高等学校化学学报2024，Vol.45Issue(12)：10-21,12.DOI:10.7503/cjcu20240337
pH介导铜络合物活化过一硫酸盐选择性氧化水体四环素的分子内电子转移机制
Intramolecular Electron Transfer Mechanism of pH-Mediated Cupric Complexes Activated Peroxymonosulfate Selective Oxidation of Aqueous Tetracycline
摘要
Abstract
Although aqueous dissociative Cu(Ⅱ)could not effectively activate peroxymonosulfate(PMS),the cupric complexes formed by complexing with tetracycline(TC)could activate PMS and realize self-catalytic degradation of TC.The generation of cupric complexes was verified by UV-Vis and high performance liquid chromatography(HPLC),and the reaction pathways,molecular structure model,free energy variation,density of states(DOS),and complexation interaction of cupric complexes were revealed by density functional theory(DFT)calculation.It was found that the d orbital of Cu in Cu(H2O)42+was complexed by accepting the lone pair electrons of p orbital from hydroxyl,carbonyl,and amide group O in TC,and there were five possible complexation models constructed,all of them showed a stable bidenate ligands and hexatomic-ring coordination structure,in which the free energy of complex M1 became the smallest and its structure was the most stable.The interaction of cupric complexes formation mainly included van der Waals force,weak interaction,covalent bond,steric hindrance,coordination bond,etc.Cu(II)/PMS system had significant self-catalytic degradation of TC,which could be completely degraded within 240 min(degradation efficiency was greater than 99%).Furthermore,under alkaline conditions(pH=10),the activation of peroxymonosulfate by cupric complexes coupling Cu(III)complexes generation in situ promoted an intramolecular electron transfer(IET)process dominating the selective oxidation of TC.The pH-mediated IET mechanism of cupric complexes activated peroxymonosulfate selective oxidation of aqueous tetracycline was further elucidated through DFT calculations from dynamic and microscopic perspectives.The new findings in this paper further verified the self-catalytic selective oxidation performance and mechanism by aqueous cupric complexes activated PMS system,which provided a potential solution for the synergistic decontamination of actual wastewater contaminated heavy metals and antibiotics.关键词
铜络合物/过一硫酸盐/四环素/选择性氧化Key words
Cupric complex/Peroxymonosulfate/Tetracycline/Selective oxidation分类
化学化工引用本文复制引用
曾湘楚,叶雨婷,武哲,韦瑞松,刘欢..pH介导铜络合物活化过一硫酸盐选择性氧化水体四环素的分子内电子转移机制[J].高等学校化学学报,2024,45(12):10-21,12.基金项目
中国博士后科学基金(批准号:2024M751271)、广西现代蚕桑丝绸协同创新中心基金(批准号:2023GXCSSC03)、2023年度广西高校中青年教师科研基础能力提升项目(批准号:2024KY0623)、河池学院高层次人才科研启动项目(批准号:2023GCC015,2021GCC031)和2023年河池市本级财政科技计划项目(批准号:河科AC231107)资助.Supported by the China Postdoctoral Science Foundation(No.2024M751271),the Special Project of Guangxi Collaborative Innovation Center of Modern Sericulture and Silk,China(No.2023GXCSSC03),the 2023 Guangxi University Young and Middle-aged Teachers Research Basic Ability Improvement Project,China(No.2024KY0623),the Hechi University High-level Talent Research Project,China(Nos.2023GCC015,2021GCC031)and the 2023 Hechi City Level Financial Science and Technology Plan Project,China(No.HekeAC231107). （批准号:2024M751271）
