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-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 exothe... Mehr ...

Verfasser: Quaino, Paola Monica
Juarez, Maria Fernanda
Santos, Elizabeth del Carmen
Schmickler, Wolfgang
Dokumenttyp: Artikel
Verlag/Hrsg.: Beilstein-Institut
Schlagwörter: Electrocatalysis / Hydrogen evolution / Sabatier's principle / Volcano curve / https://purl.org/becyt/ford/1.4 / https://purl.org/becyt/ford/1
Sprache: Englisch
Permalink: https://search.fid-benelux.de/Record/base-29264975
Datenquelle: BASE; Originalkatalog
Powered By: BASE
Link(s) : http://hdl.handle.net/11336/31169

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. ; Fil: Quaino, Paola Monica. Universidad Nacional del Litoral. Facultad de Ingeniería Química. Programa de Electroquímica Aplicada e Ingeniería Electroquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina ; Fil: Juarez, Maria Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania ; Fil: Santos, Elizabeth del Carmen. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; Argentina. Universidad Nacional de Córdoba. Facultad de Matemática, Astronomía y Física; Argentina ; Fil: Schmickler, Wolfgang. Institute of Theoretical Chemistry; Alemania. Universitat Ulm; Alemania