Precisely Tailoring the Second Coordination Sphere of a Cobalt Single-Atom Catalyst for Selective Hydrogenation of
Guangyu Chen1, Juwen Gu2, Wanbing Gong1
1School of Nuclear Science and Technology, Key Laboratory of Precision and Intelligent Chemistry, National Synchrotron Radiation Laboratory, School of Chemistry and Materials Science, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
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-N4P1 coordination structure. With a combination of experimental characterizations and theoretical simulations, we find that tailoring the second coordination sphere can greatly improve H2 dissociation and product desorption. As a result, the Co-N4P1 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 H2 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.
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