Investigation of the Kinetics and Reaction Mechanism for Photodegradation Tetracycline Antibiotics over Sulfur-Doped Bi₂WO_6-x/ZnIn₂S₄ Direct Z-Scheme Heterojunction

The rational design of direct Z-scheme heterostructural photocatalysts using solar energy is promising for energy conversion and environmental remediation, which depends on the precise regulation of redox active sites, rapid spatial separation and transport of photoexcited charge and a broad visible light response. The Bi2WO6 materials have been paid more and more attention because of their unique photochemical properties. In this study, S2− doped Bi2WO6-x coupled with twin crystal ZnIn2S4 nanosheets (Sov−BWO/T−ZIS) were prepared as an efficient photocatalyst by a simple hydrothermal method for the removal of tetracycline hydrochloride (TCH). Multiple methods (XRD, TEM, XPS, EPR, UV vis DRS, PL etc.) were employed to systematically investigate the morphology, structure, composition and photochemical properties of the as-prepared samples. The XRD spectrum indicated that the S2− ions were successfully doped into the Sov−BWO component. XPS spectra and photoelectrochemical analysis proved that S2− served as electronic bridge and promoted captured electrons of surface oxygen vacancies transfer to the valence band of T−ZIS. Through both experimental and in situ electron paramagnetic resonance (in situ EPR) characterizations, a defined direct Z-scheme heterojunction in S-BWO/T−ZIS was confirmed. The improved photocatalytic capability of S-BWO/T−ZIS results ascribed that broadened wavelength range of light absorption, rapid separation and interfacial transport of photoexcited charge, precisely regulated redox centers by optimizing the interfacial transport mode. Particularly, the Sov−50BWO/T−ZIS Z-scheme heterojunction exhibited the highest photodegradation rate was 95% under visible light irradiation. Moreover, this heterojunction exhibited a robust adsorption and degradation capacity, providing a promising photocatalyst for an organic pollutant synergistic removal strategy