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Inorganics 2015, 3(3), 374-387;

Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers

CNR-IOM DEMOCRITOS, Istituto Officina dei Materiali, c/o SISSA, Via Bonomea 265, Trieste 34136, Italy
Author to whom correspondence should be addressed.
Academic Editors: Greta Ricarda Patzke and Pierre-Emmanuel Car
Received: 15 April 2015 / Revised: 3 July 2015 / Accepted: 24 July 2015 / Published: 2 September 2015
(This article belongs to the Special Issue Polyoxometalates)
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Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM) molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV). In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent. View Full-Text
Keywords: water oxidation; DFT; polyoxometalates; electrochemistry water oxidation; DFT; polyoxometalates; electrochemistry

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Piccinin, S.; Fabris, S. Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers. Inorganics 2015, 3, 374-387.

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