期刊
BEILSTEIN JOURNAL OF NANOTECHNOLOGY
卷 5, 期 -, 页码 846-854出版社
BEILSTEIN-INSTITUT
DOI: 10.3762/bjnano.5.96
关键词
electrocatalysis; hydrogen evolution; Sabatier's principle; volcano curve
资金
- Deutsche Forschungsgemeinschaft [344/34-1, 344/34-2, SA 1770/1-1, SA 1770/1-2, FOR 1376]
- DAAD-Mincyt
- Agencia Nacional de Promocion CientIfica y Tecnologica, FONCYT [PIP-CONICET 112-2010001-00411, PICT-2012-2324]
- CAID [501 201101 00276 LI UNL]
- Baden-Wurttemberg
Sabatier's principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier's principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst.
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