生物成因次生铁矿物催化类芬顿反应降解氟苯尼考  

Degradation of flufenicol by Fenton-like reaction catalyzed by biosynthetic secondary iron minerals

作　　者：宋永伟[1,2] 邓茹月 覃琦露 郭泽浩 罗浩伟 杨俊[2,3] 申祖武 SONG Yong-wei;DENG Ru-yue;QIN Qi-lu;GUO Ze-hao;LUO Hao-wei;YANG Jun;SHEN Zu-wu(Modern Technology Convergence and Engineering Management Research Center,Zhongnan University of Economics and Law,Wuhan 430073,China;Department of Environmental Science and Engineering,Zhongnan University of Economics and Law,Wuhan 430073,China;Institute of Environmental Management and Policy,Zhongnan University of Economics and Law,Wuhan 430073,China)

机构地区：[1]中南财经政法大学现代技术融合与工程管理研究中心,湖北武汉430073 [2]中南财经政法大学环境科学与工程系,湖北武汉430073 [3]中南财经政法大学环境管理与政策研究所,湖北武汉430073

出　　处：《中国环境科学》2025年第3期1321-1332,共12页China Environmental Science

基　　金：国家自然科学基金资助项目(21906183);中南财经政法大学中央高校基本科研业务费专项资金资助项目(202451417)。

摘　　要：以氟苯尼考(FFC)为目标污染物,嗜酸性氧化亚铁硫杆菌(A.ferrooxidans)介导合成施氏矿物和黄钾铁矾作为催化剂,研究催化类芬顿反应降解FFC效果.首先通过扫描电子显微镜(SEM)、X-射线衍射(XRD)、傅里叶变换红外(FTIR)、比表面积(BET)对两种矿物进行表征,接着研究矿物投加量、H_(2)O_(2)浓度、p H值和温度4个关键变量对催化类芬顿反应降解FFC的影响,最后分析FFC降解机理并检验矿物重复利用性能.结果表明,生物合成施氏矿物和黄钾铁矾平均粒径分别约为2.5和5.0μm,黄钾铁矾团聚现象更明显;施氏矿物和黄钾铁矾比表面积分别为116.67m^(2)/g和87.52m^(2)/g,总孔体积分别为0.098和0.065cm^(3)/g,平均孔径分别为2.986和2.867nm.矿物投加量的增加有助于提高FFC催化降解效率;FFC降解效率随着H_(2)O_(2)浓度的增加呈先增后减趋势;酸性和高温条件更有利于FFC的催化降解.在矿物投加量10g/L,H_(2)O_(2)浓度200mg/L,p H值3.00,温度36℃的共同实验条件下,结合液相色谱-质谱联用仪(LC-MS)测试结果,推断两种矿物催化降解FFC机理如下:矿物将H_(2)O_(2)吸附在表面,催化其分解产生·OH,·OH氧化FFC为中间产物,最终氧化为无机物.类芬顿反应过程中共检测到6种中间产物,包括含有苯环、酰胺基团或胺基团的醇类、醛类或羧酸类小分子有机物,以及甲基苯基砜.经循环利用10次后,两种矿物的晶型和官能团没有发生明显改变,具有良好的稳定性.Using florfenicol(FFC)as the target pollutant,schwertmannite and jarosite as catalysts synthesized by the mediation of A.ferrooxidans to investigate their effectiveness in catalyzing Fenton-like reactions for FFC degradation.Initially,the two minerals were characterized using SEM,XRD,FTIR and BET analysis.Subsequently,the impact of four key variables—mineral dosage,H_(2)O_(2)concentration,p H,and temperature—on FFC degradation was studied.Finally,the degradation mechanism of FFC and the reusability of the minerals were analyzed.The results indicated that the biosynthesized schwertmannite and jarosite were pure minerals,with average particle diameters of approximately 2.5μm and 5.0μm and jarosite exhibiting more noticeable aggregation.The specific surface areas of schwertmannite and jarosite were 116.67m^(2)/g and 87.52m^(2)/g,respectively,with total pore volumes of0.098cm^(3)/g and 0.065cm^(3)/g and average pore diameters of 2.986nm and 2.867nm.Increasing the mineral dosage enhanced the degradation efficiency of FFC by both minerals.The degradation efficiency of FFC initially increased and then decreased with an increase in the H_(2)O_(2)concentration.Under acidic conditions,both minerals exhibited better degradation effects.The degradation rate increased with rising temperature.Under the combined experimental conditions of a mineral dosage of 10g/L,an H_(2)O_(2)concentration of 200mg/L,an pH of 3.00,and a temperature of 36℃,combined with Liquid Chromatography-Mass Spectrometry(LC-MS)test results,the degradation mechanism of FFC by the two minerals was inferred as follows:The minerals adsorbed H_(2)O_(2)onto their surfaces,catalyzing its decomposition to produce hydroxyl radicals(·OH),which oxidized FFC into intermediate products,ultimately leading to inorganic substances.A total of six intermediate products were detected during the Fenton-like reaction,including small organic molecules such as alcohols,aldehydes,or carboxylic acids containing benzene rings,amide groups,or amine groups,as well as methyl

关 键 词：氟苯尼考 催化剂 施氏矿物 黄钾铁矾 类芬顿反应 

分 类 号：X703[环境科学与工程—环境工程]