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Reaction Pathways for Oxygen Evolution Promoted by Cobalt Catalyst
journal contribution
posted on 2016-02-18, 15:18 authored by Giuseppe Mattioli, Paolo Giannozzi, Aldo Amore Bonapasta, Leonardo GuidoniThe in-depth understanding of the
molecular mechanisms regulating
the water oxidation catalysis is of key relevance for the rationalization
and the design of efficient oxygen evolution catalysts based on earth-abundant
transition metals. Performing ab initio DFT+U molecular dynamics calculations
of cluster models in explicit water solution, we provide insight into
the pathways for oxygen evolution of a cobalt-based catalyst (CoCat).
The fast motion of protons at the CoCat/water interface and the occurrence
of cubane-like Co-oxo units at the catalyst boundaries are the keys
to unlock the fast formation of O–O bonds. Along the resulting
pathways, we identified the formation of Co(IV)-oxyl species as the
driving ingredient for the activation of the catalytic mechanism,
followed by their geminal coupling with O atoms coordinated by the
same Co. Concurrent nucleophilic attack of water molecules coming
directly from the water solution is discouraged by high activation
barriers. The achieved results suggest also interesting similarities
between the CoCat and the Mn4Ca-oxo oxygen evolving complex
of photosystem II.
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