Theoretical analysis of the influence of surface defects on the reactivity of hypophosphite ions

To elucidate the influence of surface defects, such as steps, on the oxidation of a reducing agent that is used in the electroless deposition process, we theoretically analyzed the reaction behavior of hypophosphite ion around the defect using density functional theory calculations. The reason why we chose the hypophosphite ion is that it is a typical reducing agent and reacts through a universal reaction mechanism. In this analysis, we focused on the dehydrogenation reaction, which is the rate-determining step in the oxidation pathway. Pd and Cu surfaces were chosen as the metal surfaces, because they exhibit completely different catalytic activity from each other, both experimentally and theoretically. Our calculations showed that the surface defect stabilized the final state of dehydrogenation on both Pd and Cu surfaces, which indicates that the defect accelerates the oxidation of the hypophosphite ion. In the final state of dehydrogenation, dissociated hydrogen adsorbs on the hollow site, which appears on the slope of the defect. More detailed analyses of the final state indicate that the stabilization effect by the surface defect originates from the highly efficient interactions between the dissociated hydrogen and the slope. The molecular orbital structure on this slope is distorted, which leads to high electron density around the slope that enables the highly efficient interactions between the hydrogen and the slope.