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Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis

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05 Apr 2013: Vol. 340, Issue 6128, pp. 60-63 DOI: 10.1126/science.1233638
Rodney D. L. Smith
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Mathieu S. Prévot
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Randal D. Fagan
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Zhipan Zhang
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Pavel A. Sedach
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Man Kit Jack Siu
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Simon Trudel
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.
Curtis P. Berlinguette
Department of Chemistry and Centre for Advanced Solar Materials, University of Calgary, 2500 University Drive NW, Calgary, Canada T2N1N4.

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Amorphous and More Active

The electrochemical generation of hydrogen from water could help in the storage of energy generated by renewable resources at off-peak times. However, catalysts for the slow step of this reaction, the oxygen evolution reaction (OER), are based on oxides of noble metals (iridium and ruthenium) that have limited abundance. A strategy for improving the performance of earth-abundant elements is to explore mixed-metal oxides and to prepare these as amorphous phases. Smith (p. 60 , published online 28 March) developed a general method for preparing amorphous oxides, based on photodecomposition of organometallic precursors. Amorphous mixed-metal oxides of iron, nickel, and cobalt were more active than comparable crystalline materials and provided OER performance comparable to noble metal oxides.

Abstract

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of -FeCoNiO are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.

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Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis

By Rodney D. L. Smith , Mathieu S. Prévot , Randal D. Fagan , Zhipan Zhang , Pavel A. Sedach , Man Kit Jack Siu , Simon Trudel , Curtis P. Berlinguette

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Shavelson RJ , Webb NM. . London: Sage, 1991.
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