石墨烯材料在水中重金属检测中的应用

doi:10.16085/j.issn.1000-6613.2017-1126

摘要/Abstract

摘要： 近几年，石墨烯及其复合材料的制备及应用受到广泛关注，在环境污染物检测方面取得了显著进展，尤其是水中重金属分析方法的研究。本文综述了各类石墨烯材料用于水中重金属离子检测的研究现状，着重分析了石墨烯改性电极的制备、性能及其电化学检测方法的机理和优缺点。发现石墨烯材料的优异电子传输性能，使其在重金属离子电化学测试方法开发方面具有天然优势，有助于实现在线、原位、实时检测水体中重金属离子；但是石墨烯改性电极研究刚刚起步，存在诸如抗干扰能力和选择性差、电极重复使用性能差、实际应用研究少等问题，有必要继续开展石墨烯修饰的新型复合电极制备，进一步提高电化学测试方法的选择性和抗干扰能力，增加电极使用寿命和非常规环境下的应用研究，拓展石墨烯基复合电极的应用范围等。

关键词: 石墨烯, 复合材料, 重金属, 电化学

Abstract: In recent years,the preparation and application of graphene and its composites have gained more and more attention. The detection methods of environmental pollutants using graphene materials have acquired significant progress,especially with respect to the analysis of heavy metals in water. This paper reviews the research status of the method to analyze heavy metals in the water by the various types of graphene materials,with the focus on the preparation and performance of gaphene matrix composite electrode. The mechanisms and advantages of detection methods are also compared. It is found that graphene materials have natural advantages in heavy metal ion detection due to their excellent electronic transmission performance,which helps to achieve the online,in situ,and real-time detection of heavy metal ion in water. Nevertheless,the research of graphene modified electrode is just in its infancy,and its anti-interference ability and selectivity,and electrode reuse performance are poor,and the practical application is limited. Therefore,it is highly demanded to conduct the preparation of graphene modified new composite electrode,to improve the anti-jamming ability and selectivity of electrochemical analysis methods,to increase the life of the electrode and its application in unconventional environment,and to develop the application scope of graphene matrix composite electrode.

Key words: graphene, composites, heavy metals, electrochemistry

中图分类号:

X703

彭雪, 高彬, 高泽, 秦丽丽, 杨雯晴, 石凡可, 滕洪辉. 石墨烯材料在水中重金属检测中的应用[J]. 化工进展, 2018, 37(05): 1868-1874.

PENG Xue, GAO Bin, GAO Ze, QIN Lili, YANG Wenqing, SHI Fanke, TENG Honghui. Detection of heavy metal in water by graphene composites[J]. Chemical Industry and Engineering Progress, 2018, 37(05): 1868-1874.

参考文献

[1] NOVOSOLOV K S,GEIM A K,MOROZOV S V,et al. Electric field effect in atomically thin carbon films[J]. Sci.,2004,306(5696):666-669.
[2] ZHU J H,CHEN M J,HE Q L,et al. An overview of the engineered graphene nanostructures and nanocomposites[J]. RSC Adv.,2013,3(45):22790-22824.
[3] LÜ M,LI J,YANG X,et al. Applications of graphene-based materials in environmental protection and detection[J]. Chin. Sci. Bull.,2013,58(22):2698-2710.
[4] KEMP K C,SEEMA H,SALEH M,et al. Environmental applications using graphene composites:water remediation and gas adsorption[J]. Nanoscale,2013,5(8):3149-3171.
[5] JIA X,HAN Y,LIU X,et al. Dispersive liquid-liquid microextraction combined with flow injection inductively coupled plasma mass spectrometry for simultaneous determination of cadmium,lead and bismuth in water samples[J]. Microchim Acta,2010,171:49-56.
[6] TOKALIOGLU S,OYMAK T,KARTAL S. Coprecipitation of lead and cadmium using copper (Ⅱ) mercaptobenzothiazole prior to flame atomic absorption spectrometric determination[J]. Microchim Acta,2007,159:133-139.
[7] AFKHAMI A,MADRAKIAN T,AHMADI R,et al. Chemically modified alumina nanoparticles for selective solid phase extraction and preconcentration of trace amounts of Cd(Ⅱ)[J]. Microchim Acta,2011,175:69-77.
[8] ZHU X,ZHU X,WANG B. Determination of trace cadmium in water samples by graphite furnace atomic absorption spectrometry after cloud point extraction[J]. Microchim Acta,2006,154:95-100.
[9] SAMCZYNSKI Z,DYBCZYNSKI R. Ion exchange behavior of cadmium,mercury,silver and zinc on Retardion 11A8 and Chelex 100 ion exchangers in ammonia medium and its application for radiochemical separations[J]. Microchim Acta,2004,144:4.
[10] 陈腊梅. 含汞废水处理技术发展现状及趋势[J]. 化学工程与装备,2014,9:187-189. CHENG Lamei. Situation and progress in treatment of mercury wastewater[J]. Chemical Engineering & Equipment,2014,9:187-189.
[11] 翟玉秀,郝林华. 氢化物发生原子荧光光谱法测定食品和饲料中的铅[J]. 分析化学,2000,28(2):176-179. ZHAI Yuxiu,HAO Linhua. Determination of lead in food and feed samples using hydride generation-atomic fluorescence spectrometry[J]. Chin. J. Anal. Chem.,2000,28(2):176-179.
[12] HUANG Z Y,ZHUANG Z X,WANG X R,et al. Preparation and characterization of radix salvia reference material for heavy metals under GAP control[J]. China J. Chin. Mater. Med.,2003,28(9):808-811.
[13] 方红,杨晓兵. 电感耦合等离子体原子发射光谱法测定化妆品中砷、铅、汞[J]. 光谱实验室,2002(1):74-77. FANG Hong,YANG Xiaobing. Determination of As,Pb and Hg in cosmetics by inductively coupled plasma atomic emission spectrometry[J].Chin. J. Spectro. Lab.,2002(1):74-77.
[14] 台希,李海涛,李德良,等. 固相萃取富集高效液相色谱法测定环境水样中的重金属元素[J]. 干旱环境监测,2004,18(2):67-70. TAI Xi,LI Haitao,LI Deliang,et al. Determination of heavy metal element in water samples by solid phase extraction concentration high efficiency liquid phase chromatography[J]. Arid. Enviro. Monit.,2004,18(2):67-70.
[15] 华银峰,路贻通. 脲酶抑制法检测环境样品中重金属离子研究[J]. 上海环境科学,2003(12):939-942,1047. HUA Yinfeng,LU Yitong. Study on detecting heavy metal ions in environmental samples with urease inhibition method[J]. Shanghai Environmental Sciences,2003(12):939-942,1047.
[16] WYLIE D E,LU D,CARLSON L D,et al. Monoclonal antibodies specific for mercuric ions[J]. Proceedings of the National Academy of Sciences,1992,89:4104-4108.
[17] TADEUSZ K,MALGORZATA M,TROJANOWICZ M. Inhibitive determination of mercury and other metal irons by potentiometric urea biosenor[J]. Biosensors and Bioelectronics,2000,15:681-691.
[18] DENG D,JIANG X,YANG L,et al. Organic solvent-free cloud point extraction-like methodology using aggregation of graphene oxide[J]. Anal. Chem.,2014,86(1):758-765.
[19] LONG Y,HUI J F,WANG P P,et al. Alpha-MnO₂ nanowires as building blocks for the construction of 3D macro-assemblies[J]. Chem. Commun.,2012,48(47):5925-5927.
[20] ALVAND M,SHEMIRANI F. Preconcentration of trace cadmium ion using magnetic graphene nanoparticles as an efficient adsorbent[J]. Microchim. Acta.,2013,181(1/2):181-188.
[21] SAHOO P K,PANIGRAHY B,SAHOO S,et al. In situ synthesis and properties of reduced graphene oxide/Bi nanocomposites:as an electroactive material for analysis of heavy metals[J]. Biosens Bioelectron,2013,43:293-296.
[22] ZHU L,XU L,HUANG B,et al. Simultaneous determination of Cd(Ⅱ) and Pb(Ⅱ)using square wave anodic stripping voltammetry at a gold nanoparticle-graphene-cysteine composite modified bismuth film electrode[J]. Electrochim Acta,2014,115:471-477.
[23] GAO C,YU X Y,XU R X,et al. AlOOH-reduced graphene oxide nanocomposites:one-pot hydrothermal synthesis and their enhanced electrochemical activity for heavy metal ions[J]. ACS Appl. Mater. Interfaces,2012,4(9):4672-4682.
[24] HUANGFU C,FU L,LI Y,et al. Sensitive stripping determination of cadmium(Ⅱ) and lead(Ⅱ)on disposable graphene modified screen-printed electrode[J]. Electroanal,2013,25(9):2238-2243.
[25] WANG Z,LI L,LIU E. Graphene ultrathin film electrodes modified with bismuth nanoparticles and polyaniline porous layers for detection of lead and cadmium ions in acetate buffer solutions[J]. Thin Solid Films,2013,544:362-367.
[26] WONSAWAT W,CHUANUWATANAKUL S,DUNGCHAI W,et al. Graphene-carbon paste electrode for cadmium and lead ion monitoring in a flow-based system[J]. Talanta,2012,100:282-289.
[27] WILLEMSE C M,TLHOMELANG K,JAHED N,et al. Metallo-graphene nanocomposite electrocatalytic platform for the determination of toxic metal ions[J]. Sens,2011,11(4):3970-3987.
[28] LI J,GUO S,ZHAI Y,et al. High-sensitivity determination of lead and cadmium based on the Nafion-graphene composite film[J]. Anal. Chim. Acta.,2009,649(2):196-201.
[29] SUN Y-F,CHEN W-K,LI W-J,et al. Selective detection toward Cd²⁺ using Fe₃O₄/RGO nanoparticle modified glassy carbon electrode[J]. J. Electroanal. Chem.,2014,714/715:97-102.
[30] GUO Z,LIU Z G,YAO X Z,et al. A molecular-gap device for specific determination of mercury ions[J]. Sci. Rep.,2013,3:3115.
[31] GONG J,ZHOU T,SONG D,et al. Monodispersed Au nanoparticles decorated graphene as an enhanced sensing platform for ultrasensitive stripping voltammetric detection of mercury(Ⅱ)[J]. Sens. Actuators B:Chem.,2010,150(2):491-497.
[32] LIU F,HA H D,HAN D J,et al. Photoluminescent graphene oxide microarray for multiplex heavy metal ion analysis[J]. Small,2013,9(20):3410-3414.
[33] CHEN K,LU G,CHANG J,et al. Hg(Ⅱ)ion detection using thermally reduced graphene oxide decorated with functionalized gold nanoparticles[J]. Anal. Chem,2012,84(9):4057-4062.
[34] AN J H,PARK S J,KWON O S,et al. High-performance flexible graphene aptasensor for mercury detection in mussels[J]. ACS Nano,2013,7(12):10563-10571.
[35] CHANG Q,SONG S,WANG Y,et al. Application of graphene as a sorbent for preconcentration and determination of trace amounts of chromium(Ⅲ)in water samples by flame atomic absorption spectrometry[J]. Anal. Methods,2012,4(4):1110.
[36] PRAKASH A,CHANDRA S,BAHADUR D. Structural,magnetic,and textural properties of iron oxide-reduced graphene oxide hybrids and their use for the electrochemical detection of chromium[J]. Car,2012,50(11):4209-4219.
[37] LIU C,HE C,XIE T,et al. Reduction of graphite oxide using ammonia solution and detection Cr(Ⅵ) with graphene-modified electrode[J]. Fuller Nanotube Car N,2014,23(2):125-130.
[38] CAI F,LIU X,LIU S,et al. A simple one-pot synthesis of highly fluorescent nitrogen-doped graphene quantum dots for the detection of Crn(Ⅵ) in aqueous media[J]. RSC Adv.,2014,4:52016-52022.
[39] CHEN Y,DONG Y,WU H,et al. Electrochemiluminescence sensor for hexavalent chromium based on the graphene quantum dots/peroxodisulfate system[J]. Electrochim Acta,2015,151:552-557.
[40] KONG N,LIU J,KONG Q,et al. Graphene modified gold electrode via π-π stacking interaction for analysis of Cu²⁺ and Pb²⁺[J]. Sens. Actuators B:Chem.,2013,178:426-433.
[41] WANG B,LUO B,LIANG M,et al. Chemical amination of graphene oxides and their extraordinary properties in the detection of lead ions[J]. Nanoscale,2011,3(12):5059-5066.
[42] JIAN J M,LIU Y Y,ZHANG Y L,et al. Fast and sensitive detection of Pb²⁺ in foods using disposable screen-printed electrode modified by reduced graphene oxide[J]. Sens,2013,13(10):13063-13075.
[43] ZHANG J-T,JIN Z-Y,LI W-C,et al. Graphene modified carbon nanosheets for electrochemical detection of Pb(Ⅱ) in water[J]. J Mater. Chem. A,2013,1(42):13139.
[44] ZHENG Q,CAI Z,GONG S. Green synthesis of polyvinyl alcohol (PVA)-cellulose nanofibril(CNF)hybrid aerogels and their use as superabsorbents[J]. J. Mater. Chem. A,2014,2(9):3110.
[45] WANG B,CHANG Y-H,ZHI L-J. High yield production of graphene and its improved property in detecting heavy metal ions[J]. New Car Mater,2011,26(1):31-35.
[46] HADI M,ROUHOLLAHI A,YOUSEFI M. Application of nanocrystalline graphite-like pyrolytic carbon film electrode for voltammetric sensing of lead[J]. J. Appl. Electrochem.,2012,42(3):179-187.
[47] LOKMAN N F,BAKAR A A A,SUJA F,et al. Highly sensitive SPR response of Au/chitosan/graphene oxide nanostructured thin films toward Pb(Ⅱ)ions[J]. Sens Actuators B:Chem.,2014,195:459-466.
[48] BROWNSON D A C,BANKS C E. Limitations of CVD graphene when utilised towards the sensing of heavy metals[J]. RSC Advances,2012,2(12):5385.
[49] LIU F,HA H D,HAN D J,et al. Photoluminescent graphene oxide microarray for multiplex heavy metal ion analysis[J]. Small,2013,9(20):3410-3414.