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Computational investigation and design of cobalt aqua complexes for homogeneous water oxidation


Schilling, Mauro; Patzke, Greta R; Hutter, Jürg; Luber, Sandra (2016). Computational investigation and design of cobalt aqua complexes for homogeneous water oxidation. Journal of Physical Chemistry C, 120(15):7966-7975.

Abstract

We study the water oxidation mechanism of the cobalt aqua complex [Co(H2O)6]2+ in a photocatalytic setup by means of density functional theory. Assuming a water-nucleophilic-attack or radical coupling mechanism, we investigate how the oxidation state and spin configuration change during the catalytic cycle. In addition, different ligand environments are employed by substituting a water ligand with a halide, pyridine, or derivative thereof. This allows exploration of the effect of such ligands on the frontier orbitals and the thermodynamics of the water oxidation process. Moreover, the thermodynamically most promising water oxidation catalyst can be identified by comparing the computed free energy profiles to the one of an “ideal catalyst”. Examination of such simple (hypothetical) water oxidation catalysts provides a basis for the derivation of design guidelines, which are highly sought for the development of efficient homogeneous water oxidation catalysts.

Abstract

We study the water oxidation mechanism of the cobalt aqua complex [Co(H2O)6]2+ in a photocatalytic setup by means of density functional theory. Assuming a water-nucleophilic-attack or radical coupling mechanism, we investigate how the oxidation state and spin configuration change during the catalytic cycle. In addition, different ligand environments are employed by substituting a water ligand with a halide, pyridine, or derivative thereof. This allows exploration of the effect of such ligands on the frontier orbitals and the thermodynamics of the water oxidation process. Moreover, the thermodynamically most promising water oxidation catalyst can be identified by comparing the computed free energy profiles to the one of an “ideal catalyst”. Examination of such simple (hypothetical) water oxidation catalysts provides a basis for the derivation of design guidelines, which are highly sought for the development of efficient homogeneous water oxidation catalysts.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2016
Deposited On:16 Dec 2016 10:07
Last Modified:02 Feb 2018 10:56
Publisher:American Chemical Society (ACS)
ISSN:1932-7447
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.jpcc.6b00712

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