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

Abstract 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.