The elementary steps of the reactions of hypophosphite ions with Cu, Ni, and Pd were calculated theoretically using Density Functional Theory (DFT) to demonstrate the reaction mechanism and gain insight at the molecular level. The elementary steps of these reactions are adsorption, dehydrogenation, and oxidation (hydroxyl base attack). In the adsorption step, hypophosphite ions adsorb onto each surface spontaneously with stabilities in the order of Ni (111) > Pd (111) > Cu (111). In the dehydrogenation step, hypophosphite ions dehydrogenate on Ni (111) and Pd (111) with small reaction barriers, whereas they react on Cu (111) with a large reaction barrier. The large reaction barrier on Cu (111) is not compensated for by the adsorption energy on the surface. In the oxidation step, dehydrogenated anions on each metal surface react spontaneously with the hydroxyl base. The reaction barriers on each metal surface in this step are not so significant compared to the adsorption energies on each surface, suggesting that a reaction barrier of hypophosphite ion oxidation should exist in the dehydrogenation step and only be observed for Cu (111). This proposition elucidates the experimental catalytic behaviors of metal surfaces in the electroless deposition process using hypophosphite ions.
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