碳纳米管/聚苯胺化学修饰电极的制备及其对抗坏血酸的检测

doi:10.15541/jim20170191

无机材料学报 ›› 2018, Vol. 33 ›› Issue (1): 53-59.DOI: 10.15541/jim20170191 CSTR: 32189.14.10.15541/jim20170191

碳纳米管/聚苯胺化学修饰电极的制备及其对抗坏血酸的检测

邓敏, 江奇, 方渊, 李欢, 邱家欣, 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:2017-04-20 修回日期:2017-05-27 出版日期:2018-01-23 网络出版日期:2017-12-15
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;四川省成都市科技惠民工程(2014-HM01-00073-SF)

Carbon Nanotubes/Polyaniline Chemically Modified Electrode: Preparation and Ascorbic Acid Detection

DENG Min, JIANG Qi, FANG Yuan, LI Huan, QIU Jia-Xin, LU Xiao-Ying

Key Laboratory of Advanced Technologies of Materials (Ministry of Education of China), Superconductivity and New Energy R&D Centre, School of Life Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China

Received:2017-04-20 Revised:2017-05-27 Published:2018-01-23 Online:2017-12-15
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;Chengdu Science and Technology Huimin Project (2014-HM01- 00073-SF)

摘要/Abstract

摘要：

通过恒电压沉积法将纳米金属镍沉积于石墨电极表面, 经化学气相沉积法在石墨电极表面原位生长出碳纳米管(CNTs), 通过电化学聚合法在CNTs表面原位聚合聚苯胺, 从而获得化学修饰电极。采用扫描电子显微镜对所得电极形貌结构进行表征, 并研究CNTs与PNAI复合电极对抗坏血酸(AA)的检测效果。研究结果表明: 制备的CNTs都能均匀地生长在石墨电极表面, 纳米中空管状结构都保持完好; PANI均匀地包覆在CNTs管壁上, 复合材料呈现出典型的三维网状结构。所制备的CNTs/PANI修饰电极对AA具有良好的电化学响应, 其中管径较小CNTs的修饰电极对AA的电化学响应更强: 具有更宽的检测范围和更低的检出限。其检测线性范围为1.0×10^-6~4.5×10^-4 mol/L, 检出限为1.0×10^-7mol/L (S/N = 3)。且具有良好的稳定性、重复性和可靠性。

关键词: 抗坏血酸, 碳纳米管/聚苯胺, 化学修饰电极, 电化学检测, 碳纳米管管径

Abstract:

Nickel catalyst was deposited on a graphite electrode (GE) surface by constant voltage deposition method. With the nickel catalyst, carbon nanotubes (CNTs) were grown in situ on the GE surface to prepare CNTs chemically modified electrode (GSCNTs-CME) by catalytic chemical vapor deposition. After that, polyaniline (PANI) was polymerized in situ on the GSCNTs-CME to obtain GSCNTs/PANI-CME by electrochemical polymerization. Morphology and structure of the obtained electrodes were characterized by scanning electron microscope. Detection performances of the GSCNTs/PANI-CME on ascorbic acid (AA) were evaluated on an electrochemical workstation. Results show that the CNTs grow uniformly on the GE surface and the original tubular structure is remained well. PANI is coated uniformly on the surface of CNTs in the obtained composite with a typical three-dimensional network structure. The GSCNTs/PANI-CMEs show excellent electrochemical response to AA, amongst which the GSCNTs/PANI-CME with small-diameter CNTs shows stronger electrochemical response (wider linear detection range and lower detection limit) to AA. And its linear detection range and detection limit are 1.0×10^-6~4.5×10^-4 mol/L and 1.0×10^-7mol/L (S/N = 3), respectively. Therefore, the GSCNTs/PANI-CME shows excellent stability, repeatability and reliability.

Key words: ascorbic acid, carbon nanotubes/polyaniline, chemically modified electrode, electrochemical detection, carbon nanotube diameter

中图分类号:

O657

邓敏, 江奇, 方渊, 李欢, 邱家欣, 卢晓英. 碳纳米管/聚苯胺化学修饰电极的制备及其对抗坏血酸的检测[J]. 无机材料学报, 2018, 33(1): 53-59.

DENG Min, JIANG Qi, FANG Yuan, LI Huan, QIU Jia-Xin, LU Xiao-Ying. Carbon Nanotubes/Polyaniline Chemically Modified Electrode: Preparation and Ascorbic Acid Detection[J]. Journal of Inorganic Materials, 2018, 33(1): 53-59.

图/表 7

图1 在扫速为20 mV/s时, 三种电极上电化学聚合PANI得到的CV曲线

Fig. 1 CV curves of the PANI electrochemical polymerization on different electrodes at 20 mV/s scan rate^E (A), electrodeⅠ(B) and electrodeⅡ(C)

图2 所得修饰电极的SEM照片

Fig. 2 SEM images of the obtained CMEs^Electrode (A)Ⅰ; (B) Ⅲ; (C)Ⅱ; (D, E) Ⅳ; (F) PANI-CME

图3 所得电极在基底溶液(a, pH=6.0 PBS)和检测溶液(b, 含有5.0×10-5 mol/L AA 的pH=6.0 PBS)中的CV曲线

Fig. 3 CV curves of the obtained electrodes in substrate solution (a, pH=6.0 PBS) and detection solution (b, pH=6.0 PBS containing 5.0×10-5 mol/L AA) at a scan rate of 20 mV/s^Electrode: (A) GE; (B)Ⅰ; (C)Ⅱ; (D) PANI-CME; (E) Ⅲ; F, Ⅳ)

图4 电极Ⅳ对AA电化学检测的标准曲线(A)不同浓度AA的CV曲线图(从内到外浓度分别为0.5、1.0、5.0、10.0、50.0、100.0、200.0、400.0、450.0和500.0×10-6 mol/L, 插图为部分放大图, 扫速为20 mV/s); (B) AA浓度与其对应的氧化峰峰电流(Ip)之间的关系图; (C) AA浓度与其Ip之间的标准曲线)和电极Ⅲ对AA电化学检测的标准曲线; (D)不同浓度AA CV曲线图(从内到外浓度分别为1.0、5.0、10.0、50.0、100.0、200.0、400.0、450.0×10-6 mol/L, 插图为部分放大图, 扫速为20 mV/s); (E) AA浓度与其Ip之间的关系图; (F) AA浓度与其Ip之间的标准曲线)

Fig. 4 Electrochemical test calibration curves of the AA based on the electrode Ⅳ ((A) CV curves at different AA concentrations: 0.5, 1.0, 5.0, 10.0, 50.0, 100.0, 200.0, 400.0, 450.0 and 500.0×10-6 mol/L in pH=6.0 PBS with 20 mV/s scan rate, the inset is an enlarged view; (B) relationship between the Ip and AA concentrations; (C) the calibration curve of AA concentration and Ip) and electrode Ⅲ ((D) CV curves in different AA concentrations: 1.0, 5.0, 10.0, 50.0, 100.0, 200.0, 400.0 and 450.0×10-6 mol/L in pH=6.0 PBS with 20 mV/s scan rate, the inset is an enlarged view; (E) relationship between the Ip and AA concentrations; (F) the calibration curve of AA concentration and Ip)

表1 不同修饰电极对AA的电化学测试性能

Table 1 Electrochemical determination performances of different electrodes for the AA

Modified electrode	Linear range/(mol·L^-1)	Detection limit/(mol·L^-1)	Ref.
PAn-p-aminobenzene sulfonic acid	(3.5-17.5)×10^-5	7.5×10^-6	[31]
Molecularly imprinted PAn	(5.0-40.0)×10^-5	1.8×10^-5	[32]
Poly (acriflavine) modified electrode	(3.0-20.0)×10^-5	1.5×10^-6	[33]
DBSA doped Polyaniline nanoparticles	(0.3-8.0)×10^-6	8.3×10^-6	[34]
modified electrode

图5 稳定性测试数据((A)电极Ⅳ在含有2×10-4 mol/L AA的pH=6 PBS溶液中, 扫描速率为20 mV/s进行CV测试, 所得IP和储存时间的关系图)和抗干扰测试数据((B)干扰物: DA, 多巴胺; Glc, 葡萄糖; UA, 尿酸)

Fig. 5 Data of the stability testing ((A) relationship between Ip and the storing time of the Ⅳwith 2.0×10-4 mol/L AA solution in pH 6.0 PBS at 20 mV/s scan rate) and data of the anti-jamming testing ((B) interferences: DA, dopamine; Glc, glucose; UA, uric acid))

表2 所得电极对AA的回收实验数据

Table 2 Determination of AA in the recovery experiments

Samples	Detected (×10^-6, mol·L^-1)	Added (×10^-6, mol·L^-1)	Found (×10^-6, mol·L^-1)	Recovery/%	RSD/ (%, n=6)
1	10.54	20.00	30.02	97.4	2.5
2		40.00	51.37	102.1	1.9
3		60.00	69.86	98.9	0.8
4		80.00	91.48	101.2	1.0

参考文献 36

[1]	WU G, WU Y, LIU X, et al.An electrochemical ascorbic acid sensor based on palladium nanoparticles supported on graphene oxide.Analytica Chimica Acta, 2012, 745: 33-37.
[2]	XI L, REN D, LUO J, et al.Electrochemical analysis of ascorbic acid using copper nanoparticles/polyaniline modified glassy carbon electrode.Journal of Electroanalytical Chemistry, 2010, 650(1): 127-134.
[3]	DONG Y P, HUANG L, ZhANG J,et al.. Electro-oxidation of ascorbic acid at bismuth sulfide nanorod modified glassy carbon electrode.Electrochimica Acta, 2012, 74: 189-193.
[4]	ZHANG Y J, WEN Y, LIU Y, et al.Functionalization of single-walled carbon nanotubes with Prussian blue.Electrochemistry Communications, 2004, 6: 1180-1184.
[5]	WANG Y, LI Y M, TANG L H, et al.Application of graphene-modified electrode for selective detection of dopamine.Electrochemistry Communications, 2009, 11: 889-892.
[6]	ZUO X, ZHANG H, LI N.An electrochemical biosensor for determination of ascorbic acid by cobalt (II) phthalocyanine- multi-walled carbon nanotubes modified glassy carbon electrode.Sensors and Actuators B: Chemical, 2012, 161(1): 1074-1079.
[7]	LI F, TANG C, LIU S, et al.Development of an electrochemical ascorbic acid sensor based on the incorporation of a ferricyanide mediator with a polyelectrolyte-calcium carbonate microsphere.Electrochimica Acta, 2010, 55(3): 838-843.
[8]	ZHANG L, SHI H W, WANG C, et al.Preparation of a nanocomposite film from poly(diallydimethyl ammonium chloride) and gold nanoparticles by in-situ electrochemical reduction, and its application to SERS spectroscopy and sensing of ascorbic acid.Microchimica Acta, 2011, 173(3/4): 401-406.
[9]	XI L, REN D, LUO J, et al.Electrochemical analysis of ascorbic acid using copper nanoparticles/polyaniline modified glassy carbon electrode.Journal of Electroanalytical Chemistry, 2010, 650(1): 127-134.
[10]	RANA U, PAUL N D, MONDAL S, et al.Water soluble polyaniline coated electrode: a simple and nimble electrochemical approach for ascorbic acid detection.Synthetic Metals, 2014, 192: 43-49.
[11]	IIJIMA S.Helical microtubules of graphitic carbon.Nature, 1991, 354(6348): 56.
[12]	MUSAMEH M, WANG J, MERKOCI A, et al.Low-potential stable NADH detection at carbon-nanotube-modified glassy carbon electrodes.Electrochemistry Communications, 2002, 4(10): 743-746.
[13]	DEO R P, WANG J.Electrochemical detection of carbohydrates at carbon-nanotube modified glassy-carbon electrodes.Electrochemistry Communications, 2004, 6(3): 284-287.
[14]	DONG S, ZHANG S, CHI L, et al.Electrochemical behaviors of amino acids at multiwall carbon nanotubes and Cu2O modified carbon paste electrode.Analytical Biochemistry, 2008, 381(2): 199-204.
[15]	ZIYATDINOVA G, ZIGANSHINA E, BUDNIKOV H.Electrooxidation of morin on glassy carbon electrode modified by carboxylated single-walled carbon nanotubes and surfactants.Electrochimica Acta, 2014, 145: 209-216.
[16]	LI Y, UMASANKAR Y, CHEN S M.Polyaniline and poly (flavin adenine dinucleotide) doped multi-walled carbon nanotubes for p-acetamidophenol sensor.Talanta, 2009, 79(2): 486-492.
[17]	YUN J, IM J S, KIM H I, et al.Effect of oxyfluorination on gas sensing behavior of polyaniline-coated multi-walled carbon nanotubes.Applied Surface Science, 2012, 258(8): 3462-3468.
[18]	ZOU Y, SUN L X, XU F.Biosensor based on polyaniline-Prussian Blue/multi-walled carbon nanotubes hybrid composites.Biosensors and Bioelectronics, 2007, 22(11): 2669-2674.
[19]	YANG T, ZHOU N, ZHANG Y, et al.Synergistically improved sensitivity for the detection of specific DNA sequences using polyaniline nanofibers and multi-walled carbon nanotubes composites.Biosensors and Bioelectronics, 2009, 24(7): 2165-2170.
[20]	MANISANKAR P, SUNDARI P L A,SASIKUMAR R, et al..Electroanalysis of some common pesticides using conducting polymer/multiwalled carbon nanotubes modified glassy carbon electrode.Talanta, 2008, 76(5): 1022-1028.
[21]	PILAN L, RAICOPOL M.Highly selective and stable glucose biosensors based on polyaniline/carbon nanotubes composites.Journal of Scientific Bulletin, 2014, 76(1): 155-166.
[22]	LUO X, KILLARD A J, MORRIN A, et al.Enhancement of a conducting polymer-based biosensor using carbon nanotube-doped polyaniline.Analytica Chimica Acta, 2006, 575(1): 39-44.
[23]	XI L, ZHU Z, WANG F.Electrocatalytic oxidation of ascorbic acid on quaternized carbon nanotubes/ionic liquid-polyaniline composite film modified glassy carbon electrode.Journal of the Electrochemical Society, 2013, 160(6): H327-H334.
[24]	CHAWLA S, RAWAL R, SHARMA S, et al.An amperometric biosensor based on laccase immobilized onto nickel nanoparticles/ carboxylated multiwalled carbon nanotubes/polyaniline modified gold electrode for determination of phenolic content in fruit juices.Biochemical Engineering Journal, 2012, 68: 76-84.
[25]	FENG X, LI R, MA Y, et al.The synthesis of highly electroactive N-doped carbon nanotube/polyaniline/Au nanocomposites and their application to the biosensor.Synthetic Metals, 2011, 161(17): 1940-1945.
[26]	DING L, LI Q, ZHOU D, et al.Modification of glassy carbon electrode with polyaniline/multi-walled carbon nanotubes composite: application to electro-reduction of bromate.Journal of Electroanalytical Chemistry, 2012, 668: 44-50.
[27]	XU L, ZHU Y, YANG X, et al.Amperometric biosensor based on carbon nanotubes coated with polyaniline/dendrimer-encapsulated Pt nanoparticles for glucose detection.Materials Science and Engineering: C, 2009, 29(4): 1306-1310.
[28]	JIANG Q, YANG R, HE Z, et al.Preparation and characterization of a graphite electrode containing carbon nanotubes grown in situ by flame synthesis.Electrochimica Acta, 2011, 56(14): 5205-5209.
[29]	JIANG Q, SONG L J, YANG H, et al.Preparation and characterization on the carbon nanotube chemically modified electrode grown in situ.Electrochemistry Communications, 2008, 10(3): 424-427.
[30]	MANESH K M, SANTHOSH P, KOMATHI S, et al.Electrochemical detection of celecoxib at a polyaniline grafted multiwall carbon nanotubes modified electrode.Analytica Chimica Acta, 2008, 626(1): 1-9.
[31]	ZHANG L, ZHANG C, LIAN J.Electrochemical synthesis of polyaniline nano-networks on p-aminobenzene sulfonic acid functionalized glassy carbon electrode: its use for the simultaneous determination of ascorbic acid and uric acid.Biosensors and Bioelectronics, 2008, 24(4): 690-695.
[32]	ROY A K, DHAND C, MALHOTRA B D.Molecularly imprinted polyaniline film for ascorbic acid detection.Journal of Molecular Recognition, 2011, 24(4): 700-706.
[33]	NIEN P C, CHEN P Y, HO K C.On the amperometric detection and electrocatalytic analysis of ascorbic acid and dopamine using a poly (acriflavine)-modified electrode.Sensors and Actuators B: Chemical, 2009, 140(1): 58-64.
[34]	AMBROSI A, MORRIN A, SMYTH M R, et al.The application of conducting polymer nanoparticle electrodes to the sensing of ascorbic acid.Analytica Chimica Acta, 2008, 609(1): 37-43.
[35]	DEVI R, YADAV S, PUNDIR C S.Electrochemical detection of xanthine in fish meat by xanthine oxidase immobilized on carboxylated multiwalled carbon nanotubes/polyaniline composite film.Biochemical Engineering Journal, 2011, 58: 148-153.
[36]	ZHONG H, YUAN R, CHAI Y, et al.In situ chemo-synthesized multi-wall carbon nanotube-conductive polyaniline nanocomposites: characterization and application for a glucose amperometric biosensor.Talanta, 2011, 85(1): 104-111.

碳纳米管/聚苯胺化学修饰电极的制备及其对抗坏血酸的检测

Carbon Nanotubes/Polyaniline Chemically Modified Electrode: Preparation and Ascorbic Acid Detection

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 36

相关文章 5

编辑推荐

Metrics

本文评价

[1]	程琴, 杨勇, 杨莉莉. 具有高类氧化酶活性的铂-金枝状纳米粒子用于检测抗坏血酸[J]. 无机材料学报, 2020, 35(10): 1169-1176.
[2]	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.
[3]	要美娜, 杨贤金, 崔振铎, 朱胜利, 李朝阳, 梁砚琴. 铋膜电极阳极溶出伏安法检测痕量Cd金属[J]. 无机材料学报, 2019, 34(1): 91-95.
[4]	樊懋, 王琳, 裴承新, 石伟群. 碱化插层二维过渡金属碳化物的制备及其对铀酰离子的电化学检测[J]. 无机材料学报, 2019, 34(1): 85-90.
[5]	赵晓锋,江奇,郭亚楠,张楠,单长星,赵勇. 有机化学合成法制备碳纳米管/聚苯胺复合材料[J]. 无机材料学报, 2010, 25(1): 91-95.