Tuning the Properties of Graphdiyne by Introducing Electron‐Withdrawing/Donating Groups

Abstract

The properties of graphdiyne (GDY), such as energy gap, morphology, and affinity to alkali metals, can be adjusted by including electron‐withdrawing/donating groups. The push–pull electron ability and size differences of groups play a key role on the partial property adjusting of GDY derivatives MeGDY, HGDY, and CNGDY. Cyano groups (electron‐withdrawing) and methyl groups (electron‐donating) decrease the band gap and increase the conductivity of the GDY network. The cyano and methyl groups affects the aggregation of GDY, providing a higher number of micropores and specific surface area. These groups also endow the original GDY additional advantages: the stronger electronegativity of cyano groups increase the affinity of GDY frameworks to lithium atoms, and the larger atomic volume of methyl groups increases the interlayer distance and provides more storage space and diffusion tunnels.

Porous 3D Silicon‐Diamondyne Blooms Excellent Storage and Diffusion Properties for Li, Na, and K Ions

“…The high specific capacities in LIBs are highly prominent, and better than that of numerous other materials such as hard carbon, heteroatom‐doped graphene, and so on (Figure 4g; Table S2, Supporting Information). [ 35–40 ]…”

“…The high specific capacities in LIBs are highly prominent, and better than that of numerous other materials such as hard carbon, heteroatomdoped graphene, and so on (Figure 4g; Table S2, Supporting Information). [35][36][37][38][39][40] The 3D diamond-like structure of Si-DY can offer numerous sites and channels to satisfy the storage and diffusion of alkali metal ions (Figure 5a). Notably, the Si-DY based electrodes can also be well utilized in NIBs and KIBs.…”

Selective CO2‐to‐CH4 Photoconversion in Aqueous Solutions Catalyzed by Atomically Dispersed Copper Sites Anchored on Ultrathin Graphdiyne Oxide Nanosheets

“…The peak at 128.7 ppm can be assigned to the carbon atoms in the benzene ring, whereas the peaks at ≈77.7 and 87.5 ppm can be attributed to the carbon atoms in the diacetylene moiety. [ 35 ] The newly appeared peaks at 167–194 and 12–62 ppm in the GDYO nanosheets were the characteristic peaks of carbon atoms in the carboxyl and hydroxyl groups. X‐ray photoelectron spectroscopy (XPS) of the GDYO nanosheets revealed that the contents of CO and CO increased (Figure S6 and S7, Supporting Information), implying that oxygen‐containing groups are formed after oxidation.…”

Porphyrin and phthalocyanine: from molecular materials to aggregates

“…二氯苯(0.9 mL)、丁醇(0.8 mL) 和乙酸水溶液(6 M, 0.213 mL)中合成的，溶剂比是精 确 调节 的 [82] 。 模板 法 具有 合 成制 备过 程 简单 的 优 点，但所制备的卟啉酞菁薄膜难以转移且缺陷密度 高。 Zhao 等人以铜箔为模板，通过 Glaser-Hay 偶联 反应制备了基于钴卟啉结构单元的石墨炔材料(图 4a) [79,83,84] 。该材料富含 sp 杂化形式碳,具有本征的 活性催化位点和高的结晶性 [85][86][87][88][89][90][91][92][93][94] 。 此外，卟啉基团 的引入扩展了二维多孔结构，为小分子的扩散提供 有效的传输通道。 Zhang 等人利用碳纳米管(CNTs) 作为模板与卟啉共轭骨架杂化，在没有其他支撑的 情 况下 通 过简 单 的过 滤制 备 了有 机共 价 薄 膜 [95] 。…”