Room‐Temperature Chemoselective Hydrogenation of Nitroarene Over Atomic Metal–Nonmetal Catalytic Pair

Abstract Constructing atomic catalytic pair emerges as an attractive strategy to achieve better catalytic performance. Herein, an atomic Ir₁─P₁/NPG catalyst with asymmetric Ir─N₂P₁ sites that delivers superb activity and selectivity for hydrogenation of various functionalized nitrostyrene is reported. In the hydrogenation reaction of 3‐nitrostyrene, Ir₁─P₁/NPG (NPG refers to N, P‐codoped graphene) shows a turnover frequency of 1197 h⁻¹, while the reaction cannot occur over Ir₁/NG (NG refers to N‐doped graphene). Compared to Ir₁/NG, the charge density of the Ir site in Ir₁─P₁/NPG is greatly elevated, which is conducive to H₂ dissociation. Moreover, as revealed by density functional theory calculations and poisoning experiments, the P site in Ir₁─P₁/NPG is found able to bind nitrostyrene, while the neighboring Ir site provides H to reduce the nitro group in chemoselective hydrogenation of nitrostyrene. This work offers a successful example of establishing atomic catalytic pair for driving important chemical reactions, paving the way for the development of more advanced catalysts to further improve the catalytic performance.