Visible-light induced tetracycline degradation catalyzed by dual Z-scheme InVO4/CuBi2O4/BiVO4 composites: The roles of oxygen vacancies and interfacial chemical bonds

Abstract

Dual Z-scheme InVO4/CuBi2O4/BiVO4 (CuInBi) composites with rich oxygen vacancies and chemical bonds at the heterojunction interfaces were fabricated, for the first time, through hydrothermal method with post annealing treatment, in which CuBi2O4 acts as a bridge to connect InVO4 and BiVO4. The as-prepared composites exhibited superior photocatalytic activity compared with the individual semiconductors. Specifically, the degradation rate of tetracycline (20 mg/L) in the presence of CuInBi-1 (1.0 g/L) was up to 5.4, 2.8, and 3.1 times faster than those in the presence of CuBi2O4, InVO4, and BiVO4, respectively. The enhanced photocatalytic performance could be partially attributed to the good light absorption of CuBi2O4, which broadens the visible light response of the InVO4/CuBi2O4/BiVO4 composites. Meanwhile, the interfacial chemical bonds in the dual Z-scheme heterojunction help accelerate charge separation and maintain strong redox activity. In addition, the oxygen vacancies, induced mainly by the low-valent vanadium atoms, facilitate the production of singlet oxygen (1O2) through energy transfer, which easily attacks the electron-rich groups, including phenolic group, dimethylamino group, amine group, and double bonds, in tetracycline. The InVO4/CuBi2O4/BiVO4 composite exhibited excellent reusability and stability, and performed well in photocatalytic degradation of tetracycline in river water and under natural sunlight, demonstrating great potential for practical application. The probable photocatalytic mechanism of InVO4/CuBi2O4/BiVO4 composite was proposed according to the results of density functional theory (DFT) calculations, and the reactive oxygen species (ROSs) and major degradation intermediates detected in the photocatalytic system. This work demonstrates the important roles of oxygen vacancies and interfacial chemical bonds in boosting the photocatalytic activity of Z-scheme heterojunctions and provides a reference for the construction of high-activity photocatalysts for efficient degradation of antibiotics.