Cover Feature: Tailoring a Zinc Oxide Nanorod Surface by Adding an Earth‐Abundant Cocatalyst for Induced Sunlight Water Oxidation (ChemPhysChem 6/2020)

Water oxidation is the primary step in both natural and artificial photosynthesis to convert solar energy in into chemical fuels. Herein, we report the first cobalt-based pincer catalyst for electrolytic water oxidation at neutral pH with high efficiency under electrochemical conditions. Most importantly, ligand (pseudo)aromaticity is identified to play an important role in the electrocatalysis. A significant potential jump (~300 mV) was achieved towards a lower positive value when the aromatized cobalt complex was transformed to a (pseudo)dearomatized cobalt species. This complex catalyzes the water oxidation in its high valent oxidation state at a much lower overpotential (~ 340 mV vs. NHE) based on the onset potential (0.5 mA/cm<sup>2</sup>) of catalysis at pH 10.5, outperforming all the other literature systems. These observations may provide a new strategy for the design of earth-abundant transition metal-based water oxidation catalysts.

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Photocatalytic water oxidation with a Prussian blue modified brown TiO2

Chemical Communications ◽

10.1039/d0cc07077g ◽

2021 ◽

Author(s):

Gulsum Gundogdu ◽

T. Gamze Ulusoy Ghobadi ◽

Sina Sadigh Akbari ◽

Ekmel Ozbay ◽

Ferdi Karadas

Keyword(s):

Prussian Blue ◽

Water Oxidation ◽

Prussian Blue Analogue ◽

Earth Abundant

A CoFe Prussian blue analogue is coupled with brown TiO2 nanoparticles to achieve an earth-abundant photocatalytic water oxidation assembly.

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Earth-abundant metal complexes as catalysts for water oxidation; is it homogeneous or heterogeneous?

Catalysis Science & Technology ◽

10.1039/c5cy01251a ◽

2015 ◽

Vol 5 (11) ◽

pp. 4901-4925 ◽

Cited By ~ 40

Author(s):

Md. Ali Asraf ◽

Hussein A. Younus ◽

Mekhman Yusubov ◽

Francis Verpoort

Keyword(s):

Metal Complexes ◽

Water Oxidation ◽

Earth Abundant

This minireview focuses on the aspects that determine whether particular catalysts for the oxidation of water are homogeneous or heterogeneous.

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Earth-Abundant Heterogeneous Water Oxidation Catalysts

Chemical Reviews ◽

10.1021/acs.chemrev.6b00398 ◽

2016 ◽

Vol 116 (22) ◽

pp. 14120-14136 ◽

Cited By ~ 700

Author(s):

Bryan M. Hunter ◽

Harry B. Gray ◽

Astrid M. Müller

Keyword(s):

Water Oxidation ◽

Oxidation Catalysts ◽

Earth Abundant

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Cobalt salophen complexes for light-driven water oxidation

Catalysis Science & Technology ◽

10.1039/c5cy02157j ◽

2016 ◽

Vol 6 (12) ◽

pp. 4271-4282 ◽

Cited By ~ 15

Author(s):

Md. Ali Asraf ◽

Hussein A. Younus ◽

Chizoba I. Ezugwu ◽

Akshay Mehta ◽

Francis Verpoort

Keyword(s):

Water Oxidation ◽

Oxidation Reaction ◽

Molecular Complexes ◽

Earth Abundant

Earth-abundant molecular complexes have been found to be excellent catalysts for the light-driven water oxidation reaction.

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Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes

Australian Journal of Chemistry ◽

10.1071/ch11178 ◽

2011 ◽

Vol 64 (9) ◽

pp. 1221 ◽

Cited By ~ 14

Author(s):

Karin J. Young ◽

Yunlong Gao ◽

Gary W. Brudvig

Keyword(s):

Tin Oxide ◽

Water Oxidation ◽

Polymer Membranes ◽

Wavelength Dependence ◽

Applied Potential ◽

Solvent Water ◽

Earth Abundant ◽

Manganese Dioxide Nanoparticles ◽

Glass Electrodes ◽

Manganese Compounds

Robust water oxidation catalysts using earth abundant metals are required as part of an overall scheme to convert sunlight into fuels. Here, we report the immobilization of [Mn4IVO5(terpy)4(H2O)2](ClO4)6 (terpy = 2,2′;6′,2′′-terpyridine), [Mn4O6(tacn)4](ClO4)4 (tacn = 1,4,7-triazacyclononane), and manganese dioxide nanoparticles in Nafion on fluorine-doped tin oxide conducting glass electrodes. The electrodes are illuminated with white light in the presence of an applied potential and the resulting photocurrent is assigned to the oxidation of solvent water. Photodecomposition of the tetrameric complexes results in a material that is more active for light-driven electrooxidation of water. The reactivity, wavelength dependence, and stability of the compounds in Nafion under illumination are discussed.

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Photoelectrochemical studies on earth abundant pentanickel polyoxometalates as co-catalysts for solar water oxidation

Sustainable Energy & Fuels ◽

10.1039/c7se00523g ◽

2018 ◽

Vol 2 (4) ◽

pp. 827-835 ◽

Cited By ~ 1

Author(s):

Arun Sridhar Siddarth ◽

Wujian Miao

Keyword(s):

Water Oxidation ◽

Zero Bias ◽

First Report ◽

Solar Water ◽

Co Catalysts ◽

Earth Abundant ◽

Solar Water Oxidation ◽

Photoelectrochemical Studies

This is the first report on a FTO/TiO2–Ni5-POM system, and results obtained display a notable zero bias photocurrent.

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Spectroelectrochemical study of water oxidation on nickel and iron oxyhydroxide electrocatalysts

Nature Communications ◽

10.1038/s41467-019-13061-0 ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 20

Author(s):

Laia Francàs ◽

Sacha Corby ◽

Shababa Selim ◽

Dongho Lee ◽

Camilo A. Mesa ◽

...

Keyword(s):

Water Oxidation ◽

Reactive Intermediates ◽

Reaction Rates ◽

Iron Oxyhydroxide ◽

Rate Limiting Step ◽

Limiting Step ◽

Earth Abundant ◽

Fe Oxyhydroxides ◽

Rate Limiting ◽

Kinetics Of

AbstractNi/Fe oxyhydroxides are the best performing Earth-abundant electrocatalysts for water oxidation. However, the origin of their remarkable performance is not well understood. Herein, we employ spectroelectrochemical techniques to analyse the kinetics of water oxidation on a series of Ni/Fe oxyhydroxide films: FeOOH, FeOOHNiOOH, and Ni(Fe)OOH (5% Fe). The concentrations and reaction rates of the oxidised states accumulated during catalysis are determined. Ni(Fe)OOH is found to exhibit the fastest reaction kinetics but accumulates fewer states, resulting in a similar performance to FeOOHNiOOH. The later catalytic onset in FeOOH is attributed to an anodic shift in the accumulation of oxidised states. Rate law analyses reveal that the rate limiting step for each catalyst involves the accumulation of four oxidised states, Ni-centred for Ni(Fe)OOH but Fe-centred for FeOOH and FeOOHNiOOH. We conclude by highlighting the importance of equilibria between these accumulated species and reactive intermediates in determining the activity of these materials.

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