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

Anders Filsøe Pedersen, Maria Escudero Escribano, Bela Sebok, Anders Bodin, Elisa Antares Paoli, Rasmus Frydendal, Daniel Friebel, Ifan Stephens, Jan Rossmeisl, Ib Chorkendorff, Anders Nilsson*

*Corresponding author for this work

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Abstract

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.
Original languageEnglish
JournalJournal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Volume122
Issue number2
Pages (from-to)878–887
ISSN1520-6106
DOIs
Publication statusPublished - 2018

Cite this

Pedersen, Anders Filsøe ; Escribano, Maria Escudero ; Sebok, Bela ; Bodin, Anders ; Paoli, Elisa Antares ; Frydendal, Rasmus ; Friebel, Daniel ; Stephens, Ifan ; Rossmeisl, Jan ; Chorkendorff, Ib ; Nilsson, Anders. / 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. In: Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical. 2018 ; Vol. 122, No. 2. pp. 878–887.
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title = "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",
abstract = "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.",
author = "Pedersen, {Anders Fils{\o}e} and Escribano, {Maria Escudero} and Bela Sebok and Anders Bodin and Paoli, {Elisa Antares} and Rasmus Frydendal and Daniel Friebel and Ifan Stephens and Jan Rossmeisl and Ib Chorkendorff and Anders Nilsson",
year = "2018",
doi = "10.1021/acs.jpcb.7b06982",
language = "English",
volume = "122",
pages = "878–887",
journal = "Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "2",

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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. / Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela; Bodin, Anders; Paoli, Elisa Antares; Frydendal, Rasmus; Friebel, Daniel; Stephens, Ifan; Rossmeisl, Jan; Chorkendorff, Ib; Nilsson, Anders.

In: Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical, Vol. 122, No. 2, 2018, p. 878–887.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - 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

AU - Pedersen, Anders Filsøe

AU - Escribano, Maria Escudero

AU - Sebok, Bela

AU - Bodin, Anders

AU - Paoli, Elisa Antares

AU - Frydendal, Rasmus

AU - Friebel, Daniel

AU - Stephens, Ifan

AU - Rossmeisl, Jan

AU - Chorkendorff, Ib

AU - Nilsson, Anders

PY - 2018

Y1 - 2018

N2 - 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.

AB - 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.

U2 - 10.1021/acs.jpcb.7b06982

DO - 10.1021/acs.jpcb.7b06982

M3 - Journal article

VL - 122

SP - 878

EP - 887

JO - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

JF - Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

SN - 1520-6106

IS - 2

ER -