Construction of functionalized In-based metal organic framework/BiOCl1−xIx Z-scheme heterojunction for efficient photocatalytic degradation of tetracycline: Performance and mechanism

Abstract

The environmental implications of antibiotics have drawn widespread attention. Numerous monomer-based bismuth oxide halide catalysts have been extensively studied to remove tetracycline (TC) from aquatic environments. Integrating bismuth oxide halide composites with In-based metal organic framework (NH2-MIL-68(In)) might potentially serve as a novel strategy. By meticulously adjusting Cl and I within the composite bismuth halide oxide (B-x), a suite of purpose built heterojunctions (NMB-x) were synthesized, which were engineered to facilitate the efficient photodegradation of TC in simulated and actual aquatic environments. The incorporation of Z-scheme heterojunctions yielded a significant enhancement in photocatalytic responsiveness and charge carrier separation. Notably, NMB-0.3 demonstrated remarkable TC removal efficiency of 88.52 ± 3.05%, which is 3.74 times of B-0.3 within 90 min. The apparent quantum yield was also increased from 8.97% (B-0.3) to 19.68% (NMB-0.3). The removal of TC from natural water bodies was also assessed. Moreover, the photocatalyst concentration, assessed using response surface method, was found to show influential factors on TC removal. In addition, density functional theory (DFT) simulations were employed to identify vulnerable sites within TC. Intermediates and pathways in the photodegradation of TC have also been inferred. Furthermore, a comprehensive environmental toxicity assessment of representative intermediates demonstrated that these intermediates exhibited significantly reduced environmental toxicity compared to TC. This study provides a new approach to the design strategy of efficient and environmentally friendly MOF-based photocatalysts.