The electrocatalytic activity for the hydrogen evolution reaction on alloys is determined by element-specific...

Trends of the electrocatalytic activities for the hydrogen evolution reaction (HER) across transition metals are typically explained by d-band properties such as center or upper edge positions in relation to Fermi levels. Here, the universality of this relation is questioned for alloys, exemplified for the AuPt system which is examined with electrocatalytic measurements and density functional theory (DFT) calculations. At small overpotentials, linear combinations of the pure-metals' Tafel kinetics normalized to the alloy compositions are found to precisely resemble the measured HER activities. DFT calculations show almost neighbor-independent adsorption energies on Au and Pt surface-sites, respectively, as the adsorbed hydrogen influences the electron density mostly locally at the adsorption site itself. In contrast, the density of states of the d-band describe the delocalized conduction electrons in the alloys, which are unable to portray the local electronic environments at adsorption sites and related bonding strengths. The adsorption energies at element-specific surface sites are related to overpotential-dependent reaction mechanisms in a multidimensional reinterpretation of the volcano plot for alloys, which bridges the found inconsistencies between activity and bonding strength descriptors of the common electrocatalytic theory for alloys.