米粒状氧化铜化学修饰电极的制备及其对葡萄糖的检测

doi:10.15541/jim20180200

无机材料学报 ›› 2019, Vol. 34 ›› Issue (2): 152-158.DOI: 10.15541/jim20180200 CSTR: 32189.14.10.15541/jim20180200

米粒状氧化铜化学修饰电极的制备及其对葡萄糖的检测

邓敏,江奇,段志虹,刘青青,蒋理,卢晓英

西南交通大学超导与新能源研发中心, 生命科学与工程学院, 材料先进技术教育部重点实验室, 成都 610031

收稿日期:2018-04-27 修回日期:2018-05-28 出版日期:2019-02-20 网络出版日期:2019-01-24
作者简介:邓敏(1991-),女,硕士研究生.E-mail: 3105a@swjtu.cn
基金资助:
国家自然科学基金(50907056, 51602266);四川省重点研发计划(2017GZ0109);四川省科技支撑项目(2016GZ0273, 2016GZ0275);四川省学术与技术带头人培养基金

Rice-like CuO Chemically Modified Electrode: Preparation and Detection for Glucose

DENG Min, JIANG Qi, DUAN Zhi-Hong, LIU Qing-Qing, JIANG Li, LU Xiao-Ying

Key Laboratory of Advanced Technologies of Materials (Ministry of Education of China), School of Life Science and Engineering, School of Electrical Engineering, Southwest Jiaotong University, Chengdu 610031, China

Received:2018-04-27 Revised:2018-05-28 Published:2019-02-20 Online:2019-01-24
About author:DENG Min. E-mail: 3105a@swjtu.cn
Supported by:
National Natural Science Foundation of China (50907056, 51602266);Sichuan Key Research and Development Program (2017GZ0109);Sichuan Science and Technology Support Projects (2016GZ0273, 2016GZ0275);Sichuan Academic and Technical Leaders Training Fund

摘要/Abstract

摘要：

采用水热合成法与原位分解法相结合, 在不使用软模板和强碱条件下制备得到了米粒状氧化铜(CuO)。将得到的CuO材料与Nafion溶液混合, 制作成化学修饰电极(CME), 开展葡萄糖的无酶检测。采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)分别对所制备的材料和电极的结构、形貌进行表征、分析。采用线性扫描伏安法、循环伏安法、安培响应和交流阻抗技术对所制备电极进行电化学性能测试。研究结果表明: 所制备的CuO形貌在微观下酷似米粒, 长度为0.5~ 1.0 μm, 直径为250~320 nm。当CuO修饰量为0.35 mg (电极表面积为0.22 cm²)时, 修饰电极对葡萄糖具有较好的电化学检测性能。在0.0357~2.361 mmol/L浓度范围内存在良好的线性关系, 其线性方程为: I_pa(mA)= -0.00187+0.05239c (mmol/L), R²=0.998。检出限为 0.0647 μmol/L, 灵敏度为950.36 μA·L/(mmol·cm²), 且具有良好的选择性和可靠性。

关键词: 米粒状CuO, 化学修饰电极, 葡萄糖, 检测

Abstract:

A novel rice-like copper oxide (CuO) was synthesized without using soft template and alkali by hydrothermal and in-situ decomposition methods. This rice-like CuO material was made into the chemically modified electrode (CME) with Nafion solution for non-enzymatic glucose sensing. Structure and morphology of the prepared material and electrode were characterized by X-ray diffraction and scanning electron microscopy. Electrochemical performances of the obtained electrodes were investigated by linear sweep voltammetry, cyclic voltammetry, amperometric response, and electrochemical impedance spectroscopy. Results show that morphology of the obtained CuO particle is similar to rice grain. And its length and diameter are between 0.5-1.0 μm and 250-320 nm, respectively. The CME with 0.35 mg rice-like CuO (with 0.22 cm² electrode surface area) has an obvious current response for glucose with the linear range from 0.0357 to 2.361 mmol/L, the linear equation I_pa(mA)= -0.00187+0.05239 c(mmol/L) (R²=0.998), the detection limit 0.0647 μmol/L, and the sensitivity 950.36 μA·L/(mmol·cm²). Therefore, the prepared CuO CME shows a promise selectivity and reliability for detecting glucose.

Key words: rice-like CuO, chemically modified electrode, glucose, detection

中图分类号:

O657

邓敏,江奇,段志虹,刘青青,蒋理,卢晓英. 米粒状氧化铜化学修饰电极的制备及其对葡萄糖的检测[J]. 无机材料学报, 2019, 34(2): 152-158.

DENG Min, JIANG Qi, DUAN Zhi-Hong, LIU Qing-Qing, JIANG Li, LU Xiao-Ying. Rice-like CuO Chemically Modified Electrode: Preparation and Detection for Glucose[J]. Journal of Inorganic Materials, 2019, 34(2): 152-158.

图/表 7

图1 CuO和CME的制备过程示意图(a)及CuO的XRD图谱(b)及其SEM照片(c)~(d)

Fig. 1 Schematic diagram of the CuO and CME preparation process (a), and XRD patterns of CuO (b) and SEM images of CuO (c-d)

图2 不同CMEs在空白溶液和检测溶液中的CV曲线(a); 不同修饰量CuO/Nafion-CMEs在10 mmol/L K3Fe(CN)6/ K4Fe(CN)6的0.5 mol/L KCl溶液中的EIS图谱(b, c, 插图为其等效电路图)和电荷转移电阻(Rct)与CuO修饰量之间的关系曲线(d)

Fig. 2 CV curves of different CMEs in blank and samples (a), EIS curves of the different CuO/Nafion-CMEs in 0.5 mol/L KCl solution and 10 mmol/L K3Fe(CN)6/K4Fe(CN)6 (b, c) with inset showing the equivalent circuit diagram, and the relationship between the electron transfer resistance (Rct) and the CuO modified amount (d)

图3 不同修饰量CuO修饰电极在检测溶液中的LSV曲线(a)和所得峰电流、峰电位与CuO修饰量之间的关系(b)

Fig. 3 LSV curves of the different CuO/Nafion-CMEs in sample solution (a) and relationship between the peak current, the peak potential and the CuO modified amount (b)

图4 S电极在检测溶液中不同扫速下的CV曲线(a)和所得氧化峰峰电流与扫速之间的关系曲线(b)

Fig. 4 CV curves of the S electrode in detection solution at different scan rates (a) and relationship between the oxidation peak current and the scan rate (b)

图5 S电极在空白溶液中连续加入葡萄糖的I-t曲线(a), 所得响应电流与葡萄糖浓度之间的关系曲线(b), 抗干扰测试实验(c)和稳定性测试实验(d)结果

Fig. 5 I-t curves of the S electrode in blank solution with continuous dropping glucose (a), the relationship between the response current and the glucose concentration (b), the results of anti-interference experiments (c), and the stability experiments (d)

表1 S电极与其他报道的无酶葡萄糖传感器检测性能的比较

Table 1 Comparison of detection performances of the S electrode and those non-enzymatic glucose sensors reported elsewhere

Electrode materials	Linear range/(mmol·L^-1)	Sensitivity/(μA·L·mmol^-1·cm^-2)	Detection limit/ (μmol·L^-1)	Ref.
Flower-structured CuO	0.01-0.20	1830	8	[5]
Microspheres-structured CuO	0.001-4.000	349.6	0.50	[8]
Microflowers-structured CuO	0.05-3.00	383	10	[10]
Sandwich-structured CuO	0-3.2	5342.8	1.0	[14]
Microspheres-structured CuO	2-9	26.59	20.6	[22]
Cob-like CuO	0.005-1.600	726.9	2	[23]
Peony-like CuO	0.001-4.000	1322	0.5	[24]
Rice-like CuO	0.0357-2.3610	950.36	0.0647	This work

表2 S电极对葡萄糖的回收率

Table 2 Data of recovery experiments of the S electrode for glucose

Samples	Detected/(mmol·L^-1)	Added/(mmol·L^-1)	Found/(mmol·L^-1)	Recovery/%	RSD/(%, n=5)
1	0.893	0.200	1.088	97.50	1.9
2	0.893	0.400	1.279	96.50	2.3
3	0.893	0.600	1.482	98.17	1.5
4	0.893	0.800	1.672	97.38	2.5

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米粒状氧化铜化学修饰电极的制备及其对葡萄糖的检测

Rice-like CuO Chemically Modified Electrode: Preparation and Detection for Glucose

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