ll
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throughput, energy efficiency, and
selectivity.10
ACKNOWLEDGMENTS
The authors would like to acknowledge
the financial support of the National
Science Foundation and NYU Tandon
School of Engineering through
M.A.M.’s startup fund. This material is
based upon work supported by the Na-
tional Science Foundation under grant
no. 1943972.
DECLARATION OF INTERESTS
M.A.M. is a co-founder of and has finan-
cial interests in Sunthetics Inc., a com-
pany operating on the sustainable
chemical manufacturing space. M.A.M.
is also listed as an inventor on a related
The search for intermediates
formed during water-oxidation catalysis
Rosalie K. Hocking1,*
The development of new methods to explore catalysts under condi-
tions of operation is critical for materials innovation. In this issue of
Chem Catalysis, Pushkar and co-workers investigate the photo-
system II analog cubane compound [Co4O4Py4 Ac4] (Py= pyridine
and Ac= CH3COO ) under conditions of water-oxidation catalysis
at low pH.
Since people first began to appreciate
photosynthesis, we have tried to under-
stand it.1 The reasons for this are clear:
if we could mimic water oxidation, we
would have a clean way to reduce atmo-
spheric carbon dioxide and manufac-
ture key commodity products in the
process.
Similarly, if we could understand engi-
neered "man-made" materials such as
metal-oxides thin-film water-oxidation
catalysts, we could understand how
248 Chem Catalysis 1, 241–257, July 15, 2021 Crown Copyright ª 2021 Published by Elsevier Inc.
U.S. Provisional Patent Application No.
63/023,173.
1. Rissman, J., Bataille, C., Masanet, E., Aden,
N., Morrow, W.R., Zhou, N., Elliott, N., Dell,
R., Heeren, N., Huckestein, B., et al. (2020).
Technologies and policies to decarbonize
global industry: Review and assessment of
mitigation drivers through 2070. Appl.
Energy 266, 114848.
2. DOE, U.S. (2015). Bandwidth Study on Energy
Use and Potential Energy Saving
Opportunities in U.S. Chemical
Manufacturing. https://www.energy.gov/
sites/prod/files/2015/08/f26/
chemical_bandwidth_report.pdf.
3. Schiffer, Z.J., and Manthiram, K. (2017).
Electrification and Decarbonization of the
Chemical Industry. Joule 1, 10–14.
4. Biddinger, E.J., and Modestino, M.A. (2020).
Electro-organic Syntheses for Green
Chemical Manufacturing. Electrochem. Soc.
Interface 29, 43–47.
5. De Luna, P., Hahn, C., Higgins, D., Jaffer, S.A.,
Jaramillo, T.F., and Sargent, E.H. (2019). What
they work and improve their selectivity
and durability. However, there are still
many unanswered questions about
how these processes work. Although
we know the basic structure of photo-
system II (PSII), there are still key ques-
tions about the processes that precede
O-O bond formation.2 The same is true
with our benchmark electrocatalysts
made from thin films of metal-ox-
ides—the most active of which are
observed to be both disordered and
nanostructured.3–5
would it take for renewably powered
electrosynthesis to displace petrochemical
processes? Science 364, eaav3506.
6. Zhang, D., Chen, J., Hao, Z., Jiao, L., Ge, Q.,
Fu, W.-F., and Lv, X.-J. (2021). Highly efficient
electrochemical hydrogenation of
acetonitrile to ethylamine for primary amine
synthesis and promising hydrogen storage.
Chem Catalysis 1, 393–406.
7. Xia, R., Tian, D., Kattel, S., Hasa, B., Shin, H.,
Ma, X., Chen, J.G., and Jiao, F. (2021).
Electrochemical reduction of acetonitrile to
ethylamine. Nat. Commun. 12, 1949.
8. Blanco, D.E., Dookhith, A.Z., and Modestino,
M.A. (2020). Controlling Selectivity in the
Electrocatalytic Hydrogenation of
Adiponitrile through Electrolyte Design. ACS
Sustain. Chem.& Eng. 8, 9027–9034.
9. Song, Y., and Pintauro, P.N. (1991). The
electrochemical synthesis of aminonitriles I.
H-cell studies with adiponitrile and
azelanitrile. J. Appl. Electrochem. 21, 21–27.
10. Blanco, D.E., and Modestino, M.A. (2019).
Organic Electrosynthesis for Sustainable
Chemical Manufacturing. Trends in
Chemistry 1, 8–10.
From an analytical perspective, two sig-
nificant challenges limit our ability to
characterize materials in their ‘‘func-
tional, active’’ states, which are key
for materials innovation. Historically
analytical techniques work best at two
extremes. They work well for molecular
materials, as seen in Figure 1, top left.
For molecular materials, spectroscopy
is more straightforward than for clus-
ters. This means transitions, whether
magnetic or electronic, can be fully as-
signed, and materials can be under-
stood well.6 As clusters get bigger,
transitions overlap and interact with
each other, making assignments com-
plex. At the other extreme shown in Fig-
ure 1, at right we have crystalline mate-
rials; when the material is a single
crystal, we generally know its structure
unambiguously. Unfortunately, the
1Department of Chemistry and Biotechnology
and Centre for Translational Atomaterials,
Swinburne University of Technology, Hawthorn,
Melbourne, VIC 3122, Australia
*Correspondence: rhocking@swin.edu.au
https://doi.org/10.1016/j.checat.2021.06.004

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Figure 1. The challenges of characterizing materials
A scale from molecules to single crystals. The most complex materials to understand analytically
are not simple molecules nor ordered crystals but rather those that structurally lie between the two
limits.
most active catalyst materials for water
oxidation are almost always species
that are not described well at either
end of the spectrum depicted in Fig-
ure 1. PSII is composed of four manga-
nese atoms and one calcium atom,
forming a cube (Figure 1, blue text).
The most functional2 known electroca-
talysts for water oxidation are often
thin films of disordered metal oxides—
making characterization of these impor-
tant functional materials very chal-
lenging before we even begin to think
about how they change under catalysis
conditions.
In order to really study water oxidation,
the catalyst material itself needs to be
subject to conditions of catalysis; in
most cases, these conditions have the
effect of oxidizing the catalyst, produc-
ing an intermediate, and the nature of
that intermediate and the states that
follow are key for understanding water
oxidation mechanistically. Studying
this state of materials is not easy. Key
adaptions need to be made to enable
data collection in situ. Then these ex-
periments need to be carefully moni-
tored. Typically, intermediate materials
can be very unstable, and careful
checks need to be made to ensure the
material’s robustness. Many design
considerations need to be made to do
this effectively, including preserving
the species under conditions of analysis
and adapting experimental setups for
electrochemistry.7,8
In this issue of Chem Catalysis, Ezhov
et al.9 describe their investigations of
the PSII analogue [Co4O4Py4Ac4] under
conditions of water-oxidation catalysis.
The authors employ in situ X-ray ab-
sorption spectroscopy (XAS) and elec-
tron paramagnetic resonance (EPR)
coupled with density functional theory
calculations to conclude that a CoIV=O
intermediate forms before O-O bond
formation. The observation is fasci-
nating because we don’t generally see
stable M=O species for d-electron con-
figurations beyond d5,10 but the work
shows such species could be critical in-
termediates in water-oxidation catal-
ysis. The work also provides an inter-
esting link between water oxidation in
biology and thin-film metal-oxide-
based electrolyzer materials.
A key question in the water-oxidation
mechanism by transition-metal cata-
lysts is understanding the distribution
of electrons between the catalyst and
the substrate (H2O) before and during
catalysis.
We must ask how the material itself is
oxidized and the role of any other func-
tional groups in the mechanism. Is the
oxidation process primarily localized
on the oxygen or on the metal? Ezhov
ll
et al. show that for the cubane system,
a CoIV=O species is formed during the
processes, probably from the equilib-
rium between CoIV=O + H2O #
CoOOH + H+, with no evidence for a
CoV intermediate. Notably, the work
also shows that the organic groups
present in [Co4O4Py4 Ac4] the acetate
is not needed to turn the system over.
This observation is fascinating because
one of the significant distinctions be-
tween biological and materials systems
is organic groups interacting at the sur-
face of the oxides.
Beyond intermediates, there are still
critical questions about biological and
materials catalysts that need to be
answered. Even when redox states are
the same, the thermodynamic stability
of analogues such as the [Co4O4Py4Ac4]
species is likely to be fundamentally
different biology where protein struc-
ture will affect overall stability. In nano-
structured materials, key questions
about electron transfer and the role of
structure in electron-transfer time scales
are being asked and could be key for
future materials design and innovation.
ACKNOWLEDGEMENTS
R.K.H. is grateful to Swinburne University
of Technology for a Vice Chancellors
Women in STEM fellowship, the Austra-
lian Research Council (ARC) for funding
DP200101878, and the Australian Syn-
chrotron and staff for for ongoing support
of her research work in catalysis.
DECLARATION OF INTERESTS
The authors declare no competing
interests.
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with Oxygen. Acc. Chem. Res. 51, 1850–1857.
2. Cox, N., Pantazis, D.A., and Lubitz, W. (2020).
Current Understanding of the Mechanism of
Water Oxidation in Photosystem II and Its
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Radical-mediated and co-workers in 2017 (Figure 1B, a).4

Inspired by the fact that the oxidation
1,2-Brook rearrangements potential of pentacoordinate silicates
could be significantly reduced to
ca. +0.6 V,5 they applied a mild cata-
Ziqiang Wang1 and Chen Zhu1,2,*
lytic photoredox system to oxidize the
in-situ-formed cyclic hypervalent Si
Classic Brook rearrangements via anionic migration of silyl groups anion. The C–Si bond was readily
are employed extensively in the transformation of organosilicon cleaved via single-electron oxidation,
compounds. However, radical-mediated Brook rearrangements leading to the a-oxy alkyl radicals.
remain underexplored. In this issue of Chem Catalysis, Shen These nucleophilic radicals were then
and co-workers disclose an organophotocatalytic 1,2-Brook rear- intercepted by electron-deficient ole-
rangement to efficiently provide allyl tert-(hetero)cyclobutanols fins, such as vinyl ketones, affording
and investigate their subsequent ring-opening and -expansion the Giese-type alkylation products.
functionalizations. The reaction could also proceed with
electron-deficient arenes and give rise
to the arylation product. Mechanistic
The seminal Brook rearrangements Alternatively, the intramolecular 1,2- studies ruled out the possibility of pro-
were unveiled in the late 1950s1 and migration of silyl groups can also be ton-coupled electron transfer (PCET),
proceed through intramolecular realized through radical pathways. In which could also enable the generation
anionic migration of silyl groups from early studies, the alkoxy radicals of alkoxy radicals directly from O–H
a C to an O atom. The reaction is facili- showed the propensity of Si atom bonds. It should be noted that only
tated by the formation of a strong O–Si abstraction from the a-C–Si bonds.3 the aryl-substituted hydoxysilanes
bond from a relatively weak C–Si bond, However, such radical-mediated Brook were demonstrated as substrates in
resulting in a carbanion that undergoes rearrangements have not been exten- the reaction.
subsequent nucleophilic additions (Fig- sively investigated, probably because
ure 1A). Of note, the reaction provides it is difficult to gain alkoxy radicals via
a polarity-reversal strategy, affording single-electron transfer, in particular 1Key Laboratory of Organic Synthesis of Jiangsu
the nucleophilic carbanion from origi- from a-hydoxysilanes. Alcoholic O–H Province, College of Chemistry, Chemical
Engineering, and Materials Science, Soochow
nally electrophilic carbonyl com- bonds, in general, have high oxidation University, 199 Ren-Ai Road, Suzhou, Jiangsu
pounds. By virtue of this unique charac- potential (Eox > +2.0 V versus satu- 215123, China
teristic, Brook rearrangements have rated calomel electrode) and are resis- 2Key Laboratory of Synthetic Chemistry of Natural
been extensively applied in the trans- tant to routine oxidative conditions. Substances, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 345
formations of organosilicon com- Lingling Road, Shanghai 200032, China
pounds into other useful chemical A landmark study for 1,2-radical Brook *Correspondence: chzhu@suda.edu.cn
products over the past half-century.2 rearrangements was revealed by Smith https://doi.org/10.1016/j.checat.2021.04.006

250 Chem Catalysis 1, 241–257, July 15, 2021 ª 2021 Elsevier Inc.