Cooperative Redox Transitions Drive Electrocatalysis of the Oxygen Evolution 
Reaction on Cobalt–Iron Core–Shell Nanoparticles

Royer, Lisa; Bonnefont, Antoine; Asset, Tristan; Rotonnelli, Benjamin; Velasco Vélez, Juan; Holdcroft, Steven; Hettler, Simon; Arenal, Raul; Pichon, Benoit; Savinova, Elena

doi:10.1021/acscatal.2c04512

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Cooperative Redox Transitions Drive Electrocatalysis of the Oxygen Evolution Reaction on Cobalt–Iron Core–Shell Nanoparticles

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Velasco Vélez, Juan
Inorganic Chemistry, Fritz Haber Institute, Max Planck Society;

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Royer, L., Bonnefont, A., Asset, T., Rotonnelli, B., Velasco Vélez, J., Holdcroft, S., et al. (2023). Cooperative Redox Transitions Drive Electrocatalysis of the Oxygen Evolution Reaction on Cobalt–Iron Core–Shell Nanoparticles. ACS Catalysis, 13(1), 280-286. doi:10.1021/acscatal.2c04512.

Cite as: https://hdl.handle.net/21.11116/0000-000C-159A-F

Abstract

Transition metal oxides are promising materials for the development of cost-effective catalysts for the oxygen evolution reaction (OER) in alkaline media. Understanding the catalysts’ transformations occurring during the harsh oxidative conditions of the OER remains a bottleneck for the development of stable and active catalysts. Here, we studied redox transformations of core–shell Fe₃O₄@CoFe₂O₄ oxide nanoparticles over a wide range of potentials by using operando near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in total electron yield (TEY) detection mode. The analysis of the NEXAFS spectra reveals that the Fe₃O₄ core strongly affects the surface chemistry of the CoFe₂O₄ shell under the OER conditions. The spinel structure of the particles with Co (II) in the shell is preserved at potentials as high as 1.8 V vs RHE, at which Co (II) is expected to be oxidized into Co (III); whereas Fe (II) in the core is reversibly oxidized to Fe (III).