Efficient reduction of nitrobenzene to aniline by metal-free B-doped graphdiyne

Aniline is an important chemical, which can be obtained by nitrobenzene electrocatalytic reduction (NBER), while searching for efficient electrocatalysts is still a challenge. In this work, the reaction mechanism of B-doped graphdiyne (GDY) with different doped sites for NBER was investigated by density functional theory (DFT) methods. In comparison with pristine GDY, the conductivity of B-doped GDY is increased which is beneficial to the electrocatalytic reaction. Ph-NO2 can be activated by B-doped GDY that the B atom is doped at the acetylenic carbon site. Particularly, B doping at sp-sp2 hybridized acetylenic site of GDY has high catalytic performance for NBER with low limiting potential of - 0.30 V, and the rate-determining step is Ph-NO2* hydrogenation to PhNOOH*. This work demonstrates that B-doping is an effective strategy to improve the performance of catalysts and advance the development of metal-free electrocatalysts for Ph-NH2 production.