TY - DATA T1 - Reaction Pathways for Oxygen Evolution Promoted by Cobalt Catalyst PY - 2016/02/18 AU - Giuseppe Mattioli AU - Paolo Giannozzi AU - Aldo Amore Bonapasta AU - Leonardo Guidoni UR - https://acs.figshare.com/articles/journal_contribution/Reaction_Pathways_for_Oxygen_Evolution_Promoted_by_Cobalt_Catalyst/2365819 DO - 10.1021/ja401797v.s001 L4 - https://ndownloader.figshare.com/files/4005268 KW - Oxygen Evolution Promoted KW - Concurrent nucleophilic attack KW - activation KW - water solution KW - formation KW - oxygen evolution catalysts KW - water oxidation catalysis KW - DFT KW - CoCat KW - mechanism KW - pathway KW - Mn 4Ca oxygen KW - II N2 - The 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. ER -