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

Abstract 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.