Influence of the work function on electron transfer processes at metals: Application to the hydrogen evolution reaction

The exchange current density and the corresponding free energy of activation for the hydrogen evolution reaction at metal surfaces was analyzed using the work function of the substrate, desolvation energy of the reactant, solvation numbers. The electronic structure of metals was incorporated via their work function in the kinetics of heterogeneous electron-transfer reactions. The computed values were in satisfactory agreement with experimental data for a large number of metals.