Examining the Structure Sensitivity of the Oxygen Evolution Reaction on Pt Single-Crystal Electrodes: A Combined Experimental and Theoretical Study.

density functional theory oxygen evolution reaction platinum single crystals structure sensitivity

Journal

Chemphyschem : a European journal of chemical physics and physical chemistry
ISSN: 1439-7641
Titre abrégé: Chemphyschem
Pays: Germany
ID NLM: 100954211

Informations de publication

Date de publication:
19 11 2019
Historique:
received: 29 01 2019
revised: 29 03 2019
pubmed: 3 4 2019
medline: 3 4 2019
entrez: 3 4 2019
Statut: ppublish

Résumé

In the present work we investigate the structure sensitivity of the oxygen evolution reaction (OER) combining electrochemistry, in situ spectroscopy and density functional theory calculations. The intrinsic difficulty of such studies is the fact that at electrode potentials where the OER is observed, the electrode material is highly oxidized. As a consequence, the surface structure during the reaction is in general ill-defined and only scarce knowledge exists concerning the structure-activity relationship of this important reaction. To alleviate these challenging conditions, we chose as starting point well-defined Pt single-crystal electrodes, which we exposed to well-defined conditioning before studying their OER rate. Using this approach, a potential region is identified where the OER on Pt is indeed structure-sensitive with Pt(100) being significantly more active than Pt(111). This experimental finding is in contrast to a DFT analysis of the adsorption strength of the reaction intermediates O*, OH*, and OOH* often used to plot the activity in a volcano curve. It is proposed that as a consequence of the highly oxidizing conditions, the structure-sensitive charge-transfer resistance through the interface determines the observed reaction rate.

Identifiants

pubmed: 30938896
doi: 10.1002/cphc.201900193
doi:

Types de publication

Journal Article Research Support, Non-U.S. Gov't

Langues

eng

Sous-ensembles de citation

IM

Pagination

3154-3162

Subventions

Organisme : SNF Professorship
ID : PP00P2_157615
Pays : International
Organisme : UBELIX
Pays : International
Organisme : University of Bern
Pays : International

Informations de copyright

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Auteurs

Francesco Bizzotto (F)

Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland.

Hassan Ouhbi (H)

Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland.

Yongchun Fu (Y)

Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland.
present address: College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, China.

Gustav K H Wiberg (GKH)

Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland.
present address: Department of Physical Science, Harold Washington College, City colleges of Chicago, 30 E Lake St, Chicago, IL 60601, USA.

Ulrich Aschauer (U)

Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland.

Matthias Arenz (M)

Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012, Bern, Switzerland.

Classifications MeSH