Activating black phosphorene's inert basal plane via nonprecious metal–nonmetal co-doping for visible-light-driven photocatalytic H2 evolution

Abstract

Black phosphorene (BP) is a metal-free two-dimensional photocatalyst with potential for visible-light-driven photocatalytic H₂ evolution. However, its inert basal plane toward the HER hinders its practical application. To overcome this problem, we design a novel nonprecious metal–nonmetal co-doping method of BP to activate its inert basal plane and improve photocatalytic HER performance. Through density functional theory (DFT) calculations, we systematically investigate the photocatalytic performance of nonprecious metal and nonmetal co-doped BPs. Our results show that V–N co-doped BP exhibits excellent thermodynamic stability, suitable band structure, improved carrier separation, superior adsorption and dissociation energies and enhanced visible-light absorption coefficient. Importantly, V–N co-doping successfully activates the inert basal plane of BP, allowing it to drive the HER under illumination (ΔG_H = −0.12 eV). This study highlights the potential of nonprecious metal–nonmetal co-doping to enhance the photocatalytic activity of BP, providing invaluable insights for advancing the field of co-doped BP in photocatalysis.