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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Vydané v:Beilstein journal of nanotechnology Ročník 5; číslo 1; s. 846 - 854
Hlavní autori: Quaino, Paola, Juarez, Fernanda, Santos, Elizabeth, Schmickler, Wolfgang
Médium: Journal Article
Jazyk:English
Vydavateľské údaje: Germany Beilstein-Institut 13.06.2014
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ISSN:2190-4286, 2190-4286
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Abstract 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.
AbstractList 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.
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.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.
Author Santos, Elizabeth
Juarez, Fernanda
Quaino, Paola
Schmickler, Wolfgang
AuthorAffiliation 2 Institute of Theoretical Chemistry, Ulm University, D-89069 Ulm, Germany
1 PRELINE, Universidad Nacional del Litoral, Santa Fe, Argentina
3 Faculdad de Matemática, Astronomía y Física, IFEG-CONICET, Universidad Nacional de Córdoba, Córdoba, Argentina
AuthorAffiliation_xml – name: 1 PRELINE, Universidad Nacional del Litoral, Santa Fe, Argentina
– name: 3 Faculdad de Matemática, Astronomía y Física, IFEG-CONICET, Universidad Nacional de Córdoba, Córdoba, Argentina
– name: 2 Institute of Theoretical Chemistry, Ulm University, D-89069 Ulm, Germany
Author_xml – sequence: 1
  givenname: Paola
  surname: Quaino
  fullname: Quaino, Paola
– sequence: 2
  givenname: Fernanda
  surname: Juarez
  fullname: Juarez, Fernanda
– sequence: 3
  givenname: Elizabeth
  surname: Santos
  fullname: Santos, Elizabeth
– sequence: 4
  givenname: Wolfgang
  surname: Schmickler
  fullname: Schmickler, Wolfgang
BackLink https://www.ncbi.nlm.nih.gov/pubmed/24991521$$D View this record in MEDLINE/PubMed
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Issue 1
Keywords hydrogen evolution
volcano curve
electrocatalysis
Sabatier’s principle
Language English
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Snippet 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...
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...
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SubjectTerms electrocatalysis
Full Research Paper
hydrogen evolution
Nanoscience
Nanotechnology
Sabatier’s principle
volcano curve
Title Volcano plots in hydrogen electrocatalysis – uses and abuses
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