Journal
ELECTROCHIMICA ACTA
Volume 52, Issue 18, Pages 5715-5724Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2006.12.007
Keywords
electrocatalysis; hydrogen adsorption; hydrogen evolution reaction; Pt; IR spectroscopy
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Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm(-1). This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction. (c) 2007 Elsevier Ltd. All rights reserved.
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