阳光驱动下苝酰亚胺负载膜光催化降解海水养殖废水中氟喹诺酮类药物的研究  

Sunlight driven photocatalytic degradation of fluoroquinolones in mariculture wastewater by perylene imide loaded membrane

作　　者：肖震钧 陈平[1] 吕文英[1] 石紫瑶 朱乔泽 刘国光[1] XIAO Zhenjun;CHEN Ping;LÜWenying;SHI Ziyao;ZHU Qiaoze;LIU Guoguang(School of Environmental Science and Engineering,Guangdong University of Technology,Guangzhou 510006;School of Environmental and Energy,South China University of Technology,Guangzhou 510006)

机构地区：[1]广东工业大学环境科学与工程学院,广州510006 [2]华南理工大学环境与能源学院,广州510006

出　　处：《环境科学学报》2023年第3期52-64,共13页Acta Scientiae Circumstantiae

基　　金：国家自然科学基金项目(No.21906029,22076029,22176042);广州市科技计划项目(No.202102020774,201903010080)。

摘　　要：海水养殖废水中新污染物残留问题引起人们的关注.本研究将有机超分子光催化剂苝酰亚胺(PDI)负载于醋酸纤维膜上制备了苝酰亚胺负载膜(PDI膜)并将其应用于海水养殖废水中去除氟喹诺酮类药物(FQs).PDI膜的微观结构通过扫描电子显微镜进行了确定.紫外可见漫反射光谱表明PDI膜保留了PDI的光响应能力.傅里叶红外变化光谱证明了15次循环降解FQs后PDI膜化学结构仍保持稳定.阳光下,PDI膜在海水养殖废水中对二氟沙星(DIF)等FQs的表观降解速率常数在4.2×10^(−2)min^(−1)以上.在DIF的降解过程中,h^(+)、·OH、O_(2)^(·-)和^(1)O_(2)起主要作用,其中·OH、O_(2)^(·-)和^(1)O_(2)的稳态浓度分别为4.8×10^(-14)、1.8×10^(-9)和1.1×10^(-11) mol·L^(-1).PDI膜在阳光下可在水中产生H_(2)O_(2),其生成量与太阳光功率密度以及水中含有的电子供体都呈正相关.单因素实验表明,海水中常见共存物质会抑制DIF的光催化降解,但高盐度对PDI膜的光催化活性影响不大.通过三维荧光技术证实了阳光下PDI膜对海水养殖废水中的DIF具有长效矿化能力.另外,PDI膜在海水养殖废水中的15次循环利用后仍保持良好的光催化性能.结合LC-MS/MS技术推断出DIF降解途径主要包括甲基哌嗪环的开环以及喹诺酮结构的开环、亲电取代和氧化反应.最后,抗菌活性实验直观展现了PDI膜在阳光下清除FQs抑菌药性残留的能力.The residues of emerging pollutants in mariculture wastewater have aroused concern.In this study,a perylene imide loaded membrane(PDI membrane)was prepared by loading the organic supramolecular perylene imide(PDI)on cellulose acetate membrane,which was used for the removal of fluoroquinolones(FQs)in mariculture wastewater.The microstructure of the PDI membrane was determined by scanning electron microscopy.UV-Vis diffuse reflectance spectroscopy spectrum indicated that the PDI membrane retained the photo-response ability of PDI.Fourier transform infrared spectroscopy spectrum demonstrated that the chemical structure of the PDI membrane remained stable after 15 times of FQs degrading.Under sunlight,the apparent degradation rate constant of FQs,such as difloxacin(DIF),by PDI membrane in marine aquaculture wastewater was above 4.2×10^(−2)min^(−1).During the degradation of DIF,h^(+),·OH,O_(2)^(·-)and ^(1)O_(2) played the main roles,and the steady-state concentrations of·OH,O_(2)^(·-)and ^(1)O_(2) were 4.8×10^(-14),1.8×10^(-9) and 1.1×10^(-11) mol·L^(-1),respectively.PDI membrane can produce H_(2)O_(2) in water under sunlight,and the generation amount of H_(2)O_(2) was positively correlated with the power density of sunlight and the electron donor in water.Single factor experiments results show that common coexisting substances in seawater can inhibit the photocatalytic degradation of DIF,while high salinity has little effect on the photocatalytic activity of PDI membrane.The long-term mineralization of DIF in mariculture wastewater by PDI membrane under sunlight was confirmed by three-dimensional fluorescence technology.In addition,the PDI membrane still maintained good photocatalytic performance after 15 cycles of treatment for mariculture wastewater.Combined with LC-MS/MS analysis,it was deduced that the degradation pathways of DIF mainly included the ring cleavage reaction of methyl piperazine ring and the ring-opening,electrophilic substitution and oxidation reactions of quinolone structure.Finally,t

关 键 词：苝酰亚胺 光催化膜 二氟沙星 海水养殖废水 

分 类 号：X703[环境科学与工程—环境工程]