Metal-Free B@g-CN: Visible/Infrared Light-Driven Single Atom Photocatalyst Enables Spontaneous Dinitrogen Reduction to Ammonia

Abstract

Conversion of naturally abundant dinitrogen (N 2 ) to ammonia (NH 3 ) is one of the most attractive and challenging topics in chemistry. Current studies mainly focus on electrocatalytic nitrogen reduction reaction (NRR) using metal-based electrocatalysts, while metal-free and solar-driven photocatalysts have been rarely explored. Here, on the basis of the “σ donation– π* back-donation” concept, single B atom supported on holey g -CN (B@ g -CN) can serve as metal-free photocatalyst for highly efficient N 2 fixation and reduction under visible and even infrared spectra. Our results reveal that N 2 can be efficiently activated and reduced to NH 3 with extremely low overpotential of 0.15 V and activation barrier of 0.61 eV, lower than most of metal-based NRR catalysts, thereby guaranteeing low energy cost and fast kinetics of NRR. The inherent properties of B@ g -CN, such as centralized spin-polarization on the B atom, efficient prohibition of competitive hydrogen evolution reaction (HER), and reduced exciton binding energy, are responsible for the high selectivity and Faradaic efficiency for NRR under ambient conditions. Moreover, for the first time, we theoretically disclose that the external potential provided by photogenerated electrons for NRR/HER endowing B@ g -CN spontaneous NRR and inaccessible HER. This work may provide a promising lead for designing efficient and robust metal-free single atom catalysts toward photocatalytic NRR under visible/infrared spectrum.