Efficient photoreduction of carbon dioxide to ethanol using diatomic nitrogen-doped black phosphorus.

Successful conversion of CO 2 into C 2 products requires the development of new catalysts that overcome the difficulties in efficient light harvesting and CO-CO coupling. Herein, density functional theory (DFT) is used to assess the photoreduction properties of nitrogen-doped black phosphorus. The geometric structure, redox potential, first step of hydrogenation activation, CO desorption, and CO-CO coupling are systematically calculated, based on which the diatomic nitrogen-doped black phosphorus (N 2 @BP V ) stands out. The calculated results of the CO 2 RR pathway demonstrate that N 2 @BP V has excellent selectivity and high activity for CH 3 CH 2 OH production. The results of the time-dependent ab initio nonadiabatic molecular dynamics simulation show that the diatomic N active sites of N 2 @BP V facilitate charge separation and inhibit electron-hole recombination. In addition, the activation mechanism of CO 2 is studied. The main reason for CO 2 activation is attributed to the imbalance in electron transfer that destroys the symmetry of CO 2 . We expect that our study will offer some theoretical guidance in CO 2 conversion.