双金属阳极膜电催化原位产臭氧去除废水中的盐酸四环素  

Removal of tetracycline from wastewater by in situ-produced ozone through bimetallic anode membrane electrocatalysis

作　　者：程心悦 张晓楠 高兆鹤 何亮 关清卿[1] 周华晶 CHENG Xinyue;ZHANG Xiaonan;GAO Zhaohe;HE Liang;GUAN Qingqing;ZHOU Huajing(Faculty of Civil Engineering and Mechanics,Kunming University of Science and Technology,Kunming 650500,China;Faculty of Chemical Engineering,Kunming University of Science and Technology,Kunming 650500,China)

机构地区：[1]昆明理工大学建筑工程学院,昆明650500 [2]昆明理工大学化学工程学院,昆明650500

出　　处：《环境工程学报》2025年第3期595-604,共10页Chinese Journal of Environmental Engineering

基　　金：国家自然科学基金重点资助项目(52260009);云南省科技厅科技计划项目(202303AG100002-03)。

摘　　要：采用静电纺丝技术合成钴钼电催化阳极膜(CoMo-ECM)并将其用于盐酸四环素(TC-HCl)的降解。结果表明,TC-HCl的降解遵循准一级动力学,在电流密度为10mA·cm^(2)时,降解速率常数为0.24 min^(−1),半衰期为2.9 min。在中性或偏酸性条件(pH=5~6)下TC-HCl降解速率最大,40 min时去除率接近100%。在电化学降解过程中鉴定出5种中间产物,其中主要的降解路径依赖于阳极催化膜原位产生的高浓度臭氧裂解产生的活性氧物种(ROS),主要包括·OH、^(1)O_(2)和·O_(2)^(−)3种活性氧物种。羟甲基附近的碳碳双键是·OH攻击的首要位置,Co-N键的断裂是TC-HCl电化学降解的限速步骤。TC-HCl中的氮主要转化为硝酸盐和铵。以上研究结果表明CoMo-ECM作为阳极膜可以原位产臭氧进而高效降解TC-HCl。In this study,the electrospinning technology was used to synthesize the CoMo-electrocatalytic anode membrane(CoMo-ECM)for the degradation of tetracycline(TC-HCl).The results showed that the degradation of TC-HCl followed a quasi-first-order kinetic,with a degradation rate constant and half-life of 0.24 min^(−1) and 2.9 min,respectively,at a current density of 10 mA·cm^(2).The highest degradation rate occurred under neutral partial acid conditions(pH=5~6),and the removal rate approached to100%at 40 min.During electrochemical degradation,five intermediate products were identified.The main degradation pathways relied on reactive oxygen species(ROS)derived from the cracking of ozone with high concentrations,which was produced in situ by anodic catalytic membranes,mainly including three types of ROSs:·OH,^(1)O_(2) and·O_(2)^(−).The double-bonded carbon atom near the hydroxymethyl group is the location where·OH attacked,and the cleavage of the Co-N bond is the rate-limiting step of the electrochemical degradation of the TC-HCl.The nitrogen in TC-HCl mainly converted to nitrate and ammonium.The results showed that CoMo-ECM,as an anode membrane,can in-situ produce ozone and efficiently degrade TC-HCl.

关 键 词：静电纺丝 形貌控制 电催化 盐酸四环素 臭氧 

分 类 号：X703[环境科学与工程—环境工程]