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Electromodified NiFe Alloys as Electrocatalysts for Water Oxidation: Mechanistic Implications of Time-Resolved UV/Vis Tracking of Oxidation State Changes
Free Univ Berlin, Inst Expt Phys, Arnimallee 14, D-014195 Berlin, Germany;Fraunhofer Inst Mfg Technol & Adv Mat IFAM, Winterbergstr 28, D-01277 Dresden, Germany.
Free Univ Berlin, Inst Expt Phys, Arnimallee 14, D-014195 Berlin, Germany.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics. Free Univ Berlin, Inst Expt Phys, Arnimallee 14, D-014195 Berlin, Germany.ORCID iD: 0000-0002-2836-838X
Tech Univ Bergakad Freiberg, Inst Phys Chem, Leipziger Str 29, D-09599 Freiberg, Germany.
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2019 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 12, no 9, p. 1966-1976Article in journal (Refereed) Published
Abstract [en]

Facile electromodification of metallic NiFe alloys leads to a series of NiFe oxyhydroxide surface films with excellent electrocatalytic performance in alkaline water oxidation. During cyclic voltammetry and after sudden potential jumps between noncatalytic and catalytic potentials, Ni oxidation/reduction was tracked with millisecond time resolution by a UV/Vis reflectance signal. Optimal catalysis at intermediate Ni/Fe ratios is explained by two opposing trends for increasing Fe content: a)pronounced slowdown of the Ni2+/Ni3+ oxidation step and b)increased reactivity of the most oxidized catalyst state detectable at catalytic potentials. This state may involve an equilibrium between Ni4+ ions and Ni2+ ions with neighboring ligand holes, possibly in the form of bound peroxides.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2019. Vol. 12, no 9, p. 1966-1976
Keywords [en]
electrocatalysis, NiFe oxyhydroxides, spectroelectrochemistry, water oxidation, X-ray photoelectron spectroscopy
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-389827DOI: 10.1002/cssc.201802737ISI: 000471314900020PubMedID: 30694602OAI: oai:DiVA.org:uu-389827DiVA, id: diva2:1339365
Funder
German Research Foundation (DFG), SPP1613German Research Foundation (DFG), DA 402/7-1Available from: 2019-07-29 Created: 2019-07-29 Last updated: 2019-07-29Bibliographically approved

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Chernev, Petko

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