Precisely Tailoring the Second Coordination Sphere of a Cobalt Single‐Atom Catalyst for Selective Hydrogenation of Halogenated Nitroarenes

Abstract The development of highly efficient and cost‐effective nonprecious metal catalysts for the selective hydrogenation of halogenated nitroarenes is very appealing yet challenging. Here, we demonstrate that the hydrogenation activity and selectivity of Co single‐atom catalyst (SAC) can be tuned by tailoring the structure of second coordination sphere via P doping. As revealed by synchrotron radiation‐based X‐ray absorption spectroscopy characterizations, such a P doping on N‐coordinated Co SAC results in the unsymmetric Co‐N 4 P 1 coordination structure. With a combination of experimental characterizations and theoretical simulations, we find that tailoring the second coordination sphere can greatly improve H 2 dissociation and product desorption. As a result, the Co‐N 4 P 1 SAC exhibits superior activity, selectivity and stability for the hydrogenation of halogenated nitroarenes to corresponding amines (20 examples, >99 % yields) at 80 °C under 0.5 MPa H 2 pressure, significantly outperforming most heterogeneous catalysts reported in the literature. We expect that this work opens a new avenue for the design of highly efficient nonprecious metal SACs for important hydrogenation reactions.