The Key Ru V=O Intermediate of Site-Isolated Mononuclear Water Oxidation Catalyst Detected by in Situ X-ray Absorption Spectroscopy

J Am Chem Soc. 2018 Jan 10;140(1):451-458. doi: 10.1021/jacs.7b11388. Epub 2017 Dec 20.

Abstract

Improvement of the oxygen evolution reaction (OER) is a challenging step toward the development of sustainable energy technologies. Enhancing the OER rate and efficiency relies on understanding the water oxidation mechanism, which entails the characterization of the reaction intermediates. Very active Ru-bda type (bda is 2,2'-bipyridine-6,6'-dicarboxylate) molecular OER catalysts are proposed to operate via a transient 7-coordinate RuV═O intermediate, which so far has never been detected due to its high reactivity. Here we prepare and characterize a well-defined supported Ru(bda) catalyst on porous indium tin oxide (ITO) electrode. Site isolation of the catalyst molecules on the electrode surface allows trapping of the key 7-coordinate RuV═O intermediate at potentials above 1.34 V vs NHE at pH 1, which is characterized by electron paramagnetic resonance and in situ X-ray absorption spectroscopies. The in situ extended X-ray absorption fine structure analysis shows a Ru═O bond distance of 1.75 ± 0.02 Å, consistent with computational results. Electrochemical studies and density functional theory calculations suggest that the water nucleophilic attack on the surface-bound RuV═O intermediate (O-O bond formation) is the rate limiting step for OER catalysis at low pH.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.