore, even if the materials have the same crystal
structures in the electrocatalysts.48 To prevent the degradation structure and geometry, the shape-controlled materials might
of electrocatalysts, an understanding of the surrounding atoms have different properties when the vacancy is formed on the
adjacent to the vacant sites and their overall chemical environ- exposed surface. Shape-controlled materials that expose the
ments is necessary to design highly robust electrocatalysts with different specific facets can have facet-specific vacancy types
numerous active sites. Although a few studies on the theoreti- on the surface of the catalysts due to the differences in the
cal investigation of thermodynamic stability and vacancy for- coordination environments for different facet types. Investi-
mation has been reported,50–52 experimental research demon- gation of catalysis on facet-specific vacancy might allow us to
strating the relationship between an optimal vacancy understand further structural details of the highly active va-
formation and stability of electrocatalysts should also be cancies toward water electrolysis.
conducted to verify the theory-based predictions.
5. Conclusion
4.4. Efforts on the elaborate control of the vacancy In summary, vacancy engineering has been considered as an ef-
distribution
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fective strategy for the development of highly efficient electro-

To aid the development of vacancy formation, advances in catalysts for water electrolysis. The vacancy-controlled catalysts
synthetic methods (both physical and chemical) to form and are endowed with useful properties such as exposure of low-
identify vacancies are greatly required. The energy to create coordination sites, optimized adsorption energies of intermedi-
vacancies can be provided by physical methods, such as ates, and enhanced electrical conductivity. In addition, the
plasma etching,9 thermal treatment,53 liquid exfoliation,27,54 vacancy-engineered electrocatalysts show great potential toward
and electrochemical etching.11,21 These physical methods the water-splitting reactions, namely OER and HER. However,
used to create vacancies could be modulated by varying the synthetic approaches are quite underdeveloped toward
processing time and energy input.18 Meanwhile, the creation position-controlled and quantity-controlled vacancy formation
of vacancies can occur simultaneously with chemical reac- within the nanostructures. Therefore, the development of
tions, such as chemical reduction,55 hydrothermal synthe- atomic-scale engineering for the precise tuning of vacancies
sis,56 and elemental doping.57 Therefore, because it is diffi- and alteration of coordination environments for vacancies
cult to predict and precisely control the vacancy distribution, should be developed for further improvement of active and sta-
elemental doping into existing materials might be an effec- ble electrocatalysts. We hope that this review can motivate ac-
tive route to create atomically controlled vacancies.58 tive developments of vacancy-engineered electrocatalysts for
Depending on the type of dopants with different ionic sizes, water electrolysis and other related energy applications.
the positions and sizes of the formed vacancy sites could be
deterministically controlled. For example, in perovskites Conflicts of interest
(ABO3, where A and B are cations, with A atoms larger than B
atoms; X is an anion that bonds with both cations), small There are no conflicts to declare.
ions are exclusively doped on the B-site and oxygen vacancies
are created for charge composition if the dopant has a rela- Acknowledgements
tively low valence.57,58 This can also result in the partial oxi-
dation or reduction of ions on the B sites or result in the ap- This study was supported by the National Research Foundation
pearance of B-site vacancies if the dopant has a high valence. of Korea (NRF-2017R1A2B3005682, NRF2019R1A6A1A11044070),
Conversely, if large ions are substituted only on the A-site, A- and the Hydrogen Energy Innovation Technology Develop-
site, B-site, or oxygen vacancies can be created, depending on ment Program of the National Research Foundation of Korea
the induced charge balance of the crystal structure. There- (NRF) funded by the Korean Government (Ministry of Science
fore, the choice of doping element types can determine the and ICT(MSIT)) (No. NRF-2019M3E6A1064709).
different sizes and sites of vacancies, which can lead to the
discovery of more active sites on the electrocatalysts. As with References
the case of perovskites, the atomically modulated vacancies
via elemental doping might be applied to various types of 1 T. Zhang, M.-Y. Wu, D.-Y. Yan, J. Mao, H. Liu, W.-B. Hu,
crystal structures, such as hetero-interface structures. Nano- X.-W. Du, T. Ling and S.-Z. Qiao, Nano Energy, 2018, 43,
structures with hetero-interfaces can be promising platforms 103–109.
for providing a pathway through which dopants can easily 2 Z. Chen, C. X. Kronawitter, Y.-W. Yeh, X. Yang, P. Zhao, N.
move between different phases under relatively low energy, Yao and B. E. Koel, J. Mater. Chem. A, 2017, 5, 842–850.
compared to nanostructures without interfaces. This might 3 R. Zhang, Y.-C. Zhang, L. Pan, G.-Q. Shen, N. Mahmood,
lead to the formation of numerous vacancies after leaching Y.-H. Ma, Y. Shi, W. Jia, L. Wang, X. Zhang, W. Xu and J.-J.
out the dopants. The position and number of vacancies Zou, ACS Catal., 2018, 8, 3803–3811.
might be conveniently controlled by modulating the diffusion 4 Y. Sun, S. Gao, F. Lei and Y. Xie, Chem. Soc. Rev., 2015, 44,
zone width within the nanocrystals.58 623–636.

This journal is © The Royal Society of Chemistry 2020 CrystEngComm, 2020, 22, 1500–1513 | 1511
 View Article Online

Highlight CrystEngComm

5 S. H. Brodersen, U. Grønbjerg, B. Hvolbæk and J. Schiøtz, 29 S. Hirai, K. Morita, K. Yasuoka, T. Shibuya, Y. Tojo, Y.
J. Catal., 2011, 284, 34–41. Kamihara, A. Miura, H. Suzuki, T. Ohno, T. Matsuda and S.
6 Y. Sun, S. Gao, F. Lei, J. Liu, L. Liang and Y. Xie, Chem. Sci., Yagi, J. Mater. Chem. A, 2018, 6, 15102–15109.
2014, 5, 3976–3982. 30 L. Han, S. Dong and E. Wang, Adv. Mater., 2016, 28,
7 J. V. Lauritsen, J. Kibsgaard, S. Helveg, H. Topsøe, B. S. 9266–9291.
Clausen, E. Lægsgaard and F. Besenbacher, Nat. 31 M. Asnavandi, Y. Yin, Y. Li, C. Sun and C. Zhao, ACS Energy
Nanotechnol., 2007, 2, 53–58. Lett., 2018, 3, 1515–1520.
8 T. F. Jaramillo, K. P. Jørgensen, J. Bonde, J. H. Nielsen, S. 32 T. Ling, D.-Y. Yan, Y. Jiao, H. Wang, Y. Zheng, X. Zheng, J.
Horch and I. Chorkendorff, Science, 2007, 317, 100. Mao, X.-W. Du, Z. Hu, M. Jaroniec and S.-Z. Qiao, Nat.
9 H. Li, C. Tsai, A. L. Koh, L. Cai, A. W. Contryman, A. H. Commun., 2016, 7, 12876.
Fragapane, J. Zhao, H. S. Han, H. C. Manoharan, F. Abild- 33 A.-Y. Lu, X. Yang, C.-C. Tseng, S. Min, S.-H. Lin, C.-L. Hsu,
Pedersen, J. K. Nørskov and X. Zheng, Nat. Mater., 2016, 15, H. Li, H. Idriss, J.-L. Kuo, K.-W. Huang and L.-J. Li, Small,
48–53. 2016, 12, 5530–5537.
10 S. Jayabal, G. Saranya, J. Wu, Y. Liu, D. Geng and X. Meng, 34 B. T. Sneed, A. P. Young and C.-K. Tsung, Nanoscale, 2015, 7,
Published on 07 January 2020. Downloaded on 5/21/2020 9:33:22 AM.

J. Mater. Chem. A, 2017, 5, 24540–24563. 12248–12265.

11 Y. Chen, H. Li, J. Wang, Y. Du, S. Xi, Y. Sun, M. Sherburne, J. W. 35 J. Suntivich, K. J. May, H. A. Gasteiger, J. B. Goodenough
Ager, A. C. Fisher and Z. J. Xu, Nat. Commun., 2019, 10, 572. and Y. Shao-Horn, Science, 2011, 334, 1383.
12 H. Jin, C. Guo, X. Liu, J. Liu, A. Vasileff, Y. Jiao, Y. Zheng 36 Y. Liu, H. Cheng, M. Lyu, S. Fan, Q. Liu, W. Zhang, Y. Zhi, C.
and S.-Z. Qiao, Chem. Rev., 2018, 118, 6337–6408. Wang, C. Xiao, S. Wei, B. Ye and Y. Xie, J. Am. Chem. Soc.,
13 Q. Ding, B. Song, P. Xu and S. Jin, Chem, 2016, 1, 699–726. 2014, 136, 15670–15675.
14 Y. Liu, C. Xiao, P. Huang, M. Cheng and Y. Xie, Chem, 37 W. L. Kwong, E. Gracia-Espino, C. C. Lee, R. Sandström, T.
2018, 4, 1263–1283. Wågberg and J. Messinger, ChemSusChem, 2017, 10, 4544–4551.
15 Z. Luo, R. Miao, T. D. Huan, I. M. Mosa, A. S. Poyraz, W. 38 W. L. Kwong, C. C. Lee and J. Messinger, J. Phys. Chem. C,
Zhong, J. E. Cloud, D. A. Kriz, S. Thanneeru, J. He, Y. Zhang, 2017, 121, 284–292.
R. Ramprasad and S. L. Suib, Adv. Energy Mater., 2016, 6, 39 S. Liu, X. Mu, W. Li, M. Lv, B. Chen, C. Chen and S. Mu,
1600528. Nano Energy, 2019, 61, 346–351.
16 Y.-W. Cheng, J.-H. Dai, Y.-M. Zhang and Y. Song, J. Mater. 40 P. Zhou, Y. Wang, C. Xie, C. Chen, H. Liu, R. Chen, J. Huo
Chem. A, 2018, 6, 20956–20965. and S. Wang, Chem. Commun., 2017, 53, 11778–11781.
17 T. Reier, H. N. Nong, D. Teschner, R. Schlögl and P. Strasser, 41 Y. Wang, Y. Zhang, Z. Liu, C. Xie, S. Feng, D. Liu, M. Shao
Adv. Energy Mater., 2017, 7, 1601275. and S. Wang, Angew. Chem., Int. Ed., 2017, 56, 5867–5871.
18 M.-Q. Yang, J. Wang, H. Wu and G. W. Ho, Small, 2018, 14, 42 Z. Yuan, S.-M. Bak, P. Li, Y. Jia, L. Zheng, Y. Zhou, L. Bai, E.
1703323. Hu, X.-Q. Yang, Z. Cai, Y. Sun and X. Sun, ACS Energy Lett.,
19 K. S. Exner and H. Over, ACS Catal., 2019, 9, 6755–6765. 2019, 4, 1412–1418.
20 V. Pfeifer, T. E. Jones, S. Wrabetz, C. Massué, J. J. Velasco 43 J. Kim, M. Jun, S. Choi, J. Jo and K. Lee, Nanoscale, 2019, 11,
Vélez, R. Arrigo, M. Scherzer, S. Piccinin, M. Hävecker, A. 20392–20410.
Knop-Gericke and R. Schlögl, Chem. Sci., 2016, 7, 44 C. Zhang, Y. Shi, Y. Yu, Y. Du and B. Zhang, ACS Catal.,
6791–6795. 2018, 8, 8077–8083.
21 H. N. Nong, T. Reier, H.-S. Oh, M. Gliech, P. Paciok, T. H. T. 45 J. Du, T. Zhang, F. Cheng, W. Chu, Z. Wu and J. Chen, Inorg.
Vu, D. Teschner, M. Heggen, V. Petkov, R. Schlögl, T. Jones Chem., 2014, 53, 9106–9114.
and P. Strasser, Nat. Catal., 2018, 1, 841–851. 46 Y. Guo, Y. Tong, P. Chen, K. Xu, J. Zhao, Y. Lin, W. Chu, Z.
22 H. J. Lee, S. Back, J. H. Lee, S. H. Choi, Y. Jung and J. W. Peng, C. Wu and Y. Xie, Adv. Mater., 2015, 27, 5989–5994.
Choi, ACS Catal., 2019, 9, 7099–7108. 47 B. Liu, Y. Wang, H.-Q. Peng, R. Yang, Z. Jiang, X. Zhou, C.-S.
23 H.-S. Kim, J. B. Cook, H. Lin, J. S. Ko, S. H. Tolbert, V. Lee, H. Zhao and W. Zhang, Adv. Mater., 2018, 30, 1803144.
Ozolins and B. Dunn, Nat. Mater., 2017, 16, 454–460. 48 S. Geiger, O. Kasian, M. Ledendecker, E. Pizzutilo, A. M.
24 M. Dieterle, G. Weinberg and G. Mestl, Phys. Chem. Chem. Mingers, W. T. Fu, O. Diaz-Morales, Z. Li, T. Oellers, L.
Phys., 2002, 4, 812–821. Fruchter, A. Ludwig, K. J. J. Mayrhofer, M. T. M. Koper and
25 G. Wang, Y. Ling and Y. Li, Nanoscale, 2012, 4, 6682–6691. S. Cherevko, Nat. Catal., 2018, 1, 508–515.
26 Y. Wang, T. Zhou, K. Jiang, P. Da, Z. Peng, J. Tang, B. Kong, 49 A. A. Emery and C. Wolverton, Sci. Data, 2017, 4, 170153.
W.-B. Cai, Z. Yang and G. Zheng, Adv. Energy Mater., 2014, 4, 50 B. Liu, D. S. Aidhy, Y. Zhang and W. J. Weber, Phys. Chem.
1400696. Chem. Phys., 2014, 16, 25461–25467.
27 Y. Zhao, X. Zhang, X. Jia, G. I. N. Waterhouse, R. Shi, X. 51 S. M. Alay-e-Abbas, S. Nazir, N. A. Noor, N. Amin and A.
Zhang, F. Zhan, Y. Tao, L.-Z. Wu, C.-H. Tung, D. O'Hare and Shaukat, J. Phys. Chem. C, 2014, 118, 19625–19634.
T. Zhang, Adv. Energy Mater., 2018, 8, 1703585. 52 D. Le, T. B. Rawal and T. S. Rahman, J. Phys. Chem. C,
28 J. Bao, X. Zhang, B. Fan, J. Zhang, M. Zhou, W. Yang, X. Hu, 2014, 118, 5346–5351.
H. Wang, B. Pan and Y. Xie, Angew. Chem., Int. Ed., 2015, 54, 53 L. Li, T. Zhang, J. Yan, X. Cai and S. Liu, Small, 2017, 13,
7399–7404. 1700441.

1512 | CrystEngComm, 2020, 22, 1500–1513 This journal is © The Royal Society of Chemistry 2020
 View Article Online

CrystEngComm Highlight

54 Y. Xu, L. Wang, X. Liu, S. Zhang, C. Liu, D. Yan, Y. Zeng, Y. 61 W. Xu, F. Lyu, Y. Bai, A. Gao, J. Feng, Z. Cai and Y. Yin, Nano
Pei, Y. Liu and S. Luo, J. Mater. Chem. A, 2016, 4, Energy, 2018, 43, 110–116.
16524–16530. 62 L. Xu, Q. Jiang, Z. Xiao, X. Li, J. Huo, S. Wang and L. Dai,
55 C. Zhu, S. Fu, D. Du and Y. Lin, Chem. – Eur. J., 2016, 22, Angew. Chem., Int. Ed., 2016, 55, 5277–5281.
4000–4007. 63 Q. Feng, Z. Zhao, X.-Z. Yuan, H. Li and H. Wang, Appl.
56 Y. Zhao, C. Chang, F. Teng, Y. Zhao, G. Chen, R. Shi, G. I. N. Catal., B, 2020, 260, 118176.
Waterhouse, W. Huang and T. Zhang, Adv. Energy Mater., 64 Z. Luo, Y. Wang, X. Wang, Z. Jin, Z. Wu, J. Ge, C. Liu and W.
2017, 7, 1700005. Xing, ACS Appl. Mater. Interfaces, 2019, 11, 39782–39788.
57 Y. Wang, J. Piao, G. Xing, Y. Lu, Z. Ao, N. Bao, J. Ding, S. Li 65 Y. Wang, M. Qiao, Y. Li and S. Wang, Small, 2018, 14, 1800136.
and J. Yi, J. Mater. Chem. C, 2015, 3, 11953–11958. 66 D. Chen, M. Qiao, Y.-R. Lu, L. Hao, D. Liu, C.-L. Dong, Y. Li
58 G. Li, G. R. Blake and T. T. M. Palstra, Chem. Soc. Rev., and S. Wang, Angew. Chem., Int. Ed., 2018, 57, 8691–8696.
2017, 46, 1693–1706. 67 K. Jiang, B. Liu, M. Luo, S. Ning, M. Peng, Y. Zhao, Y.-R. Lu,
59 W. Cheng, H. Zhang, X. Zhao, H. Su, F. Tang, J. Tian and Q. T.-S. Chan, F. M. F. de Groot and Y. Tan, Nat. Commun.,
Liu, J. Mater. Chem. A, 2018, 6, 9420–9427. 2019, 10, 1743.
Published on 07 January 2020. Downloaded on 5/21/2020 9:33:22 AM.

60 L. Zhuang, L. Ge, Y. Yang, M. Li, Y. Jia, X. Yao and Z. Zhu, 68 R. Liu, Y. Wang, D. Liu, Y. Zou and S. Wang, Adv. Mater.,
Adv. Mater., 2017, 29, 1606793. 2017, 29, 1701546.

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