Design and catalytic performance of Cu/γ-Al2O3 for electrocatalytic methanol oxidation reaction by using density functional theory and molecular dynamics

Abstract

The electrocatalytic activity of methanol oxidation reaction (MOR) on Cu/γ-Al2O3 and the growth behavior of Cu on γ-Al2O3 are investigated by using density functional theory and molecular dynamics. It is found that the interaction between the Cu3 cluster and γ-Al2O3(110) is stronger than that between the Cu4 cluster and γ-Al2O3(110). Consequently, the d-band center of the Cu3 cluster locates close to the Fermi level compared to the d-band center of the Cu4 cluster, resulting in high electrocatalytic MOR activity on Cu3/γ-Al2O3(110). The electrocatalytic MOR pathway is non-CO pathway on Cu3/γ-Al2O3(110). The highest Gibbs free energy pathway is CH3O* → CH2O*, which the Gibbs free energy is 0.53 eV. To achieve a high proportion of 2D Cu cluster on γ-Al2O3, it is recommended to prepare the catalyst at temperatures below 500 K with Cu loading below 21.78 wt%. These findings provide valuable insights into the design of MOR catalysts.