Review

pubs.acs.org/CR

Earth-Abundant Heterogeneous Water Oxidation Catalysts

Bryan M. Hunter, Harry B. Gray,* and Astrid M. Müller*
Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology, M/C 139-74, Pasadena,
California 91125, United States

ABSTRACT: Water oxidation is a key chemical transformation for the conversion of solar
energy into chemical fuels. Our review focuses on recent work on robust earth-abundant
heterogeneous catalysts for the oxygen-evolving reaction (OER). We point out that
improvements in the performance of OER catalysts will depend critically on the success of
work aimed at understanding reaction barriers based on atomic-level mechanisms. We
highlight the challenge of obtaining acid-stable OER catalysts, with proposals for elements
that could be employed to reach this goal. We suggest that future advances in solar fuels
science will be accelerated by the development of new methods for materials synthesis and
characterization, along with in-depth investigations of redox mechanisms at catalytic
surfaces.

CONTENTS on our planet depend on the global availability of clean and

affordable energy. It is cause for concern that power
1. Introduction A
consumption on earth (∼13.5 TW in 2001) is expected to
1.1. Potentials of Water-Splitting Reactions B
double by 2050 and triple by 2100.2 We must call on the sun
1.2. Solar Water-Splitting Device Designs B
1.3. Materials Stability Considerations B for survival: it is by far our largest and most reliable source of
2. Earth-Abundant Water Oxidation Catalysts C energy; it delivers an entire year’s worth of energy to the earth’s
2.1. Water Oxidation Catalysts Based on First- surface within 80 min.3
Row Transition Metals C As fossil fuels have high energy density, we have become
2.2. Layered Double Hydroxides E reliant on them for most of our needs. However, combustion of
2.3. Looking Forward F fossil fuels has detrimental effects on climate and health. In
3. Mechanistic Considerations F addition to global climate change attributable to rapidly
3.1. Lessons from Nature G increasing CO2 concentrations in the atmosphere, excessive
3.2. Heterogeneous Water Oxidation Catalysts H emissions that form smog have become a big problem in many
4. Parting Shots J countries. Furthermore, the dependence of industrialized
Author Information J nations on oil, gas, and coal, and the ever-increasing demand
Corresponding Authors J for energy are roadblocks in efforts for world peace.4 A
Author Contributions J paradigm shift in our current infrastructure is needed to avoid
Notes J catastrophe.5
Biographies J Fossil fuels are byproducts of eons of photosynthesis.6 The
Acknowledgments K issues we are encountering from their use arise from the large
Abbreviations K amount we combust in the relatively short time frame of a few
References K centuries. In light of the devastating effects and even more
alarming prospects of air pollution and climate change, the
need for viable energy solutions that do not interfere with our
1. INTRODUCTION lifestyle has never been more urgent. The fight against global
warming has begun, and significant amounts of funding have
The oxidation of water to oxygen liberates the protons and
been pledged to combat it.7 Yet, as developing nations become
electrons required for the generation of fuels and other valuable
molecules. Much progress has been made recently in designing more prosperous and technology advances, worldwide demand
and synthesizing scalable, heterogeneous water oxidation for energy will continue to increase. This dilemma can only be
catalysts for solar-driven water splitting. In this review, we solved by innovation: in this review, we will focus on earth-
provide an outlook on the future of such materials, with an eye abundant materials tailored for carbon-neutral fuel generation,
toward rational design of high-performing catalysts.
The development of renewable energy systems is the greatest Received: June 23, 2016
challenge for humanity in the 21st century.1 All aspects of life

© XXXX American Chemical Society A DOI: 10.1021/acs.chemrev.6b00398

Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

as these could lead to technologies to solve problems associated Scheme 1. Water-Splitting Half Reactions at Low and High
with the energy and concomitant climate crisis. pH
1.1. Potentials of Water-Splitting Reactions
An attractive, carbon-neutral solution is solar-driven water
splitting to produce hydrogen fuel from water1 (Figure 1). All
the materials needed for efficient water splitting must consist of
earth-abundant elements to achieve global scalability.8

mature technologically but could be surpassed by fully

integrated wireless devices. Photocatalyst colloids, where the
Figure 1. Schematic of water splitting.
oxygen and hydrogen evolution reactions (OER and HER)
occur together, have issues with the formation of explosive H2
The thermodynamic potential of the water-splitting reaction, and O2 mixtures. The integrated photoelectrochemical (PEC)
2H2O (l) → 2H2 (g) + O2 (g), is E0 = −1.23 V. The stepwise devices, also called tandem or monolithic devices, strike a
oxidation of water requires large overpotentials. The over- balance between the two limits. They are wireless to avoid
potential of a redox reaction is the potential above the ohmic losses, and the components for light capture and
thermodynamic potential needed to overcome reaction catalysis as well as for OER and HER are separated. Decoupling
barriers; in electrocatalysis, it is referenced to a given turnover the processes of light capture and catalysis offers advantages
frequency or current density. At all pH values, the electrode because size matters. Optimal dimensions for light absorbers
potential for the four-electron, four-proton oxidation of water is are typically on the order of 100 nm. For catalysts, however,
substantially lower than that for some of the sequential one- smaller is better, as chemical (redox) reactions occur on a
electron steps. At pH 7, the one-electron potential for the molecular scale. Shrinking catalyst size provides more active
oxidation of water to hydroxyl radical (•OH) is −2.32 V, over surface sites per mass because the surface-to-volume ratio
1.5 V more negative than the potential for the four-electron changes favorably as particles get smaller. Several investigators
concerted oxidation (−0.815 V at pH 7).9 have discussed the advantages and disadvantages of various
In nature, water oxidation is accomplished by photosystem II photoelectrochemical device designs.25−37
(PS II), the highly conserved machinery for the production of Irrespective of device design, water oxidation catalysis is
plant fuel from sunlight. The water-oxidizing complex (WOC) crucial for harnessing solar photons. Not only water splitting
is an inorganic calcium−manganese−oxo cluster10 whose but also other green chemistry transformations require the
structure has been studied extensively by X-ray crystallog- electrons and protons generated by the oxidation of our most
raphy.11 Of critical importance is that water oxidation is carried abundant feedstock. As recent reviews summarized the design
out in a series of proton-coupled electron transfer (PCET) criteria and reactivities of molecular catalysts,38−40 we focus
steps.12 The so-called “Kok cycle” of the WOC dictates that here only on heterogeneous catalysts.
one proton leaves the reaction center for each electron that
leaves.13 The resulting effect is a “potential leveling” scheme in 1.3. Materials Stability Considerations
which subsequent oxidation steps take place at potentials Electrochemical equilibria of metals in aqueous solutions are
similar to the first. In the absence of PCET, charge build up on well described in the Pourbaix Atlas.41 The data compiled in
the WOC would necessitate prohibitively high potentials for this atlas show that, at high potentials, more stable earth-
the second, third, and fourth oxidation steps.14 A theoretical abundant metal oxide or hydroxide materials exist in high-pH
framework for PCET has been developed by Cukier15,16 and electrolyte (Figure 2). Anion exchange membranes (AEMs) are
Hammes-Schiffer.17,18 There has been much recent work on
synthetic analogues of the WOC.19−22 In one study of note,
Agapie and co-workers found that redox inactive metals
modulated the reduction potentials of the Mn ions in their
clusters.23
Depending on solution pH, water splitting proceeds by
different half reactions (Scheme 1). In aqueous acid (pH 0), the
water oxidation half reaction has E0 = −1.23 V, while the
proton reduction half reaction has E0 = 0.00 V, by definition. At
pH 14, E0 is −0.83 V for the hydrogen evolution half reaction
and −0.40 V for the water oxidation half reaction. These Figure 2. Corrosion stability of nongaseous group 1−16 elements for
potentials are milder relative to the normal hydrogen electrode, element−water systems at 25 °C under positive applied potentials;
which could have implications on catalyst stability and device adapted from the Pourbaix Atlas.41 Color code: stable against
design. It is worth noting that dioxygen reduction may compete corrosion by innate immunity or the formation of an oxide or
with proton reduction under acidic conditions. hydroxide layer at low (orange), around neutral (green), and high
(blue) pH. Elements that corrode under applied oxidative potentials
1.2. Solar Water-Splitting Device Designs
are depicted in gray. Multiple colors (blue/orange, blue/green)
Designs of solar-driven water-splitting devices come in three indicate stability over a wide pH range. The combination orange/gray
flavors.24 Photovoltaic−electrolyzer combinations are most is for stability at low pH but only for moderately positive potentials.

B DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

currently being developed to replace Nafion as the separator spectrum, the use of semiconductors to absorb visible light to
between the oxygen- and the hydrogen-evolving compartments effect water oxidation was an important development. Even
of a tandem device.42,43 Devices typically operate at extreme though TiO2 has been studied intensely the past few decades,
pH, i.e., strong aqueous base or acid.44 It is not clear at this time attempts to substantially enhance its light absorption properties
if overall acidic or alkaline conditions will work better for water- have not met with much success.59
splitting devices, given the requirements of scalability, Other metal oxides, such as ZnO,60 La:NaTaO3,61,62
efficiency, and robustness.45 WO3,63,64 and SrTiO3,65 have been investigated for solar-
Since we know that water oxidation catalysts will be required driven water splitting. All these materials have band gaps that
to operate at high potentials, we have color coded the are too large to make good use of sunlight, thereby limiting
nongaseous group 1−16 elements of the Periodic Table that overall solar-to-hydrogen efficiencies.66 A few visible-light
are corrosion resistant by innate immunity or the formation of absorbers have been examined. Shifting the absorption edge
an oxide or a hydroxide layer at different pH values in water of TiO2 toward the visible region was achieved by nitrogen
(based on data from the Pourbaix Atlas;41 Figure 2). Elements doping, which turned the material yellow (Eg = 2.9 eV).67 Also,
that are stable against corrosion under applied anodic potential molecular nitrogen intercalation decreased the band gap of
and low pH are colored orange. Those that are immune to WO3 to 1.9 eV.68 Nevertheless, neither material met all the
corrosion at neutral pH are depicted in green, and those that requirements for efficient water oxidation.69 Shao-Horn et al.
are stable at high pH are in blue. Elements that always corrode predicted and experimentally confirmed OER activity of a
under high anodic potentials are gray. We believe that this chart complex Ba−Co−Sr−Fe (BCSF) oxide perovskite material that
could serve as a roadmap for the development of stable water compared favorably with IrO2.70 Electronic structure−activity
oxidation catalysts, although it should be noted that it does not relationships in similar perovskites were reported.71 Combining
take into account mixtures or alloys. a cocatalyst with active photoanode materials has become the
Of interest is that bismuth vanadate is stable in base, even most promising methodology, evidenced by recent work by
though vanadium is orange in the table; vanadate ions by Marschall et al. on layered perovskite nanofiber photoanodes
themselves are stable at high pH under anodic polarization.41 with photodeposited Rh−Cr2O3.72
Other binary systems show similar behavior that deviates from Bismuth vanadate (BiVO4) has been identified as a promising
simple Pourbaix predictions. Although manganese is not stable photoanode material for solar water oxidation.73 It has been
in 0.1 M aqueous KOH, the Ca2Mn2O5 oxygen-deficient shown to be stable against photocorrosion in aqueous
perovskite is a stable water oxidation catalyst under these electrolytes from pH 3 to 13.74 BiVO4 crystallizes in different
conditions.46 Another strategy involves mixing base-unstable polymorphs, with monoclinic scheelite exhibiting the highest
metals into nickel-containing double hydroxides. OER catalysts photocatalytic water oxidation activity.75,76 This crystalline
based on nickel double hydroxides and Cr, Mn, or Zn are stable phase of BiVO4 is an n-type semiconductor with a direct band
in 0.1 M aqueous KOH even though Cr, Mn, and Zn are not gap of 2.4 eV (making it appear yellow) and a valence band
independently stable in base.47 Ternary systems also have been edge at ∼2.4 V vs RHE (reversible hydrogen electrode) that is
explored, with the perovskites LaCrO3, La0.7Sr0.3CrO3, and sufficiently positive to effect water oxidation.58,77 Water
La0.8Sr0.2CrO3 being stable for OER in 1 M aqueous NaOH, oxidation efficiency is mainly limited by high electron−hole
contrary to the prediction for Cr.48 recombination, inadequate water oxidation kinetics, and poor
Commercial water electrolyzers consist of OER and HER charge transport properties.73
catalysts, and the two half reactions are separated by a Large variations of photocurrents have been reported for
membrane.49 In high-current-density systems, both catalysts are BiVO4 photoanodes.78−87 In recent work, we correlated the
based on scarce metals, Pt for HER and IrO2 for OER.50 Noble morphology and chemical surface composition of this material
metal oxides (Rh, Ir, Ru) were identified as highly active to its photoelectrochemical performance, with the aim to
heterogeneous catalysts for water oxidation.51 Iridium oxide differentiate contributions from different properties.88 We
(IrO2), though not earth abundant, was subsequently found to devised a novel anodic electrodeposition procedure with
be one of the most active materials.52 Further investigations different amounts of iodide added to the aqueous plating
demonstrated that molecular precursors can form highly active bath, which allowed us to prepare BiVO4 films with virtually
heterogeneous catalysts based on iridium oxide.53 In related identical thicknesses but different morphologies, and we could
work, a quartz crystal microbalance was employed to control surface Bi content (Figure 3).88
differentiate between homogeneous and heterogeneous iridium
Optimized photocurrent generation of BiVO4 photoanodes
catalysis.54 Interestingly, Osterloh et al. used iridium dioxide
resulted from intertwined material properties, whose interplay
nanocrystals as both photoanode and catalyst to split water with
was probed by bivariate data analysis. Our data showed that a
visible and UV light,55 and iridium-doped metal−organic
near-stoichiometric surface Bi/V ratio in combination with
frameworks were found to be competent for water oxidation.56
high-aspect-ratio crystallites, which were small enough to
Iridium-based catalysts will not be able to provide a globally
provide efficient charge separation yet sufficiently large to
scalable solution to our energy problem because Ir is the
overcome mass transport limitations, led to highest photo-
scarcest element in earth’s upper crust.8
current generation.88
2. EARTH-ABUNDANT WATER OXIDATION 2.1. Water Oxidation Catalysts Based on First-Row
CATALYSTS Transition Metals
In 1972, Fujishima and Honda showed that TiO2 was capable Bioinspired manganese oxides have also received considerable
of splitting water as both a photoanode (light absorber attention. In 1977, Morita et al. discovered that MnO2
providing holes, h+) and a water oxidation catalyst.57 Although electrocatalytically evolved O2 in alkaline aqueous electrolyte.89
TiO2 is not an efficient catalyst for water oxidation and its large Later, Harriman et al. observed Mn2O3-catalyzed water
band gap Eg of >3.0 eV58 limits its overlap with the solar oxidation.51 Frei et al. reported water oxidation catalysis by
C DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

formed in situ during electrodeposition on indium tin oxide,

was highly active for water oxidation and virtually indefinitely
stable in phosphate buffer at pH 7.106 Further work on this
system demonstrated that CoIV was generated at potentials at
which water oxidation occurred.107 Dau et al., who found that
all cobalt oxide films active for water oxidation featured edge-
sharing CoO6 octahedra, concluded that O−O bond formation
occurred at the edges of the cobalt oxide clusters.108 They
noted that there is no specific “recipe” for synthesizing a
catalyst that works, e.g., specific anions or redox-inactive
cations, but that these factors play a large role in determining
Figure 3. Effect of BiVO4 preparation conditions on photocurrent size and potential.
generation (blue, without; red, with iodide in the electrodeposition Cobalt−oxide water oxidation catalysts have received
bath).88 (Left) Photos of the plating baths, (center) measured attention for more than 65 years. Initial electrochemical
chopped-illumination photocurrent densities as a function of bias characterization of the behavior of cobalt metal in alkaline
potential vs the reversible hydrogen electrode (RHE), (right) SEM conditions indicated that three oxides, namely, CoO, Co2O3,
images of the resulting BiVO4 photoanodes; scale bars are 1 μm.
and CoO2, were accessible under anodic bias.109 The
Experimental details are given in ref 88.
development of alternative structures, such as Co3O4, has
shown increased promise (there has been success incorporating
various nanostructured Mn oxides on mesoporous silica Co3O4 in a silica scaffold).110 Two polymorphs of lithium
supports, with Mn2O3 exhibiting the highest activity.90 Jaramillo cobalt oxide were synthesized by Dismukes et al., and it was
et al. identified layered Na−birnessite MnO2 as an oxygen- determined that the presence of a Co4O4 cubic core was
evolving photoanode material.91 Dau and Kurz et al. prepared indicative of water oxidation activity.111 (We note that this
birnessite Mn oxides with intercalated divalent cations; they cubane motif is present in PS II, albeit with manganese instead
found a Ca2+ > Sr2+ > Mg2+ order for catalytic activities.92 Stahl of cobalt.) Cobalt−manganese hydroxide was more active than
et al. reported that activities of Mn oxides depended on the the respective single-metal oxides.112 Wang and co-workers
choice of oxidation method.93 Many different Mn oxide were able to synthesize size-controlled Co3O4 nanoparticles
precatalysts converted into layered structures under OER without supporting ligands and found that both size control
conditions, as predicted by the Mn−H2O Pourbaix dia- and the absence of ligands that prevented species from diffusing
gram.41,94 Dau and co-workers found that cyclical electro- to the surface were essential for activity.113 In an electro-
chemical deposition of MnO2 produced MnIII sites that were chemical study, Lyons et al. concluded that CoIV was the active
active for water oxidation at pH 7.95 Further, it was shown96 species.114
that as-prepared α-Mn2O3 and Ca−MnIII oxide hydrates, We employed pulsed laser ablation in liquids (PLAL) as a
CaMn2O4·xH2O, catalyzed water oxidation in the presence of technique for the synthesis of surfactant-free, size- and
either Oxone,97 a two-electron oxygen-transfer oxidant composition-controlled < 5 nm cobalt oxide nanoparticles.115
(HSO5−), or CeIV, a one-electron oxidant. As with molecular In PLAL, a high-energy laser pulse is focused on a solid target
iridium precursors, Zaharieva et al. found that the binuclear
that is submerged in liquid. The pulse creates a plasma plume,
manganese complex [(OH 2)(terpy)Mn(μ-O)2Mn(terpy)-
which is confined at high temperature and pressure by the
(OH2)]3+ (terpy is 2,2′;6′,2″-terpyridine) was transformed
liquid. Extreme pressure triggers a shock wave in the confining
into layered Mn oxide particles on clay, which served as the
liquid, causing the plasma to rapidly expand and cool.
active water oxidation catalyst.98 In other work of note,
Jaramillo et al. prepared nanostructured MnIII oxides that Nanoparticles condense out and are injected into the
showed activity similar to noble metals for both water oxidation surrounding liquid. Our Co3O4 nanoparticles synthesized by
and oxygen reduction.99,100 PLAL had an overpotential for water oxidation of 314 mV
Iron oxide water oxidation materials have been heavily (measured at 0.5 mA cm−2), comparing favorably with the best
studied. Iron oxides are appealing materials for globally scalable, electrodeposited cobalt oxide species; our material also featured
clean energy conversion applications because of the abundance a very high mass activity of more than 10 A m−2 g−1 at 500 mV
and low cost of iron. Somorjai et al. determined that the active overpotential (Figure 4).115
optical component of an iron oxide electrode is α-Fe2O3.101 Another first-row transition metal oxide, NiOx, which was
Iron(III) oxide showed excellent long-term stability but had identified as a water oxidation catalyst by Bode in 1966,116 was
low efficiency (0.05%) for solar conversion to H2 and O2.101 studied in depth in the 1980s.117 Soon it was discovered that
The very short hole lifetime of hematite (a few picoseconds)102 even tiny amounts of iron improved the water oxidation activity
presents a major obstacle. Berlinguette et al. found that of NiOx.118,119 In a thorough study of iron incorporation into
amorphous Fe2O3 showed improved water oxidation activity.103 nickel oxide films, Boettcher et al. found that even accidental
By doping Fe2O3 with silicon, Grätzel et al. were able to incorporation of iron enhanced catalytic activity.120 Electro-
increase the conversion efficiency to a theoretical 2.1% in a chemical investigations of nickel oxide electrodes by Lyons et
tandem device.104 Detailed electrochemical studies on al. concluded that the likeliest mechanisms involve NiIII or NiIV,
passivated iron oxide electrodes by Lyons et al. suggested again in a physisorbed peroxide scheme. Lyons et al. did not
that a physisorbed peroxide pathway is dominant and that the invoke multiple oxidation states of nickel, instead using the
active site is a stabilized FeVI species.105 electrode as the hole (h+) acceptor throughout.121 In other
Cobalt oxide (CoOx) is stable only at high pH under positive work, Stahl et al. synthesized an inverse spinel NiFeAlO4
potentials.41 Yet, Nocera et al. found that a heterogeneous material that had an overpotential for water oxidation of 330
catalyst based on CoII phosphate (CoPi), which had been mV at 0.5 mA cm−2 per active nickel.122 Interestingly, the
D DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

dramatically improved by in situ generation of copper oxide

films from a copper(II) ethylenediamine complex.130 A current
density of 10 mA cm−2 was obtained at an overpotential of
∼475 mV in 1.0 M aqueous KOH. It also has been shown that
the extent to which copper complexes perform water oxidation
homogeneously vs heterogeneously is pH dependent.131
Functioning photoelectrochemical (PEC) devices have been
fabricated with copper oxide/silicon photoanodes, showing
good stability and electrocatalytic behavior.132 The current
work on copper-based catalysts is encouraging, but the
electrocatalytic activities of these materials remain far inferior
to Fe-, Co-, and Ni-based systems.
Figure 4. (Left) Mass activity for water oxidation in 1.0 M aqueous Zinc oxide (ZnO) nanowire arrays exhibit a moderate
KOH on flat graphite electrodes as a function of applied potential vs photocurrent density (0.62 mA cm−2 at 1.0 V vs RHE under 1
the normal hydrogen electrode (NHE): yellow, Co3O4 nanoparticles sun illumination) but can be improved by the addition of Co−
synthesized by PLAL at 90 mJ pulse−1; black, commercial 50 μm Pi or Ni−B cocatalysts.133 Importantly, these materials are very
diameter Co3O4 powder. (Right) PLAL preparation of Co3O4 stable to corrosion, showing no loss in photocurrent over
nanoparticles from Co powder in water at different synthesis
prolonged testing. Choi et al. synthesized a spinel-type
durations.
ZnCo2O4 thin film that showed a relatively low overpotential
(390 mV at 10 mV cm−2).134 Although this finding underscored
addition of a redox-inert metal enhanced the water oxidation the advantage of incorporating more active metals, the resulting
activity of this material. material is more active than that of Co3O4 electrodes prepared
The effect of scandium on electrodeposited NiP has been from the same synthesis conditions with comparable thickness
explored.123 Briefly, increasing the Sc2O3 composition in an and morphology. It is unclear whether zinc is playing a direct
amorphous NiP layer lowered the overpotential for water role in catalysis or simply in tuning the redox potential of the
oxidation up to an ideal concentration of ∼10%. Above ∼10%, cobalt material. Similarly, it has been shown that the
a decrease in activity was observed. overpotential of ZnO can be lowered by doping with Mn, Fe,
Very few vanadium-only materials have been tested for water Co, and Ni.135 The largest effect (by almost 150 mV) was seen
oxidation activity. Binary and tertiary materials have been the with cobalt doping.
primary focus, likely because of the poor performance of In other work of note, polyoxometallates based on first-row
vanadium oxide alone. Bismuth vanadate has been employed as transition metals have been shown to act as heterogeneous
a photoanode, as previously discussed; it also is catalytically water oxidation catalysts.136,137 Polyoxometallates (POMs) are
active. Kudo et al. synthesized bismuth vanadates with varying polyoxoanions that can contain between 5 and 50 transition
V:Bi ratios and crystal forms that showed oxygen evolution metal centers. Because of their unusual oxidative stability, high-
rates from 2.5 to 421 μmol h−1 (the best-performing material valent states of the metal atoms are accessible (e.g., NiIV and
was in the monoclinic crystal form) under visible light CrV).138,139 Although most clusters are generally believed to be
irradiation.75 The addition of copper (BiCu2VO6) reduced active in homogeneous solutions, Co4POM has been shown to
the band gap, allowing greater absorption of visible light.124 be a precursor to an active heterogeneous CoOx catalyst. Other
Finally, the addition of a more active metal, such as cobalt, has researchers have utilized POM frameworks to synthesize
been shown greatly to increase the activity of vanadium-based mesoporous structures of first-row transition metal oxides,
catalysts, and binary nanoparticles, such as Co3V2O8, have such as Co3O4.140 These types of hybrid materials are
improved performance.125 promising water oxidation catalysts.141
Several chromium-based catalysts have been screened for Among first-row transition metals, cobalt, iron, and nickel
water oxidation activity. Bockris and Otagawa measured current oxides and hydroxides are most active for water oxidation, at
density in terms of real surface area for a number of perovskites least in alkaline electrolytes. Because higher electrocatalytic
at 0.3 V overpotential.48 They found that the La0.8Sr0.2CrO3 activities have been observed in layered double hydroxides, we
perovskite only passed 3.2 × 10−8 A cm−2, the lowest value turn our attention to this class of materials.
observed with the exception of LaVO3. Solid Cr2O3 also has
2.2. Layered Double Hydroxides
been employed as a water oxidation catalyst under supercritical
conditions, with the active species believed to be chromic acid, Much recent research has focused on layered double hydroxides
H2CrO4.126 On the other hand, small amounts of Cr2O3 on a (LDHs), mineral-like compounds that contain a sheet of
Ba5Ta4O15 perovskite surface produced a stable photoanode, M12+(OH)6 shared-edge octahedra with M23+ atoms occupying
with an oxygen evolution rate of 228 μmol h−1 when some of the M1 sites.142,143 Intercalated anions balance the
illuminated with a 500 W Hg immersion lamp.127 additional positive charge of M23+, while layers between sheets
Copper-based water oxidation catalysts have recently carry water. Dai et al. demonstrated that a composite of α-
attracted attention. Meyer et al. synthesized transparent and Ni(OH)2 on carbon nanotubes was efficient for water
flexible Cu/CuO nanowire films that were active for water oxidation.144 Nickel−titanium LDHs were shown by O’Hare
oxidation. 128 The CuO film prevented electrochemical et al. to be very active photocatalysts.145
corrosion of the material, although the overpotential was 580 On the basis of previous work on iron-doped nickel oxides,
mV at 10 mA cm−2. Other groups have reported using [NiFe]-LDH materials have become a target for many groups.
Cu(OH)2 as an inexpensive, earth-abundant material for water Boettcher et al. suggested that layered structures are particularly
oxidation in base but with similarly high overpotentials.129 useful for highly efficient water oxidation catalysis.146
Recently, the performance of Cu-based catalysts has been Exfoliation of [NiFe]-LDHs into individual layers led to
E DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

increased water oxidation activity.147 Other iron-containing at concentrations as low as 17 nM was shown to catalyze water
LDHs, [MFe]-LDH nanoplatelet arrays where M is Ni, Co, or oxidation in aqueous electrolytes, with stable (tens of hours)
Li, have been prepared by short-time electrodeposition on foam current densities of 1 mA cm−2 at overpotentials as low as 540
nickel substrates; all OER overpotentials were assessed on mV at pH 9.2 and 400 mV at pH 13.154 Thin film nickel oxide
rough supporting electrodes of unknown microscopic area.148 with iron impurities reached 8 mA cm−2 at 230 mV,119 while β-
We used PLAL to synthesize [NiFe]-LDH nanosheet water NiOOH exhibited an overpotential of 500 mV at a current
oxidation catalysts.149 The X-ray diffraction (XRD) patterns of density of 5 mA cm−2.155 Nickel−borates on glassy carbon and
our materials were characteristic of layered double hydroxides, mixed Fe−Ni oxides on carbon paper reached 1 mA cm−2 at
since the intensities of the basal (00l) reflections decreased as l overpotentials of 425 and 375 mV, respectively.156,157
increased.150 The observed reflections were indexed in a three- Amorphous α-Fe20Ni80Ox on fluorine doped tin oxide (FTO)
layer 3R polytype with rhombohedral symmetry, such as in glass had an overpotential of 210 mV at 0.5 mA cm−2.158 The
synthetic hydrotalcite (Figure 5).151 The XRD data of LDH same current density was reached at 265 mV overpotential by
high-surface-area nickel metal oxides,159 and NiOx deposited
from molecular [Ni(en)3]2+ on glassy carbon featured an
overpotential of 390 mV at 0.1 mA cm−2.160
Other iron- and nickel-based catalysts showed higher
overpotentials for water oxidation or they were measured on
high-surface-area electrodes, which leads to an enlargement of
the electrode substrate surface area relative to the apparent
geometric area, thereby inflating overpotential numbers. Thin-
film solution-cast Ni0.9Fe0.1Ox reached 10 mA cm−2 at 336 mV
overpotential,146 while electrodeposited NiFeOx reached the
Figure 5. (Left) Schematic illustration152 of the structure of [NiFe]- same current density at 360 mV.153 A similar result was
LDH nanosheet water oxidation catalysts.149 (Center) Indexed XRD obtained with nanostructured α-Ni(OH)2 (331 mV at 10 mA
data that evidence the layered double-hydroxide structure of our cm−2).161 With an iron content of 40%, thin-film electro-
materials. (Right) Photo of [NiFe]-LDH nanosheets during water deposited Ni−Fe on gold yielded an overpotential of 280
oxidation catalysis under anodic bias in aqueous alkaline electrolyte. mV.162 A graphene FeNi double hydroxide material was
reported on a nickel foam electrode with unspecified pore size
materials provide rich information on the basal spacing, the and thus real electrode area.163 Very recently, homogeneously
interlamellar electron density stemming from interlayer water dispersed Fe−Co−W oxyhydroxide gels were reported to have
and anions, and the nanosheet size, i.e., lateral diameter and overpotentials of ≥315 mV on flat Au electrodes.164
stack thickness.150
The [NiFe]-LDH nanosheet water oxidation catalysts 2.3. Looking Forward
synthesized by PLAL showed outstanding performance on The overpotentials for water oxidation for many catalysts are
flat graphite electrodes; the best catalyst had a 260 mV within the range needed to construct viable devices, but there is
overpotential at 10 mA cm−2.149 Overpotentials of earth- still a need to optimize the photoanode/catalyst junction. Light
abundant catalysts at 10 mA cm−2 typically range from 350 to capture in the presence of a catalyst remains a concern, since
430 mV in pH 14 aqueous electrolytes153 (Figure 6). We note parasitic light absorption, reflection, and scattering by catalyst
particles or layers reduce the efficiency of a device. In addition,
optical properties related to the size of the catalyst material
become important, especially once devices become highly
functional. Employing optimally sized catalyst particles may
mitigate light reflection and scattering. These constraints
dictate that catalyst mass activity must be high, since using
less catalyst overall will improve device performance. Smaller
catalysts such as nanoparticles, however, have a tendency to
aggregate; methods must be developed for robust attachment
Figure 6. Comparison of overpotentials of our (1−3)149 and other under the demanding conditions of water oxidation.
(4−7)153 reported water oxidation electrocatalysts operating in 1.0 M Clearly, it is difficult to pinpoint a common characteristic that
aqueous base. Materials are Ti- and La-doped [NiFe]-LDH nanosheets makes earth-abundant water oxidation catalysts particularly
(1), Ti-doped [NiFe]-LDH nanosheets (2), [NiFe]-LDH nanosheets active or inactive. We can say, however, that particle size and
with 22% Fe (3), IrOx (4), NiFeOx (5), CoOx (6), and NiOx (7). method of preparation are both centrally important. Ion and
electron conductivity165 as well as carrier mobilities through the
materials also matter.
that McCrory tested the activities of our PLAL-made Co3O4
water oxidation catalysts and confirmed the overpotentials we
reported.115 His findings suggest that our overpotential 3. MECHANISTIC CONSIDERATIONS
assessment method was equivalent to the benchmarking A major challenge is obtaining a clearer mechanistic picture of
technique reported by McCrory, Peters, and Jaramillo et water oxidation. Elucidation of atomistic details during turnover
al.,153 indicating that electrocatalytic activities of different is no easy feat, since most highly active earth-abundant
materials are directly comparable between the two laboratories. heterogeneous catalysts are multimetal materials. What is the
Other nickel-based materials have been reported with site of catalysis? Are all metals catalytically active, or are some
overpotentials at current densities other than 10 mA cm−2, species simply necessary to tune the electronics of the system?
rendering a direct comparison problematic. Adventitious nickel What is the local structure? Are catalytic sites comprised of one
F DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

or more metal centers? Also, are oxidized active sites

electronically localized or delocalized? These questions are
difficult to answer, particularly because catalytically active
transient species are short lived by definition. Experiments that
detect such transient intermediates spectroscopically while the
material is under positive potentials and immersed in
electrolyte are badly needed.
3.1. Lessons from Nature
The vast body of research on photosynthetic oxygen evolution
highlights the enormous scientific challenges associated with
gaining mechanistic information on complex, heterogeneous
systems during catalytic turnover. Nature’s way of evolving
oxygen in PS II may serve as a mechanistic model for manmade Figure 7. Schematic S-state cycle of the PS II WOC, including the
heterogeneous water oxidation. However, the mechanism of PS likely oxidation states of metal ions.13,180,181 The catalytic cycle
II catalysis is still hotly debated. consists of the states S0−S4, where the subscript denotes the number
The first mechanistic proposal was set forth by Blackman and of oxidizing equivalents abstracted from the WOC.13 Photons (hν),
Matthaei in 1905, when they suggested that photosynthesis is a electron (e−), proton releases, and substrate turnovers are also shown.
two-step process: a photochemical (light) reaction and a light-
independent (dark) reaction that required elevated temperature smaller, isolated PS II complex, which retained full activity for
and was thus indicative of an enzymatic reaction.166 In the oxygen evolution.179
1920s, Warburg observed that the rate of photosynthesis was Great progress has been made in understanding the
inhibited by high oxygen concentrations and postulated that biochemistry of PS II, since Deisenhofer, Huber, and Michel
oxygen was produced from CO2 during photosynthesis; this is (Nobel Prize in Chemistry in 1988) determined the three-
known as the Warburg hypothesis.167−169 Many scientists dimensional structure of a photosynthetic reaction center.
agreed with Warburg that the primary reaction in photosyn- Their work established the architecture of trans-membrane
thesis was the splitting of CO2 by light into oxygen and carbon, proteins, quinones and cytochromes. This structural informa-
which would subsequently be reduced to carbohydrates by tion can be used analogously as the scaffold around the WOC
water. Van Niel presented a fundamentally different view in the in PS II. Work by Marcus on the theory of electron transfer
1930s from his work on anaerobic sulfur bacteria. He reactions in chemical systems (Nobel Prize in Chemistry in
demonstrated that photosynthesis is a light-driven redox 1992) inspired work by Debus, Barry, Babcock, and McIntosh
reaction following the general equation CO2 + 2H2A + in 1988, which provided the first molecular biological evidence
photons → [CH2O] + 2A + H2O, where [CH2O] is a that tyrosine radicals are involved in long-range electron
carbohydrate and A an electron acceptor. Van Niel’s discovery transfer through P680.182,183 Importantly, the tyrosine electron
predicted that water is split into hydrogen and oxygen.170 In carriers mediate the sequential electron transfers through the
1937, Hill investigated the light-driven transfer of electrons PS II protein machinery to cycle the WOC through its
from water to nonphysiological oxidants in isolated chloroplasts intermediates at moderate potentials (see Introduc-
and found that oxygen was generated in the absence of carbon tion).13,184,185
dioxide.171−173 The development of advanced electron paramagnetic
A major breakthrough came in 1941 at the dawn of resonance (EPR) and X-ray spectroscopy and diffraction
radioisotope tracer studies, when 18O-labeling experiments by techniques enabled the determination of increasingly refined
structures of the CaMn4O5 WOC.186−189 Britt et al. were the
Ruben and co-workers established that oxygen in photosyn-
first to demonstrate a CaMn3O4 cubane structure with an Mn
thesis came from water rather than from carbon dioxide.174 In
dangler from EPR data.190,191 Barber et al. obtained a 3.5 Å
addition to this landmark publication, Ruben and Kamen
resolution X-ray diffraction structure of the WOC in 2004,
discovered the long-lived radioactive carbon isotope 14C in which confirmed Britt’s cubane/Mn dangler motif, but the
1940,175 which paved the way for the elucidation of carbon reported interatomic distances indicated partial reduction of the
pathways in photosynthetic metabolism by Calvin, for which he CaMn4O5 cluster by the X-ray beam.192,193 Two years later,
received the Nobel Prize in Chemistry in 1961. Isotope-labeling Messinger, Zouni, Yachandra, and co-workers examined the
studies remain some of the most powerful ways to elucidate the structure of the manganese−calcium water-splitting complex of
mechanisms of homogeneous and heterogeneous water PS II using X-ray pulses from a femtosecond free-electron laser
oxidation catalysts. They allow for spectroscopic determination source; the short time scale of the X-ray pulses minimized
of intermediates and tracking of products from substrates. radiation damage because diffraction data were collected before
By the mid-20th century, PS II was still a black box regarding beam-induced reduction of the WOC could occur.194 Finally, in
its structure and molecular mechanism. Groundbreaking work 2011, Shen, Kamiya et al. reported a crystal structure of the
by Joliot et al. in the 1960s established that the yield of oxygen WOC with 1.9 Å resolution and located all of the metal atoms
evolution in the water-splitting enzyme system follows a period- of the Mn4CaO5 cluster together with all of their ligands, again
four oscillation upon irradiation with saturating light verifying the Barber CaMn3O4 cube structure with a manganese
flashes.176−178 In 1970, Kok developed a kinetics scheme, dangler that is connected to the cube via an O bridge.11
known as the Kok or S-state cycle for PS II oxygen evolution Knowledge of the WOC structure enabled more detailed
(Figure 7).13 Further insights into the mechanism of water mechanistic insights into oxygen formation from water. The
oxidation on a molecular scale were enabled by the advent of WOC catalyzes water oxidation to O2 with a maximal turnover
gene sequencing and the discovery of the BBY preparation of a frequency of ∼500 s−1 and a high turnover number of 106,195
G DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

indicating that nature solved the difficult problems of four- following reactions: water dissociation, OH disproportionation,
electron oxidation to form molecular oxygen and simultaneous OOH formation, OOH dissociation that resulted in O2
avoidance of excessive oxidative damage to the enzyme. Several formation, and finally H dissolution to form an electron and
key questions remained unanswered: How does the substrate a solvated proton.215 In other reports of note, Llobet et al.
for oxygen evolution bind, how does it turn over, and what are reviewed O−O bond formation pathways promoted by Ru
the molecular intermediates? Also what are the oxidation states complexes,216 such as the “blue dimer”, whose water oxidation
of the individual manganese centers associated with each S mechanism has been studied in great detail,217−221 and Nocera
state? Dismukes et al. established the manganese oxidation et al. discussed electronic design criteria for O−O bond
states of the S2 state.196 Cox, Lubitz et al. characterized the S3 formation via metal oxos.222
state (the intermediate directly prior to O−O bond formation) Manganese oxides support multiple metal oxidation states,223
and reported that all manganese centers are in the IV oxidation facilitating four-electron water oxidation. Manganese oxides
state.181 Three competing models predict how molecular occur in many different compositions and crystal phases, which
oxygen is formed and through which pathway the S3 state affect OER activity.224,225 Kinetics measurements on MnO2
spontaneously decays to the S0 resting state, closing the catalysts suggested that surface MnIII sites were active.226 The
catalytic cycle.197 Babcock proposed a metalloradical hydrogen mechanism involved fast Mn oxidation coupled to deprotona-
abstraction mechanism, where S0 is directly formed from S3 tion, followed by a slower chemical step.95 The basicity of
with concomitant O2 release.198 Yet, structural data from high- surface oxido bridges may assist in proton abstraction from
resolution X-ray experiments are not in accord with a direct O2 substrate water.92 Najafpour et al. detected MnII and
generation mechanism.11 Brudvig suggested that a single MnV permanganate upon MnO2-catalyzed water oxidation in the
oxo species could form an O−O bond with a Ca2+-bound presence of CeIV ammonium nitrate.227 Undercoordinated
hydroxide or water in the S4 transient.199,200 However, MnIIIO5 units at amorphous boundaries were essential for high
Siegbahn obtained DFT results that favored radical O−O activity.228 Nocera et al. obtained enhanced activity upon a
coupling in S4 involving a MnIV−oxyl.201,202 Recent work phase change of the birnessite MnO2 precatalyst.229 They also
revealed that NH3 binds at the dangler Mn site but not in a discovered that different mechanisms were operative, depend-
bridging position; this finding supports both high-valent Mn− ing on pH: a one-electron one-proton PCET pathway
O models.203 Molecular oxygen is released about 1 ms after the dominated in alkaline conditions, whereas MnIII disproportio-
fourth photon is absorbed,195,204 rendering structural determi- nation occurred in acid.230
nation of the S4 species particularly difficult. Work by Zaharieva and Dau et al. has shown that disordering
The lessons learned in photosynthetic WOC research should of initially more crystalline birnessite structures led to better
be of help in investigations of earth-abundant heterogeneous catalytic performance. Similarly, amorphous cobalt, iron, and
catalysts.205 The higher stability of metal (hydr)oxide materials nickel oxides exhibited higher activities than crystalline bulk
compared to PS II facilitates mechanistic work. Also helpful is counterparts.103,158,231 Amorphization may not be necessary in
the availability of analytical and spectroscopic methods that small, nanoparticulate materials, where lattice strains from
have been developed in the course of PS II work. Yet, even in rearrangements during turnover may be dissipated due to
robust materials, highly active species are short lived and the favorably large surface-to-volume ratios.
identification of catalytic pathways remains challenging. Mechanisms of cobalt oxide-catalyzed water oxidation have
3.2. Heterogeneous Water Oxidation Catalysts also been studied. A possible mechanism based on reports
outlined below is shown in Figure 8. Currently, there is broad
In heterogeneous catalysts, only small numbers of metal centers
consensus that two cofacial surface Co(O)OH moieties
are active.206 Inactive sites are likely needed to keep the
undergo two initial oxidations and deprotonations to generate
material intact by providing an environment around an active
terminal CoIV oxos. Substrate water turnover likely produces a
site that supports high oxidation states required for water
oxidation, by acting as hole reservoirs, by assisting in surface-bound peroxo species, which converts to a superoxo
deprotonations, or by tuning redox potentials. Ligands assume intermediate that may be bridging. Addition of a second water
this role in molecular catalysts, polypeptide chains in
biocatalysts. In the case of water oxidation, there is intense
debate if catalysis proceeds in a homo- or heterogeneous
fashion.207 Robust, highly active, inorganic materials have
largely regular, periodic structures, and only a few special sites
are catalytically active, rendering their identification during
turnover particularly challenging.
Great strides have been made with single-metal electro-
catalysts, both computationally and experimentally. Rossmeisl
et al. used density functional theory (DFT) calculations to shed
light on water oxidation reactions on metal oxide surfaces that
involve surface-adsorbed OOH intermediates.208−210 Nørskov
et al. described how computational methods provide
mechanistic understanding essential for the design of new
catalysts, with much emphasis on thermochemical volcano
plots.211−214 Fortunelli and Goddard et al. examined OER rate-
limiting steps and barriers associated with fundamental reaction Figure 8. Possible mechanism of cobalt oxide-catalyzed water
steps on Pt(111) surfaces in silico. They assumed a reaction oxidation. Co3O4 structure232 is depicted in the center. Colors: CoII,
pathway in which surface-adsorbed species underwent the cyan; CoIII, green; O, gray.

H DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

molecule, together with loss of the fourth proton and electron, balance additional positive charges that arise from FeIII
leads to O2 release. occupying NiII sites; water is also intercalated.142 Hence, NiII
Using DFT calculations, Van Voorhis et al. predicted and FeIII constitute the resting state of this catalyst. Corrigan
energetics and barriers for water oxidation in a Co4O4 cubane and Boettcher et al. noted that Fe is required for high water
cluster.233 They suggested a mechanism in which the resting oxidation activity,118−120 suggesting that iron is a component of
state, a (surface) μ-oxo-bridged CoIII hydroxide dimer, the active site. On the basis of mechanisms occurring in nature
underwent metal oxidations. Radical coupling of two cofacial and monometallic heterogeneous catalysts, oxidation states
CoIV oxo groups formed an O−O single bond. Two substrate higher than in the resting state must be generated during
turnover steps followed by proton transfer closed the catalytic turnover.
cycle. In contrast, computations by Berlinguette and Baik et al. Yet, Friebel and Bell et al. identified mononuclear FeIII as the
favored a mononuclear biradicaloid mechanism.234 Siegbahn et active site by DFT calculations and operando X-ray absorption
al., who performed calculations on several Co oxide model spectroscopy (XAS) experiments on electrodeposited
clusters, pointed out that cobalt (in contrast to manganese in [NiIIFeIII]-LDH catalysts in strong aqueous base. They
PS II) prefers low-spin coupling in the relevant high oxidation observed edge shapes that were unusual for octahedrally
states, forcing a change of electronic structure during O−O coordinated FeIII and a shortening of the Fe−O distance but
bond formation. They postulated that a CoIV−oxyl radical excluded FeIV based on their data. Instead, they invoked
would be needed for reactivity,235 similar to their proposed inductive ligand effects, where oxidized Ni ions withdrew
mechanism for PS II.201,202 Dismukes et al. showed that one of charge from O ligands shared with Fe centers, thus disfavoring
the studied clusters, the “Dismukes Co4O4 cubane”, did not FeIII oxidation; a small amount of tetrahedrally coordinated
react with water; instead, two hydroxide ions led to O2 FeIII may also have been present.248 Higher valent Fe species
formation by an inner-sphere mechanism.236 Water oxidation were likely too short lived under turnover conditions in this
may be catalyzed by CoII impurities in CoIII4O4 cubanes.237 In highly active catalyst to be detected by XAS, where the signal
other work of note, Tilley et al. found spectroscopic evidence was overwhelmingly that of inactive FeIII.
for a highly oxidized terminal oxo intermediate in a Co4O4 Stahl et al. used operando Mössbauer spectroscopy during
cubane model compound; turnover required hydroxide.238 water oxidation catalysis in alkaline aqueous electrolyte and
Nocera, Britt et al. detected CoIV species by in situ EPR and identified FeIII and FeIV in isotopically enriched [NiFe]-LDH
X-ray techniques in water oxidation catalysts generated via materials, which were synthesized hydrothermally. Data
electrodeposition from aqueous solutions containing phosphate acquisition times ranged from 18 to 24 h. The FeIV species
and CoII (CoPi).107,239 Phosphorus NMR data supported the appeared when applied anodic potentials were high enough for
idea that electrocatalytically active CoPi resembled an LDH water oxidation, and FeIV remained for many hours even after
with phosphate ions located in the interlamellar galleries.240 the applied potential was lowered below the onset of catalysis.
Frei et al. identified oxidized Co species in Co3O4 nanocatalysts Therefore, the detected FeIV was not deemed kinetically
during turnover by in situ infrared spectroscopy.241 In other competent to serve as the site of water oxidation;249 in other
work, time-dependent redox titration experiments on CoPi by words, FeIV was not on path of the [NiFe]-LDH catalytic cycle.
Bard et al. indicated that both CoIII and CoIV oxidized water, Bard et al. observed “fast” and “slow” kinetics in electro-
with pseudo-first-order rate constants of 0.19 and >2 s−1, deposited [NiFe]-LDH films by surface interrogation scanning
respectively.242 electrochemical microscopy (SI-SECM).250 This technique
Obtaining structural and mechanistic details of heteroge- allows for spatially resolved quantitative detection of redox-
neous catalysts during turnover is more straightforward with active surface species, without spectroscopic identification of
monometallic materials. However, activities of multimetallic, individual intermediates. Time-dependent redox titrations
earth-abundant catalysts are much higher, presumably because revealed associated kinetics; notably, unusually high densities
redox potentials and catalytic pathways are fine tuned by of catalytically participating metal sites (∼300 atoms nm−2)
involving multiple metal species. For example, at a water were observed, indicating fast hole conduction through [NiFe]-
oxidation overpotential of 280 mV, PLAL-made Co3O 4 LDH. For comparison, similar SI-SECM studies on Co3O4 and
nanoparticles exhibited a current density of only 0.1 mA IrO2 yielded densities of 11 and 25 nm−2, respectively.242,251
cm−2, whereas [NiFe]-LDH nanosheets reached 10 mA cm−2; We recently investigated the effect of interlayer anions on
both materials, which we investigated under virtually the same water oxidation activity of PLAL-made [NiFe]-LDH nano-
conditions in strong aqueous base on flat graphite supporting sheets in strong aqueous base (Figure 9). We found that
electrodes, had 100% faradaic efficiency.115,149 carbonate replaced other interlayer anions in alkaline aqueous
Some progress has been made in studies of even more electrolyte in ambient air. Carbonate is of course ubiquitous
complex materials. Bockris et al. investigated the mechanism of and self-buffered in strong aqueous base in ambient air, as it is
oxygen evolution on perovskites and found that OH desorption favored by dissolution speciation of CO2 at high pH.252 We
was the rate-limiting step.243 Shao-Horn et al. observed discovered that carbonate-containing [NiFe]-LDH nanosheets
amorphization of select, highly active perovskite OER were much more active and stable than corresponding nitrate
catalysts.244,245 Surface reorganization, electronic structure, catalysts, which we assessed in carbonate-free electrolyte in an
and participation of lattice oxygen in the mechanism were inert atmosphere.253 Hence, all water oxidation electrocatalysis
assessed to rationalize trends in OER activities of cobaltite in high pH aqueous electrolyte in ambient air occurs in the
perovskites.246,247 presence of carbonate, which facilitates catalytic turnover.
Layered materials, especially [NiFe]-LDHs with approx- We observed a sigmoidal dependence of OER activity on
imately 20−40% Fe, have recently attracted much attention anion basicity. In plots of overpotentials, which we determined
(see also previous section). They consist of slabs of NiII(OH)6 in carbonate-free electrolyte, as a function of the pKa values of
edge-shared octahedra with FeIII centers substituting Ni sites. the conjugate acids of the interlayer anions, we found an
Anions in the interlamellar space between the stacked slabs apparent pKa of (3.4 ± 0.7) during turnover. Mechanistically,
I DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

Mechanistic work suggests that high-valent metal−oxo centers

that are accessible at moderate anodic potentials promote
electrocatalytic activity. Importantly, the availability of holes in
the vicinity surface-accessible sites also enhances the perform-
ance of catalytic materials.

4. PARTING SHOTS
In this review, we covered recent advances in the design,
synthesis, and performance of heterogeneous catalysts that
potentially could be functional components of globally scalable
devices for the production of solar fuels. We discussed the
catalytic properties of mixed-metal materials, with emphasis on
robust Ni−Fe layered double hydroxide nanosheet catalysts
Figure 9. Schematic of a [NiIIFeIII]-LDH structure in strong aqueous that exhibit exceptional activities, and we pointed out that
base (left). Overpotentials of [NiFe]-LDH catalysts with the formula strategic incorporation of anions into these layered catalysts
[Ni0.78Fe0.22(OH)2](Am−)(0.22−n)/m(OH−)n·xH2O and different inter-
improved both stability and activity. We emphasized the
layer anions Am− at 1.0 mA cm−2 (adapted from ref 253; right).
challenges associated with the design of acid-stable earth-
abundant catalysts and offered proposals for elements that
our results imply that interlayer anions act as Brønsted bases could be incorporated in functional systems.
that assist deprotonation or Lewis bases, which lower oxidation We highlighted how lessons from nature in combination with
potentials at the active site. The apparent pKa of 3.4 suggests identification of catalytic intermediates in manmade materials
that a higher valent metal oxo species is a catalytically active aid the development of superior catalysts. We believe that
intermediate.253 further advances in this field will depend to a large measure on
We also probed the likely sites of water oxidation (i.e., at the success of mechanistic work, unraveling the details of the
edges or within the [NiFe]-LDH nanosheets). XPS data in complicated proton-coupled electron transfer processes needed
combination with DFT calculations suggested that a previously for efficient water oxidation.
unassigned N 1s species in the precatalyst, which correlated Moving forward, we must develop innovative ways to meet
with higher water oxidation activity,149 was nitrite bound our energy demand in a scalable, environmentally benign
through its N atom to edge-site iron.253 Further support for fashion. In one relevant area, we are encouraged that great
water oxidation occurring at edge sites came from our strides have been made in developing potentially scalable
observation that catalytic activity did not correlate with basal heterogeneous water oxidation catalysts for the conversion of
spacings of various [NiFe]-LDH nanosheet materials, which we solar photons to chemical fuels.
prepared with different interlayer anions; slab-to-slab distances
would only matter if reactants and products had to diffuse AUTHOR INFORMATION
through the interlamellar galleries. Our findings indicate that Corresponding Authors
edge-site Fe plays a major role in water oxidation catalysis in
*E-mail: [email protected].
[NiFe]-LDH nanosheets.253
*E-mail: [email protected].
Why does iron improve the water oxidation activity of many
mixed-metal oxide/hydroxide catalysts? Could it be related to Author Contributions
the ease of generation of high-valent oxos on the left side of the The manuscript was written through contributions of all
oxo wall?254 Is it really that simple? Surely manganese should authors. All authors have given approval to the final version of
be well suited for water oxidation if a high-valent metal−oxo the manuscript.
center were the only criterion. However, we know that Notes
inorganic and biological manganese oxo clusters differ greatly
in water oxidation activity. Why is the manganese−calcium The authors declare no competing financial interest.
cluster in PS II so much better than purely inorganic Mn Biographies
compounds? We think it likely that noncovalent peptide−
cluster interactions elevate the reduction potentials of the Bryan M. Hunter is a graduate student in Professor Harry Gray’s group
various Ca−Mn−oxo redox states, making water oxidation at the California Institute of Technology. He uses in situ spectros-
energetically feasible. Of course multiple oxidizing equivalents copies to elucidate water oxidation mechanisms of heterogeneous,
(holes) must be coupled to the active center (or centers) to earth-abundant catalysts. He graduated from Yale University in 2008,
support the removal of electrons from initially generated simultaneously receiving his B.S. and M.S. degrees in Chemistry with
“oxidized-oxo” (peroxo?) intermediates to promote the Distinction. While at Yale, he performed research in Professor Gary
reductive elimination of oxygen. In PS II, the required holes Brudvig’s group that focused on determining covalent bonding modes
can be stored within the cluster complex itself; in a of siloxane adsorbates on TiO2. He then spent a year as Adjunct
heterogeneous Fe−Ni catalyst, we suggest that hole transfer Instructor and Research Associate at Occidental College in Los
from electro- (or photo-) generated oxidized nickel centers to Angeles with Professor Michael Hill. At Caltech, he was awarded a
nearby iron active sites would produce Fe−oxos capable of Resnick Graduate Research Fellowship in 2015 and an NSF Graduate
oxidizing water. Research Fellowship in 2011. He received the Wohlenberg Prize from
In summary, water oxidation is essential for the storage of Berkeley College at Yale University in 2008 and was a 2004
solar energy in chemical fuels. Catalysts for this critical four- Presidential Scholar.
electron−four-proton reaction must be highly active, robust, After completing a doctoral thesis on inorganic reaction mechanisms
and based on nonprecious elements to enable global scalability. at Northwestern University and working on ligand field theory as a

J DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

postdoctoral fellow in Copenhagen, Harry Gray joined the chemistry REFERENCES

faculty at Columbia University, where in the early 1960s he (1) Gray, H. B. Powering the Planet with Solar Fuel. Nat. Chem.
investigated the electronic structures of metal complexes. He moved 2009, 1 (1), 7−7.
to Caltech in 1966, where he is the Arnold O. Beckman Professor of (2) Lewis, N. S.; Nocera, D. G. Powering the Planet: Chemical
Chemistry and the Founding Director of the Beckman Institute. As Challenges in Solar Energy Utilization. Proc. Natl. Acad. Sci. U. S. A.
Director of NSF CCI Solar Fuels, he works with colleagues on 2006, 103 (43), 15729−15735.
inorganic photochemistry as well as on discovery and investigation of (3) International Energy Agency: World Energy Outlook, 2015.
redox catalysts. Other interests include inorganic electronic structure (4) Lewis, N. S.; Crabtree, G. Basic Research Needs for Solar Energy
and mechanism and biological inorganic chemistry. Utilization: Report of the Basic Energy Sciences Workshop on Solar
Energy Utilization, Apr 18−21, 2005. US Department of Energy Office
Astrid M. Müller obtained her Ph.D. degree in Chemistry from the of Basic Energy Sciences, 2005.
Ludwig-Maximilians-Universität München (Germany) for her work at (5) Davis, S. J.; Caldeira, K.; Matthews, H. D. Future CO2 Emissions
the Max-Planck-Institute of Quantum Optics in Professor Karl-Ludwig and Climate Change from Existing Energy Infrastructure. Science 2010,
Kompa’s group. She moved to the United States through a DFG 329 (5997), 1330−1333.
Fellowship. After postdoctoral work with Professor Stephen R. Leone (6) Vinyard, D. J.; Ananyev, G. M.; Dismukes, G. C. Photosystem II:
at University of Colorado Boulder and the University of California, the Reaction Center of Oxygenic Photosynthesis. Annu. Rev. Biochem.
Berkeley and with Professor Christopher J. Bardeen at University of 2013, 82, 577−606.
California, Riverside, she joined the Beckman Institute at Caltech as a (7) http://www.breakthroughenergycoalition.com.
Staff Scientist. Her current research focuses on the development of (8) Haxel, G. B.; Hedrick, J. B.; Orris, G. J.; Stauffer, P. H.; Hendley,
J. W., II Rare Earth Elements: Critical Resources for High Technology;
novel materials for solar energy conversion into storable, carbon-
USGS, 2002.
neutral fuels that are essential to sustainably power the planet.
(9) Wood, P. M. The Potential Diagram for Oxygen at pH 7.
Biochem. J. 1988, 253 (1), 287−289.
ACKNOWLEDGMENTS (10) Britt, R. D. In Oxygenic Photosynthesis: The Light Reactions; Ort,
D. R., Yocum, C. F., Heichel, I. F., Eds.; Springer: Dordrecht,
We thank Dave Britt and Troy Stich for helpful discussions. Netherlands, 1996.
Research was performed in the Laser Resource Center and the (11) Umena, Y.; Kawakami, K.; Shen, J.-R.; Kamiya, N. Crystal
Molecular Materials Research Center of the Beckman Institute Structure of Oxygen-Evolving Photosystem II at a Resolution of 1.9 Å.
of the California Institute of Technology. The NSF CCI Solar Nature 2011, 473 (7345), 55−60.
Fuels Program (CHE-1305124) and the Arnold and Mabel (12) Meyer, T. J.; Huynh, M. H. V.; Thorp, H. H. The Possible Role
Beckman Foundation supported this work. B.M.H. is a fellow of of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by
the Resnick Sustainability Institute at Caltech. Photosystem II. Angew. Chem., Int. Ed. 2007, 46 (28), 5284−5304.
(13) Kok, B.; Forbush, B.; McGloin, M. Cooperation of Charges in
Photosynthetic O2 Evolution−I. A Linear Four Step Mechanism.
ABBREVIATIONS Photochem. Photobiol. 1970, 11 (6), 457−475.
AEM alkaline exchange membrane (14) Brudvig, G. W. Water Oxidation Chemistry of Photosystem II.
Am− anion Philos. Trans. R. Soc., B 2008, 363 (1494), 1211−1219.
DFT density functional theory (15) Cukier, R. Mechanism for Proton-Coupled Electron-Transfer
Reactions. J. Phys. Chem. 1994, 98 (9), 2377−2381.
E0 thermodynamic potential
(16) Cukier, R. Proton-Coupled Electron Transfer through an
Eg band gap Asymmetric Hydrogen-Bonded Interface. J. Phys. Chem. 1995, 99 (43),
e− electron 16101−16115.
en ethylenediamine (17) Hammes-Schiffer, S. Theoretical Perspectives on Proton-
EPR electron paramagnetic resonance Coupled Electron Transfer Reactions. Acc. Chem. Res. 2001, 34 (4),
g gaseous 273−281.
HER hydrogen evolution reaction (18) Hammes-Schiffer, S. Introduction: Proton-Coupled Electron
hν photon Transfer. Chem. Rev. 2010, 110 (12), 6937−6938.
h+ hole (19) Kanady, J. S.; Tsui, E. Y.; Day, M. W.; Agapie, T. A Synthetic
l liquid, Miller index Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in
LDH layered double hydroxide Photosystem II. Science 2011, 333 (6043), 733−736.
NHE normal hydrogen electrode (20) Zhang, C.; Chen, C.; Dong, H.; Shen, J.-R.; Dau, H.; Zhao, J. A
Synthetic Mn4Ca-Cluster Mimicking the Oxygen-Evolving Center of
OER oxygen evolution reaction
Photosynthesis. Science 2015, 348 (6235), 690−693.
PCET proton-coupled electron transfer (21) Borovik, A. S. Bioinspired Hydrogen Bond Motifs in Ligand
PEC photoelectrochemical Design: the Role of Noncovalent Interactions in Metal Ion Mediated
Pi phosphate Activation of Dioxygen. Acc. Chem. Res. 2005, 38 (1), 54−61.
PLAL pulsed-laser ablation in liquids (22) Vrettos, J. S.; Limburg, J.; Brudvig, G. W. Mechanism of
PS II photosystem II Photosynthetic Water Oxidation: Combining Biophysical Studies of
RHE reversible hydrogen electrode Photosystem II with Inorganic Model Chemistry. Biochim. Biophys.
SI-SECM surface interrogation scanning electrochemical mi- Acta, Bioenerg. 2001, 1503 (1), 229−245.
croscopy (23) Tsui, E. Y.; Tran, R.; Yano, J.; Agapie, T. Redox-Inactive Metals
WOC water-oxidizing complex Modulate the Reduction Potential in Heterometallic Manganese−
XAS X-ray absorption spectroscopy Oxido Clusters. Nat. Chem. 2013, 5 (4), 293−299.
XPS X-ray photoelectron spectroscopy (24) McKone, J. R.; Lewis, N. S.; Gray, H. B. Will Solar-Driven
Water-Splitting Devices See the Light of Day? Chem. Mater. 2014, 26
XRD X-ray diffraction
(1), 407−414.
(25) Parkinson, B. On the Efficiency and Stability of Photo-
electrochemical Devices. Acc. Chem. Res. 1984, 17 (12), 431−437.

K DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

(26) Khaselev, O.; Turner, J. A. A Monolithic Photovoltaic- (45) Load changes, as they occur in sun-light-driven devices because
Photoelectrochemical Device for Hydrogen Production via Water of the diurnal nature of solar illumination, will be another major
Splitting. Science 1998, 280 (5362), 425−427. consideration regarding optimal pH conditions.
(27) Newman, J.; Hoertz, P. G.; Bonino, C. A.; Trainham, J. A. (46) Kim, J.; Yin, X.; Tsao, K.-C.; Fang, S.; Yang, H. Ca2Mn2O5 as
Review: an Economic Perspective on Liquid Solar Fuels. J. Electrochem. Oxygen-Deficient Perovskite Electrocatalyst for Oxygen Evolution
Soc. 2012, 159 (10), A1722−A1729. Reaction. J. Am. Chem. Soc. 2014, 136 (42), 14646−14649.
(28) Tachibana, Y.; Vayssieres, L.; Durrant, J. R. Artificial (47) Diaz-Morales, O.; Ledezma-Yanez, I.; Koper, M. T.; Calle-
Photosynthesis for Solar Water-Splitting. Nat. Photonics 2012, 6 (8), Vallejo, F. Guidelines for the Rational Design of Ni-Based Double
511−518. Hydroxide Electrocatalysts for the Oxygen Evolution Reaction. ACS
(29) Osterloh, F. E. Inorganic Nanostructures for Photoelectrochem- Catal. 2015, 5 (9), 5380−5387.
ical and Photocatalytic Water Splitting. Chem. Soc. Rev. 2013, 42 (6), (48) Bockris, J. O.; Otagawa, T. The Electrocatalysis of Oxygen
2294−2320. Evolution on Perovskites. J. Electrochem. Soc. 1984, 131 (2), 290−302.
(30) Pinaud, B. A.; Benck, J. D.; Seitz, L. C.; Forman, A. J.; Chen, Z.; (49) Mauritz, K. A.; Moore, R. B. State of Understanding of Nafion.
Deutsch, T. G.; James, B. D.; Baum, K. N.; Baum, G. N.; Ardo, S.; et al. Chem. Rev. 2004, 104 (10), 4535−4586.
Technical and Economic Feasibility of Centralized Facilities for Solar (50) Carmo, M.; Fritz, D. L.; Mergel, J.; Stolten, D. A
Comprehensive Review on PEM Water Electrolysis. Int. J. Hydrogen
Hydrogen Production via Photocatalysis and Photoelectrochemistry.
Energy 2013, 38 (12), 4901−4934.
Energy Environ. Sci. 2013, 6 (7), 1983−2002.
(51) Harriman, A.; Pickering, I. J.; Thomas, J. M.; Christensen, P. A.
(31) Döscher, H.; Geisz, J. F.; Deutsch, T. G.; Turner, J. A. Sunlight
Metal Oxides as Heterogeneous Catalysts for Oxygen Evolution under
Absorption in Water−Efficiency and Design Implications for Photo-
Photochemical Conditions. J. Chem. Soc., Faraday Trans. 1 1988, 84
electrochemical Devices. Energy Environ. Sci. 2014, 7 (9), 2951−2956. (8), 2795−2806.
(32) Gu, S.; Xu, B.; Yan, Y. Electrochemical Energy Engineering: a (52) Chen, X.; Chen, G.; Yue, P. L. Stable Ti/IrOx−Sb2O5−SnO2
New Frontier of Chemical Engineering Innovation. Annu. Rev. Chem. Anode for O2 Evolution with Low Ir Content. J. Phys. Chem. B 2001,
Biomol. Eng. 2014, 5, 429−454. 105 (20), 4623−4628.
(33) Luo, J.; Im, J.-H.; Mayer, M. T.; Schreier, M.; Nazeeruddin, M. (53) Blakemore, J. D.; Schley, N. D.; Olack, G. W.; Incarvito, C. D.;
K.; Park, N.-G.; Tilley, S. D.; Fan, H. J.; Grätzel, M. Water Photolysis Brudvig, G. W.; Crabtree, R. H. Anodic Deposition of a Robust
at 12.3% Efficiency via Perovskite Photovoltaics and Earth-Abundant Iridium-Based Water-Oxidation Catalyst from Organometallic Pre-
Catalysts. Science 2014, 345 (6204), 1593−1596. cursors. Chem. Sci. 2011, 2 (1), 94−98.
(34) Chen, Y.; Sun, K.; Audesirk, H.; Xiang, C.; Lewis, N. S. A (54) Schley, N. D.; Blakemore, J. D.; Subbaiyan, N. K.; Incarvito, C.
Quantitative Analysis of the Efficiency of Solar-Driven Water-Splitting D.; D’Souza, F.; Crabtree, R. H.; Brudvig, G. W. Distinguishing
Device Designs Based on Tandem Photoabsorbers Patterned with Homogeneous from Heterogeneous Catalysis in Electrode-Driven
Islands of Metallic Electrocatalysts. Energy Environ. Sci. 2015, 8 (6), Water Oxidation with Molecular Iridium Complexes. J. Am. Chem. Soc.
1736−1747. 2011, 133 (27), 10473−10481.
(35) Dumortier, M.; Haussener, S. Design Guidelines for (55) Frame, F. A.; Townsend, T. K.; Chamousis, R. L.; Sabio, E. M.;
Concentrated Photo-Electrochemical Water Splitting Devices Based Dittrich, T.; Browning, N. D.; Osterloh, F. E. Photocatalytic Water
on Energy and Greenhouse Gas Yield Ratios. Energy Environ. Sci. 2015, Oxidation with Nonsensitized IrO2 Nanocrystals under Visible and
8 (11), 3069−3082. UV Light. J. Am. Chem. Soc. 2011, 133 (19), 7264−7267.
(36) Verlage, E.; Hu, S.; Liu, R.; Jones, R. J. R.; Sun, K.; Xiang, C.; (56) Wang, C.; Xie, Z.; deKrafft, K. E.; Lin, W. Doping Metal−
Lewis, N. S.; Atwater, H. A. A Monolithically Integrated, Intrinsically Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction,
Safe, 10% Efficient, Solar-Driven Water-Splitting System Based on and Organic Photocatalysis. J. Am. Chem. Soc. 2011, 133 (34), 13445−
Active, Stable Earth-Abundant Electrocatalysts in Conjunction with 13454.
Tandem III-V Light Absorbers Protected by Amorphous TiO2 Films. (57) Fujishima, A.; Honda, K. Electrochemical Photolysis of Water at
Energy Environ. Sci. 2015, 8 (11), 3166−3172. a Semiconductor Electrode. Nature 1972, 238 (5358), 37−38.
(37) Doscher, H.; Young, J. L.; Geisz, J. F.; Turner, J. A.; Deutsch, T. (58) Walsh, A.; Yan, Y.; Huda, M. N.; Al-Jassim, M. M.; Wei, S.-H.
G. Solar-to-Hydrogen Efficiency: Shining Light on Photoelectrochem- Band Edge Electronic Structure of BiVO4: Elucidating the Role of the
ical Device Performance. Energy Environ. Sci. 2016, 9 (1), 74−80. Bi s and V d Orbitals. Chem. Mater. 2009, 21 (3), 547−551.
(38) Kärkäs, M. D.; Verho, O.; Johnston, E. V.; Åkermark, B. (59) Prévot, M. S.; Sivula, K. Photoelectrochemical Tandem Cells for
Artificial Photosynthesis: Molecular Systems for Catalytic Water Solar Water Splitting. J. Phys. Chem. C 2013, 117 (35), 17879−17893.
(60) Liu, M.; Nam, C.-Y.; Black, C. T.; Kamcev, J.; Zhang, L.
Oxidation. Chem. Rev. 2014, 114 (24), 11863−12001.
Enhancing Water Splitting Activity and Chemical Stability of Zinc
(39) Blakemore, J. D.; Crabtree, R. H.; Brudvig, G. W. Molecular
Oxide Nanowire Photoanodes with Ultrathin Titania Shells. J. Phys.
Catalysts for Water Oxidation. Chem. Rev. 2015, 115 (23), 12974−
Chem. C 2013, 117 (26), 13396−13402.
13005. (61) Kato, H.; Asakura, K.; Kudo, A. Highly Efficient Water Splitting
(40) Kärkäs, M.; Åkermark, B. Water Oxidation using Earth-
into H2 and O2 over Lanthanum-Doped NaTaO3 Photocatalysts with
Abundant Transition Metal Catalysts: Opportunities and Challenges. High Crystallinity and Surface Nanostructure. J. Am. Chem. Soc. 2003,
Dalton Trans. 2016, 45 (37), 14421−14461. 125 (10), 3082−3089.
(41) Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous (62) Lau, L. C.; Lee, K. T. The Effect of Band Engineering of
Solutions; Pergamon Press: New York, 1966. Semiconductors on Photocatalytic Water Splitting: A Review. IJRET
(42) Leng, Y.; Chen, G.; Mendoza, A. J.; Tighe, T. B.; Hickner, M. A.; 2013, 2 (11), 195−206.
Wang, C.-Y. Solid-State Water Electrolysis with an Alkaline (63) Mi, Q.; Zhanaidarova, A.; Brunschwig, B. S.; Gray, H. B.; Lewis,
Membrane. J. Am. Chem. Soc. 2012, 134 (22), 9054−9057. N. S. A Quantitative Assessment of the Competition between Water
(43) Varcoe, J. R.; Atanassov, P.; Dekel, D. R.; Herring, A. M.; and Anion Oxidation at WO3 Photoanodes in Acidic Aqueous
Hickner, M. A.; Kohl, P. A.; Kucernak, A. R.; Mustain, W. E.; Electrolytes. Energy Environ. Sci. 2012, 5 (2), 5694−5700.
Nijmeijer, K.; Scott, K. Anion-Exchange Membranes in Electro- (64) Miseki, Y.; Sayama, K. High-Efficiency Water Oxidation and
chemical Energy Systems. Energy Environ. Sci. 2014, 7 (10), 3135− Energy Storage Utilizing Various Reversible Redox Mediators under
3191. Visible Light over Surface-Modified WO3. RSC Adv. 2014, 4 (16),
(44) Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; 8308−8316.
Mi, Q.; Santori, E. A.; Lewis, N. S. Solar Water Splitting Cells. Chem. (65) Kawasaki, S.; Nakatsuji, K.; Yoshinobu, J.; Komori, F.;
Rev. 2010, 110 (11), 6446−6473. Takahashi, R.; Lippmaa, M.; Mase, K.; Kudo, A. Epitaxial Rh-Doped

L DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

SrTiO3 Thin Film Photocathode for Water Splitting under Visible Photooxidation of Water over Porous BiVO4 Film Photoelectrode
Light Irradiation. Appl. Phys. Lett. 2012, 101 (3), 033910. under Visible Light. Chem. Lett. 2010, 39 (1), 17−19.
(66) Bolton, J. R.; Strickler, S. J.; Connolly, J. S. Limiting and (86) Seabold, J. A.; Choi, K.-S. Efficient and Stable Photo-Oxidation
Realizable Efficiencies of Solar Photolysis of Water. Nature 1985, 316 of Water by a Bismuth Vanadate Photoanode Coupled with an Iron
(6028), 495−500. Oxyhydroxide Oxygen Evolution Catalyst. J. Am. Chem. Soc. 2012, 134
(67) Sakthivel, S.; Janczarek, M.; Kisch, H. Visible Light Activity and (4), 2186−2192.
Photoelectrochemical Properties of Nitrogen-Doped TiO2. J. Phys. (87) Su, J.; Guo, L.; Yoriya, S.; Grimes, C. A. Aqueous Growth of
Chem. B 2004, 108 (50), 19384−19387. Pyramidal-Shaped BiVO4 Nanowire Arrays and Structural Character-
(68) Mi, Q.; Ping, Y.; Li, Y.; Cao, B.; Brunschwig, B. S.; Khalifah, P. ization: Application to Photoelectrochemical Water Splitting. Cryst.
G.; Galli, G. A.; Gray, H. B.; Lewis, N. S. Thermally Stable N2- Growth Des. 2010, 10 (2), 856−861.
Intercalated WO3 Photoanodes for Water Oxidation. J. Am. Chem. Soc. (88) Sinclair, T. S.; Hunter, B. M.; Winkler, J. R.; Gray, H. B.; Müller,
2012, 134 (44), 18318−18324. A. M. Factors Affecting Bismuth Vanadate Photoelectrochemical
(69) A TiO2 band gap of 2.9 eV is still too large for efficient light Performance. Mater. Horiz. 2015, 2 (3), 330−337.
absorption, and tungsten oxide is not stable in alkaline media in which (89) Morita, M.; Iwakura, C.; Tamura, H. The Anodic Characteristics
highly active, earth-abundant water oxidation catalysts operate. of Manganese Dioxide Electrodes Prepared by Thermal Decom-
(70) Suntivich, J.; May, K. J.; Gasteiger, H. A.; Goodenough, J. B.; position of Manganese Nitrate. Electrochim. Acta 1977, 22 (4), 325−
Shao-Horn, Y. A Perovskite Oxide Optimized for Oxygen Evolution 328.
Catalysis from Molecular Orbital Principles. Science 2011, 334 (6061), (90) Jiao, F.; Frei, H. Nanostructured Manganese Oxide Clusters
1383−1385. Supported on Mesoporous Silica as Efficient Oxygen-Evolving
(71) Liu, H.; Moré, R.; Grundmann, H.; Cui, C.; Erni, R.; Patzke, G. Catalysts. Chem. Commun. 2010, 46 (17), 2920−2922.
R. Promoting Photochemical Water Oxidation with Metallic Band (91) Pinaud, B. A.; Chen, Z.; Abram, D. N.; Jaramillo, T. F. Thin
Structures. J. Am. Chem. Soc. 2016, 138 (5), 1527−1535. Films of Sodium Birnessite-Type MnO2: Optical Properties,
(72) Hildebrandt, N. C.; Soldat, J.; Marschall, R. Layered Perovskite Electronic Band Structure, and Solar Photoelectrochemistry. J. Phys.
Nanofibers via Electrospinning for Overall Water Splitting. Small Chem. C 2011, 115 (23), 11830−11838.
2015, 11 (17), 2051−2057. (92) Wiechen, M.; Zaharieva, I.; Dau, H.; Kurz, P. Layered
(73) Park, Y.; McDonald, K. J.; Choi, K.-S. Progress in Bismuth Manganese Oxides for Water-Oxidation: Alkaline Earth Cations
Vanadate Photoanodes for use in Solar Water Oxidation. Chem. Soc. Influence Catalytic Activity in a Photosystem II-Like Fashion. Chem.
Rev. 2013, 42 (6), 2321−2337. Sci. 2012, 3 (7), 2330−2339.
(74) Abdi, F. F.; Firet, N.; Dabirian, A.; van de Krol, R. Spray- (93) Pokhrel, R.; Goetz, M. K.; Shaner, S. E.; Wu, X.; Stahl, S. S. The
Deposited Co-Pi Catalyzed BiVO4: a Low-Cost Route towards Highly “Best Catalyst” for Water Oxidation Depends on the Oxidation
Efficient Photoanodes. MRS Online Proc. Libr. 2012, 1446, 7−12. Method Employed: A Case Study of Manganese Oxides. J. Am. Chem.
(75) Kudo, A.; Omori, K.; Kato, H. A Novel Aqueous Process for Soc. 2015, 137 (26), 8384−8387.
Preparation of Crystal Form-Controlled and Highly Crystalline BiVO4 (94) Najafpour, M. M.; Sedigh, D. J. Water Oxidation by Manganese
Powder from Layered Vanadates at Room Temperature and Its Oxides, a New Step towards a Complete Picture: Simplicity is the
Photocatalytic and Photophysical Properties. J. Am. Chem. Soc. 1999, Ultimate Sophistication. Dalton Trans. 2013, 42 (34), 12173−12178.
121 (49), 11459−11467. (95) Zaharieva, I.; Chernev, P.; Risch, M.; Klingan, K.; Kohlhoff, M.;
(76) Tokunaga, S.; Kato, H.; Kudo, A. Selective Preparation of Fischer, A.; Dau, H. Electrosynthesis, Functional, and Structural
Monoclinic and Tetragonal BiVO4 with Scheelite Structure and Their Characterization of a Water-Oxidizing Manganese Oxide. Energy
Photocatalytic Properties. Chem. Mater. 2001, 13 (12), 4624−4628. Environ. Sci. 2012, 5 (5), 7081−7089.
(77) Kudo, A.; Ueda, K.; Kato, H.; Mikami, I. Photocatalytic O2 (96) Najafpour, M. M.; Ehrenberg, T.; Wiechen, M.; Kurz, P.
Evolution under Visible Light Irradiation on BiVO4 in Aqueous Calcium Manganese(III) Oxides (CaMn2O4·xH2O) as Biomimetic
AgNO3 Solution. Catal. Lett. 1998, 53 (3−4), 229−230. Oxygen-Evolving Catalysts. Angew. Chem., Int. Ed. 2010, 49 (12),
(78) Abdi, F. F.; Firet, N.; van de Krol, R. Efficient BiVO4 Thin Film 2233−2237.
Photoanodes Modified with Cobalt Phosphate Catalyst and W-doping. (97) Kurz, P.; Berggren, G.; Anderlund, M. F.; Styring, S. Oxygen
ChemCatChem 2013, 5 (2), 490−496. Evolving Reactions Catalysed by Synthetic Manganese Complexes: A
(79) Alarcon-Llado, E.; Chen, L.; Hettick, M.; Mashouf, N.; Lin, Y.; Systematic Screening. Dalton Trans. 2007, 2007 (38), 4258−4261.
Javey, A.; Ager, J. W. BiVO4 Thin Film Photoanodes Grown by (98) Najafpour, M.; Moghaddam, A. N.; Dau, H.; Zaharieva, I.
Chemical Vapor Deposition. Phys. Chem. Chem. Phys. 2014, 16 (4), Fragments of Layered Manganese Oxide are the Real Water Oxidation
1651−1657. Catalyst after Transformation of Molecular Precursor on Clay. J. Am.
(80) Berglund, S. P.; Flaherty, D. W.; Hahn, N. T.; Bard, A. J.; Chem. Soc. 2014, 136 (20), 7245−7248.
Mullins, C. B. Photoelectrochemical Oxidation of Water Using (99) Gorlin, Y.; Jaramillo, T. F. A Bifunctional Nonprecious Metal
Nanostructured BiVO4 Films. J. Phys. Chem. C 2011, 115 (9), Catalyst for Oxygen Reduction and Water Oxidation. J. Am. Chem. Soc.
3794−3802. 2010, 132 (39), 13612−13614.
(81) Chen, L.; Alarcón-Lladó, E.; Hettick, M.; Sharp, I. D.; Lin, Y.; (100) Gorlin, Y.; Lassalle-Kaiser, B.; Benck, J. D.; Gul, S.; Webb, S.
Javey, A.; Ager, J. W. Reactive Sputtering of Bismuth Vanadate M.; Yachandra, V. K.; Yano, J.; Jaramillo, T. F. In Situ X-ray
Photoanodes for Solar Water Splitting. J. Phys. Chem. C 2013, 117 Absorption Spectroscopy Investigation of a Bifunctional Manganese
(42), 21635−21642. Oxide Catalyst with High Activity for Electrochemical Water
(82) Choi, S. K.; Choi, W.; Park, H. Solar Water Oxidation using Oxidation and Oxygen Reduction. J. Am. Chem. Soc. 2013, 135 (23),
Nickel-Borate Coupled BiVO4 Photoelectrodes. Phys. Chem. Chem. 8525−8534.
Phys. 2013, 15 (17), 6499−6507. (101) Turner, J.; Hendewerk, M.; Parmeter, J.; Neiman, D.;
(83) Jeong, H. W.; Jeon, T. H.; Jang, J. S.; Choi, W.; Park, H. Somorjai, G. The Characterization of Doped Iron Oxide Electrodes
Strategic Modification of BiVO4 for Improving Photoelectrochemical for the Photodissociation of Water Stability, Optical, and Electronic
Water Oxidation Performance. J. Phys. Chem. C 2013, 117 (18), Properties. J. Electrochem. Soc. 1984, 131 (8), 1777−1783.
9104−9112. (102) Joly, A. G.; Williams, J. R.; Chambers, S. A.; Xiong, G.; Hess,
(84) Kim, T. W.; Choi, K. S. Nanoporous BiVO4 Photoanodes with W. P.; Laman, D. M. Carrier Dynamics in α-Fe2O3 (0001) Thin Films
Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting. and Single Crystals Probed by Femtosecond Transient Absorption and
Science 2014, 343 (6174), 990−994. Reflectivity. J. Appl. Phys. 2006, 99 (5), 053521.
(85) Sayama, K.; Wang, N.; Miseki, Y.; Kusama, H.; Onozawa- (103) Smith, R. D. L.; Prévot, M. S.; Fagan, R. D.; Zhang, Z.; Sedach,
Komatsuzaki, N.; Sugihara, H. Effect of Carbonate Ions on the P. A.; Siu, M. K. J.; Trudel, S.; Berlinguette, C. P. Photochemical Route

M DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

for Accessing Amorphous Metal Oxide Materials for Water Oxidation (122) Chen, J. Y. C.; Miller, J. T.; Gerken, J. B.; Stahl, S. S. Inverse
Catalysis. Science 2013, 340 (6128), 60−63. Spinel NiFeAlO4 as a Highly Active Oxygen Evolution Electrocatalyst:
(104) Cesar, I.; Kay, A.; Gonzalez Martinez, J. A.; Grätzel, M. Promotion of Activity by a Redox-Inert Metal Ion. Energy Environ. Sci.
Translucent Thin Film Fe2O3 Photoanodes for Efficient Water 2014, 7 (4), 1382−1386.
Splitting by Sunlight: Nanostructure-Directing Effect of Si-Doping. J. (123) Niedbala, J.; Budniok, A.; Surowka, J.; Gierlotka, D. Electrolytic
Am. Chem. Soc. 2006, 128 (14), 4582−4583. Oxygen Evolution on Ni-P-Sc2O3 Composite Layers. Thin Solid Films
(105) Lyons, M. E. G.; Brandon, M. P. The Oxygen Evolution 1996, 287 (1−2), 164−168.
Reaction on Passive Oxide Covered Transition Metal Electrodes in (124) Liu, H.; Nakamura, R.; Nakato, Y. Bismuth-Copper Vanadate
Aqueous Alkaline Solution. Part III-Iron. Int. J. Electrochem. Sci. 2008, 3 BiCu2VO6 as a Novel Photocatalyst for Efficient Visible-Light-Driven
(12), 1463−1503. Oxygen Evolution. ChemPhysChem 2005, 6 (12), 2499−2502.
(106) Kanan, M. W.; Nocera, D. G. In Situ Formation of an Oxygen- (125) Xing, M.; Kong, L.-B.; Liu, M.-C.; Liu, L.-Y.; Kang, L.; Luo, Y.-
Evolving Catalyst in Neutral Water Containing Phosphate and Co2+. C. Cobalt Vanadate as Highly Active, Stable, Noble Metal-Free
Science 2008, 321 (5892), 1072−1075. Oxygen Evolution Electrocatalyst. J. Mater. Chem. A 2014, 2 (43),
(107) McAlpin, J. G.; Surendranath, Y.; Dincǎ, M.; Stich, T. A.; 18435−18443.
Stoian, S. A.; Casey, W. H.; Nocera, D. G.; Britt, R. D. EPR Evidence (126) Aki, S. N. V. K.; Ding, Z.-Y.; Abraham, M. A. Catalytic
for Co(IV) Species Produced During Water Oxidation at Neutral pH. Supercritical Water Oxidation: Stability of Cr2O3 Catalyst. AIChE J.
J. Am. Chem. Soc. 2010, 132 (20), 6882−6883. 1996, 42 (7), 1995−2004.
(108) Risch, M.; Klingan, K.; Ringleb, F.; Chernev, P.; Zaharieva, I.; (127) Soldat, J.; Busser, G. W.; Muhler, M.; Wark, M. Cr2O3
Fischer, A.; Dau, H. Water Oxidation by Electrodeposited Cobalt Nanoparticles on Ba5Ta4O15 as a Noble-Metal-Free Oxygen
OxidesRole of Anions and Redox-Inert Cations in Structure and Evolution Co-Catalyst for Photocatalytic Overall Water Splitting.
Function of the Amorphous Catalyst. ChemSusChem 2012, 5 (3), ChemCatChem 2016, 8 (1), 153−156.
542−549. (128) Du, J.; Chen, Z.; Ye, S.; Wiley, B. J.; Meyer, T. J. Copper as a
(109) El Wakkad, S. E. S.; Hickling, A. The Anodic Behaviour of Robust and Transparent Electrocatalyst for Water Oxidation. Angew.
Metals. Part VI.-Cobalt. Trans. Faraday Soc. 1950, 46 (0), 820−824. Chem., Int. Ed. 2015, 54 (7), 2073−2078.
(110) Pandey, A. D.; Jia, C.; Schmidt, W.; Leoni, M.; Schwickardi, (129) Cui, S.; Liu, X.; Sun, Z.; Du, P. Noble Metal-Free Copper
M.; Schüth, F.; Weidenthaler, C. Size-Controlled Synthesis and Hydroxide as an Active and Robust Electrocatalyst for Water
Microstructure Investigation of Co3O4 Nanoparticles for Low- Oxidation at Weakly Basic pH. ACS Sustainable Chem. Eng. 2016, 4
Temperature CO Oxidation. J. Phys. Chem. C 2012, 116 (36), (5), 2593−2600.
19405−19412. (130) Liu, X.; Cui, S.; Qian, M.; Sun, Z.; Du, P. In Situ Generated
(111) Gardner, G. P.; Go, Y. B.; Robinson, D. M.; Smith, P. F.; Highly Active Copper Oxide Catalysts for the Oxygen Evolution
Hadermann, J.; Abakumov, A.; Greenblatt, M.; Dismukes, G. C. Reaction at Low Overpotential in Alkaline Solutions. Chem. Commun.
Structural Requirements in Lithium Cobalt Oxides for the Catalytic 2016, 52 (32), 5546−5549.
Oxidation of Water. Angew. Chem., Int. Ed. 2012, 51 (7), 1616−1619. (131) Prevedello, A.; Bazzan, I.; Dalle Carbonare, N.; Giuliani, A.;
(112) Song, F.; Hu, X. Ultrathin Cobalt−Manganese Layered Double Bhardwaj, S.; Africh, C.; Cepek, C.; Argazzi, R.; Bonchio, M.;
Hydroxide Is an Efficient Oxygen Evolution Catalyst. J. Am. Chem. Soc. Caramori, S.; et al. Heterogeneous and Homogeneous Routes in
2014, 136 (47), 16481−16484. Water Oxidation Catalysis Starting from CuII Complexes with
(113) Grzelczak, M.; Zhang, J.; Pfrommer, J.; Hartmann, J.; Driess, Tetraaza Macrocyclic Ligands. Chem. - Asian J. 2016, 11 (8), 1281−
M.; Antonietti, M.; Wang, X. Electro- and Photochemical Water 1287.
Oxidation on Ligand-free Co3O4 Nanoparticles with Tunable Sizes. (132) Shi, Y.; Gimbert-Surinach, C.; Han, T.; Berardi, S.; Lanza, M.;
ACS Catal. 2013, 3 (3), 383−388. Llobet, A. CuO-Functionalized Silicon Photoanodes for Photo-
(114) Lyons, M. E. G.; Brandon, M. P. The Oxygen Evolution electrochemical Water Splitting Devices. ACS Appl. Mater. Interfaces
Reaction on Passive Oxide Covered Transition Metal Electrodes in 2016, 8 (1), 696−702.
Aqueous Alkaline Solution. Part II-Cobalt. Int. J. Electrochem. Sci. 2008, (133) Jiang, C.; Moniz, S. J. A.; Khraisheh, M.; Tang, J. Earth-
3 (12), 1425−1462. Abundant Oxygen Evolution Catalysts Coupled onto ZnO Nanowire
(115) Blakemore, J. D.; Gray, H. B.; Winkler, J. R.; Müller, A. M. Arrays for Efficient Photoelectrochemical Water Cleavage. Chem. - Eur.
Co3O4 Nanoparticle Water-Oxidation Catalysts Made by Pulsed- J. 2014, 20 (40), 12954−12961.
Laser Ablation in Liquids. ACS Catal. 2013, 3 (11), 2497−2500. (134) Kim, T. W.; Woo, M. A.; Regis, M.; Choi, K.-S. Electro-
(116) Bode, H.; Dehmelt, K.; Witte, J. Zur Kenntnis der chemical Synthesis of Spinel Type ZnCo2O4 Electrodes for Use as
NickelhydroxidelektrodeI. Ü ber das Nickel(II)-Hydroxidhydrat. Oxygen Evolution Reaction Catalysts. J. Phys. Chem. Lett. 2014, 5 (13),
Electrochim. Acta 1966, 11 (8), 1079−IN1071. 2370−2374.
(117) Oliva, P.; Leonardi, J.; Laurent, J. F.; Delmas, C.; Braconnier, J. (135) Jang, D. M.; Kwak, I. H.; Kwon, E. L.; Jung, C. S.; Im, H. S.;
J.; Figlarz, M.; Fievet, F.; Guibert, A. d. Review of the Structure and the Park, K.; Park, J. Transition-Metal Doping of Oxide Nanocrystals for
Electrochemistry of Nickel Hydroxides and Oxy-Hydroxides. J. Power Enhanced Catalytic Oxygen Evolution. J. Phys. Chem. C 2015, 119 (4),
Sources 1982, 8 (2), 229−255. 1921−1927.
(118) Młynarek, G.; Paszkiewicz, M.; Radniecka, A. The Effect of (136) Pope, M. T.; Müller, A. Polyoxometalate Chemistry: an Old
Ferric Ions on the Behaviour of a Nickelous Hydroxide Electrode. J. Field with New Dimensions in Several Disciplines. Angew. Chem., Int.
Appl. Electrochem. 1984, 14 (2), 145−149. Ed. Engl. 1991, 30 (1), 34−48.
(119) Corrigan, D. A. The Catalysis of the Oxygen Evolution (137) Sumliner, J. M.; Lv, H.; Fielden, J.; Geletii, Y. V.; Hill, C. L.
Reaction by Iron Impurities in Thin Film Nickel Oxide Electrodes. J. Polyoxometalate Multi-Electron-Transfer Catalytic Systems for Water
Electrochem. Soc. 1987, 134 (2), 377−384. Splitting. Eur. J. Inorg. Chem. 2014, 2014 (4), 635−644.
(120) Trotochaud, L.; Young, S. L.; Ranney, J. K.; Boettcher, S. W. (138) Gouzerh, P.; Che, M. From Scheele and Berzelius to Müller.
Nickel-Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: the Actual. Chim. 2006, No. 298, 1.
Role of Intentional and Incidental Iron Incorporation. J. Am. Chem. (139) Pope, M. T.; Kortz, U. In Encyclopedia of Inorganic and
Soc. 2014, 136 (18), 6744−6753. Bioinorganic Chemistry; John Wiley & Sons, Ltd., 2011.
(121) Lyons, M. E. G.; Brandon, M. P. The Oxygen Evolution (140) Armatas, G. S.; Katsoulidis, A. P.; Petrakis, D. E.; Pomonis, P.
Reaction on Passive Oxide Covered Transition Metal Electrodes in J.; Kanatzidis, M. G. Nanocasting of Ordered Mesoporous Co3O4-
Aqueous Alkaline Solution. Part I-Nickel. Int. J. Electrochem. Sci. 2008, Based Polyoxometalate Composite Frameworks. Chem. Mater. 2010,
3 (12), 1386−1424. 22 (20), 5739−5746.

N DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

(141) Lv, H.; Geletii, Y. V.; Zhao, C.; Vickers, J. W.; Zhu, G.; Luo, Z.; Hydroxide as an Electrocatalyst. J. Am. Chem. Soc. 2014, 136 (19),
Song, J.; Lian, T.; Musaev, D. G.; Hill, C. L. Polyoxometalate Water 7077−7084.
Oxidation Catalysts and the Production of Green Fuel. Chem. Soc. Rev. (162) Louie, M. W.; Bell, A. T. An Investigation of Thin-Film Ni−Fe
2012, 41 (22), 7572−7589. Oxide Catalysts for the Electrochemical Evolution of Oxygen. J. Am.
(142) Duan, X.; Evans, D. G. Layered Double Hydroxides; Springer Chem. Soc. 2013, 135 (33), 12329−12337.
Science & Business Media, 2006. (163) Long, X.; Li, J.; Xiao, S.; Yan, K.; Wang, Z.; Chen, H.; Yang, S.
(143) Fan, G.; Li, F.; Evans, D. G.; Duan, X. Catalytic Applications of A Strongly Coupled Graphene and FeNi Double Hydroxide Hybrid as
Layered Double Hydroxides: Recent Advances and Perspectives. an Excellent Electrocatalyst for the Oxygen Evolution Reaction. Angew.
Chem. Soc. Rev. 2014, 43 (20), 7040−7066. Chem., Int. Ed. 2014, 53 (29), 7584−7588.
(144) Gong, M.; Li, Y.; Wang, H.; Liang, Y.; Wu, J. Z.; Zhou, J.; (164) Zhang, B.; Zheng, X.; Voznyy, O.; Comin, R.; Bajdich, M.;
Wang, J.; Regier, T.; Wei, F.; Dai, H. An Advanced Ni−Fe Layered García-Melchor, M.; Han, L.; Xu, J.; Liu, M.; Zheng, L.; et al.
Double Hydroxide Electrocatalyst for Water Oxidation. J. Am. Chem. Homogeneously Dispersed Multimetal Oxygen-Evolving Catalysts.
Soc. 2013, 135 (23), 8452−8455. Science 2016, 352 (6283), 333−337.
(145) Zhao, Y.; Li, B.; Wang, Q.; Gao, W.; Wang, C. J.; Wei, M.; (165) Burke, M. S.; Enman, L. J.; Batchellor, A. S.; Zou, S.; Boettcher,
Evans, D. G.; Duan, X.; O’Hare, D. NiTi-Layered Double Hydroxides S. W. Oxygen Evolution Reaction Electrocatalysis on Transition Metal
Nanosheets as Efficient Photocatalysts for Oxygen Evolution from Oxides and (Oxy)hydroxides: Activity Trends and Design Principles.
Water using Visible Light. Chem. Sci. 2014, 5 (3), 951−958. Chem. Mater. 2015, 27 (22), 7549−7558.
(146) Trotochaud, L.; Ranney, J. K.; Williams, K. N.; Boettcher, S. (166) Blackman, F. F.; Matthaei, G. L. C. A Quantitative Study of
W. Solution-Cast Metal Oxide Thin Film Electrocatalysts for Oxygen Carbon Dioxide Assimilation and Leaf Temperature in Natural
Evolution. J. Am. Chem. Soc. 2012, 134 (41), 17253−17261. Illumination. Proc. R. Soc. London, Ser. B 1905, 76, 402−460.
(147) Song, F.; Hu, X. Exfoliation of Layered Double Hydroxides for (167) Warburg, O. Ü ber die Geschwindigkeit der photochemischen
Enhanced Oxygen Evolution Catalysis. Nat. Commun. 2014, 5, 4477− Kohlensäurezersetzung in lebenden Zellen. Biochem. Zeit. 1919, 100,
4486. 230−270.
(148) Li, Z.; Shao, M.; An, H.; Wang, Z.; Xu, S.; Wei, M.; Evans, D. (168) Warburg, O. Ü ber die Geschwindigkeit der photochemischen
G.; Duan, X. Fast Electrosynthesis of Fe-Containing Layered Double Kohlensäurezersetzung in lebenden Zellen II. Biochem. Zeit. 1919, 103,
Hydroxide Arrays toward Highly Efficient Electrocatalytic Oxidation 188−217.
Reactions. Chem. Sci. 2015, 6 (11), 6624−6631. (169) Warburg, O. Theorie der Kohlensäureassimilation. Natur-
(149) Hunter, B. M.; Blakemore, J. D.; Deimund, M.; Gray, H. B.; wissenschaften 1921, 9 (18), 354−358.
Winkler, J. R.; Müller, A. M. Highly Active Mixed-Metal Nanosheet (170) van Niel, C. B. On the Morphology and Physiology of the
Water Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids. Purple and Green Sulphur Bacteria. Arch. Microbiol. 1932, 3 (1), 1−
J. Am. Chem. Soc. 2014, 136 (38), 13118−13121. 112.
(150) Evans, D. G.; Slade, R. C. Structural Aspects of Layered (171) Hill, R. Oxygen Evolved by Isolated Chloroplasts. Nature 1937,
Double Hydroxides. Struct. Bonding (Berlin) 2006, 119, 1−87. 139, 881−882.
(151) Stanimirova, T. S.; Kirov, G.; Dinolova, E. Mechanism of (172) Hill, R. Oxygen Produced by Isolated Chloroplasts. Proc. R.
Hydrotalcite Regeneration. J. Mater. Sci. Lett. 2001, 20 (5), 453−455. Soc. London, Ser. B 1939, 127 (847), 192−210.
(152) The depicted LDH structure is based on that of α-Ni(OH)2 (173) Hill, R.; Scarisbrick, R. Production of Oxygen by Illuminated
reported in the American Mineralogist Crystal Structure Database Chloroplasts. Nature 1940, 146, 61−62.
(AMCSD) #0015759. (174) Ruben, S.; Randall, M.; Kamen, M.; Hyde, J. L. Heavy Oxygen
(153) McCrory, C. C. L.; Jung, S.; Peters, J. C.; Jaramillo, T. F. (O18) as a Tracer in the Study of Photosynthesis. J. Am. Chem. Soc.
Benchmarking Heterogeneous Electrocatalysts for the Oxygen 1941, 63 (3), 877−879.
Evolution Reaction. J. Am. Chem. Soc. 2013, 135 (45), 16977−16987. (175) Ruben, S.; Kamen, M. D. Radioactive Carbon of Long Half-
(154) Roger, I.; Symes, M. D. Efficient Electrocatalytic Water Life. Phys. Rev. 1940, 57 (6), 549.
Oxidation at Neutral and High pH by Adventitious Nickel at (176) Joliot, P. Cinétiques des Réactions Liées a l’É mission
Nanomolar Concentrations. J. Am. Chem. Soc. 2015, 137 (43), d’Oxygène Photosynthétique. Biochim. Biophys. Acta, Biophys. Incl.
13980−13988. Photosynth. 1965, 102 (1), 116−134.
(155) Yeo, B. S.; Bell, A. T. In Situ Raman Study of Nickel Oxide and (177) Joliot, P.; Joliot, A. A Polarographic Method for Detection of
Gold-Supported Nickel Oxide Catalysts for the Electrochemical Oxygen Production and Reduction of Hill Reagent by Isolated
Evolution of Oxygen. J. Phys. Chem. C 2012, 116 (15), 8394−8400. Chloroplasts. Biochim. Biophys. Acta, Bioenerg. 1968, 153 (3), 625−
(156) Dincă, M.; Surendranath, Y.; Nocera, D. G. Nickel-Borate 634.
Oxygen-Evolving Catalyst that Functions under Benign Conditions. (178) Bennoun, P.; Joliot, A. Etude de la Photooxydation de
Proc. Natl. Acad. Sci. U. S. A. 2010, 107 (23), 10337−10341. l’Hydroxylamine par les Chloroplastes d’Epinards. Biochim. Biophys.
(157) Landon, J.; Demeter, E.; Iṅ oğlu, N.; Keturakis, C.; Wachs, I. E.; Acta, Bioenerg. 1969, 189 (1), 85−94.
Vasić, R.; Frenkel, A. I.; Kitchin, J. R. Spectroscopic Characterization (179) Berthold, D. A.; Babcock, G. T.; Yocum, C. F. A Highly
of Mixed Fe−Ni Oxide Electrocatalysts for the Oxygen Evolution Resolved, Oxygen-Evolving Photosystem II Preparation from Spinach
Reaction in Alkaline Electrolytes. ACS Catal. 2012, 2 (8), 1793−1801. Thylakoid Membranes. FEBS Lett. 1981, 134 (2), 231−234.
(158) Smith, R. D. L.; Prévot, M. S.; Fagan, R. D.; Trudel, S.; (180) Klauss, A.; Haumann, M.; Dau, H. Alternating Electron and
Berlinguette, C. P. Water Oxidation Catalysis: Electrocatalytic Proton Transfer Steps in Photosynthetic Water Oxidation. Proc. Natl.
Response to Metal Stoichiometry in Amorphous Metal Oxide Films Acad. Sci. U. S. A. 2012, 109 (40), 16035−16040.
Containing Iron, Cobalt, and Nickel. J. Am. Chem. Soc. 2013, 135 (31), (181) Cox, N.; Retegan, M.; Neese, F.; Pantazis, D. A.; Boussac, A.;
11580−11586. Lubitz, W. Electronic Structure of the Oxygen-Evolving Complex in
(159) Li, X.; Walsh, F. C.; Pletcher, D. Nickel Based Electrocatalysts Photosystem II Prior to OO Bond Formation. Science 2014, 345
for Oxygen Evolution in High Current Density, Alkaline Water (6198), 804−808.
Electrolyzers. Phys. Chem. Chem. Phys. 2011, 13 (3), 1162−1167. (182) Debus, R.; Barry, B.; Sithole, I.; Babcock, G. T.; McIntosh, L.
(160) Singh, A.; Chang, S. L. Y.; Hocking, R. K.; Bach, U.; Spiccia, L. Directed Mutagenesis Indicates that the Donor to P 680+ in
Highly Active Nickel Oxide Water Oxidation Catalysts Deposited from Photosystem II is Tyrosine-161 of the D1 Polypeptide. Biochemistry
Molecular Complexes. Energy Environ. Sci. 2013, 6 (2), 579−586. 1988, 27 (26), 9071−9074.
(161) Gao, M.; Sheng, W.; Zhuang, Z.; Fang, Q.; Gu, S.; Jiang, J.; (183) Debus, R. J.; Barry, B. A.; Babcock, G. T.; McIntosh, L. Site-
Yan, Y. Efficient Water Oxidation Using Nanostructured α-Nickel- Directed Mutagenesis Identifies a Tyrosine Radical Involved in the

O DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

Photosynthetic Oxygen-Evolving System. Proc. Natl. Acad. Sci. U. S. A. (203) Oyala, P. H.; Stich, T. A.; Debus, R. J.; Britt, R. D. Ammonia
1988, 85 (2), 427−430. Binds to the Dangler Manganese of the Photosystem II Oxygen-
(184) Britt, R. D.; Campbell, K. A.; Peloquin, J. M.; Gilchrist, M. L.; Evolving Complex. J. Am. Chem. Soc. 2015, 137 (27), 8829−8837.
Aznar, C. P.; Dicus, M. M.; Robblee, J.; Messinger, J. Recent Pulsed (204) Yano, J.; Yachandra, V. Mn4Ca Cluster in Photosynthesis:
EPR Studies of the Photosystem II Oxygen-Evolving Complex: Where and How Water is Oxidized to Dioxygen. Chem. Rev. 2014, 114
Implications as to Water Oxidation Mechanisms. Biochim. Biophys. (8), 4175−4205.
Acta, Bioenerg. 2004, 1655, 158−171. (205) Barber, J. Photosynthetic Energy Conversion: Natural and
(185) Nugent, J. H. A.; Ball, R. J.; Evans, M. C. W. Photosynthetic Artificial. Chem. Soc. Rev. 2009, 38 (1), 185−196.
Water Oxidation: the Role of Tyrosine Radicals. Biochim. Biophys. Acta, (206) Small portions of catalytic species are active when the species
Bioenerg. 2004, 1655, 217−221. are very short lived and hot, so that one catalytic pathway kinetically
(186) Britt, R. D. Oxygen Evolution. Oxygenic Photosynthesis: The outcompetes other reaction paths; larger portions of active sites may
Light Reactions; Advances in Photosynthesis and Respiration; Springer: exist when turnover is inefficient and slow.
Netherlands, 1996; Vol. 4, pp 137−164. (207) Artero, V.; Fontecave, M. Solar Fuels Generation and
(187) Britt, R. D. Electron Spin Echo Methods in Photosynthesis Molecular Systems: Is it Homogeneous or Heterogeneous Catalysis?
Research. Biophysical Techniques in Photosynthesis; Advances in Chem. Soc. Rev. 2013, 42 (6), 2338−2356.
Photosynthesis and Respiration; Springer: Netherlands, 1996; Vol. 3, (208) Rossmeisl, J.; Qu, Z. W.; Zhu, H.; Kroes, G. J.; Nørskov, J. K.
pp 235−253. Electrolysis of Water on Oxide Surfaces. J. Electroanal. Chem. 2007,
(188) Britt, R. D.; Force, D. A.; Campbell, K. A.; Randall, D. W.; 607 (1−2), 83−89.
Gilchrist, L. M.; Clemens, K. L.; Gingell, D. M.; Peloquin, J. M.; Pham, (209) Man, I. C.; Su, H.-Y.; Calle-Vallejo, F.; Hansen, H. A.;
D. P.; Debus, R. J. Progress in Characterization of the Photosystem II Martínez, J. I.; Inoglu, N. G.; Kitchin, J.; Jaramillo, T. F.; Nørskov, J.
Oxygen Evolving Complex using Advanced EPR Methods. Spectro- K.; Rossmeisl, J. Universality in Oxygen Evolution Electrocatalysis on
scopic Methods in Bioinorganic Chemistry; ACS Symposium Series; Oxide Surfaces. ChemCatChem 2011, 3 (7), 1159−1165.
American Chemical Society: Washington, DC, 1998; Vol. 692, pp (210) Rossmeisl, J.; Logadottir, A.; Nørskov, J. K. Electrolysis of
272−285. Water on (Oxidized) Metal Surfaces. Chem. Phys. 2005, 319 (1), 178−
(189) Sauer, K.; Yachandra, V. K.; Britt, R. D.; Klein, M. P. The 184.
Photosynthetic Water Oxidation Complex Studied by EPR and X-ray (211) Nørskov, J. K.; Bligaard, T.; Rossmeisl, J.; Christensen, C. H.
Absorption Spectroscopy. In Manganese Redox Enzymes; Pecoraro, V. Towards the Computational Design of Solid Catalysts. Nat. Chem.
2009, 1 (1), 37−46.
L., Ed.; VCH Publishers: New York, 1992; pp 141−175.
(212) Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.;
(190) Britt, R. D.; Peloquin, J. M.; Campbell, K. A.; Pulsed; Parallel-
Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the Overpotential for
Polarization, E. P. R. Characterization of the Photosystem II Oxygen-
Oxygen Reduction at a Fuel-Cell Cathode. J. Phys. Chem. B 2004, 108
Evolving Complex. Annu. Rev. Biophys. Biomol. Struct. 2000, 29, 463−
(46), 17886−17892.
495.
(213) Viswanathan, V.; Hansen, H. A.; Nørskov, J. K. Selective
(191) Peloquin, J. M.; Britt, R. D. EPR/ENDOR Characterization of
Electrochemical Generation of Hydrogen Peroxide from Water
the Physical and Electronic Structure of the OEC Mn Cluster. Biochim.
Oxidation. J. Phys. Chem. Lett. 2015, 6 (21), 4224−4228.
Biophys. Acta, Bioenerg. 2001, 1503 (1−2), 96−111. (214) Vojvodic, A.; Nørskov, J. K. Optimizing Perovskites for the
(192) Ferreira, K. N.; Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata,
Water-Splitting Reaction. Science 2011, 334 (6061), 1355−1356.
S. Architecture of the Photosynthetic Oxygen-Evolving Center. Science (215) Fortunelli, A.; Goddard Iii, W. A.; Sementa, L.; Barcaro, G.
2004, 303 (5665), 1831−1838. Optimizing the Oxygen Evolution Reaction for Electrochemical Water
(193) Barber, J. Crystal Structure of the Oxygen-Evolving Complex Oxidation by Tuning Solvent Properties. Nanoscale 2015, 7 (10),
of Photosystem II. Inorg. Chem. 2008, 47 (6), 1700−1710. 4514−4521.
(194) Yano, J.; Kern, J.; Sauer, K.; Latimer, M. J.; Pushkar, Y.; (216) Romain, S.; Vigara, L.; Llobet, A. Oxygen−Oxygen Bond
Biesiadka, J.; Loll, B.; Saenger, W.; Messinger, J.; Zouni, A. Where Formation Pathways Promoted by Ruthenium Complexes. Acc. Chem.
Water is Oxidized to Dioxygen: Structure of the Photosynthetic Res. 2009, 42 (12), 1944−1953.
Mn4Ca Cluster. Science 2006, 314 (5800), 821−825. (217) Chronister, C. W.; Binstead, R. A.; Ni, J.; Meyer, T. J.
(195) Cox, N.; Pantazis, D. A.; Neese, F.; Lubitz, W. Biological Water Mechanism of Water Oxidation Catalyzed by the μ-Oxo Dimer
Oxidation. Acc. Chem. Res. 2013, 46 (7), 1588−1596. [(bpy)2 (OH2) RuIIIORuIII (OH2)(bpy)2]4+. Inorg. Chem. 1997, 36
(196) Dismukes, G. C.; Siderer, Y. Intermediates of a Polynuclear (18), 3814−3815.
Manganese Center Involved in Photosynthetic Oxidation of Water. (218) Gersten, S. W.; Samuels, G. J.; Meyer, T. J. Catalytic Oxidation
Proc. Natl. Acad. Sci. U. S. A. 1981, 78 (1), 274−278. of Water by an Oxo-Bridged Ruthenium Dimer. J. Am. Chem. Soc.
(197) Britt, R. D.; Oyala, P. H. One Step Closer to O2. Science 2014, 1982, 104 (14), 4029−4030.
345 (6198), 736−736. (219) Hurst, J. K.; Zhou, J.; Lei, Y. Pathways for Water Oxidation
(198) Hoganson, C. W.; Babcock, G. T. A Metalloradical Mechanism Catalyzed by the [(bpy)2Ru(OH2)]2O 4+ ion. Inorg. Chem. 1992, 31
for the Generation of Oxygen from Water in Photosynthesis. Science (6), 1010−1017.
1997, 277 (5334), 1953−1956. (220) Gilbert, J. A.; Eggleston, D. S.; Murphy, W. R.; Geselowitz, D.
(199) Limburg, J.; Szalai, V. A.; Brudvig, G. W. A Mechanistic and A.; Gersten, S. W.; Hodgson, D. J.; Meyer, T. J. Structure and Redox
Structural Model for the Formation and Reactivity of a MnV = O Properties of the Water-Oxidation Catalyst [(bpy)2(OH2)RuORu-
Species in Photosynthetic Water Oxidation. J. Chem. Soc., Dalton (OH2)(bpy)2]4+. J. Am. Chem. Soc. 1985, 107 (13), 3855−3864.
Trans. 1999, 9, 1353−1362. (221) Liu, F.; Concepcion, J. J.; Jurss, J. W.; Cardolaccia, T.;
(200) Limburg, J.; Vrettos, J. S.; Liable-Sands, L. M.; Rheingold, A. Templeton, J. L.; Meyer, T. J. Mechanisms of Water Oxidation from
L.; Crabtree, R. H.; Brudvig, G. W. A Functional Model for OO Bond the Blue Dimer to Photosystem II. Inorg. Chem. 2008, 47 (6), 1727−
Formation by the O2-Evolving Complex in Photosystem II. Science 1752.
1999, 283 (5407), 1524−1527. (222) Betley, T. A.; Wu, Q.; Van Voorhis, T.; Nocera, D. G.
(201) Siegbahn, P. E. Water Oxidation Mechanism in Photosystem Electronic Design Criteria for O−O Bond Formation via Metal−Oxo
II, Including Oxidations, Proton Release Pathways, O−O Bond Complexes. Inorg. Chem. 2008, 47 (6), 1849−1861.
Formation and O2 Release. Biochim. Biophys. Acta, Bioenerg. 2013, (223) Sherman, D. M. The Electronic Structures of Manganese
1827 (8), 1003−1019. Oxide Minerals. Am. Mineral. 1984, 69, 788−799.
(202) Siegbahn, P. E. M. Theoretical Studies of O−O Bond (224) Gorlin, Y.; Nordlund, D.; Jaramillo, T. F. The Role of Heat
Formation in Photosystem II. Inorg. Chem. 2008, 47 (6), 1779−1786. Treatment in Enhanced Activity of Manganese Oxides for the Oxygen

P DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX
Chemical Reviews Review

Reduction and Evolution Reactions. ECS Trans. 2013, 58 (1), 735− (242) Ahn, H. S.; Bard, A. J. Surface Interrogation of CoP(i) Water
750. Oxidation Catalyst by Scanning Electrochemical Microscopy. J. Am.
(225) Najafpour, M. M.; Renger, G.; Hołyńska, M.; Moghaddam, A. Chem. Soc. 2015, 137 (2), 612−615.
N.; Aro, E.-M.; Carpentier, R.; Nishihara, H.; Eaton-Rye, J. J.; Shen, J.- (243) Bockris, J. O.; Otagawa, T. Mechanism of Oxygen Evolution
R.; Allakhverdiev, S. I. Manganese Compounds as Water-Oxidizing on Perovskites. J. Phys. Chem. 1983, 87 (15), 2960−2971.
Catalysts: From the Natural Water-Oxidizing Complex to Nanosized (244) May, K. J.; Carlton, C. E.; Stoerzinger, K. A.; Risch, M.;
Manganese Oxide Structures. Chem. Rev. 2016, 116 (5), 2886−2936. Suntivich, J.; Lee, Y.-L.; Grimaud, A.; Shao-Horn, Y. Influence of
(226) Morita, M.; Iwakura, C.; Tamura, H. The Anodic Character- Oxygen Evolution during Water Oxidation on the Surface of
istics of Massive Manganese Oxide Electrode. Electrochim. Acta 1979, Perovskite Oxide Catalysts. J. Phys. Chem. Lett. 2012, 3 (22), 3264−
24 (4), 357−362. 3270.
(227) Najafpour, M. M.; Kompany-Zareh, M.; Zahraei, A.; Jafarian (245) Risch, M.; Grimaud, A.; May, K. J.; Stoerzinger, K. A.; Chen, T.
Sedigh, D.; Jaccard, H.; Khoshkam, M.; Britt, R. D.; Casey, W. H. J.; Mansour, A. N.; Shao-Horn, Y. Structural Changes of Cobalt-Based
Mechanism, Decomposition Pathway and New Evidence for Self- Perovskites upon Water Oxidation Investigated by EXAFS. J. Phys.
Healing of Manganese Oxides as Efficient Water Oxidizing Catalysts: Chem. C 2013, 117 (17), 8628−8635.
New Insights. Dalton Trans. 2013, 42 (40), 14603−14611. (246) Kim, H.; Park, J.; Park, I.; Jin, K.; Jerng, S. E.; Kim, S. H.; Nam,
(228) Mattioli, G.; Zaharieva, I.; Dau, H.; Guidoni, L. Atomistic K. T.; Kang, K. Coordination Tuning of Cobalt Phosphates towards
Texture of Amorphous Manganese Oxides for Electrochemical Water Efficient Water Oxidation Catalyst. Nat. Commun. 2015, 6, 8253.
Splitting Revealed by Ab Initio Calculations Combined with X-ray (247) Mefford, J. T.; Rong, X.; Abakumov, A. M.; Hardin, W. G.; Dai,
Spectroscopy. J. Am. Chem. Soc. 2015, 137 (32), 10254−10267. S.; Kolpak, A. M.; Johnston, K. P.; Stevenson, K. J. Water Electrolysis
(229) Huynh, M.; Shi, C.; Billinge, S. J. L.; Nocera, D. G. Nature of on La1-xSrxCoO3-δ Perovskite Electrocatalysts. Nat. Commun. 2016,
7, 11053.
Activated Manganese Oxide for Oxygen Evolution. J. Am. Chem. Soc.
(248) Friebel, D.; Louie, M. W.; Bajdich, M.; Sanwald, K. E.; Cai, Y.;
2015, 137 (47), 14887−14904.
Wise, A. M.; Cheng, M.-J.; Sokaras, D.; Weng, T.-C.; Alonso-Mori, R.;
(230) Huynh, M.; Bediako, D. K.; Nocera, D. G. A Functionally
et al. Identification of Highly Active Fe Sites in (Ni,Fe)OOH for
stable Manganese Oxide Oxygen Evolution Catalyst in Acid. J. Am.
Electrocatalytic Water Splitting. J. Am. Chem. Soc. 2015, 137 (3),
Chem. Soc. 2014, 136 (16), 6002−6010. 1305−1313.
(231) Indra, A.; Menezes, P. W.; Sahraie, N. R.; Bergmann, A.; Das, (249) Chen, J. Y. C.; Dang, L.; Liang, H.; Bi, W.; Gerken, J. B.; Jin, S.;
C.; Tallarida, M.; Schmeißer, D.; Strasser, P.; Driess, M. Unification of Alp, E. E.; Stahl, S. S. Operando Analysis of NiFe and Fe
Catalytic Water Oxidation and Oxygen Reduction Reactions: Oxyhydroxide Electrocatalysts for Water Oxidation: Detection of
Amorphous Beat Crystalline Cobalt Iron Oxides. J. Am. Chem. Soc. Fe4+ by Mössbauer Spectroscopy. J. Am. Chem. Soc. 2015, 137 (48),
2014, 136 (50), 17530−17536. 15090−15093.
(232) Smith, W. L.; Hobson, A. D. The Structure of Cobalt Oxide, (250) Ahn, H. S.; Bard, A. J. Surface Interrogation Scanning
Co3O4. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1973, Electrochemical Microscopy of Ni1−xFexOOH (0 < x < 0.27) Oxygen
29 (2), 362−363. Evolving Catalyst: Kinetics of the “fast” Iron Sites. J. Am. Chem. Soc.
(233) Wang, L.-P.; Van Voorhis, T. Direct-Coupling O2 Bond 2016, 138 (1), 313−318.
Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts. J. (251) Arroyo-Currás, N.; Bard, A. J. Iridium Oxidation as Observed
Phys. Chem. Lett. 2011, 2 (17), 2200−2204. by Surface Interrogation Scanning Electrochemical Microscopy. J.
(234) Crandell, D. W.; Ghosh, S.; Berlinguette, C. P.; Baik, M. H. Phys. Chem. C 2015, 119 (15), 8147−8154.
How a [CoIV = O]2+ Fragment Oxidizes Water: Involvement of a (252) Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements
Biradicaloid [CoII−(•O•)] 2+ Species in Forming the O−O Bond. 1984, 427−465.
ChemSusChem 2015, 8 (5), 844−852. (253) Hunter, B. M.; Hieringer, W.; Winkler, J. R.; Gray, H. B.;
(235) Li, X.; Siegbahn, P. E. Water Oxidation Mechanism for Müller, A. M. Effect of Interlayer Anions on [NiFe]-LDH Nanosheet
Synthetic Co-Oxides with Small Nuclearity. J. Am. Chem. Soc. 2013, Water Oxidation Activity. Energy Environ. Sci. 2016, 9 (5), 1734−1743.
135 (37), 13804−13813. (254) Winkler, J. R.; Gray, H. B. Electronic Structures of Oxo-Metal
(236) Smith, P. F.; Hunt, L.; Laursen, A. B.; Sagar, V.; Kaushik, S.; Ions. Struct. Bonding (Berlin, Ger.) 2011, 142, 17−28.
Calvinho, K. U. D.; Marotta, G.; Mosconi, E.; De Angelis, F.;
Dismukes, G. C. Water Oxidation by the [Co4O4(OAc)4(py)4]+
Cubium is Initiated by OH− Addition. J. Am. Chem. Soc. 2015, 137
(49), 15460−15468.
(237) Ullman, A. M.; Liu, Y.; Huynh, M.; Bediako, D. K.; Wang, H.;
Anderson, B. L.; Powers, D. C.; Breen, J. J.; Abruña, H. D.; Nocera, D.
G. Water Oxidation Catalysis by Co(II) Impurities in Co(III)4O4
Cubanes. J. Am. Chem. Soc. 2014, 136 (50), 17681−17688.
(238) Nguyen, A. I.; Ziegler, M. S.; Oña-Burgos, P.; Sturzbecher-
Hohne, M.; Kim, W.; Bellone, D. E.; Tilley, T. D. Mechanistic
Investigations of Water Oxidation by a Molecular Cobalt Oxide
Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive
Terminal Oxo Participation. J. Am. Chem. Soc. 2015, 137 (40), 12865−
12872.
(239) Kanan, M. W.; Yano, J.; Surendranath, Y.; Dinca, M.;
Yachandra, V. K.; Nocera, D. G. Structure and Valency of a
Cobalt−Phosphate Water Oxidation Catalyst Determined by In Situ
X-Ray Spectroscopy. J. Am. Chem. Soc. 2010, 132 (39), 13692−13701.
(240) Harley, S. J.; Mason, H. E.; McAlpin, J. G.; Britt, R. D.; Casey,
W. H. A (31) P NMR Investigation of the CoPi Water-Oxidation
Catalyst. Chem. - Eur. J. 2012, 18 (34), 10476−10479.
(241) Zhang, M.; de Respinis, M.; Frei, H. Time-Resolved
Observations of Water Oxidation Intermediates on a Cobalt Oxide
Nanoparticle Catalyst. Nat. Chem. 2014, 6 (4), 362−367.

Q DOI: 10.1021/acs.chemrev.6b00398
Chem. Rev. XXXX, XXX, XXX−XXX