石墨烯基微电极的制备及其在电化学传感中的应用

doi:10.11944/j.issn.1000-0518.2018.03.170399

摘要/Abstract

摘要：

微电极由于灵敏度高、响应快、样品用量少、操作简便等特点,近年来在化学分析、生物医学、食品安全、环境检测等领域引起人们的广泛关注。石墨烯具有超高的比表面积、优异的电子迁移率及良好的生物相容性等优点,近年来在电化学传感领域展示出巨大的发展前景。本文围绕石墨烯基微电极的制备及其在电化学传感中的应用展开,总结了近年来国内外同行基于石墨烯修饰微电极和石墨烯微电极在重金属离子、多巴胺、葡萄糖、H₂O₂等分子检测方面取得的研究成果。同时探讨了石墨烯基微电极在电化学传感方面面临的挑战和发展前景。

关键词: 石墨烯, 微电极, 电化学传感

Abstract:

Due to the high sensitivity, fast response, less sample usage, and simple operation, microelectrodes have attracted increasing attention in the fields of chemical analysis, biomedicine, food safety and environmental monitor recently. Given its high specific surface area, excellent electron mobility and good biocompatibility, graphene has shown a huge development potential in the field of electrochemical sensing. This review summarizes recent advances in the preparations and applications of graphene-based microelectrodes(including graphene modified microelectrode and graphene microelectrode) in sensing, such as the detection of heavy metal ions, dopamine, glucose, H₂O₂ and other molecules. Simultaneously, the major problems and opportunities of these graphene-based microelectrodes in sensing for future development are also discussed.

Key words: graphene, microelectrode, electrochemical sensing

陈立伟,韩庆,张慧敏,曲良体. 石墨烯基微电极的制备及其在电化学传感中的应用[J]. 应用化学, 2018, 35(3): 286-298.

CHEN Liwei,HAN Qing,ZHANG Huimin,QU Liangti. Preparation of Graphene-Based Microelectrode and Its Application in Electrochemical Sensing[J]. Chinese Journal of Applied Chemistry, 2018, 35(3): 286-298.

参考文献

[1]	PING Jianfeng.Rapid Detection Method and Instrument for Dairy Safety and Quality Based on Nanofunctional Materials[D]. Hnagzhou:Zhejiang University,2012(in Chinese). 平建峰. 基于纳米功能材料的乳品安全和品质快速检测方法与仪器研究[D]. 杭州:浙江大学,2012.
[2]	Wightman R M.Microvoltammetric Electrodes[J]. Anal Chem,1981,53(9):1125A-1134A.
[3]	Fleischmann M,Lasserre F,Robinson J.The Application of Microelectrodes to the Study of Homogeneous Processes Coupled to Electrode Reactions:Part II.ECE and DISP 1 Reactions[J]. J Electroanal Chem,1984,177(1):115-127.
[4]	Ahn B Y,Lewis J A.Omnidirectional Printing of Flexible, Stretchable, and Spanning Silver Microelectrodes[J]. Science,2009,323(5921):1590-1593.
[5]	Bond A M.Past, Present and Future Contributions of Microelectrodes to Analytical Studies Employing Voltammetric Detection. A Review[J]. Analyst,1994,119(11):1R-21R.
[6]	Balandin A A,Ghosh S,Bao W,et al.Superior Thermal Conductivity of Single-Layer Graphene[J]. Nano Lett,2008,8(3):902-907.
[7]	Chen H,Müller M B,Gilmore K J,et al.Mechanically Strong, Electrically Conductive, and Biocompatible Graphene Paper[J]. Adv Mater,2010,20(18):3557-3561.
[8]	Chen D,Feng H,Li J.Graphene Oxide:Preparation, Functionalization, and Electrochemical Applications[J]. Chem Rev,2012,112(11):6027-6053.
[9]	Liu Y,Dong X,Chen P.Biological and Chemical Sensors Based on Graphene Materials[J]. Chem Soc Rev,2012,41(6):2283-2307.
[10]	Novoselov K S,Geim A K,Morozov S V,et al.Electric Field Effect in Atomically Thin Carbon Films[J]. Science,2004,306(5696):666-669.
[11]	An X,Yu J C.Graphene-based Photocatalytic Composites[J]. RSC Adv,2011,1:1426-1434.
[12]	Wan X,Huang Y,Chen Y.Focusing on Energy and Optoelectronic Applications:A Journey for Graphene and Graphene Oxide at Large Scale[J]. Acc Chem Res,2012,45(4):598-607.
[13]	Lee S H,Dreyer D R,An J,et al.Polymer Brushes via Controlled, Surface-Initiated Atom Transfer Radical Polymerization(ATRP) from Graphene Oxide[J]. Macromol Rapid Commun,2010,31(3):281-288.
[14]	Ambrosi A,Chee S Y,Khezri B,et al.Metallic Impurities in Graphenes Prepared from Graphite can Dramatically Influence their Properties[J]. Angew Chem,2012,51(2):500-503.
[15]	Hammers W S,Offeman R E.Preparation of Graphitic Oxide[J]. J Am Chem Soc,1958,80(6):1339.
[16]	Bai H,Li C,Shi G.Functional Composite Materials Based on Chemically Converted Graphene[J]. Adv Mater,2015,23(9):1089-1115.
[17]	Zhu Y,Murali S,Cai W,et al.Graphene-based Materials:Graphene and Graphene Oxide:Synthesis, Properties, and Applications[J]. Adv Mater,2010,22(35):3906-3924.
[18]	Eda G,Ball J,Mattevi C,et al.Partially Oxidized Graphene as a Precursor to Graphene[J]. J Mater Chem,2011,21(30):11217-11223.
[19]	Marcano D C,Kosynkin D V,Berlin J M,et al.Improved Synthesis of Graphene Oxide[J]. ACS Nano,2010,4(8):4806-4814.
[20]	Xu Y,Sheng K,Li C,et al.Highly Conductive Chemically Converted Graphene Prepared from Mildly Oxidized Graphene Oxide[J]. J Mater Chem,2011,21(20):7376-7380.
[21]	Ambrosi A,Chua C K,Bonanni A,et al.Electrochemistry of Graphene and Related Materials[J]. Chem Rev,2014,114(14):7150-7188.
[22]	Park S,An J,Jung I,et al.Colloidal Suspensions of Highly Reduced Graphene Oxide in a Wide Variety of Organic Solvents[J]. Nano Lett,2009,9(4):1593-1597.
[23]	Scott G,Han S,Wang M S,et al.A Chemical Route to Graphene for Device Applications[J]. Nano Lett,2007,7(11):3394-3398.
[24]	Shin H J,Kim K K,Benayad A,et al.Efficient Reduction of Graphite Oxide by Sodium Borohydride and Its Effect on Electrical Conductance[J]. Adv Funct Mater,2009,19(12):1987-1992.
[25]	Stankovich S,Dikin D A,Piner R D,et al.Synthesis of Graphene-based Nanosheets via Chemical Reduction of Exfoliated Graphite Oxide[J]. Carbon,2007,45(7):1558-1565.
[26]	Liao K H,Lin Y S,Macosko C W,et al.Cytotoxicity of Graphene Oxide and Graphene in Human Erythrocytes and Skin Fibroblasts[J]. ACS Appl Mater Interfaces,2011,3(7):2607-2615.
[27]	Zhang J,Yang H,Shen G,et al.Reduction of Graphene Oxide via L-Ascorbic Acid[J]. Chem Commun,2010,46(7):1112-1114.
[28]	Zhou X,Zhang J,Wu H,et al.Reducing Graphene Oxide via Hydroxylamine:A Simple and Efficient Route to Graphene[J]. J Phys Chem C,2011,115(24):11957-11961.
[29]	Zhao J,Pei S,Ren W,et al.Efficient Preparation of Large-area Graphene Oxide Sheets for Transparent Conductive Films[J]. ACS Nano,2010,4(9):5245-5252.
[30]	Pei S,Zhao J,Du J,et al.Direct Reduction of Graphene Oxide Films into Highly Conductive and Flexible Graphene Films by Hydrohalic Acids[J]. Carbon,2010,48(15):4466-4474.
[31]	Rao C N R,Sood A K,Subrahmanyam K S,et al. Graphen, Das Neue Zweidimensionale Nanomaterial[J]. Angew Chem,2009,121(42):7890-7916.
[32]	Li D,Müller M B,Gilje S,et al.Processable Aqueous Dispersions of Graphene Nanosheets[J]. Nat Nanotechnol,2008,3(2):101-105.
[33]	Stankovich S,Piner R D,Chen X,et al.Stable Aqueous Dispersions of Graphitic Nanoplatelets via the Reduction of Exfoliated Graphite Oxide in the Presence of Poly(sodium 4-styrenesulfonate)[J]. J Mater Chem,2006,16(2):155-158.
[34]	Dey R S,Hajra S,Sahu R K,et al.A Rapid Room Temperature Chemical Route for the Synthesis of Graphene:Metal-mediated Reduction of Graphene Oxide[J]. Chem Commun,2012,48(12):1787-1789.
[35]	Guo H L,Wang X F,Qian Q Y,et al.A Green Approach to the Synthesis of Graphene Nanosheets[J]. ACS Nano,2009,3(9):2653-2659.
[36]	Yang M,Jiang T J,Wang Y,et al.Enhanced Electrochemical Sensing Arsenic(Ⅲ) with Excellent Anti-interference Using Amino-functionalized Graphene Oxide Decorated Gold Microelectrode:XPS and XANES Evidence[J]. Sens Actuators B,2017,245:230-237.
[37]	Zhu M,Zeng C,Ye J.Graphene-Modified Carbon Fiber Microelectrode for the Detection of Dopamine in Mice Hippocampus Tissue[J]. Electroanalysis,2011,23(4):907-914.
[38]	Fang J,Xie Z,Wallace G,et al.Co-deposition of Carbon Dots and Reduced Graphene Oxide Nanosheets on Carbon-fiber Microelectrode Surface for Selective Detection of Dopamine[J]. Appl Surf Sci,2017,412:131-137.
[39]	Wang L,Xu H,Song Y,et al.Highly Sensitive Detection of Quantal Dopamine Secretion from Pheochromocytoma Cells Using Neural Microelectrode Array Electrodeposited with Polypyrrole Graphene[J]. ACS Appl Mater Interfaces,2015,7(14):7619-7626.
[40]	Shi Y,Li X,Ye M,et al.An Imperata Cylindrical Flowers-Shaped Porous Graphene Microelectrode for Direct Electrochemistry of Glucose Oxidase[J]. J Electrochem Soc,2015,162(7):B138-B144.
[41]	Li X,Jiang Y,Xu B,et al.Glucose Oxidase Immobilization by Volume Shrinkage of Graphene as “Door-Function” Microelectrode[J]. J Electrochem Soc,2016,163(5):B169-B175.
[42]	Bai J,Qi P,Ding X,et al.Graphene Composite Coated Carbon Fiber:Electrochemical Synthesis and Application in Electrochemical Sensing[J]. RSC Adv,2016,6(14):11250-11255.
[43]	Bai J,Wu L,Wang X,et al.Hemoglobin-Graphene Modified Carbon Fiber Microelectrode for Direct Electrochemistry and Electrochemical H2O2 Sensing[J]. Electrochim Acta,2015,185:142-147.
[44]	Yu Y,Chen J,Zhou J.Enzyme-free Electroreduction of Hydrogen Peroxide at Polypyrrole/Graphene/Au Microelectrode Based on Three-electrode-system Array[C]. IEEE-Nano,2013:1067-1070.
[45]	Abdurhman A A M,Zhang Y,Zhang G,et al. Hierarchical Nanostructured Noble Metal/Metal Oxide/Graphene-coated Carbon Fiber:In Situ Electrochemical Synthesis and Use as Microelectrode for Real-time Molecular Detection of Cancer Cells[J]. Anal Bioanal Chem,2015,407(26):8129-8136.
[46]	Wang L,Dong Y,Zhang Y,et al.PtAu Alloy Nanoflowers on 3D Porous Ionic Liquid Functionalized Graphene-wrapped Activated Carbon Fiber as a Flexible Microelectrode for Near-cell Detection of Cancer[J]. NPG Asia Mater,2016,8(337):1-11.
[47]	Ng A M,Kenry,Teck L C,et al. Highly Sensitive Reduced Graphene Oxide Microelectrode Array Sensor[J]. Biosens Bioelectron,2015,65:265-273.
[48]	Li F,Xue M,Ma X,et al.Facile Patterning of Reduced Graphene Oxide Film into Microelectrode Array for Highly Sensitive Sensing[J]. Anal Chem,2011,83(16):6426-6430.
[49]	Xing X,Faruk H M,Yeong P J.A Fully Integrated and Miniaturized Heavy-metal-detection Sensor Based on Micro-patterned Reduced Graphene Oxide[J]. Sci Rep,2016,6(33125):1-8.
[50]	Dickinson J W,Andrieux F,Ferrer M,et al.Fabrication and Characterisation of Graphene and Its Use in Formation of Graphene Ring Microelectrodes(GRiMEs)[C]. ECS Meeting,2013,53(14):11-22.
[51]	Ding X,Bai J,Xu T,et al.A Novel Nitrogen-doped Graphene Fiber Microelectrode with Ultrahigh Sensitivity for the Detection of Dopamine[J]. Electrochem Commun,2016,72:122-125.
[52]	Ding X,Xu T,Gao J,et al.Dimensional Confinement of Graphene in a Polypyrrole Microbowl for Sensor Applications[J]. J Mater Chem B,2017,5:5733-5737.
[53]	Chen R S,Huang W H,Tong H,et al.Carbon Fiber Nanoelectrodes Modified by Single-walled Carbon Nanotubes[J]. Anal Chem,2003,75(22):6341-6345.
[54]	Michael H A.An Arsenic Forecast for China[J]. Science,2013,341(6148):852-853.
[55]	Nordstrom D K.Worldwide Occurrences of Arsenic in Ground Water[J]. Science,2002,296(5576):2143-2145.
[56]	Gumpu M B,Sethuraman S,Krishnan U M,et al.A Review on Detection of Heavy Metal Ions in Water-An Electrochemical Approach[J]. Sens Actuators B,2015,213(3):515-533.
[57]	Wightman R M,May L J,Michael A C.Detection of Dopamine Dynamics in the Brain[J]. Anal Chem,1988,60(13):769A-779A.
[58]	Damier P,Hirsch E C,Agid Y,et al.The Substantia Nigra of the Human Brain[J]. Brain,1999,122(8):1421-1436.
[59]	Adams R N.Probing Brain Chemistry with Electroanalytical Techniques[J]. Anal Chem,1976,48(14):1126A-1138A.
[60]	Boulton A A,Baker G B,Adams R N.Voltammetric Methods in Brain Systems[M]. New Jersey:Humana Press,1995:153-154.
[61]	Wang J.Electrochemical Glucose Biosensors[J]. Chem Rev,2008,108(2):814-825.
[62]	Wang J.Glucose Biosensors: 40 Years of Advances and Challenges[J]. Electroanalysis,2010,13(12):983-988.
[63]	Zhang Y,Zhang L,Zhou C.Review of Chemical Vapor Deposition of Graphene and Related Applications[J]. Acc Chem Res,2013,46:2329-2339.
[64]	Tang L,Li Y,Hui X,et al.A Sensitive Acupuncture Needle Microsensor for Real-time Monitoring of Nitric Oxide in Acupoints of Rats[J]. Sci Rep,2017,7(6446):1-10.
[65]	Du X,Wu L,Cheng J,et al.Graphene Microelectrode Arrays for Neural Activity Detection[J]. J Biol Phys,2015,41(4):339-347.
[66]	Zhao S,Liu X,Zheng X,et al.Graphene Encapsulated Copper Microwires as Highly MRI Compatible Neural Electrodes[J]. Nano Lett,2016,16(12):7731-7738.
[67]	Ping J,Blum J E,Vishnubhotla R,et al.pH Sensing Properties of Flexible, Bias-Free Graphene Microelectrodes in Complex Fluids:From Phosphate Buffer Solution to Human Serum[J]. Small,2017:1-22.