Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis

Stuart A. Bartlett; Emma V. Sackville; Emma K. Gibson; Veronica Celorrio; Peter P. Wells; Maarten Nachtegaal; Stafford W. Sheehan; Ulrich Hintermair

doi:10.1039/C9CC02088H

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Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis†

Stuart A. Bartlett,

*^a Emma V. Sackville,^b Emma K. Gibson,

^ac Veronica Celorrio,

^a Peter P. Wells,

^ad Maarten Nachtegaal,^e Stafford W. Sheehan

^f and Ulrich Hintermair

*^b

Author affiliations

* Corresponding authors

^a Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, UK
E-mail: stuart.bartlett@diamond.ac.uk

^b Centre for Sustainable Chemical Technologies, University of Bath, Bath BA2 7AY, UK
E-mail: u.hintermair@bath.ac.uk

^c School of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK

^d School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK

^e Paul Scherrer Institute, 5232 Villigen, Switzerland

^f Catalytic Innovations, Fall River, MA, 02723, USA

Abstract

The structure of a highly active pyridine-alkoxide iridium water oxidation catalyst (WOC) is examined by X-ray absorption spectroscopy (XAS). A detailed comparison with IrO₂ points to a rigid molecular unit of low nuclearity, with the best analysis suggesting a novel tetrameric iridium-oxo cubane as the resting state.

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Article information

DOI: https://doi.org/10.1039/C9CC02088H
Article type: Communication
Submitted: 14 Mar 2019
Accepted: 11 Jun 2019
First published: 11 Jun 2019
This article is Open Access

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Chem. Commun., 2019,55, 7832-7835

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Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis

S. A. Bartlett, E. V. Sackville, E. K. Gibson, V. Celorrio, P. P. Wells, M. Nachtegaal, S. W. Sheehan and U. Hintermair, Chem. Commun., 2019, 55, 7832 DOI: 10.1039/C9CC02088H

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Chemical Communications

Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis†

Abstract

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Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis

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