可见光下Cu_2O_TiO...臭氧氧化头孢曲松钠性能研究_孟冠华.pdf

第 23 卷第 2 期2023年 2月过 程 工 程 学 报The Chinese Journal of Process EngineeringVol.23 No.2Feb.2023Photocatalytic ozonation of ceftriaxone sodium by Cu2O/TiO2 under visible lightGuanhua MENG1,2*,Linsen ZHANG1,Baohe LIU1,2,Yu WANG1,Zhenghui LI1,Wen LI1,Yongbin JIANG1,21.School of Energy and Environment,Anhui University of Technology,Maanshan,Anhui 243002,China2.Ministry of Education Biofilm Process Water Purification and Utilization Technology Engineering Research Center,Maanshan,Anhui 243032,ChinaAbstract:Antibiotics are commonly used drugs for the treatment of various infectious diseases in humans and animals,but the residual antibiotics released into the aquatic environment will threaten the ecological system.Therefore,it is important to explore efficient methods to remove antibiotics from the water environment.Photocatalytic ozonation technology has received extensive attention for its effective degradation and mineralization of persistent organic pollutants from the water matrix.In this work,Cu2O/TiO2 composite was prepared by the impregnation-chemical reduction method and was used as a catalyst for photocatalytic ozonation of ceftriaxone sodium(CRO)under visible light irradiation.The morphology,structure,and optical properties were investigated by X-ray diffraction(XRD),Fourier transforms infrared spectroscopy(FT-IR),scanning electron microscope(SEM),transmission electron microscopy(TEM),nitrogen adsorption-desorption isotherms(BET)and ultraviolet-visible diffuse reflection(UV-Vis DRS).The effects of Cu2O/TiO2 ratio,Cu2O/TiO2 dosage,ozone concentration,initial concentration of ceftriaxone sodium,and initial pH value of the solution on visible-light-induced photocatalytic ozonation of ceftriaxone sodium were comprehensively investigated.The results showed that the doping of Cu2O on TiO2 increased the specific surface area and pore volume,reduced the energy gap,and improved the catalytic performance under visible light.The photocatalytic ozonation process had achieved a much higher removal rate of ceftriaxone sodium from an aqueous solution than the photocatalysis and ozonation processes.When the molar ratio of Cu2O:TiO2 was 0.2:1,the visible light irradiation time was 120 min,the initial pH value of the solution was 6.12,the concentration of ceftriaxone sodium was 10 mg/L,the dosage of Cu2O/TiO2 was 0.2 g/L and ozone concentration was 1.5 mg/L,the removal rates of ceftriaxone sodium and TOC were 81.05%and 52.16%,respectively,and the ozone utilization rate was 50.84%.The free radical capture experiments showed that photogenerated holes(h+)and superoxide radicals(O2-)played a major role in the visible-light-induced photocatalytic ozonation of ceftriaxone sodium.Moreover,Cu2O/TiO2 exhibited satisfactory stability and reusability for 5 consecutive cycles.The findings of this study suggest that the photocatalytic ozonation process induced by visible light is a promising treatment technology for the abatement of ceftriaxone sodium pollution in an aqueous solution.Key words:Cu2O/TiO2;visible light;photocatalytic ozonation;ceftriaxone sodium;degradation mechanismEg=2.16 eVVisible lighte-e-e-Eg=3.47 eVe-e-e-h+h+h+h+O2h+h+VBVBCBCBH+CO2+H2O+intermediatesCROn-TiO2.O2-CROCO2+H2O+intermediatesO3.O3-HO3.OHCROCO2+H2O+intermediatesp-Cu2O研究论文DOI:10.12034/j.issn.1009-606X.222075收稿：2022-03-09，修回：2022-04-29，网络发表：2022-06-25；Received:2022-03-09,Revised:2022-04-29,Published online:2022-06-25基金项目：生物膜法水质净化及利用技术教育部工程研究中心开放基金资助项目(编号：BWPU2021ZY02)；安徽工业大学省级大学生创新创业教育训练计划项目(编号：S201910360316)作者简介：孟冠华，博士，教授，环境工程专业，E-mail:引用格式引用格式：孟冠华,张林森,刘宝河,等.可见光下Cu2O/TiO2催化臭氧氧化头孢曲松钠性能研究.过程工程学报,2023,23(2):311322.Meng G H,Zhang L S,Liu B H,et al.Photocatalytic ozonation of ceftriaxone sodium by Cu2O/TiO2 under visible light(in Chinese).Chin.J.Process Eng.,2023,23(2):311322,DOI:10.12034/j.issn.1009-606X.222075.过 程 工 程 学 报第 23 卷 可见光下Cu2O/TiO2催化臭氧氧化头孢曲松钠性能研究孟冠华1,2*，张林森1，刘宝河1,2，王 瑜1，李政辉1，李 文1，江用彬1,21.安徽工业大学能源与环境学院,安徽 马鞍山 2430022.教育部生物膜法水质净化及利用技术工程研究中心，安徽 马鞍山 243032摘要：抗生素是治疗各种传染病的常用药物，但残留在水环境中的抗生素会对生态系统造成威胁。因此，探索去除水环境中抗生素的有效方法具有重要意义。由于光催化臭氧氧化技术可以高效降解和矿化水体中的污染物，该技术受到广泛关注。本工作通过浸渍-化学还原法制备Cu2O/TiO2复合材料并将其作为可见光催化臭氧氧化头孢曲松钠(CRO)的催化剂。利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、比表面积分析仪(BET)和紫外-可见漫反射光谱仪(UV-Vis DRS)对Cu2O/TiO2形貌结构和光学性能进行表征，考察了Cu2O/TiO2配比、Cu2O/TiO2投加量、臭氧浓度、头孢曲松钠初始浓度、溶液初始pH值等因素对可见光催化臭氧氧化头孢曲松钠的影响。结果表明，Cu2O对TiO2的掺杂改性使材料孔容和平均孔径增大，能带宽度减小，可见光下的催化性能增强。在Cu2O:TiO2摩尔比为0.2:1、可见光照射120 min、溶液pH值为6.12、头孢曲松钠浓度为10 mg/L、Cu2O/TiO2投加量为0.2 g/L、臭氧浓度为1.5 mg/L条件下，头孢曲松钠和TOC的降解率分别达到81.05%和52.16%，臭氧利用率达到50.84%。自由基捕获实验表明，可见光催化臭氧氧化头孢曲松钠的过程中光生空穴(h+)和超氧自由基(O2-)起主要作用。5次循环使用实验结果表明，Cu2O/TiO2有较好的可重复利用性。本研究结果表明，对于水体中的头孢曲松钠，可见光催化臭氧氧化是一种很有前途的治理技术。关键词：Cu2O/TiO2；可见光；光催化臭氧氧化；头孢曲松钠；降解机理中图分类号：O643.36；O644.1；X703 文献标识码：A 文章编号：1009-606X(2023)020311121 前 言 抗生素是一类由细菌、霉菌等微生物代谢产生或人工合成的化学物质，广泛应用于人类及动物疾病预防和治疗中。未完全利用的抗生素随污水进入污水处理厂，但是多数污水处理厂不能有效去除抗生素，同时未彻底降解和矿化的抗生素形成的中间产物比母体化合物的毒性更高，未降解的抗生素及其降解中间产物会随着污水厂出水排入受纳水体，导致受纳水体产生抗生素污染。迄今已在世界各地的地表水、海水、地下水中检测到抗生素，对生态系统和人体健康构成了严重的威胁1-3。为了保障天然水环境的生态安全，需要确保抗生素在排入