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Validation of binuclear descriptor for mixed transition metal oxide supported electrocatalytic water oxidation

Journal article
Authors Michael Busch
Elisabet Ahlberg
Itai Panas
Published in Catalysis Today
Volume 202
Pages 114-119
ISSN 0920-5861
Publication year 2013
Published at Department of Chemistry and Molecular Biology
Pages 114-119
Language en
Keywords Water oxidation; Mechanism; Electrocatalysis; Transition metal oxides, Mixed transition metal oxides; Density functional theory
Subject categories Quantum chemistry, Catalysis


The energy profiles of the di-hydroxo – di-oxo – peroxo pathway are discussed for a set of 3d transition metal oxides comprising V(III–V), Cr(III–V), Mn(II–IV, Mn(III–V), Fe(II–IV), Co(II–IV) and Ni(II–IV) using density functional theory (DFT). Two classes of oxides were identified. The first class, comprising V(III–V), Cr(III–V) and Fe(II–IV), displays exothermicity for the oxidation of di-hydroxo to di-oxo versus the tyrosine/tyrosyl-radical (TyrOH/TyrO) couple and endothermicity for the subsequent O-O bond formation ([−/+] class), while the second class, comprising Mn(III–V), Co(II–IV) and Ni(II–IV), shows endothermicity with respect to the oxidation step and exothermicity for the O-O bond formation ([+/−] class). The energetics of the endothermicity (exothermicity) for the oxidation step is reflected in the exothermicity (endothermicity) of the subsequent O-O bond formation step. Mn(II–IV) is not part of any of the two classes. Instead it shows zero exothermicity with respect to TyrOH/TyrO for the oxidation step and a small endothermicity for the O-O bond formation step. Despite the promising energy profile Mn(II–IV) is argued to be inactive due to a large activation barrier. A set of improved hetero-nuclear candidate catalysts is predicted by mixing [−/+] with [+/−] transition metal oxides. A simple and efficient method to estimate the energy profile of mixed transition metal oxides from the homo-nuclear systems is demonstrated. The validity of this procedure is checked and agreement with the explicitly calculated values is found. All considered heteronuclear candidate catalysts display enhanced performance compared to the pure homonuclear systems.

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