P-N Bonds-Mediated Atomic-Level Charge-Transfer Channel Fabricated between Violet Phosphorus and Carbon Nitride Favors Charge Separation and Water Splitting

Heterostructures are widely employed in photocatalysis to promote charge separation and photocatalytic activity. However, their benefits are limited by the linkages and contact environment at the interface. Herein, violet phosphorus quantum dots (VPQDs) and graphitic carbon nitride (g-C3N4) are employed as model materials to form VPQDs/g-C3N4 heterostructures by a simple ultrasonic pulse excitation method. The heterostructure contains strong interfacial P-N bonds that mitigate interfacial charge-separation issues. P-P bond breakage occurs in the distinctive cage-like [P9] VPQD units during longitudinal disruption, thereby exposing numerous active P sites that bond with N atoms in g-C3N4 under ultrasonic pulse excitation. The atomic-level interfacial P-N bonds of the Z-scheme VPQDs/g-C3N4 heterostructure serve as photogenerated charge-transfer channels for improved electron-hole separation efficiency. This results in excellent photocatalytic performance with a hydrogen evolution rate of 7.70 mmol g-1 h-1 (over 9.2 and 8.5 times greater than those of pure g-C3N4 and VPQDs, respectively) and apparent quantum yield of 11.68% at 400 nm. Using atomic-level chemical bonds to promote interfacial charge separation in phosphorene heterostructures is a feasible and effective design strategy for photocatalytic water-splitting materials. P-N bonds-mediated atomic-level charge-transfer channel is constructed in VPQDs/g-C3N4 heterostructure by ultrasonic pulse excitation. The strong P-N bonds significantly accelerate charge transfer between g-C3N4 and VPQDs by a Z-scheme pathway, bestowing the VPQDs/g-C3N4 heterostructure with a record high photocatalytic hydrogen evolution rate of 7.70 mmol g-1 h-1 and apparent quantum yield of 11.68% at 400 nm. image