Volcano plots in hydrogen electrocatalysis – uses and abuses

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-cov...

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Vydáno v:Beilstein journal of nanotechnology Ročník 5; číslo 1; s. 846 - 854
Hlavní autoři: Quaino, Paola, Juarez, Fernanda, Santos, Elizabeth, Schmickler, Wolfgang
Médium: Journal Article
Jazyk:angličtina
Vydáno: Germany Beilstein-Institut 13.06.2014
Témata:
electrocatalysis
Full Research Paper
hydrogen evolution
Nanoscience
Nanotechnology
Sabatier’s principle
volcano curve
hydrogen evolution
volcano curve
electrocatalysis
Sabatier’s principle
ISSN:2190-4286, 2190-4286
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Popis
Shrnutí: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.
Bibliografie:ObjectType-Article-1
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ISSN:2190-4286
2190-4286
DOI:10.3762/bjnano.5.96