Imperial College London
Portrait Picture

Professor James Durrant, CBE, FRS

Faculty of Natural Sciences, Department of Chemistry

Professor of Photochemistry
 
 
 
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Contact

 

+44 (0)20 7594 5321j.durrant Website

 
 
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Assistant

 

Miss Lisa Benbow +44 (0)20 7594 5883

 
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Location

 

G22CMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Rao:2022:10.1021/jacs.1c08152,
author = {Rao, RR and Corby, S and Bucci, A and Garcia-Tecedor, M and Mesa, CA and Rossmeisl, J and Gimenez, S and Lloret-Fillol, J and Stephens, IEL and Durrant, JR},
doi = {10.1021/jacs.1c08152},
journal = {Journal of the American Chemical Society},
pages = {7622--7633},
title = {Spectroelectrochemical analysis of the water oxidation mechanism on doped nickel oxides},
url = {http://dx.doi.org/10.1021/jacs.1c08152},
volume = {144},
year = {2022}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - Metal oxides and oxyhydroxides exhibit state-of-the-art activity for the oxygen evolution reaction (OER); however, their reaction mechanism, particularly the relationship between charging of the oxide and OER kinetics, remains elusive. Here, we investigate a series of Mn-, Co-, Fe-, and Zn-doped nickel oxides using operando UV–vis spectroscopy coupled with time-resolved stepped potential spectroelectrochemistry. The Ni2+/Ni3+ redox peak potential is found to shift anodically from Mn- < Co- < Fe- < Zn-doped samples, suggesting a decrease in oxygen binding energetics from Mn- to Zn-doped samples. At OER-relevant potentials, using optical absorption spectroscopy, we quantitatively detect the subsequent oxidation of these redox centers. The OER kinetics was found to have a second-order dependence on the density of these oxidized species, suggesting a chemical rate-determining step involving coupling of two oxo species. The intrinsic turnover frequency per oxidized species exhibits a volcano trend with the binding energy of oxygen on the Ni site, having a maximum activity of ∼0.05 s–1 at 300 mV overpotential for the Fe-doped sample. Consequently, we propose that for Ni centers that bind oxygen too strongly (Mn- and Co-doped oxides), OER kinetics is limited by O–O coupling and oxygen desorption, while for Ni centers that bind oxygen too weakly (Zn-doped oxides), OER kinetics is limited by the formation of oxo groups. This study not only experimentally demonstrates the relation between electroadsorption free energy and intrinsic kinetics for OER on this class of materials but also highlights the critical role of oxidized species in facilitating OER kinetics.
AU  - Rao,RR
AU  - Corby,S
AU  - Bucci,A
AU  - Garcia-Tecedor,M
AU  - Mesa,CA
AU  - Rossmeisl,J
AU  - Gimenez,S
AU  - Lloret-Fillol,J
AU  - Stephens,IEL
AU  - Durrant,JR
DO  - 10.1021/jacs.1c08152
EP  - 7633
PY  - 2022///
SN  - 0002-7863
SP  - 7622
TI  - Spectroelectrochemical analysis of the water oxidation mechanism on doped nickel oxides
T2  - Journal of the American Chemical Society
UR  - http://dx.doi.org/10.1021/jacs.1c08152
UR  - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000798986400017&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
UR  - https://pubs.acs.org/doi/10.1021/jacs.1c08152
UR  - http://hdl.handle.net/10044/1/99797
VL  - 144
ER  -
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