基于新型多孔TiO<sub>2</sub>复合CdS量子点的电化学发光传感器用于检测铜离子

引用本文: 韦富存, 欧盼盼, 吴叶宇, 吴佳雯, 林瑜, 杜方凯, 谭学才. 基于新型多孔TiO₂复合CdS量子点的电化学发光传感器用于检测铜离子[J]. 分析化学, 2021, 49(8): 1308-1317. doi: 10.19756/j.issn.0253-3820.201678 shu

Citation: WEI Fu-Cun, OU Pan-Pan, WU Ye-Yu, WU Jia-Wen, LIN Yu, DU Fang-Kai, TAN Xue-Cai. Construction of Electrochemiluminescence Sensor for Detection of Coper Ion Based on Novel Porous Titanium Dioxide Coupled Cadmium Sulfide Quantum Dots[J]. Chinese Journal of Analytical Chemistry, 2021, 49(8): 1308-1317. doi: 10.19756/j.issn.0253-3820.201678 shu

基于新型多孔TiO₂复合CdS量子点的电化学发光传感器用于检测铜离子

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

通讯作者: 谭学才,E-mail:gxuntan@126.com

基金项目:
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）和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-TiO₂），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-TiO₂表面，制备了P-TiO₂/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（Cu²⁺）。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-TiO₂/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，Cu²⁺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Cu²⁺浓度在3~530 nmol/L范围内呈良好的线性关系，相关系数R²=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Cu²⁺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。

关键词:

English

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

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

Corresponding author: TAN Xue-Cai, gxuntan@126.com

Received Date: 15 November 2020
Revised Date: 22 April 2021
Fund Project:
Supported by the National Natural Science Foundation of China (No.21365004), the Key Research and Development Project of Guangxi (No.AB18126048), the Guangxi Innovation-driven Development Special Fund Project (No.AA18118013-10), the Specific Research Project of Guangxi for Research Bases and Talents (No.AD18126005), the Young and Middle Aged Teachers Basic Ability Promotion Project by Guangxi Education Department (No.2019KY0162), and the Graduate Education Innovation Plan of Guangxi University for Nationalities (No.gxun-chxzs2019018).

Abstract: A novel porous titanium dioxide (P-TiO₂) was successfully synthesized via calcination of metal-organic framework MIL-125(Ti). Then P-TiO₂ was coated with massive polyethyleneimine films and further bound covalently with 3-mercaptopropionic acid stabilized cadmium sulfide quantum dots (CdS QDs) to prepare P-TiO₂/CdS QDs composites. The as-prepared P-TiO₂/CdS QDs was modified on the surface of glassy carbon electrode to develop a sensitive electrochemiluminescence (ECL) sensor for detection of Cu²⁺. 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 (R²=0.9989) and a detection limit of 0.01 nmol/L (S/N=3) for Cu²⁺. This method exhibited excellent stability, reproducibility and selectivity. In addition, the detection results of Cu²⁺ 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%.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

基于新型多孔TiO₂复合CdS量子点的电化学发光传感器用于检测铜离子

通讯作者: 谭学才,E-mail:gxuntan@126.com

English

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

Corresponding author: TAN Xue-Cai, gxuntan@126.com

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

基于新型多孔TiO2复合CdS量子点的电化学发光传感器用于检测铜离子

通讯作者: 谭学才,E-mail:gxuntan@126.com

English

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

Corresponding author: TAN Xue-Cai, gxuntan@126.com

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

基于新型多孔TiO₂复合CdS量子点的电化学发光传感器用于检测铜离子

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs