Issue 5, 2014

Domain structure for an amorphous iridium-oxide water-oxidation catalyst characterized by X-ray pair distribution function analysis

Abstract

The domain structure of an amorphous, “blue layer” iridium-oxide water-oxidation catalyst film (BL) electrodeposited from the soluble precursor complex, [Cp*Ir(H2O)3]SO4, was characterized by X-ray pair distribution function (PDF) analysis. The results show that the experimental PDF can be fit remarkably well using a single Ir5O22 cluster extracted from the rutile lattice. The model includes distortions that indicate the presence of Ir(μ-O)3Ir or distorted Ir(μ-O)2Ir substructures, and hence deviations from a rutile structure. The five Ir atom cluster is suggested to represent the population-averaged distribution of metal–oxo clusters in the film. BL is found to be distinguished from other amorphous film water-oxidation catalysts because of the remarkably small domain size and homogeneity. As such, the blue layer catalyst provides a model for investigating ligand-determined metal-oxide cluster assembly and catalyst mechanism.

Graphical abstract: Domain structure for an amorphous iridium-oxide water-oxidation catalyst characterized by X-ray pair distribution function analysis

Supplementary files

Article information

Article type
Communication
Submitted
19 Nov 2013
Accepted
19 Nov 2013
First published
03 Dec 2013

Phys. Chem. Chem. Phys., 2014,16, 1814-1819

Domain structure for an amorphous iridium-oxide water-oxidation catalyst characterized by X-ray pair distribution function analysis

J. Huang, J. D. Blakemore, D. Fazi, O. Kokhan, N. D. Schley, R. H. Crabtree, G. W. Brudvig and D. M. Tiede, Phys. Chem. Chem. Phys., 2014, 16, 1814 DOI: 10.1039/C3CP54878C

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