ZHAO Yasong , ZHANG Lijuan , QI Jian , JIN Quan , LIN Kaifeng , WANG Dan ,＊

1 School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, P. R. China.

2 State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190,P. R. China.

Abstract: As a new member of the carbon allotrope family,graphdiynes (GDs) consist of both sp- and sp2-hybridized carbon atoms, possessing unique π-conjugated carbon skeletons and expanded 18C-hexagonal pores in two dimensions. In contrast with the zero band gap graphene (GR), GD is a semiconductor with a direct band gap of 1.22 eV calculated according to the density functional theory (DFT) using the HSE06 method; this makes it a potential semiconductor material that can supplant silicon in the integrated circuit industry. Moreover, owing to the presence of diacetylenic linkages between its hexagonal carbon rings, GD shows electron-deficient properties, which lead to its electron-accepting tendency. Graphdiynes exhibit unusual semiconducting properties with excellent charge mobilities and electron transport properties that are associated with its distinct topological and electronic structures. Graphdiynes play the role of not only electron-acceptors that efficiently collect the electrons from other materials but also electron-donors that inject electrons into other systems, thus exhibiting excellent electron-transfer enhancement characteristics. The unique electron-transfer enhancement property of GDs inspired us to summarize the interactions between GDs and other materials including metal oxides, metal nano-particles, and organic molecules. In this review paper, we first introduce the TiO2/GD nanocomposite, because the linking of GDs and titania nanoparticles (P25) through the Ti―O―C bond sets an important precedent for exploring the electron-transfer behaviors involving GDs and the metal oxide. These results indicate that the GDs can act as acceptors of the photogenerated electrons in the TiO2/GD system, effectively suppressing charge recombination and resulting in excellent photocatalytic properties. Nevertheless, the GDs in CdSe quantum dots (QDs)/GD composites are able to collect photogenerated holes from the QDs and perform as promising hole-transfer materials in the photoelectrochemical cell for water splitting. As a result, the interactions between GDs and various metal compounds should be explored to deeply understand the electrontransfer properties of GDs. Furthermore, GDs can be also used as electron donors to reduce PdCl42− to Pd nanoparticles that can subsequently be used for the electroless deposition of highly dispersed Pd nanoparticles. Based on electrostatic potential surface analysis over the Pt2/GD, GDs can attract the electron cloud from the Pt nanoparticles and produce a positive polarization of the metal atom surface. However, due to its large π-conjugated system, GD can also collect and transfer electrons from the electrode under a bias voltage, making it a new type of electrocatalyst material, especially for single-atom catalysts. The interactions between GDs and metal particles/clusters/atoms have attracted the broad attention of the rapidly developing field of single-atom catalysis. Finally, research on the interactions between GDs and organic molecules, especially biomolecules, is still in its infancy and requires development. In summary, we overview the recent research progress on GD and its enhanced ability for electron transfer in this review paper, including metal oxides/GD,metal nano-particles/GD, polymers/GD, and organic molecules/GD, from both experimental and theoretical perspectives,and emphasize the interactions and electron-transfer enhancement properties. It is expected that this review can promote the development and applications of GD chemistry.

Key Words: Graphdiyne; GD-based composites; Electron-transfer enhancement; π-conjugated skeleton

1 引言

碳原子通过sp3、sp2和sp杂化态构造出了数量极大、性能迥异的碳材料家族1–5。碳原子可通过 sp3杂化态形成自然界天然存在的最坚硬的金刚石结构，可通过sp2杂化态形成零维笼状富勒烯结构6、一维碳纳米管结构7、二维石墨烯(GR)结构8,9，亦可通过sp2杂化态结合层间相互作用力形成三维软滑石墨结构，碳材料科学一直为化学学科贡献着自己的神奇成果1–5。

炔键由sp杂化态碳原子构成，其碳原子高度不饱和，具有直线型结构且无顺反异构。早在1987年，Baughman等10已经通过半经验的MNDO量子化学方法理论预测了石墨一炔(graphyne，GY)稳定存在的可能性，国际上一些著名课题组也开始了相关的实验合成探索。上世纪90年代，Haley等11,12就试图将炔键引入到二维碳材料中，以期获得性能优异的光、电、磁及催化材料。2008年，Haley13报道了以脱氢苯并轮烯为基础的石墨二炔微单元的合成策略，但是只得到了一些微区片段，并未实现真正意义上的石墨二炔亚单元的合成。直到2010年，中国科学院化学研究所李玉良课题组14从表面化学结合固态生长化学的新视角出发15，首次报道了在铜箔表面大面积合成石墨二炔(graphdiyne，GD)，开辟了人工化学合成碳同素异形体的先例。

王丹，中国科学院过程工程研究所研究员，于1994年获吉林大学化学专业学士学位，1997年获吉林大学硕士学位，2001年获日本国立山梨大学博士学位。2004年 2月入选中国科学院“百人计划”并加入中国科学院过程工程研究所任研究员。2013年获国家杰出青年科学基金，2014年当选英国皇家化学会会士，2014年入选科技部“中青年科技创新领军人才”。……