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 Ir1P1/NPG catalyst with asymmetric IrN2P1 sites that delivers superb activity and selectivity for hydrogenation of various functionalized nitrostyrene is reported. In the hydrogenation reaction of 3-nitrostyrene, Ir1P1/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 Ir1P1/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 Ir1P1/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. An atomic Ir1P1/NPG catalyst with asymmetric Ir1N2P1 sites is designed, delivering superb activity and selectivity for the hydrogenation of nitroarene. Revealed by density functional theory calculations and poisoning experiments, the P site in Ir1P1/NPG is found able to bind nitroarene, while the neighboring Ir site activates H2 to provide H to reduce the nitro group in chemoselective hydrogenation of nitroarene.image