Rational Design and Precise Synthesis of Single-Atom Alloy Catalysts for the Selective Hydrogenation of Nitroarenes.

Single-atom alloys (SAAs) have gained increasing prominence in the field of selective hydrogenation reactions due to their uniform distribution of active sites and the unique host-guest metal interactions. Herein, 15 SAAs are constructed to comprehensively elucidate the relationship between host-guest metal interaction and catalytic performance in the selective hydrogenation of 4-nitrostyrene (4-NS) by density functional theory (DFT) calculations. The results demonstrate that the SAAs with strong host-guest metal interactions exhibit a preference for N─O bond cleavage, and the reaction energy barrier of the hydrogenation process is primarily influenced by the host metal. Among them, Ir 1 Ni SAA stands out as the prime catalyst candidate, showcasing exceptional activity and selectivity. Furthermore, the Ir 1 Ni SAA is subsequently prepared through precise synthesis techniques and evaluated in the selective hydrogenation of 4-NS to 4-aminostyrene (4-AS). As anticipated, the Ir 1 Ni SAA demonstrates extraordinary catalytic performance (yield > 96%). In situ FT-IR experiments and DFT calculations further confirmed that the unique host-guest metal interaction at the Ir-Ni interface site of Ir 1 Ni SAA endows it with excellent 4-NS selective hydrogenation ability. This work provides valuable insights into enhancing the performance of SAAs catalysts in selective hydrogenation reactions by modulating the host-guest metal interactions.