High‐Density and Thermally Stable Palladium Single‐Atom Catalysts for Chemoselective Hydrogenations

Single-atom catalysts (SACs) have shown superior activity and/or selectivity for many energy- and environment-related reactions, but their stability at high site density and under reducing atmosphere remains unresolved. Herein, we elucidate the intrinsic driving force of a Pd single atom with high site density (up to 5 wt %) under reducing atmosphere, and its unique catalytic performance for hydrogenation reactions. In situ experiments and calculations reveal that Pd atoms tend to migrate into the surface vacancy-enriched MoC surface during the carburization process by transferring oxide crystals to carbide crystals, leading to the surface enrichment of atomic Pd instead of formation of particles. The Pd1 /α-MoC catalyst exhibits high activity and excellent selectivity for liquid-phase hydrogenation of substituted nitroaromatics (>99 %) and gas-phase hydrogenation of CO2 to CO (>98 %). The Pd1 /α-MoC catalyst could endure up to 400 °C without any observable aggregation of single atoms.