Mechanistic analysis of water oxidation catalyzed by mononuclear copper in aqueous bicarbonate solutions

Stuart G. Winikoff, Chris Cramer

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

We characterize a mechanism for a monomeric copper catalyst reported to oxidize water in bicarbonate solution when subject to sufficiently high external potentials at near neutral pH values. Density functional computations establish the thermochemical equilibria associated with microscopic redox and proton transfer steps and further reveal that O-O bond formation is associated with the unusual reaction of a coordinated hydroxide and carbonate ligand to generate a peroxycarbonate intermediate. The peroxycarbonate complex then decomposes through a retrocyclization to liberate O2 andCO2 and ultimately complete the catalytic cycle.

Original languageEnglish (US)
Pages (from-to)2484-2489
Number of pages6
JournalCatalysis Science and Technology
Volume4
Issue number8
DOIs
StatePublished - Aug 2014

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