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Journal article

Operando XAS Study of the Surface Oxidation State on a Monolayer IrOx on RuOx and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

From

Department of Physics, Technical University of Denmark1

Neutrons and X-rays for Materials Physics, Department of Physics, Technical University of Denmark2

Surface Physics and Catalysis, Department of Physics, Technical University of Denmark3

Stanford University4

University of Copenhagen5

Stockholm University6

Herein we present surface sensitive operando XAS L-edge measurements on IrOx/RuO2 thin films as well as mass-selected RuOx and Ru nanoparticles. We observed shifts of the white line XAS peak toward higher energies with applied electrochemical potential. Apart from the case of the metallic Ru nanoparticles, the observed potential dependencies were purely core-level shifts caused by a change in oxidation state, which indicates no structural changes.

These findings can be explained by different binding energies of oxygenated species on the surface of IrOx and RuOx. Simulated XAS spectra show that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy.

This observation is consistent with the notion that the metal-oxygen bond is stronger than ideal.

Language: English
Publisher: American Chemical Society (ACS)
Year: 2018
Pages: 878-887
ISSN: 15205207 and 15206106
Types: Journal article
DOI: 10.1021/acs.jpcb.7b06982
ORCIDs: 0000-0002-6432-3015 , 0000-0001-7749-6567 , Pedersen, Anders Filsøe , Sebok, Bela , Bodin, Anders , Stephens, Ifan , Chorkendorff, Ib and 0000-0003-1968-8696

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