Enhanced degradation of tetracycline under natural sunlight through the synergistic effect of Ag₃PO₄/MIL-101(Fe) photocatalysis and Fenton catalysis: Mechanism, pathway, and toxicity assessment

Here, we show that the adverse environmental and health effects of tetracycline (TC) can be efficiently reduced by encapsulating Ag₃PO₄ into MIL-101(Fe) to construct a Ag₃PO₄/MIL-101(Fe) heterojunction composite through advanced oxidation processes, such as Fenton catalysis, photocatalysis, and photo-Fenton catalysis. Notably, the reaction can be driven by natural sunlight and does not require any artificial energy source. Remarkably, the optimal degradation of TC can be achieved under different compositions of the composite system through photocatalysis and photo-Fenton catalysis. For photo-Fenton catalysis, the maximum degradation rate of TC (2.5730 min⁻¹) is achieved when the mass ratio of MIL-101(Fe) to Ag₃PO₄ in the composite is 5:1, which is 31.65- and 3.12-fold of that in the Ag₃PO₄ + PDS + Sunlight and MIL-101(Fe) + PDS+ Sunlight catalyst systems, respectively. Moreover, the internal conversion of matrix during photocatalysis and Fenton catalysis processes inhibits the photocorrosion of Ag₃PO₄ and improves the reusability of the composite. Furthermore, it is found that both radical and non-radical species participate in the TC degradation. Besides, the degradation products and catalytic mechanism of Ag₃PO₄ and Ag₃PO₄/MIL-101(Fe) systems are explored. The toxicity evaluation results suggest that the intermediates produced during Ag₃PO₄/MIL-101(Fe) catalysis have a lower biotoxicity than those produced during Ag₃PO₄ catalysis. Overall, this work provides an effective strategy to inhibit the inherent photocorrosion of Ag₃PO₄ and establishes an efficient catalytic system for the treatment of organic-contaminated wastewater under natural sunlight conditions.