石墨烯结构独特,在电子、聚合物、汽车和生物制药等领域具有巨大的应用潜力,石墨烯的功能化研究已成为国内外研究热点。综述了近年来石墨烯表面功能化改性研究进展。石墨烯表面功能化改性方法主要包括非共价键功能化和共价键功能化改性。非共价键功能化改性分为π-π键相互作用、离子键作用和氢键作用3种。共价键功能化改性分为聚合物功能化和有机小分子功能化。总结了石墨烯与改性分子的相互作用、反应类型及相关应用,对石墨烯功能化发展前景进行了展望。
Graphene has a unique structure and great application potential in the fields of electronics,polymers,automobiles and bio-pharmaceuticals.The functionalization of graphene has become a hot area of research at home and abroad.The research progress of graphene surface functional modification in recent years was reviewed.Graphene surface functional modification methods mainly included non-covalent bond functionalization and covalent bond functionalization.Non-covalent bond functionalization was divided into three categories:π-π stacking,ionic bonding and hydrogen bonding effect.Meanwhile,covalent bond functionalization was divided into twocategories:polymer functionalization and organic small molecular functionalization.The interactions between graphene and modified molecules,reaction types and related applications were summarized.Finally,current challenges and future research directions were also presented in terms of surface functional modification for graphene.
[1] Novoselov K S,Geim A K,Morozov S V,et al.Electricfield effect in atomically thin carbon films[J].Science,2004,306:666-669.
[2] 黄毅,陈永胜.石墨烯的功能化及其相关应用[J].中国科学,2009,39(9):887-896.
[3] Li Y,Hu Y,Zhao Y,et al.An electrochemical avenue to green-luminescent graphene quantum dots as potential electron-acceptors for photovoltaics[J].Adv Mater,2011,23(6):776-780.
[4] Zhao Shuai,Xie Shicheng,Sun Peipei,et al.Synergistic effect of graphene and silicon dioxide hybrids through hydrogen bonding self-assembly in elastomer composites[J].RSC Adv,2018,8:17813-17825.
[5] Zeng Xin,Yuan Yi,Wang Ting,et al.Targeted imaging and induction of apoptosis of drug-resistant hepatoma cells by miR-122-loaded graphene-InP nanocompounds[J].Nanobiotechnol,2017(15):9.
[6] Chul Chung,Young-Kwan Kim,Dolly Shin,et al.Biomedical applications of graphene and graphene oxide[J].Accounts Chem Res,2013,46(10):2211-2224.
[7] 吴力.石墨烯功能化改性及其聚氨酯纳米复合材料的制备[D].广州:华南理工大学,2014.
[8] Georgakilas V,Otyepka M,Bourlinos A B,et al.Functionalization of graphene:covalent and non-covalent approaches,derivatives and applications[J].Chem Rev,2012,112(11):6156-6214.
[9] 吕鹏,冯奕钰,张学全,等.功能化石墨烯的应用研究新进展[J].中国科学:技术科学,2010,40(11):1247-1256.
[10] Cui J,Song Z,Xin L,et al.Exfoliation of graphite to few-layer graphene in aqueous media with vinylimidazole-based polymer as high-performance stabilize[J].Carbon,2016,99:249-260.
[11] 凌良仲.石墨烯/PET复合导电纤维的制备与性能研究[D].天津:天津工业大学,2017.
[12] 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].Journal of Materials Chemistry,2006,16(2):155-158.
[13] Su Q,Pang S,Alijani V,et al.Composites of graphene with large aromatic molecules[J].Advanced Materials,2009,21(31):3191-3195.
[14] Liu J Q,Yang W R,Tao L,et al.Thermosensitive graphene nanocomposites formed using pyrene-terminal polymers made by RAFT polymerization[J].Journal of Polymer Science Part A:Polymer Chemistry,2010,48(2):425-433.
[15] Bai H,Xu Y X,Zhao L,et al.Non-covalent func-tionalization of graphene sheets by sulfonated polyaniline[J].Chemical Communacations,2009,13:1667-1669.
[16] Park S,An J,Piner R D,et al.Aqueous suspension and characte rization of chemically modified graphene sheets[J].Chemistry of Materials,2008,20(21):6592-6594.
[17] Chang H,Wang G,Yang A,et al.A transparent,flexible,low-temperature,and solution-processible graphene composite electrode[J].Advanced Functional Materials,2010,20(17):2893-2902.
[18] Mustafa Lotya,Yenny Hernandez,Paul King J,et al.Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions[J].American Chemical Society,2009,131:3611-3620.
[19] Yue Huanjuan,Sun Hongjuan,Peng Tongjiang,et al.Evolution of structure and functional groups in the functionalization of grapheme oxide with L-cysteine[J].Journal of Molecular Structure,2018,1163:449-454.
[20] Yang X,Li L,Shang S,et al.Synthesis and characterization of layer-aligned poly (vinyl alcohol)/graphene nanocomposites[J].Polymer,2010,51(15):3431-3435.
[21] Patil A J,Vickery J L,Mann S,et al.Aqueous stabilization and self-assembly of graphene sheets into layered bio-nanocomposites using DNA[J].Adv Mater ASAP,2009,21(31):3159-3164.
[22] Long B,Manning M,Burke M,et al.Non-covalent functionalization of graphene using self-assembly of alkane-amines[J].Advanced Function Materials,2012,22:717-725.
[23] 杜士彬.功能化氧化石墨烯作为药物基因载体在肿瘤治疗中的应用[D].天津:天津工业大学,2018.
[24] Salavagione H J,Gomez M A,Martinez G.Polymericmodification of graphene through esterification of graphite oxide and poly (vinyl alcohol)[J].Macromolecules,2009,42:6331-6334.
[25] Shen J F,Hu Y Z,Li C,et al.Synthesis of amphiphilic graphene nanoplatelets[J].Small,2009,5:82-85.
[26] Li Jing,Jiang Zhiyuan,Gan Lingzhu,et al.Functionalized graphene/polymer composite coatings for autonomous early-warning of steel corrosion[J].Composites Communications,2018,9:6-10.
[27] Ma X,Li F,Wang Y,et al.Functionalization of pristine graphene with conjugated polymers through diradical addition and propagation[J].Chem Asian J,2012,7:2547-2550.
[28] Cao Y,Feng J,Wu P.Alkyl-functionalized graphene nanosheets with improved lipophilicity[J].Carbon,2010,48(5):1683-1685.
[29] Salavagione H J,Gomez M A,Martinez G.Polymericmodification of graphene through esterification of graphite oxide and poly (vinyl alcohol)[J].Macromolecules,2009,42:6331-6334.
[30] Ma W S,Li J,Zhao X S.Improving the thermal and mechanical properties of silicone polymer by incorporating functionalized graphene oxide[J].Journal of Materials Science,2013,48(15):1-8.
[31] 吕生华,刘晶晶,崔亚亚,等.石墨烯的功能化研究进展[J].化工时刊,2013,27(8):35-40.
[32] 白静静,尹建宇,高雄.异氰酸酯功能化氧化石墨烯/热塑性聚氨酯弹性体复合材料的制备与性能[J].复合材料学报,2018,35(7):1683-1690.
[33] Bekyarova E,Itkis M E,Ramesh P,et al.Chemical modification of epitaxial graphene:spontaneous grafting of aryl groups[J].Journal of the American Chemical Society,2009,131(4):1336-1337.
[34] 靳飞.功能化石墨烯的制备及其复合材料的性能研究[D].淄博:山东理工大学,2016.
[35] 于璐洋,王会才,赵修青,等.巯基功能化石墨烯修饰玻碳电极测定水中痕量重金属镉[J].天津工业大学学报,2014,3(33):34-39.
[36] 何云凤,顾健,张小平,等.石墨烯功能化修饰进展及应用[J].功能材料,2018,49(3):03031-03041.
[37] Georgakilas V,Bourlinos A,Gournis D,et al.Multi-purpose organically modified carbon nanotubes:from functionalization to nanotube composites[J].Journal of the American Chemical Society,2008,130(27):8733-8740.
[38] Georgakilas V,Guldi D M,Signorini R,et al.Organicfunctionalization and optical properties of carbon onions[J].Journal of the American Chemical Society,2003,125(47):14268-14269.
[39] Kordatos K,Da R T,Bosi S,et al.Novel versatilefullerene synthons[J].Journal of Organic Chemistry,2001,66(14):4915-4920.
[40] Cioffi C,Campidelli S,Brunetti F G,et al.Functional-isation of carbon nanohorns[J].Chemical Communica-tions,2006,20(20):2129-2131.
[41] Singh R,Kostarelos K.Tissuebiodistribution and bloodclearance rates of intravenously administered carbon nanotube radiotracers[J].Proceedings of the National Academy of Sciences of the United States of America,2006,103(9):3357-3362.
[42] Kostarelos K,Lacerda L,Pastorin G,et al.Cellular up-take of functionalized carbon nanotubes is independent of functional group and cell type[J].Nature Nanotechnology,2007,2(2):108.
基金资助
江苏省产学研前瞻性联合研究项目(BY2016030-21);江苏省研究生科研与实践创新计划项目(SJCX18-0990);江苏理工学院人才引进项目(KYY16025)
PDF
(1157KB)
