Fabrication of CuWO4/Bi2S3/ZIF67 MOF: A novel double Z-scheme ternary heterostructure for boosting visible-light photodegradation of antibiotics

A novel double Z-scheme CuWO4/Bi2S3/ZIF67 ternary heterostructure was synthesized through hydrothermal method. The catalysts were characterized by XRD, FTIR, SEM, EDX, BET, TEM, PL, and UV–vis DRS analyses. The degradations of Metronidazole (MTZ) and Cephalexin (CFX) antibiotics by ternary catalyst were investigated in the batch and continuous slurry photoreactor under LED illumination. The ternary heterostructure exhibited a remarkable improvement in photoactivity compared with CuWO4/Bi2S3, and pristine ZIF67. Indeed, higher surface area, photo-stability, bandgap suppressing as well as better charge separation based on the dual Z-scheme structure caused the enhancement. The optimum values of operating parameters were obtained by the central composite design as: catalyst dose = 0.3 g/L, pH = 7, illumination time = 80 min, and 20 ppm initial concentration of antibiotic. The maximum degradation efficiencies by the new ternary heterostructure were 95.6% and 90.1%, respectively for MTZ and CFX at optimum conditions in the continuous flow mode. Maximum total organic carbon (TOC) removal rates were 83.2% and 74% for MTZ and CFX, respectively. The degradations by ternary composite followed the first-order kinetic, by reaction rate of 9 times, 5.5 times, and 4 times higher than that obtained by Bi2S3, ZIF67, and the binary CuWO4/Bi2S3, respectively. The influences of temperature and light intensity were explored, revealing 25 °C and 400 W/m2 as the optimum values. The new ternary heterostructure demonstrated excellent reusability and chemical stability after six cycles. The dominant active species were explored by trapping tests, indicating OH. free radicals as the most primary oxidant.