Water Oxidation by Amorphous Cobalt‐Based Oxides: Volume Activity and Proton Transfer to Electrolyte Bases

Katharina Klingan; Franziska Ringleb; Ivelina Zaharieva; Jonathan Heidkamp; Petko Chernev; Diego Gonzalez‐Flores; Marcel Risch; Anna Fischer; Holger Dau

doi:10.1002/cssc.201301019

journal article Jan 21, 2014

Water Oxidation by Amorphous Cobalt‐Based Oxides: Volume Activity and Proton Transfer to Electrolyte Bases

Katharina Klingan

Franziska Ringleb Ivelina Zaharieva

Jonathan Heidkamp Petko Chernev Diego Gonzalez‐Flores Marcel Risch

Anna Fischer Holger Dau

ChemSusChem Vol. 7 No. 5 pp. 1301-1310 · Wiley

View at Publisher Save 10.1002/cssc.201301019

Abstract

AbstractWater oxidation in the neutral pH regime catalyzed by amorphous transition‐metal oxides is of high interest in energy science. Crucial determinants of electrocatalytic activity were investigated for a cobalt‐based oxide film electrodeposited at various thicknesses on inert electrodes. For water oxidation at low current densities, the turnover frequency (TOF) per cobalt ion of the bulk material stayed fully constant for variation of the thickness of the oxide film by a factor of 100 (from about 15 nm to 1.5 μm). Thickness variation changed neither the nanostructure of the outer film surface nor the atomic structure of the oxide catalyst significantly. These findings imply catalytic activity of the bulk hydrated oxide material. Nonclassical dependence on pH was observed. For buffered electrolytes with pKa values of the buffer base ranging from 4.7 (acetate) to 10.3 (hydrogen carbonate), the catalytic activity reflected the protonation state of the buffer base in the electrolyte solution directly and not the intrinsic catalytic properties of the oxide itself. It is proposed that catalysis of water oxidation occurs within the bulk hydrated oxide film at the margins of cobalt oxide fragments of molecular dimensions. At high current densities, the availability of a proton‐accepting base at the catalyst–electrolyte interface controls the rate of water oxidation. The reported findings may be of general relevance for water oxidation catalyzed at moderate pH by amorphous transition‐metal oxides.

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Metrics

208

Citations

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References

Details

Published: Jan 21, 2014
Vol/Issue: 7(5)
Pages: 1301-1310
License: View

Authors

K

Katharina Klingan

Department of Physics; Freie Universität Berlin; 14195 Berlin; Germany

Department of Physics; Freie Universität Berlin; 14195 Berlin; Germany

Diego Gonzalez‐Flores

M

Marcel Risch

Nachwuchsgruppe Gestaltung des Sauerstoffentwicklungsmechanismus, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany

A

Anna Fischer

Institute for Inorganic and Analytical Chemistry University of Freiburg Albertstraße 21 79104 Freiburg Germany; Freiburg Center for Interactive Materials and Bioinspired Technologies FIT University of Freiburg Georges-Köhler-Allee 105 79110 Freiburg Germany; Cluster of Excellence livMatS University of Freiburg 79104 Freiburg Germany; Freiburg Materials Research Center, FMF University of Freiburg Stefan-Meier-Straße 21 79104 Freiburg Germany

H

Holger Dau

Cite This Article

Katharina Klingan, Franziska Ringleb, Ivelina Zaharieva, et al. (2014). Water Oxidation by Amorphous Cobalt‐Based Oxides: Volume Activity and Proton Transfer to Electrolyte Bases. ChemSusChem, 7(5), 1301-1310. https://doi.org/10.1002/cssc.201301019

Water Oxidation by Amorphous Cobalt‐Based Oxides: Volume Activity and Proton Transfer to Electrolyte Bases

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