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Water Oxidation Catalysis: Electrocatalytic Response to Metal Stoichiometry in Amorphous Metal Oxide Films Containing Iron, Cobalt, and Nickel

TitleWater Oxidation Catalysis: Electrocatalytic Response to Metal Stoichiometry in Amorphous Metal Oxide Films Containing Iron, Cobalt, and Nickel
Publication TypeJournal Article
Year of Publication2013
AuthorsSmith, RDL, Prevot, MS, Fagan, RD, Trudel, S, Berlinguette, CP
JournalJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume135
Pagination11580-11586
Date PublishedAUG 7
ISSN0002-7863
Abstract

Photochemical metal organic deposition (PMOD) was used to prepare amorphous metal oxide films containing specific concentrations of iron, cobalt, and nickel to study how metal composition affects heterogeneous electrocatalytic water oxidation. Characterization of the films by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirmed excellent stoichiometric control of each of the 21 complex metal oxide films investigated. In studying the electrochemical oxidation of water catalyzed by the respective films, it was found that small concentrations of iron produced a significant improvement in Tafel slopes and that cobalt or nickel were critical in lowering the voltage at which catalysis commences. The best catalytic parameters of the series were obtained for the film of composition a-Fe20Ni80. An extrapolation of the electrochemical and XPS data indicates the optimal behavior of this binary film to be a manifestation of iron stabilizing nickel in a higher oxidation level. This work represents the first mechanistic study of amorphous phases of binary and ternary metal oxides for use as water oxidation catalysts, and provides the foundation for the broad exploration of other mixed-metal oxide combinations.

DOI10.1021/ja403102j