On the catalysis of the hydrogen oxidation

Abstract

A recently developed model for electrocatalysis is combined with results of quantum chemical calculations to investigate the effect of the electrode's electronic structure on the rate of the hydrogen oxidation reaction. Model calculations have been performed for three metals with widely differing properties: Cd(0001), Au(111) and Pt(111). In line with experimental findings, the energy of activation decreases in this order. These results are explained in terms of the interaction of the bonding orbital of the hydrogen molecule with the d band of the electrode as it passes the Fermi level.

Hydrogen Evolution on Single‐Crystal Copper and Silver: A Theoretical Study

“…First applications to hydrogen evolution explained the dependence on the nature of the metal well [12,13,14] and gave a reasonable order of magnitude for the rate constants. More importantly, the catalytic activities of the metals could be explained in terms of the interaction of their d bands with the hydrogen 1s orbital as it passes the Fermi level.…”

2 Surface Thermodynamics of Metal/Solution Interface: the Untapped Resources

“…198 Accumulated experience is extremely useful for modeling the reversible adsorption at the interface, but today the latter looks like a tiny brook in the vicinity of computational mainstream. The closest layer going from electrocatalysis is theoretical/ computational prediction of electrocatalytic activity in hydrogen reactions, 199,200 as it requires the modeling of hydrogen adatoms. The main problem in this case is comparison with experiment, because a lot of factors besides adlayer structure affect the observed reaction rates.…”

Hydrogen Reactions on Nanostructured Surfaces

“…Next to the more general description of reactivity in terms of chemisorption and activation energy, several theoretical approaches for hydrogen reactions on various catalyst systems are given in the literature [87,[90][91][92][93][94][95][96][97][98][99][100]. Hydrogen evolution as well as the hydrogen oxidation play an important role in electrochemical processes and technological applications [101][102][103][104][105].…”