Phosphorus-Doped and Lattice-Defective Carbon as Metal-like Catalyst for the Selective Hydrogenation of Nitroarenes

We report carbon can be activated as metal-like hydrogenation catalyst for the 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 to a metal-like one, and thus both H-2 and the nitro group are easily activated for selective hydrogenation. Then we fabricated this carbon catalyst with tunable concentration of P dopant and lattice defects 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.