School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou, 310018, China.
School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou, 310018, China.
Environ Pollut. 2024 May 1;348:123813. doi: 10.1016/j.envpol.2024.123813. Epub 2024 Mar 25.
The removal of trace amounts of antibiotics from water environments while simultaneously avoiding potential environmental hazards during the treatment is still a challenge. In this work, green, harmless, and novel asymmetric mesoporous TiO (A-mTiO) was combined with peroxodisulfate (PDS) as active components in a controlled-release material (CRM) system for the degradation of tetracycline (TC) in the dark. The formation of reactive oxygen species (ROS) and the degradation pathways of TC during catalytic PDS activation by A-mTiO powder catalysts and the CRMs were thoroughly studied. Due to its asymmetric mesoporous structure, there were abundant Ti/Ti couples and oxygen vacancies in A-mTiO, resulting in excellent activity in the activation of PDS for TC degradation, with a mineralization rate of 78.6%. In CRMs, ROS could first form during PDS activation by A-mTiO and subsequently dissolve from the CRMs to degrade TC in groundwater. Due to the excellent performance and good stability of A-mTiO, the resulting constructed CRMs could effectively degrade TC in simulated groundwater over a long period (more than 20 days). From electron paramagnetic resonance analysis and TC degradation experiments, it was interesting to find that the ROS formed during PDS activation by A-mTiO powder catalysts and CRMs were different, but the degradation pathways for TC were indeed similar in the two systems. In PDS activation by A-mTiO, besides the free hydroxyl radical (·OH), singlet oxygen (O) worked as a major ROS participating in TC degradation. For CRMs, the immobilization of A-mTiO inside CRMs made it difficult to capture superoxide radicals (·O), and continuously generate O. In addition, the formation of sulfate radicals (·SO), and ·OH during the release process of CRMs was consistent with PDS activation by the A-mTiO powder catalyst. The eco-friendly CRMs had a promising potential for practical application in the remediation of organic pollutants from groundwater.
从水环境中去除痕量抗生素的同时，在处理过程中避免潜在的环境危害仍然是一个挑战。在这项工作中，绿色、无害且新颖的不对称介孔 TiO（A-mTiO）与过一硫酸盐（PDS）结合作为活性成分，在控制释放材料（CRM）系统中用于暗态下四环素（TC）的降解。彻底研究了 A-mTiO 粉末催化剂和 CRM 中催化 PDS 活化时活性氧物种（ROS）的形成和 TC 的降解途径。由于其不对称介孔结构，A-mTiO 中存在丰富的 Ti/Ti 偶和氧空位，因此在 PDS 活化 TC 降解方面表现出优异的活性，矿化率为 78.6%。在 CRM 中，ROS 可以在 A-mTiO 活化 PDS 期间首先形成，然后从 CRM 中溶解以降解地下水的 TC。由于 A-mTiO 的优异性能和良好的稳定性，所构建的 CRM 可以有效地在模拟地下水中长时间（超过 20 天）降解 TC。通过电子顺磁共振分析和 TC 降解实验，有趣的是发现 A-mTiO 粉末催化剂和 CRM 中 PDS 活化过程中形成的 ROS 不同，但这两个体系中 TC 的降解途径确实相似。在 A-mTiO 活化 PDS 中，除了游离羟基自由基（·OH）外，单线态氧（O）作为主要的 ROS 参与 TC 降解。对于 CRM，A-mTiO 在 CRM 内部的固定化使其难以捕获超氧自由基（·O），并不断生成 O。此外，CRM 释放过程中硫酸盐自由基（·SO）和·OH 的形成与 A-mTiO 粉末催化剂活化 PDS 一致。环境友好型 CRM 具有在地下水有机污染物修复中实际应用的广阔前景。
