H2 Adsorption on Cu4-xMx (M = Au, Pt; x = 0–4) Clusters: Similarities and Differences As Predicted by Density Functional Theory

Abstract

The active search for alternatives to current fossil fuels via energy conversion mechanisms has bolstered the study of the adsorption of molecules on surfaces and clusters as a fundamental step before moving into complex heterogeneous catalysis scenarios. In this respect, intensive investigations have been thoroughly performed to obtain cheaper and more efficient catalysts, such as in the hydrogen evolution reaction (HER) in the electrocatalysis field. In this paper, we present systematic density functional theory simulations of H2 adsorption on bimetallic Cu4–xMx (M = Pt, Au; x = 0–4) neutral clusters. The molecular and dissociative adsorption mechanisms are explored, and the occurrence of one or the other is explained in terms of the reactivity of the host clusters. We begin with a global exploration of the potential energy surface to obtain the ground-state structures. The effects of H2 adsorption and host cluster composition on the interatomic distances are investigated. A detailed analysis of H2 adso...