A novel Z-scheme Ag3VO4/BiVO4 heterojunction photocatalyst: Study on the excellent photocatalytic performance and photocatalytic mechanism

A novel three-dimensional microspheres mediator-free Z-scheme Ag3VO4/BiVO4 heterojunction photocatalyst was successfully obtained for the first time. The photocatalytic performance of the as-prepared photocatalyst was systematically examined via the photocatalytic reduction of Cr6+ and oxidation of Bisphenol S under visible-light irradiation. Among these samples, 0.24-Ag3VO4/BiVO4 exhibits the highest photocatalytic performances, the photocatalytic reduction and oxidation efficiency of 74.9 and 94.8%, respectively, can be achieved. The enhanced photocatalytic performance is attributed to the build-in electric field assisted charge transfer between the Ag3VO4 and BiVO4, and the increasing lifetime of the charge carrier confirmed by the results of time-resolved fluorescence spectra and photoelectrochemical measures. Moreover, based on the results of free radical scavenging activity test, and EPR experiments, it has been verified that the Ag3VO4/BiVO4 heterostructures follow a typical Z-scheme charge transfer mechanism rather than conventional type-II heterojunction charge transfer mechanism. Furthermore, the theoretical understanding of the underlying mechanism was also supported, while the energy band structure, and Fermi level were systematically calculated using the density functional theory approach. The results show that a built-in electric field directed from Ag3VO4 to BiVO4 surface was established as an equalized Fermi level was reached, which benefits the separation of photogenerated charge carriers in the way of a Z-scheme charge transfer mechanism. The strategy to form the three-dimensional microspheres Z-scheme heterojunction photocatalyst may offer new insight into the Z-scheme charge transfer mechanism for applications in the field of solar energy conversion.