Electrochemical adsorption of hydrogen on mixed Pd₂Pt nanostructures

In the present contribution we have focused on the electrochemical adsorption of a proton from the solution-the Volmer reaction-on a variety of systems based on bimetallic nanostructures-clusters and wires-of Pd and Pt deposited on a surface of Au(111). We have calculated the free energy surface for the electron transfer step by a combination of DFT calculations, MD simulations and the theory of electrocatalysis. We analyze in detail the interaction of the metal d band with the valence orbital of the hydrogen and its effect on the catalytic activity as well as several aspects that influence the electrode reactivity such as spatial arrangements of the nanostructures, the solvation shell and chemical factors. We found that the mixed Pd₂Pt wire interacts strongly with hydrogen, and retains an almost complete solvation shell, which is reflected in a substantially reduced activation energy for the Volmer step. Thus, Pd₂Pt wires on Au(111) are predicted to be efficient electrocatalysts for the reaction.