Zhao Yunmeng, Zhang Chaojie, Xue Yin, Zhai Zhenyu, Zhou Xuefei, Zhang Yalei
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, 200092, PR China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, PR China.
State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, 200092, PR China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, PR China.
J Environ Manage. 2025 Jan;373:123721. doi: 10.1016/j.jenvman.2024.123721. Epub 2024 Dec 17.
Photocatalysis is an effective method for removing tetracycline antibiotics, which are important precursors to the potential carcinogen N-nitrosodimethylamine (NDMA). Herein, a BiOCl/ZnInS heterojunction was successfully synthesized using a simple hydrothermal method. This heterojunction was applied for the first time to degrade various tetracycline antibiotics and reduce NDMA formation potential (NDMA-FP) under visible-light irradiation. Characterization of surface morphology, crystal structure, chemical composition and photoelectrochemical properties revealed that the BiOCl/ZnInS heterojunction significantly improved light absorption, charge transport and carrier separation efficiency, thereby enhancing photocatalytic performance. The BiOCl/ZnInS catalyst achieved high degradation efficiencies of 88.0%, 90.7%, 88.7% and 91.7% for tetracycline, minocycline, chlortetracycline and doxycycline, respectively, within 60 min of visible-light irradiation. Additionally, it exhibited the lowest NDMA-FP values of 1.5%, 3%, 0.9% and 1.4%, respectively. Radical trapping studies and EPR experiments identified •O and •OH radicals as the primary reactive species involved in the photocatalytic process. Analysis of the degradation intermediates and structure-activity relationships indicated that the variations in NDMA-FP were closely associated with the number of dimethylamine groups in the antibiotics and the stability of the resulting carbocations. Notably, the BiOCl/ZnInS catalyst presented satisfactory stability and positive tetracycline degradation in real antibiotic wastewater. Incorporating BiOCl/ZnInS-loaded nonwoven fabric into a continuous-flow reactor efficiently degraded tetracycline in real wastewater under visible light. This work provides new insights on developing Z-scheme photocatalysts for the simultaneous degradation of various antibiotics and highlights their potential as commercially viable photocatalytic system.
光催化是去除四环素类抗生素的有效方法，而四环素类抗生素是潜在致癌物N-亚硝基二甲胺（NDMA）的重要前体。在此，采用简单的水热法成功合成了BiOCl/ZnInS异质结。该异质结首次应用于可见光照射下对各种四环素类抗生素的降解以及降低NDMA生成潜力（NDMA-FP）。表面形貌、晶体结构、化学成分和光电化学性质的表征表明，BiOCl/ZnInS异质结显著提高了光吸收、电荷传输和载流子分离效率，从而增强了光催化性能。在可见光照射60分钟内，BiOCl/ZnInS催化剂对四环素、米诺环素、金霉素和强力霉素的降解效率分别达到88.0%、90.7%、88.7%和91.7%。此外，它的NDMA-FP值分别为1.5%、3%、0.9%和1.4%，是最低的。自由基捕获研究和电子顺磁共振实验确定•O和•OH自由基是光催化过程中的主要活性物种。降解中间体分析和构效关系表明，NDMA-FP的变化与抗生素中二甲胺基团的数量以及所生成碳正离子的稳定性密切相关。值得注意的是，BiOCl/ZnInS催化剂在实际抗生素废水中表现出令人满意的稳定性和正的四环素降解效果。将负载BiOCl/ZnInS的无纺布纳入连续流反应器中，可在可见光下有效降解实际废水中四环素。这项工作为开发用于同时降解各种抗生素的Z型光催化剂提供了新的见解，并突出了它们作为商业可行光催化系统的潜力。
