State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, P. R. China.
State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, P. R. China.
Water Res. 2022 Jun 30;218:118454. doi: 10.1016/j.watres.2022.118454. Epub 2022 Apr 13.
Benzotriazole (BTA) is a widely used anticorrosive additive that is of endurance, bioaccumulation and toxicity, and BTA industrial wastewater treatment remains a challenge. This study reports efficient electrochemical removal of BTA by titanium oxide (TiSO) electroactive ceramic membrane (ECM), indicated by 98.1% removal at current density of 20 mA∙cm-2 and permeate flux of 692 LHM under cathode-to-anode flow pattern (1 h). Electrochemical analysis demonstrated the pH-dependent formation of anti-corrosive BTA film on the TiSO anode, which was responsible for improved BTA removal for cathode-to-anode (CA) flow pattern compared with that for anode-to-cathode (AC). The modelling results showed the CA flow pattern to be more favourable for BTA oxidation mediated by electro-generated •OH by preventing the formation of deactivation film via creating an alkaline boundary layer at the anode/electrolyte interface. Intermediates and essential active sites were identified by using experimental analysis and theoretical density functional theory (DFT) calculations, thereby the most likely degradation pathways were underlined. Toxicity analysis revealed remarkable decrease in oral rat LD50 values and bioaccumulation factor during electrochemical degradation of BTA. This study provides a proof-in-concept demonstration of effective removal for anti-corrosive emerging pollutants by TiSO-ECM under flow-through pattern.
苯并三唑（BTA）是一种广泛使用的耐腐蚀添加剂，具有耐久性、生物累积性和毒性，BTA 工业废水处理仍然是一个挑战。本研究通过钛氧化物（TiSO）电活性陶瓷膜（ECM）高效电化学去除 BTA，在电流密度为 20 mA·cm-2 和透膜通量为 692 LHM 时，阴极到阳极流动模式下去除率达到 98.1%（1 h）。电化学分析表明，TiSO 阳极上形成了依赖于 pH 值的耐腐蚀 BTA 膜，这使得与阳极到阴极（AC）流动模式相比，阴极到阳极（CA）流动模式下 BTA 的去除率得到了提高。模型结果表明，CA 流动模式更有利于电生成的•OH 介导的 BTA 氧化，通过在阳极/电解质界面处形成碱性边界层来防止失活膜的形成。通过实验分析和理论密度泛函理论（DFT）计算确定了中间体和必需的活性位点，从而强调了最可能的降解途径。毒性分析表明，在 BTA 的电化学降解过程中，口服大鼠 LD50 值和生物累积因子显著降低。本研究通过流动模式下的 TiSO-ECM 为有效去除耐腐蚀新兴污染物提供了概念验证。
