石墨炔的化学修饰及功能化  

Chemical Modification and Functionalization of Graphdiyne

作　　者：李勇军[1,2] 李玉良 LI Yongjun;LI Yuliang(Beijing National Laboratory for Molecular Sciences(BNLMS),CAS Research/Education Center for Excellence in Molecular Sciences,CAS Key Laboratory of Organic Solids,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,P.R.China;University of Chinese Academy of Sciences,Beijing 100049,P.R.China)

机构地区：[1]北京分子科学国家实验室,中国科学院分子科学科教融合卓越中心,中国科学院化学研究所有机固体院重点实验室,北京100190 [2]中国科学院大学,北京100049

出　　处：《物理化学学报》2018年第9期992-1013,共22页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(21790050,21790051,21672222),科技部国家重点研发计划(2016YFA0200104)和中国科学院前沿科学重点研究计划(QYZDY-SSW-SLH015)资助项目

摘　　要：石墨炔特殊的电子结构和孔洞结构使其在信息技术、电子、能源、催化以及光电等领域具有潜在、重要的应用前景。近几年石墨炔的基础和应用研究已取得了重要成果,并迅速成为了碳材料研究中的新领域。石墨炔中炔键单元的高活性为其化学修饰与掺杂提供了良好的平台。在这篇综述中,我们将重点介绍石墨炔的非金属杂原子掺杂、金属原子修饰以及表面改性,并深入探讨掺杂与衍生化对石墨炔材料的电子性质的影响及其对光电化学催化性能的协同增强。Graphdiyne features sp and sp2 hybridized carbon atoms.The direct natural band gap and Dirac cone structure for graphdiyne are believed to originated from inhomogeneousπ-bonding of differently hybridized carbon atoms and overlap of carbon 2pz orbitals.The special electronic structures and pore structures of graphdiyne are responsible for its potential and important applications in the fields of information technology,electronics,energy,catalysis,and optoelectronics.Recent basic and applied research studies of graphdiyne have led to important results;as a result,graphdiyne has become a new research field for carbon materials.The high activity of acetylenic units in graphdiyne provides a good platform for chemical modification and doping.Several approaches have been developed to modify the band gap of graphdiyne,including invoking strain,BN-doping,preparing nanoribbons,and hydrogenation,leading to a new graphdiyne(GDY)or graphyne(GY)derivatives.In this review,we summarize the recent progress in nonmetallic heteroatom doping,especially by nitrogen,boron,or oxygen;by modifying metal atoms for tuning electronic/spintronic properties,enhancing water splitting performance,and applying dye-sensitized solar cells and catalysts;and by surface functionalization of graphdiyne via hydrogenation,hydroxylation,and halogenation to adjust the band gap.Hence,it can be surmised that the electronic structures of graphdiynes can be tuned for specific applications.These results suggest that graphdiynes can be more advantageous than grapheme for tailoring energy band gaps for application in nanoelectronics.We also discuss the influence of doping and functionalization on the electronic properties of graphdiyne and their effects on the synergistic enhancement of photoelectrocatalytic performance.We hope that the deep and wide application of these new materials in many fields such as energy transfer and storage,catalyst,electronics,gas separation,and spintronics will draw much attention and become a widely focused research direction.

关 键 词：石墨炔 掺杂 非金属杂原子 金属原子 化学修饰 

分 类 号：O649[理学—物理化学]