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throughput, energy efficiency, and U.S. Provisional Patent Application No. would it take for renewably powered
electrosynthesis to displace petrochemical
selectivity.10 63/023,173. 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
ACKNOWLEDGMENTS 1. Rissman, J., Bataille, C., Masanet, E., Aden,
electrochemical hydrogenation of
N., Morrow, W.R., Zhou, N., Elliott, N., Dell,
The authors would like to acknowledge R., Heeren, N., Huckestein, B., et al. (2020). acetonitrile to ethylamine for primary amine
Technologies and policies to decarbonize synthesis and promising hydrogen storage.
the financial support of the National global industry: Review and assessment of Chem Catalysis 1, 393–406.
Science Foundation and NYU Tandon mitigation drivers through 2070. Appl.
Energy 266, 114848. 7. Xia, R., Tian, D., Kattel, S., Hasa, B., Shin, H.,
School of Engineering through Ma, X., Chen, J.G., and Jiao, F. (2021).
2. DOE, U.S. (2015). Bandwidth Study on Energy Electrochemical reduction of acetonitrile to
M.A.M.’s startup fund. This material is
Use and Potential Energy Saving ethylamine. Nat. Commun. 12, 1949.
based upon work supported by the Na- Opportunities in U.S. Chemical
Manufacturing. https://www.energy.gov/ 8. Blanco, D.E., Dookhith, A.Z., and Modestino,
tional Science Foundation under grant M.A. (2020). Controlling Selectivity in the
sites/prod/files/2015/08/f26/
no. 1943972. chemical_bandwidth_report.pdf. Electrocatalytic Hydrogenation of
Adiponitrile through Electrolyte Design. ACS
3. Schiffer, Z.J., and Manthiram, K. (2017). Sustain. Chem.& Eng. 8, 9027–9034.
Electrification and Decarbonization of the
DECLARATION OF INTERESTS Chemical Industry. Joule 1, 10–14. 9. Song, Y., and Pintauro, P.N. (1991). The
electrochemical synthesis of aminonitriles I.
M.A.M. is a co-founder of and has finan- 4. Biddinger, E.J., and Modestino, M.A. (2020). H-cell studies with adiponitrile and
cial interests in Sunthetics Inc., a com- Electro-organic Syntheses for Green azelanitrile. J. Appl. Electrochem. 21, 21–27.
Chemical Manufacturing. Electrochem. Soc.
pany operating on the sustainable Interface 29, 43–47. 10. Blanco, D.E., and Modestino, M.A. (2019).
Organic Electrosynthesis for Sustainable
chemical manufacturing space. M.A.M. 5. De Luna, P., Hahn, C., Higgins, D., Jaffer, S.A., Chemical Manufacturing. Trends in
is also listed as an inventor on a related Jaramillo, T.F., and Sargent, E.H. (2019). What Chemistry 1, 8–10.

The search for intermediates From an analytical perspective, two sig-

nificant challenges limit our ability to
formed during water-oxidation catalysis characterize materials in their ‘‘func-
tional, active’’ states, which are key
for materials innovation. Historically
Rosalie K. Hocking1,*
analytical techniques work best at two
extremes. They work well for molecular
The development of new methods to explore catalysts under condi- materials, as seen in Figure 1, top left.
tions of operation is critical for materials innovation. In this issue of For molecular materials, spectroscopy
Chem Catalysis, Pushkar and co-workers investigate the photo- is more straightforward than for clus-
system II analog cubane compound [Co4O4Py4 Ac4] (Py= pyridine ters. This means transitions, whether
and Ac= CH3COO ) under conditions of water-oxidation catalysis magnetic or electronic, can be fully as-
at low pH. signed, and materials can be under-
stood well.6 As clusters get bigger,
transitions overlap and interact with
Since people first began to appreciate they work and improve their selectivity
each other, making assignments com-
photosynthesis, we have tried to under- and durability. However, there are still
plex. At the other extreme shown in Fig-
stand it.1 The reasons for this are clear: many unanswered questions about
ure 1, at right we have crystalline mate-
if we could mimic water oxidation, we how these processes work. Although
rials; when the material is a single
would have a clean way to reduce atmo- we know the basic structure of photo-
crystal, we generally know its structure
spheric carbon dioxide and manufac- system II (PSII), there are still key ques-
unambiguously. Unfortunately, the
ture key commodity products in the tions about the processes that precede
process. O-O bond formation.2 The same is true
with our benchmark electrocatalysts 1Department of Chemistry and Biotechnology
Similarly, if we could understand engi- made from thin films of metal-ox- and Centre for Translational Atomaterials,
Swinburne University of Technology, Hawthorn,
neered "man-made" materials such as ides—the most active of which are Melbourne, VIC 3122, Australia
metal-oxides thin-film water-oxidation observed to be both disordered and *Correspondence: [email protected]
catalysts, we could understand how nanostructured.3–5 https://doi.org/10.1016/j.checat.2021.06.004

248 Chem Catalysis 1, 241–257, July 15, 2021 Crown Copyright ª 2021 Published by Elsevier Inc.
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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-
Figure 1. The challenges of characterizing materials
A scale from molecules to single crystals. The most complex materials to understand analytically face of the oxides.
are not simple molecules nor ordered crystals but rather those that structurally lie between the two
limits. Beyond intermediates, there are still
critical questions about biological and
most active catalyst materials for water and adapting experimental setups for materials catalysts that need to be
oxidation are almost always species electrochemistry.7,8 answered. Even when redox states are
that are not described well at either the same, the thermodynamic stability
end of the spectrum depicted in Fig- In this issue of Chem Catalysis, Ezhov of analogues such as the [Co4O4Py4Ac4]
ure 1. PSII is composed of four manga- et al.9 describe their investigations of species is likely to be fundamentally
nese atoms and one calcium atom, the PSII analogue [Co4O4Py4Ac4] under different biology where protein struc-
forming a cube (Figure 1, blue text). conditions of water-oxidation catalysis. ture will affect overall stability. In nano-
The most functional2 known electroca- The authors employ in situ X-ray ab- structured materials, key questions
talysts for water oxidation are often sorption spectroscopy (XAS) and elec- about electron transfer and the role of
thin films of disordered metal oxides— tron paramagnetic resonance (EPR) structure in electron-transfer time scales
making characterization of these impor- coupled with density functional theory are being asked and could be key for
tant functional materials very chal- calculations to conclude that a CoIV=O future materials design and innovation.
lenging before we even begin to think intermediate forms before O-O bond
about how they change under catalysis formation. The observation is fasci- ACKNOWLEDGEMENTS
conditions. nating because we don’t generally see R.K.H. is grateful to Swinburne University
stable M=O species for d-electron con- of Technology for a Vice Chancellors
In order to really study water oxidation, figurations beyond d5,10 but the work Women in STEM fellowship, the Austra-
the catalyst material itself needs to be shows such species could be critical in- lian Research Council (ARC) for funding
subject to conditions of catalysis; in termediates in water-oxidation catal- DP200101878, and the Australian Syn-
most cases, these conditions have the ysis. The work also provides an inter- chrotron and staff for for ongoing support
effect of oxidizing the catalyst, produc- esting link between water oxidation in of her research work in catalysis.
ing an intermediate, and the nature of biology and thin-film metal-oxide-
that intermediate and the states that based electrolyzer materials. DECLARATION OF INTERESTS
follow are key for understanding water
The authors declare no competing
oxidation mechanistically. Studying A key question in the water-oxidation
interests.
this state of materials is not easy. Key mechanism by transition-metal cata-
adaptions need to be made to enable lysts is understanding the distribution
1. Gray, H.B., and Winkler, J.R. (2018). Living
data collection in situ. Then these ex- of electrons between the catalyst and with Oxygen. Acc. Chem. Res. 51, 1850–1857.
periments need to be carefully moni- the substrate (H2O) before and during
2. Cox, N., Pantazis, D.A., and Lubitz, W. (2020).
tored. Typically, intermediate materials catalysis. Current Understanding of the Mechanism of
can be very unstable, and careful Water Oxidation in Photosystem II and Its
Relation to XFEL Data. Annu. Rev. Biochem.
checks need to be made to ensure the We must ask how the material itself is 89, 795–820.
material’s robustness. Many design oxidized and the role of any other func- 3. McCrory, C.C., Jung, S., Peters, J.C., and
considerations need to be made to do tional groups in the mechanism. Is the Jaramillo, T.F. (2013). Benchmarking
heterogeneous electrocatalysts for the
this effectively, including preserving oxidation process primarily localized oxygen evolution reaction. J. Am. Chem. Soc.
the species under conditions of analysis on the oxygen or on the metal? Ezhov 135, 16977–16987.

Chem Catalysis 1, 241–257, July 15, 2021 249

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4. King, H.J., Bonke, S.A., Chang, S., Spiccia, L., Transition Metal Complexes. In Inorganic and Metal Electronic States During
Johannesson, B., and Hocking, R.K. (2017). Electronic Structure and Spectroscopy, E.I. Managnese Oxide Catalysed Water
Engineering disorder into heterogenite-like Solomon and A.B.P. Lever, eds. (Wiley), Oxidation Revealed by In Situ Soft X-ray
cobalt oxides by phosphate doping: pp. 1–91. Spectroscopy. Angew. Chem. Int. Ed. 131,
Implications for the design of water oxidation 3464–3470.
catalysts. ChemCatChem 9, 511–521. 7. King, H.J., Fournier, M., Bonke, S.A., Seeman,
E., Chatti, M., Jumabekov, A.N., 9. Ezhov, R., Karbakhsh, A.K., Bury, G., Smith,
5. Chatti, M., Gardiner, J.L., Fournier, M., Johannessen, B., Kappen, P., Simonov, A.N., P.F., and Pushkar, Y. (2021). Do multi-nuclear
Johannessen, B., William, T., Gengenbach, and Hocking, R.K. (2019). Photon-Induced, 3d metal catalysts achieve O-O bond
T.R., Pai, N., Nguyen, C., MacFarlane, D.R., Timescale, and Electrode Effects Critical for formation via radical coupling or via water
Hocking, R.K., and Simonov, A.N. (2019). the in Situ X-ray Spectroscopic Analysis of nucleophilic attach? WNA leads the way in
Intrinsically stable in situ generated Electrocatalysts: The Water Oxidation Case. [Co4O4]n+. Chem Catalysis 1,
electrocatalyst for long-term oxidation of J. Phys. Chem. C 123, 28533–28549. 407–422.
acidic water at up to 80 C. Nature Catalysis 2,
457–465. 8. Tesch, M.F., Bonke, S.A., Jones, T.E., Shaker, 10. Larson, V.A., Battistella, B., Ray, K., Lehnert,
M., Xiao, J., Skorupska, K., Mom, R., Melder, N., and Nam, W. (2020). Iron and manganese
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Ligand Field Theory and the Properties of Evolution of Oxygen-Metal Electron Transfer Rev. Chem. 4, 404–419.

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: [email protected]
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.