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

The electrocatalytic activity of methanol oxidation reaction (MOR) on Cu/gamma-Al2O3 and the growth behavior of Cu on gamma-Al2O3 are investigated by using density functional theory and molecular dynamics. It is found that the interaction between the Cu-3 cluster and gamma-Al2O3(1 1 0) is stronger than that between the Cu-4 cluster and gamma-Al2O3(1 1 0). Consequently, the d-band center of the Cu-3 cluster locates close to the Fermi level compared to the d-band center of the Cu-4 cluster, resulting in high electrocatalytic MOR activity on Cu-3/gamma-Al2O3(1 1 0). The electrocatalytic MOR pathway is non-CO pathway on Cu-3/gamma-Al2O3(1 1 0). 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 gamma-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.