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

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. © 2023 Wiley-VCH GmbH.