Engineering interfacial band bending over bismuth vanadate/carbon nitride by work function regulation for efficient solar-driven water splitting

The work function of BiVO4 is modulated from smaller to larger than that of PCN by controlling the oxygen vacancy, which switches the direction of interfacial band bending in BiVO4/PCN heterojunction. Accordingly, the photoinduced charge transfer mechanism is changed from type-II to direct Z-scheme for superior solar-driven pure water splitting. [Display omitted] Nature-inspired artificial Z-scheme photocatalyst offers great promise in solar overall water splitting, but its rational design, construction and interfacial charge transfer mechanism remain ambiguous. Here, we design an approach of engineering interfacial band bending via work function regulation, which realizes directional charge transfer at interface and affords direct Z-scheme pathway. Taking BiVO4 as prototype, its oxygen vacancy concentration is reduced by slowing down the crystallization rate, thereby changing the work function from smaller to larger than that of polymeric carbon nitride (PCN). Consequently, the photoinduced charge transfer pathway of BiVO4/PCN is switched from type-II to Z-scheme as evidenced by synchronous illuminated X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption spectroscopy. Specifically, the direct Z-scheme BiVO4/PCN shows superior photocatalytic performance in water splitting. This work provides deep insights and guidelines to constructing heterojunction photocatalysts for solar utilization.