Design of a Metal/Oxide/Carbon Interface for Highly Active and Selective Electrocatalysis

Sustainable energy-conversion and chemical-production require catalysts with high activity, durability, and product-selectivity. Metal/oxide hybrid structure has been intensively investigated to achieve promising catalytic performance, especially in neutral or alkaline electrocatalysis where water dissociation is promoted near the oxide surface for (de)protonation of intermediates. Although catalytic promise of the hybrid structure is demonstrated, it is still challenging to precisely modulate metal/oxide interfacial interactions on the nanoscale. Herein, we report an effective strategy to construct rich metal/oxide nano-interfaces on conductive carbon supports in a surfactant-free and self-terminated way. When compared to the physically mixed Pd/CeO₂ system, a much higher degree of interface formation was identified with largely improved hydrogen oxidation reaction (HOR) kinetics. The benefits of the rich metal-CeO₂ interface were further generalized to Pd alloys for optimized adsorption energy, where the Pd₃Ni/CeO₂/C catalyst shows superior performance with HOR selectivity against CO poisoning and shows long-term stability. We believe this work highlights the importance of controlling the interfacial junctions of the electrocatalyst in simultaneously achieving enhanced activity, selectivity, and stability.