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Modeling the Catalyst Activation Step in a Metal–Ligand Radical Mechanism Based Water Oxidation System

Amsterdam Center for Multiscale Modeling and Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098XH Amsterdam, The Netherlands
Author to whom correspondence should be addressed.
Inorganics 2019, 7(5), 62;
Received: 14 March 2019 / Revised: 31 March 2019 / Accepted: 13 April 2019 / Published: 9 May 2019
(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)
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Designing catalysts for water oxidation (WOCs) that operate at low overpotentials plays an important role in developing sustainable energy conversion schemes. Recently, a mononuclear ruthenium WOC that operates via metal–ligand radical coupling pathway was reported, with a very low barrier for O–O bond formation, that is usually the rate-determining step in most WOCs. A detailed mechanistic understanding of this mechanism is crucial to design highly active oxygen evolution catalysts. Here, we use density functional theory based molecular dynamics (DFT-MD) with an explicit description of the solvent to investigate the catalyst activation step for the [Ru(bpy) 2 (bpy–NO)] 2 + complex, that is considered to be the rate-limiting step in the metal–ligand radical coupling pathway. We find that a realistic description of the solvent environment, including explicit solvent molecules and thermal motion, is crucial for an accurate description of the catalyst activation step, and for the estimation of the activation barriers. View Full-Text
Keywords: water oxidation; DFT-MD; explicit solvent; Ru mononuclear complexes water oxidation; DFT-MD; explicit solvent; Ru mononuclear complexes

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Govindarajan, N.; Meijer, E.J. Modeling the Catalyst Activation Step in a Metal–Ligand Radical Mechanism Based Water Oxidation System. Inorganics 2019, 7, 62.

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