title: Lowering water oxidation overpotentials using the ionisable imidazole of copper(2-(2'-pyridyl)imidazole).
abstract: Rapid and low overpotential oxidation of water to dioxygen remains a key hurdle for storage of solar energy. Here, we address this issue by demonstrating that deprotonation of 2-(2'-pyridyl)-imidazole (pimH)-ligated copper complexes promotes water oxidation at low overpotential and low catalyst loading. This improves upon other work on homogeneous copper-based water oxidation catalysts, which are highly active, but limited by high overpotentials. EPR and UV-vis spectroscopic evaluation of catalyst speciation shows that at pH ≥ 12 coordinated pimH is deprotonated and a bis(hydroxide) Cu2+active catalyst forms. Rapid electrochemical water oxidation (35 s-1, 0.85 V onset potential) was observed with 150 μM catalyst. These results demonstrate that catalytic water oxidation potentials can be shifted by hundreds of mV in homogeneous metal catalysts bearing an ionisable imidazole ligand.
authors.affiliation: Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby BC V5A 1S6, Canada. j.warren@sfu.ca.
authors.forename: Leea A
authors.initials: LA
authors.lastname: Stott
authors.affiliation: Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby BC V5A 1S6, Canada. j.warren@sfu.ca.
authors.forename: Kathleen E
authors.initials: KE
authors.lastname: Prosser
authors.affiliation: Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby BC V5A 1S6, Canada. j.warren@sfu.ca.
authors.forename: Ellan K
authors.initials: EK
authors.lastname: Berdichevsky
authors.affiliation: Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby BC V5A 1S6, Canada. j.warren@sfu.ca.
authors.forename: Charles J
authors.initials: CJ
authors.lastname: Walsby
authors.affiliation: Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby BC V5A 1S6, Canada. j.warren@sfu.ca and Canadian Institute for Applied Research, CIFAR Azrieli Global Scholar and Bio-Inspired Solar Energy Programs, Toronto, ON M5G 1Z8, Canada.
authors.forename: Jeffrey J
authors.identifier: 0000-0002-1747-3029
authors.initials: JJ
authors.lastname: Warren