In situ iridium LIII-edge X-ray absorption and surface enhanced Raman spectroscopy of electrodeposited iridium oxide films in aqueous electrolytes

被引：109

作者：

Mo, YB

Stefan, IC

Cai, WB

Dong, J

Carey, P

Scherson, DA ^{[1
]}

机构：

[1] Case Western Reserve Univ, Dept Chem, Cleveland, OH 44106 USA

[2] Case Western Reserve Univ, Dept Biochem, Cleveland, OH 44106 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2002年 / 106卷 / 14期

关键词：

D O I：

10.1021/jp014452p

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Structural and electronic aspects of IrO2 films prepared by electrodeposition on Au substrates were investigated by in situ L-III-edge X-ray absorption and surface enhanced Raman spectroscopies in both acid and alkaline aqueous solutions. Linear correlations were found between the extent of oxidation of Ir3+ in the films determined from a statistical fit of the white line, which includes contributions from each of the sites differing by a single electron, and from coulometric analysis of the voltammetric curves. Analysis of the extended X-ray absorption fine structure (EXAFS) yielded Ir-O bond lengths decreasing in the sequence 2.02, 1.97, and 1.93 Angstrom for Ir3+, Ir4+, and Ir5+ sites, respectively. Whereas SERS provided evidence for the presence of crystalline IrO2 in the highly hydrated films, the lack of intense shells in the Fourier transform of the EXAFS function beyond the nearest oxygen neighbors indicates that the films do not display long-range order.

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页码：3681 / 3686

页数：6

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