石墨炔衍生物的合成与应用

Synthesis and Applications of Graphdiyne Derivatives

石墨炔是由sp和sp2两种杂化碳构成的新型二维碳同素异形体。基于石墨炔化学合成规律和独特优势,利用其他芳炔前体替代六乙炔基苯,可以获得结构特异、尺寸可控的石墨炔基衍生物,而局域碳骨架的改变可以实现石墨炔衍生物性能调控,包括电导率、带隙、迁移率、空腔尺寸和电荷分离等。这类具有优良半导体性能的石墨炔基衍生物可以广泛应用于电化学储能、电催化、光电转换器件、非线性光学等诸多领域。本文主要综述了近年来石墨炔衍生物的优化设计、结构表征和光电性能,并对其代表性应用进行了总结和展望。

Graphdiyne(GDY)bearing sp-and sp~2-hybridized carbon networks,which is usually artificially synthesized via the in situ homocoupling reaction of hexaethylbenzene on copper foil,is an emerging two-dimensional(2D)carbon allotrope.During preparation,well-defined GDY structures including nanowires,nanowalls,and nanotubes are obtained.Such materials with varying morphologies have been shown to possess promising electronic,chemical,magnetic,and mechanical properties,rendering them applicable in various domains including energy storage,catalysis,and field emission.In addition,replacing hexaethylbenzene with other aryne derivatives under similar synthesis conditions has resulted in the generation of various GDY derivatives.Thus,a series of GDY derivatives with specific structures and controllable sizes have been readily prepared in recent years.Aryne precursors typically contain polycyclic aromatic carbocycles,heteroarenes(e.g.,N,B,S,P,Si,Ge,and Ga).The intrinsic GDY has also been doped with metal elements(e.g.,Hg,Ag,and Au).Chemical synthetic strategies such as Glaser coupling,Glaser-Hay coupling,and Eglinton coupling are also described.The structural design of various precursors has been effectively tailored to the constitution of the local carbon framework of GDY-based materials,which has enabled the realization of the targeted performance in terms of the electronic conductivity,band gap,mobility,cavity size,and charge separation.For example,three-dimensional(3D)carbyne riched nanospheres formed by the extended coupling of spatially rigid-structured spirobifluorene have provided abundant storage spaces and convenient multi-directional transmission paths for metal ions.The use of hetero-doped GDY has enabled the effective optimization of the thermal stability and mechanical,electronic,and optical properties.Metal element-based GDY,referred to as“metalated”GDY,could serve as efficient bifunctional catalysts possessing favorable transport properties to facilitate the diffusion of small molecules.By extension,such materials can be used more broadly in electrochemical energy storage,electrocatalysis,optoelectronics,nonlinear optics,oil-water separation,and numerous other fields.In this review,we have summarized the design,synthesis,and structural characterization of various GDY derivatives through the recently demonstrated substitution of various aryne precursors for hexaethylbenzene,while examining the functional relationships between the desired optoelectronic properties of GDY derivatives and their defined nanostructures and morphologies.In addition,important prospective applications of GDY derivatives have been described.These observations may motivate the construction of novel polar and electron-rich GDY derivatives with unique properties that can address practical challenges encountered in various devices.