石墨烯/铂纳米粒子杂化膜测定肾上腺素

doi:10.3724/SP.J.1095.2014.30612

摘要/Abstract

摘要： 利用循环伏安法制备了石墨烯/铂纳米粒子杂化膜修饰电极，并利用该修饰电极研究了肾上腺素（EP）的电化学行为，建立了测定肾上腺素的电化学方法。分别利用扫描电子显微镜（SEM）和循环伏安法对电极表面的形貌和电化学性能进行了表征。试验优化了修饰电极制备过程中影响电极性能的条件和EP的测定条件。试验结果表明，石墨烯/铂纳米粒子修饰电极对肾上腺素有明显的电催化作用。在pH=5.0的柠檬酸磷酸氢二钠缓冲溶液中，EP的氧化峰电流与其浓度在4.4×10-8~2.2×10-6 mol/L的范围内呈良好的线性关系。线性方程为ipa(10 μA)=0.0753c(mol/L)+3.7653×10-5，r=0.9989，检出限为2.2×10-9 mol/L（S/N=3）。修饰电极表具有良好的重现性，可用于实际样品的测定。

关键词: 石墨烯, 铂纳米粒子, 杂化材料, 肾上腺素, 应用

Abstract: Graphene/platinum nanoparticles hybrid membrane modified electrode was prepared by cyclic voltammetry(CV). The electrochemical behaviors of epinephrine(EP) were studied on this modified electrode, and an electrochemical method for determination of EP was developed. The morphology and the electrochemical properties of the modified electrode were characterized by scan electron microscopy(SEM) and cyclic voltammetry, respectively. The conditions that influenced the electrochemical properties of the modified electrode during the preparation processes and the conditions for determination of EP were optimized. Experimental results show that the modified electrode has excellent catalytic properties for the redox of EP. In the Na2HPO4citric acid buffer solution(pH=5.0), the oxidative peak current of EP is linear with its concentration in the range of 4.4×10-8~2.2×10-6 mol/L. The linear regressive equation is ipa(10 μA)=0.0753c(mol/L)+3.7653×10-5 with r=0.9989, and the detection limit of 2.0×10-9 mol/L（S/N=3）. The modified electrode shows good reproducibility, high sensitivity and selectivity. It could be used for determination of the content of EP in real samples.

Key words: graphene, platinum nanoparticle, hybrid material, epinephrine

中图分类号:

O657.1

郭宪厚, 王学亮, 郁章玉. 石墨烯/铂纳米粒子杂化膜测定肾上腺素[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30612.

GUO Xianhou1,2, WNAG Xueliang1, YU Zhangyu1,3*. Determination of Epinephrine by Graphene/Platinum Nanoparticle Hybrid Membrane Modified Electrode[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30612.

参考文献

[1] Ratinac K R，Yang W R，Gooding J J,et al. Graphene and Related Materials in Electrochemical Sensing[J]. Electroanalysis，2011，23(4)：803-826.

[2] Kuila T，Bose S，Khanra P,et al. Recent advances in Graphene-based Biosensors[J]. Biosens Bioelectron，2011，26(12)：4637-4648.

[3] Guo S J，Dong S J. Graphene Nanosheet: Synthesis, Molecular Engineering, Thin Film, Hybrids, and Energy and Analytical Applications[J]. Chem Soc Rev，2011，40(5)：2644-2672.

[4] Jiang H J. Chemical Preparation of Graphene-Based Nanomaterials and Their Applications in Chemical and Biological Sensors[J]. Small，2011，7(17)：2413-2427.

[5] Gan T，Hu S S. Electrochemical Sensors Based on Graphene Materials[J]. Microchim Acta，2011，175(1/2)：1-19.

[6] Pumera M. Graphene in Biosensing[J]. Mater Today，2011，14(7/8)：308-315.

[7] HUANG Haiping,ZHU Junjie. Preparation of Novel Carbon—Based Nanomaterial of Graphene and Its Applications for Electrochemistry[J]. Chinese J Anal Chem，2011，39(7)：963-971(in Chinese).

黄海平，朱俊杰. 新型碳材料—石墨烯的制备及其在电化学中的应用[J]. 分析化学，2011，39(7)：963-971.

[8] Wang Y，Li Z H，Wang J,et al. Graphene and Graphene Oxide:Biofunctionalization and Applications in Biotechnology[J]. Trends Biotechnol,2011,29(5)：205-212.

[9] SONG Yingpan，FENG Miao，ZHAN Hongbing. Application of Graphene Edge Effect in Electrochemical Biosensors[J]. Prog Chem，2013，25(5)：698-706(in Chinese).

宋英攀，冯苗，詹红兵. 石墨烯的边界效应在电化学生物传感器中的应用[J]. 化学进展，2013，25(5)：698-706.

[10] Lu L M，Li H B，Qu F L,et al. In situ Synthesis of Palladium Nanoparticle-graphene Nanohybrids and Their Application in Nonenzymatic Glucose Biosensors[J]. Biosens Bioelectron，2011，26(8)：3500-3504.

[11] Cui F,Zhang X L. Electrochemical Sensor for Epinephrine Based on a Glassy Carbon Electrode Modified with Graphene/gold Nanocomposites[J]. J Electroanal Chem,2012,669:35-41.

[12] Wang K，Liu Q，Guan Q M,et al. Enhanced Direct Electrochemistry of Glucose Oxidase and Biosensing for Glucose via Synergy Effect of Graphene and CdS Nanocrystals[J]. Biosens Bioelectron，2011，26(5)：2252-2257.

[13] Bo Y，Yang H Y，Hu Y,et al. A Novel Electrochemical DNA Biosensor Based on Graphene and Polyaniline Nanowires[J]. Electrochim Acta，2011，56(6)：2676-2681.

[14] Zhang S Y，Tang S，Lei J P,et al. Functionalization of Graphene Nanoribbons with Porphyrin for Electrocatalysis and Amperometric Biosensing[J]. J Electroanal Chem，2011，656(1/2)：285-288.

[15] Shan C S，Yang H F，Song J F,et al. Direct Electrochemistry of Glucose Oxidase and Biosensing for Glucose Based on Graphene[J]. Anal Chem，2009，81(6)：2378-2382.

[16] Wang Y，Li Z H，Hu D H,et al. Aptamer/graphene Oxide Nanocomplex for in situ Molecular Probing in Living Cells[J]. J Am Chem Soc，2010，132(27)：9274-9276.

[17] Yu P,Qian Q,Lin Y Q,et al. Dimensional and Uniform Pt/Carbon Nanotube Nanocomposites from Ionic Liquid/Carbon Nanotube Gel Matrix with Enhanced Electrocatalytic Activity towards Methanol Oxidation[J]. J Phys Chem C,2010,114(8)：3575-3579.

[18] Shen Q M,Jiang L P,Zhang H,et al. Three-dimensional Dendritic Pt Nanostructures:Sonoelectrochemical Synthesis and Electrochemical Applications[J]. J Phys Chem C,2008,112(42)：16385-16392.

[19] Zhang H,Yin Y J,Hu Y J,et al. Pd@Pt Core-Shell Nanostructures with Controllable Composition Synthesized by a Microwave Method and Their Enhanced Electrocatalytic Activity toward Oxygen Reduction and Methanol Oxidation[J]. J Phys Chem C,2010,114(27)：11861-11867.

[20] Meng L,Jin J,Yang G X,et al. Nonenzymatic Electrochemical Detection of Glucose Based on Palladium Single-Walled Carbon Nanotube Hybrid Nanostructures[J]. Anal Chem,2009,81(17)：7271-7280.

[21] Seger B,Kamat P V. Electrocatalytically Active Graphene-Platinum Nanocomposites. Role of 2-D Carbon Support in PEM Fuel Cells[J]. J Phys Chem C,2009,113(19)：7990-7995.

[22] Wu G H,Song X H,Wu Y F,et al. Non-enzymatic Electrochemical Glucose Sensor Based on Platinum Nanoflowers Supported on Graphene Oxide[J]. Talanta,2013,105:379-385.

[23] Wen T T,Xue C,Li Y,et al. Reduced Graphene Oxide-platinum Nanoparticles Composites Based Imprinting Sensor for Sensitively Electrochemical Analysis of 17β-Estradiol[J]. J Electroanal Chem,2012,682:121-127.

[24] Liu T,Xu M R,Yin H S,et al. A Glassy Carbon Electrode Modified with Graphene and Tyrosinase Immobilized on Platinum Nanoparticles for Sensing Organophosphorus Pesticides[J]. Microchim Acta,2011,175(1/2):129-135.