物理化学学报 >> 2018, Vol. 34 >> Issue (9): 977-991.doi: 10.3866/PKU.WHXB201801243

所属专题: 石墨炔

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石墨双炔的合成方法

周劲媛1,2,张锦1,*(),刘忠范1,*()   

  1. 1 北京大学纳米化学研究中心,北京大学化学与分子工程学院,北京 100871
    2 北京大学前沿交叉学科研究院,北京 100871
  • 收稿日期:2017-12-06 发布日期:2018-04-09
  • 通讯作者: 张锦,刘忠范 E-mail:jinzhang@pku.edu.cn;zfliu@pku.edu.cn
  • 作者简介:张锦,北京大学教授,国家杰出青年基金获得者,教育部长江学者特聘教授,英国皇家化学学会会士,中组部“万人计划”创新领军人才入选者。主要从事纳米碳材料的控制制备及其拉曼光谱学研究|刘忠范,北京大学博雅讲席教授,中国科学院院士,发展中国家科学院院士,中组部首批万人计划杰出人才,教育部首批长江学者,英国物理学会会士,英国皇家化学会会士,中国微米纳米技术学会会士。主要从事纳米碳材料、二维原子晶体材料和纳米化学研究
  • 基金资助:
    国家自然科学基金(21233001);国家自然科学基金(51432002);国家重点研发计划(2016YFA0200101);国家重点研发计划(2016YFA0200104)

Advanced Progress in the Synthesis of Graphdiyne

Jingyuan ZHOU1,2,Jin ZHANG1,*(),Zhongfan LIU1,*()   

  1. 1 Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
    2 Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, P. R. China
  • Received:2017-12-06 Published:2018-04-09
  • Contact: Jin ZHANG,Zhongfan LIU E-mail:jinzhang@pku.edu.cn;zfliu@pku.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21233001);the National Natural Science Foundation of China(51432002);the National Key R&D Program of Chinac(2016YFA0200101);the National Key R&D Program of China(2016YFA0200104)

摘要:

石墨炔是一种新型碳的同素异形体,是由spsp2两种杂化形式的碳原子组成的二维层状材料。其中,石墨双炔是石墨炔家族中重要的一员,其独特的纳米级孔隙、二维层状共轭骨架结构及半导体性质等特性,使之在电化学、光催化、非线性光学、电子学等诸多领域优势显著,因此,发展石墨双炔的制备方法有着重要的意义。本文将首先介绍石墨双炔的结构,随后主要介绍石墨双炔合成方法的研究进展,包括有机全合成、表面在位化学反应和溶液相聚合反应等几个方面,其中溶液相聚合的方法取得了较为突出的进展。在本文的最后,主要探讨了石墨双炔合成方法中的挑战与机遇,并对合成方法的未来进行了展望。

关键词: 石墨双炔, 全合成, 表面在位化学, 溶液聚合, 形貌控制

Abstract:

Graphyne is a rapidly rising star material of carbon allotropes containing only sp and sp2 hybridized carbon atoms forming extended two-dimensional layers. In particular, graphdiyne is an important member of graphyne family. With unique nanotopological pores, two-dimensional layered conjugated frameworks, and excellent semiconducting and optical properties, graphdiyne has displayed distinct superiorities in the fields of energy storage, electrocatalysis, photocatalysis, nonlinear optics, electronics, gas separation, etc. Therefore, the synthesis of high-quality graphdiyne is highly required to fulfill its potentially extraordinary applications. Furthermore, the development of a standardized and systematic set of characterization procedures is an urgent need, and would be based on intrinsic samples. However, there are still obvious barriers to synthesizing this new-born carbon allotrope that can be mainly considered as follows. The selection and stability of monomers is essential for synthesis. The synthesis process in solution also suffers from an annoying problem of the relatively free rotation possible about the alkyne-aryl single bonds, which leads to the coexistence and rapid equilibration of coplanar and twisted structures. Furthermore, the limited reaction conversion and side reactions also lead to a confusion of configuration.

In this review, we primarily focus on the state-of-the-art progress of the synthetic strategies for graphdiyne. First, we give a brief introduction about the structure of graphyne and graphdiyne. We subsequently discuss in detail the recent developments in synthetic methods that can mainly be divided into three aspects: total organic synthesis, on-surface covalent reaction, and polymerization in a solution phase. In particular, much progress in solution polymerization has been achieved since in-situ polymerization on Cu surface was reported in 2010. Liquid/liquid interface, gas/liquid interface, and surface template were also employed for confined reaction, and contribute significantly to the synthesis of a graphdiyne film. Through such strategies, graphdiyne with a well-defined structure and diverse morphologies could be achieved successfully. Finally, the opportunities and challenges for the synthesis of graphdiyne are prospected. A more rational design is desired in terms of monomer modification and reaction regulation.

Key words: Graphdiyne, Total synthesis, On-surface covalent reaction, Polymerization in solution phase, Morphology control

MSC2000: 

  • O641