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山东大学学报 (工学版) ›› 2026, Vol. 56 ›› Issue (5): 201-214.doi: 10.6040/j.issn.1672-3961.0.2025.162

• 环境工程 • 上一篇    

碳酸盐对UV/H2O2降解甲氧苄啶的影响机制研究

魏凤华1,王成霖2,谷青元2,何茂霞2*   

  1. 1. 山东大学(青岛)资产与实验室管理处, 山东 青岛 266237;2. 山东大学环境研究院, 山东 青岛 266237
  • 发布日期:2026-10-19
  • 作者简介:魏凤华(1985— ),女,山东泰安人,助理研究员,硕士,主要研究方向为高级氧化技术在危废处理中的应用. E-mail:wfh@sdu.edu.cn. *通信作者简介:何茂霞(1972— ),女,山东日照人,教授,博士生导师,博士,主要研究方向为水处理工程. E-mail:hemaox@sdu.edu.cn
  • 基金资助:
    国家自然科学基金资助项目(22276109)

Mechanistic study on the effect of carbonate on the degradation of trimethoprim in UV/H2O2

Wei Fenghua1, Wang Chenglin2, Gu Qingyuan2, He Maoxia2*   

  1. Wei Fenghua1, Wang Chenglin2, Gu Qingyuan2, He Maoxia2*(1. Assets and Laboratory Management Office, Shandong University(Qingdao), Qingdao 266237, Shandong, China;
    2. Environment Research Institute, Shandong University, Qingdao 266237, Shandong, China
  • Published:2026-10-19

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摘要： 为揭示碳酸盐在UV/H2O2降解甲氧苄啶(trimethoprim, TMP)过程中的调控机制及pH依赖性,采用理论计算方法研究TMP与CO·-3初始反应机理和TMP与HO·初始反应机理的差异性,以及碳酸盐对其反应机理的影响机制。结果表明,CO·-3对不同解离形式的分子(中性、双质子化形式、单质子化形式的TMP)具有较强的选择性,仅与中性态TMP发生单电子转移(single electron transfer, SET)反应;较HO·体系,其SET活化能降低30.98%。因此,相较于HO·对苯环、亚氨基及嘧啶环的多位点羟基化特性,CO·-3虽无法直接实现TMP的完全矿化,但通过生成自由基阳离子中间体可显著降低HO·后续反应的活化能。碳酸盐浓度存在阈值效应,在低浓度时碳酸盐作为HO·与TMP之间的电子转移介质,可加速TMP的降解;而高浓度则表现为对HO·的淬灭作用,抑制降解。中间产物毒性评估显示,除P12外,多数羟基化和羰基化中间产物的毒性低于母体化合物。碳酸盐在UV/H2O2降解TMP过程中具有浓度依赖的双重调控作用,低浓度时通过CO·-3介导电子转移并促进后续HO·反应,高浓度时则因淬灭HO·而抑制TMP降解。

关键词: 合成抗菌剂, pH, 碳酸盐, UV/H2O2, 降解机理, 降解效率

Abstract: To elucidate the regulatory mechanisms and pH dependence of carbonates in the UV/H2O2 degradation of trimethoprim(TMP), theoretical calculation methods were adopted to study the differences in the initial reaction mechanisms of TMP with CO·-3 and HO· under UV/H2O2 conditions, as well as the influence mechanism of carbonates on their reaction mechanisms. The research results showed that CO·-3 had strong selectivity for molecules in different dissociation forms(neutral, diprotonated and monoprotonated forms of TMP), and only underwent single electron transfer reaction(SET)with neutral TMP. Compared with the HO· system, its SET activation energy barrier was reduced by 30.98%. Therefore, compared with the multi-site hydroxylation characteristics of HO· on the benzene ring, imino and pyrimidine ring, although CO·-3 could not directly achieve the complete mineralization of TMP, it could significantly reduce the activation energy of the subsequent reaction of HO· by generating a radical cation intermediate. There was a threshold effect in carbonate concentration. At low concentrations, carbonate acted as an electron transfer medium between HO· and TMP, which could accelerate the degradation of TMP. High concentrations, on the other hand, exhibited a quenching effect on HO· and inhibited degradation. Toxicity assessment of the intermediate products indicates that, with the exception of P12, the toxicity of most hydroxylated and carbonylated intermediates is lower than that of the parent compound. Carbonate showed a concentration-dependent effect during UV/H2O2 degradation of TMP, low concentrations promoted TMP degradation via CO·-3-mediated electron transfer, whereas high concentrations inhibited it by quenching HO·

Key words: synthetic antimicrobial, pH, carbonate, UV/H2O2, degradation mechanism, degradation efficiency

中图分类号: 

  • X131.2
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