Several water oxidation systems exhibiting fast turnover rates have been described recently that exploit copper-based catalysts coordinated by simple ligands.  This includes Cu(II) solutions incorporating concentrated carbonate or bicarbonate counterions which generate molecular oxygen upon the application of high electric potentials.  To date, little is known about the mechanism(s) by which O2 is produced in these and analogous systems.  We have employed computational protocols based primarily on density functional theory to predict the identity of relevant Cu(II) starting complexes as a function of solution pH and applied external potential (i.e., we have determined a computational Pourbaix diagram).  We have additionally characterized full mechanistic pathways associated with oxygen generation; in the case of copper/carbonate catalysis, a peroxocarbonate intermediate is implicated the formation and decomposition of which to liberate O2 is predicted to occur with low free energies of activation.

Mechanisms of copper-catalyzed water oxidation: Theoretical insights

247th National Meeting (2014)

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