液相单根分散石墨烯纳米带的化学合成与光物理性质

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英文篇名：Single Graphene Nanoribbons in Liquid Phase:Chemical Synthesis and Photophysical Properties 作者：陆国林 ; 黄晓宇 英文作者：LU Guolin;HUANG Xiaoyu;Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences; 关键词：石墨烯纳米带 ; 聚合物功能化 ; 液相分散 ; 超分子自组装 ; 光物理性质 英文关键词：graphene nanoribbons;;polymer functionalization;;liquid-phase dispersibility;;supramolecular self-assembly;;photophysical properties 中文刊名：GNGF 英文刊名：Journal of Functional Polymers 机构：中国科学院上海有机化学研究所; 出版日期：2018-12-07 17:40 出版单位：功能高分子学报 年：2019 期：v.32 语种：中文; 页：GNGF201901002 页数：4 CN：01 ISSN：31-1633/O6 分类号：13-16

摘要

结构精确的石墨烯纳米带(GNRs)因具有独特的光、电、磁等物理性能,吸引了化学、物理、材料科学等领域研究人员的广泛关注。由于GNRs间强的π-π相互作用使得GNRs在溶液中难以分散,严重阻碍了其液相物化性能的研究和光电器件的制备。因此,实现GNRs在液相中的分散,特别是单根分散,是研究GNRs液相物化性质及其光电器件制备需首要解决的关键问题。上海交通大学麦亦勇团队在可液相分散的GNRs化学合成方面展开了研究,在纳米带的聚合物功能化、液相分散、超分子自组装,光热转化等方面取得了突破性的进展。近期,该团队通过在纳米带边缘引入大尺寸的类三蝶烯刚性基团,通过其大于石墨层间距(约0.34nm)的分子尺寸极大地减弱了GNRs主干之间π-π相互作用,实现了GNRs在常用溶剂中的高质量浓度(5mg/mL)分散,同时实现了GNRs在低质量浓度(小于0.1mg/mL)下的单根分散,并用超快光谱和二维电子谱等研究了单根分散纳米带在液相中的光物理性质。这一突破性成果为研究单根石墨烯纳米带的液相物理性质及其潜在应用探索开辟了道路。
        Structurally well-defined graphene nanoribbons(GNRs)have attracted increasing attention in recent years due to their unique optical,electrical and magnetic properties.However,the serious aggregation induced by the strongπ-πinteraction between GNRs severely limits their solution dispersibility and thus impedes the deeper fundamental studies on their physiochemical properties and the exploration of their prospective applications.Thereby,the realization of desired dispersibility,in particular single-ribbon dispersibility,is a key issue for studying the physiochemical properties of GNRs in liquid phase as well as simply preparing GNR-based photoelectric devices.To this end,Prof.Mai's group at Shanghai Jiao Tong University have been focusing on the chemical synthesis of liquid-phase dispersible GNRs.In recent years,they achieved the polymer functionalization of GNRs and their excellent dispersibility in liquid phase,which offered this group opportunities for the understanding of supramolecular self-assembly and photothermal conversion performance of GNRs in liquid phase.Very recently,they demonstrated a solution chemical synthesis of a new type of GNRs decorated with pending triptycene-like rigid group.The radius of this side group is about 0.5nm,which is larger than the interlayer spacing of graphite(about0.34nm),thus effectively hindering theπ-πstacking of GNR backbones and affording the GNRs excellent dispersibility in many common organic solvents(e.g.tetrahydrofuran,THF)with unprecedentedly high concentrations(up to 5 mg/mL).Most importantly,single GNRs were achieved at low concentrations(less than 0.1mg/mL)in liquid phase;their photophysical properties were studied,for the first time,by ultrafast spectroscopy coupling with two-dimensional electronic spectroscopy.This breakthrough paves the way for understanding the physical properties of individual GNRs in liquid phase and for exploring their potential applications.

引文

[1]NARITA A,WANG X Y,FENG X L,et al.New advances in nanographene chemistry[J].Chemical Society Reviews,2015,44(18):6616-6643.
    [2]LI X L,WANG X R,ZHANG L,et al.Chemically derived,ultrasmooth graphene nanoribbon semiconductors[J].Science,2008,319(5867):1229-1232.
    [3]RUFFIEUX P,WANG S Y,YANG B,et al.On-surface synthesis of graphene nanoribbons with zigzag edge topology[J].Nature,2016,531(7595):489-492.
    [4]TERRONESA T M,BOTELLO-MNDEZ A R,CAMPOS-DELGADO J,et al.Graphene and graphite nanoribbons:Morphology,properties,synthesis,defects and applications[J].Nano Today,2010,5(4):351-372.
    [5]DMITRY V K,HIGGINBOTHAM A L,SINITSKII A,et al.Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons[J].Nature,2009,458(7240):872-877.
    [6]WANG X R,DAI H J.Etching and narrowing of graphene from the edges[J].Nature Chemistry,2010,2(8):661-665.
    [7]HUANG Y J,MAI Y Y,BESER U,et al.Poly(ethylene oxide)functionalized graphenenanoribbons with excellent solution processability[J].Journal of the American Chemical Society,2016,138(32):10136-10139.
    [8]HUANG Y J,MAI Y Y,YANG X W,et al.Temperature-dependent multidimensional self-assembly of polyphenylenebased“rod-coil”graft polymers[J].Journal of the American Chemical Society,2015,137(36):11602-11605.
    [9]WU D D,HUANG Y J,XU F G,et al.Recent advances in the solution self-assembly of amphiphilic“rod-coil”copolymers[J].Journal of Polymer Science:Part A.Polymer Chemistry,2017,55(9):1459-1477.
    [10]WU D D,XU F G,HUANG Y J,et al.Effect of side chains on the low-dimensional self-assembly of polyphenylenebased“rod-coil”graft copolymers in solution[J].Macromolecules,2018,51(1):161-172.
    [11]HUANG Y J,DOU W T,XU F G,et al.Supramolecular nanostructures of structurally defined graphene nanoribbons in the aqueous phase[J].Angewandte Chemie International Edition,2018,57(13):3366-3371.
    [12]姜学松.结构精确石墨烯纳米带的水相超分子自组装及其光热转换应用[J].功能高分子学报,2018,31(5):442-445.
    [13]HUANG Y J,XU F G,GANZER L,et al.Intrinsic properties of single graphene nanoribbons in solution:Synthetic and spectroscopic studies[J].Journal of the American Chemical Society,2018,140(33):10416-10420.