BiNV bond: A hole-transfer bridge for high-efficient separation and transfer of carriers

Addressing the inherent holes transport limitation of BiVO₄ photoanode is crucial to achieve efficient photoelectrochemical (PEC) water splitting. The construction of the hole-transfer bridge between co-catalysts and BiVO₄ photoanode could be an effective way to overcome sluggish hole-transfer kinetics of BiVO₄ photoanode. Herein, C_xN_y/BiVO₄ photoanode was prepared by coupling carbon nitride hydrogel (CNH) containing unsaturated N on the BiVO₄ photoanode during annealing. C_xN_y/BiVO₄ photoanode exhibited excellent PEC performance and stability. Photoelectrochemical tests proved that the coupling of C_xN_y accelerated holes transfer and enhanced oxygen evolution kinetics. X-ray photoelectron spectroscopy (XPS) and theoretical calculations confirmed the existence of the BiNV bond between BiVO₄ photoanode and C_xN_y, which could serve as the hole-transfer bridge to significantly accelerate separation and transfer of carriers driven by the interfacial electric field. Moreover, it was found that the coupling of C_xN_y effectively inhibited the dissociation of metal ions through changing their coordination environment, resulting in the excellent stability of C_xN_y/BiVO₄ photoanode. This result provides unique insights into vital roles of the interfacial structure, which might have a significant impact on the construction of PEC devices.