基于新型多孔TiO_(2)复合CdS量子点的电化学发光传感器用于检测铜离子  

Construction of Electrochemiluminescence Sensor for Detection of Coper Ion Based on Novel Porous Titanium Dioxide Coupled Cadmium Sulfide Quantum Dots

作　　者：韦富存 欧盼盼 吴叶宇 吴佳雯 林瑜 杜方凯 谭学才 WEI Fu-Cun;OU Pan-Pan;WU Ye-Yu;WU Jia-Wen;LIN Yu;DU Fang-Kai;TAN Xue-Cai(Key Laboratory of Chemistry and Engineering of Forest Products,State Ethnic Affairs Commission,Guangxi Key Laboratory of Chemistry and Engineering of Forest Products,Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products,Key Laboratory of Guangxi Colleges and Universities for Food Safety and Pharmaceutical Analytical Chemistry,School of Chemistry and Chemical and Engineering,Guangxi University for Nationalities,Nanning 530008,China)

机构地区：[1]广西民族大学化学化工学院,林产化学与工程国家民委重点实验室,广西林产化学与工程重点实验室,广西林产化学与工程协同创新中心,广西高校食品安全与药物分析化学重点实验室,南宁530008

出　　处：《分析化学》2021年第8期1308-1317,共10页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.21365004);广西重点研发计划项目(No.AB18126048);广西创新驱动发展专项资金项目(No.AA18118013-10);广西科技基地和人才专项项目(No.AD18126005);广西高校中青年教师科研基础能力提升项目(No.2019KY0162);广西民族大学研究生教育创新计划项目(No.gxun-chxzs2019018)资助。

摘　　要：以金属有机骨架MIL-125(Ti)作为前驱体,通过高温煅烧制备了一种新型多孔二氧化钛(P-TiO_(2)),然后以聚乙烯亚胺(PEI)作为交联剂,通过酰胺键将3-巯基丙酸稳定的硫化镉量子点(CdS QDs)负载于P-TiO_(2)表面,制备了P-TiO_(2)/CdS QDs复合材料,用于修饰玻碳电极,构建了一种灵敏的电化学发光(ECL)传感器用于检测铜离子(Cu^(2+))。分别采用扫描电镜、X射线能谱、X射线粉末衍射仪、紫外-可见吸收光谱、荧光光谱和傅里叶红外光谱对材料的形貌、结构和物理性质进行表征,并通过循环伏安法、交流阻抗法和ECL法研究了P-TiO_(2)/CdS QDs/GCE传感器的电化学和ECL性能。结果表明,在最佳实验条件下,Cu^(2+)对此传感器的ECL响应信号有显著的抑制作用,ECL响应信号变化值与Cu^(2+)浓度在3-530 nmol/L范围内呈良好的线性关系,相关系数R^(2)=0.9989,检出限为0.01 nmol/L(S/N=3)。此传感器具有良好的稳定性、重现性和选择性,应用于检测桶装水、自来水和邕江水中的Cu^(2+)含量,加标回收率为96.9%-105.8%,与电感耦合等离子体原子发射光谱法(ICP-AES)的检测结果相近。A novel porous titanium dioxide(P-TiO_(2))was successfully synthesized via calcination of metal-organic framework MIL-125(Ti).Then P-TiO_(2) was coated with massive polyethyleneimine films and further bound covalently with 3-mercaptopropionic acid stabilized cadmium sulfide quantum dots(CdS QDs)to prepare P-TiO_(2)/CdS QDs composites.The as-prepared P-TiO_(2)/CdS QDs was modified on the surface of glassy carbon electrode to develop a sensitive electrochemiluminescence(ECL)sensor for detection of Cu^(2+).The morphology,microstructure and element composition of different materials were characterized by scanning electron microscope,X-ray powder diffraction,energy disperse spectroscopy,ultraviolet-visible absorption spectrometry,fluorescence spectrometry and infrared spectrometry,respectively.The electrochemical behavior and ECL performance of the sensor were also studied by cyclic voltammetry,electrochemical impedance and ECL technique.Under the optimized conditions,the proposed sensor demonstrated excellent analytical performance with a wide linear detection range from 3 nmol/L to 530 nmol/L(R^(2)=0.9989)and a detection limit of 0.01 nmol/L(S/N=3)for Cu^(2+).This method exhibited excellent stability,reproducibility and selectivity.In addition,the detection results of Cu^(2+)in water samples were similar to that of inductively coupled plasma-atomic emission spectrometry method(ICP-AES)with recovery rates of 96.9%-105.8%.

关 键 词：多孔二氧化钛 硫化镉量子点 电化学发光传感器 铜离子 

分 类 号：X832[环境科学与工程—环境工程] O657.1[理学—分析化学]