文献类型：期刊文献

英文题名：Mechanistic insights into natural chalcopyrite catalyzed photo-Fenton degradation of chlortetracycline: Synergistic activation pathways and environmental implications

作者：Chen, Xinyu[1];Dai, Jinxiang[1];Song, Yanyu[2];Liu, Mingtao[1];Nghiem, Long D.[3];Pan, Fei[4];Sun, Xianbo[1];Cai, Zhengqing[1,5]

机构：[1]East China Univ Sci & Technol, Natl Engn Res Ctr Ind Wastewater Detoxicat & Resou, Shanghai 200237, Peoples R China;[2]Weifang Univ Sci & Technol, Sch Civil Engn, Weifang 262700, Peoples R China;[3]Univ Technol Sydney, Ctr Technol Water & Wastewater, Sch Civil & Environm Engn, Ultimo, NSW 2007, Australia;[4]Wuhan Text Univ, Sch Resources & Environm, Wuhan 430200, Peoples R China;[5]Shanghai Inst Pollut Control & Ecol Secur, Shanghai 200237, Peoples R China

年份：2026

卷号：14

期号：1

外文期刊名：JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING

收录：;EI(收录号：20255019701741);WOS:【SCI-EXPANDED(收录号:WOS:001640771500001)】；

基金：This work was supported by the National Natural Science Foundation of China [41807340] , and the Natural Science Foundation of Shanghai [21ZR1415600] .

语种：英文

外文关键词：Chalcopyrite; Photo-Fenton; Chlortetracycline; Degradation mechanism

摘要：This study mechanistically investigates efficient chlortetracycline (CTC) degradation via natural chalcopyrite (CuFeS2) in a photo-Fenton system. Capitalizing on the synergistic interplay of light irradiation and the mineral's intrinsic redox-active sites, we achieved 99 % CTC removal within 30 min under optimized conditions (pH 7.0, CTC 40 mg/L, CuFeS2 0.75 g/L, H2O2 2 mM). The ternary light/CuFeS2/H2O2 system demonstrated remarkable activity, with a first-order kinetic constant 53.8 and 3.7 times greater than that of H2O2 alone and the CuFeS2/ H2O2 (dark) system, respectively. center dot OH is the primary reactive species, accounting for 74.67 % of CTC degradation. The second-order rate constant between center dot OH and CTC was determined as 7.76 x 109 M-1s-1, with an oxidation rate of 1.54 x 10-3 s-1. The XPS analysis attributed the high degradation efficacy to the synergistic Cu+/Cu2+ and Fe2+/Fe3+ redox cycles and electron transfer from metal sulfides to sulfur species (S2-/S22-/SO42-), which enhanced H2O2 activation and minimized metal leaching. Furthermore, the ternary light/CuFeS2/H2O2 system exhibited high efficacy under neutral pH (7.0) and in the presence of ions, which demonstrated the practicability of the system in real wastewater. LC-MS and DFT calculations identified dechlorination, deamination, and ring-opening as the primary degradation pathways, ultimately mineralizing CTC into CO2 and H2O. Toxicity was limited to short-lived intermediates, with end products being non-toxic. This work elucidates the atomic-level mechanism of the natural mineral-catalyzed photo-Fenton process, providing a sustainable and sludge-free catalyst (CuFeS2) for antibiotic wastewater treatment.