Co基碳材料双功能催化剂在电芬顿体系中高效降解环丙沙星  

Co Based Carbon Materials as Bifunctional Catalysts for Efficient Degradation of Ciprofloxacin in Electro-Fenton System

作　　者：王爽 吕月琴 刘星宇 李轶[1] WANG Shuang;LYU Yueqin;LIU Xingyu;LI Yi(School of Science,Tianjin University,Tianjin 300072,China;School of Environmental Science and Engineering,Tiangong University,Tianjin 300387,China)

机构地区：[1]天津大学理学院,天津300072 [2]天津工业大学环境科学与工程学院,天津300387

出　　处：《高等学校化学学报》2024年第9期122-132,共11页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22376157,22176140)资助.

摘　　要：抗生素的大量使用导致了环丙沙星(CIP)及其降解中间体在环境中的累积,这对环境和人类健康都具有很大的危害.近年来,使用电芬顿技术降解CIP被认为是一种具有广阔应用前景的水污染控制方法.本文以有机金属骨架ZIF-67作为前驱体,在不同温度煅烧下合成了一系列的Co基碳材料电催化剂(Co-NC-T),并用于CIP的降解.采用扫描电子显微镜、高分辨透射电子显微镜以及X射线衍射仪对所合成催化剂进行了表征.X射线光电子能谱结果显示,性能最佳的Co-NC-900材料含有最高比例的石墨N,这有利于O_(2)通过2e^(-)还原反应生成H_(2)O_(2);Co的多重价态[Co(0),Co(Ⅱ)及Co(Ⅲ)]可以促进反应过程中的H_(2)O_(2)转化为多种活性氧物种.Co-NC-900催化剂可以同时促进H_(2)O_(2)的形成和活化,这有利于CIP的降解.猝灭实验和电子自旋共振实验结果表明,体系中主要的活性氧物种依次为·O_(2)-和·OH.活性氧物种可以协同参与污染物的降解,进而提高CIP的降解效果.CIP的降解性能测试结果显示,在pH=3的条件下,Co-NC-900对CIP的降解效率在120 min可以达到94.5%.The overuse of antibiotics has resulted in a significant accumulation of ciprofloxacin(CIP)and its degradation intermediates in the environment,posing a threat to the environment and human health.In recent years,it has been considered a promising method to use heterogeneous electron-Fenton technology for antibiotic pollution treatment.In this study,we used organic metal framework ZIF-67 as precursor,and prepared a series of Co based carbon electrocatalysts(Co-NC-T)under different temperatures.The successful formation of the catalysts was confirmed by morphology and crystal structure analysis,including scanning electron microscopy,high-resolution transmission electron microscopy and X-ray diffraction patterns.On the one hand,The results of X-ray photoelectron spectroscopy showed that Co-NC-900 contained the highest proportion of graphite N,which was beneficial for O_(2)to generate H_(2)O_(2)through 2e^(-)reduction reaction.On the other hand,the multiple valence states of Co[Co(0),Co(Ⅱ),Co(Ⅲ)]could promote the conversion of H_(2)O_(2)into various reactive oxygen species during the reaction.The Co-NC-900 catalyst could simultaneously promote the formation and activation of H_(2)O_(2),which was beneficial for the degradation of CIP.The quenching experiment and electron spin resonance experiment results indicated that the main reactive oxygen species in the system were·O_(2)^(-)and·OH.Reactive oxygen species could synergistically participate in the reaction,thereby improving the degradation efficiency of CIP.Under pH=3,the removal rate of Co-NC-900 to CIP was 94.5%in 120 min.This study provided theoretical guidance for the efficient degradation of CIP in wastewater.

关 键 词：电芬顿 环丙沙星 ZIF-67 Co基碳材料 活性氧物种 

分 类 号：O646[理学—物理化学]