In:
Chemical Science, Royal Society of Chemistry (RSC), Vol. 12, No. 39 ( 2021), p. 12918-12927
Abstract:
Despite their technological importance for water splitting, the reaction mechanisms of most water oxidation catalysts (WOCs) are poorly understood. This paper combines theoretical and experimental methods to reveal mechanistic insights into the reactivity of the highly active molecular manganese vanadium oxide WOC [Mn 4 V 4 O 17 (OAc) 3 ] 3− in aqueous acetonitrile solutions. Using density functional theory together with electrochemistry and IR-spectroscopy, we propose a sequential three-step activation mechanism including a one-electron oxidation of the catalyst from [Mn 2 3+ Mn 2 4+ ] to [Mn 3+ Mn 3 4+ ], acetate-to-water ligand exchange, and a second one-electron oxidation from [Mn 3+ Mn 3 4+ ] to [Mn 4 4+ ]. Analysis of several plausible ligand exchange pathways shows that nucleophilic attack of water molecules along the Jahn–Teller axis of the Mn 3+ centers leads to significantly lower activation barriers compared with attack at Mn 4+ centers. Deprotonation of one water ligand by the leaving acetate group leads to the formation of the activated species [Mn 4 V 4 O 17 (OAc) 2 (H 2 O)(OH)] − featuring one H 2 O and one OH ligand. Redox potentials based on the computed intermediates are in excellent agreement with electrochemical measurements at various solvent compositions. This intricate interplay between redox chemistry and ligand exchange controls the formation of the catalytically active species. These results provide key reactivity information essential to further study bio-inspired molecular WOCs and solid-state manganese oxide catalysts.
Type of Medium:
Online Resource
ISSN:
2041-6520
,
2041-6539
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2021
detail.hit.zdb_id:
2559110-1
