Aniline and its derivatives are important chemical immediate for the synthesis of pharmaceuticals, agrochemicals, polymers and other fine chemicals. Heterogeneous selective hydrogenation of nitro group by hydrogen is a promising method to produce amino group. Generally molecular H<sub>2</sub> activation and dissociation is the first and crucial step in the hydrogenation reaction. In this work, we report carbon can be activated as metal-like hydrogenation catalyst for selective hydrogenation of nitroarenes. Using DFT calculations we demonstrated the combination of P-dopant and lattice defect in carbon can cause significant electron delocalization and change the band structure as metal-like one, and thus both H<sub>2</sub> and nitro group are easily activated for selective hydrogenation. Then we fabricated this carbon catalyst with tunable concentration of P-dopant and lattice defect by polymerization and carbonization of phytic acid, and found the concentration of lattice defect is closely related to that of P-dopants. The synthesized catalyst exhibits superior catalytic activity, perfect selectivity and stability in the hydrogenation of nitroarenes, outperforming the reported metal-free, metal-oxide and nickel catalysts. Importantly, the hydrogenation activity is linearly dependent on the P-doping and/or defect concentration, perfectly agreeing with the DFT calculation. This work is expected to provide a cheap way for large-scale production of anilines using metal-like carbon catalyst.

Phosphorus-doped and lattice-defective carbon as metal-like catalyst for selective hydrogenation of nitroarenes

255th National Meeting (2018)

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