基于正四面体构筑单元的多孔芳香骨架材料  

Porous aromatic frameworks derived from tetrahedral units

作　　者：景晓飞[1] 朱广山[1] Xiaofei Jing;Guangshan Zhu(Key Laboratory of Polyoxometalate Science of Ministry of Education,Department of Chemistry,Northeast Normal University,Changchun 130024,China)

机构地区：[1]东北师范大学化学学院多酸科学教育部重点实验室,长春130024

出　　处：《科学通报》2018年第22期2215-2228,共14页Chinese Science Bulletin

基　　金：国家重点基础研究发展计划(2014CB931804);国家自然科学基金(21531003;21503038;91622106)资助

摘　　要：多孔芳香骨架(porous aromatic frameworks,PAFs)材料作为一类重要的多孔材料,近十年取得了很大的研究进展.这类材料具有超高的比表面积、轻的骨架密度、灵活的骨架可修饰性以及高的热化学稳定性,被广泛地应用于气体吸附、分离、催化、传感等方面.拓扑化学理论的引入使得PAFs材料的合成更具有目标性,可以实现PAFs材料的定向设计合成.具有高度对称性的正四面体基元是构筑高稳定性PAFs材料的理想单元,可用于合成具有金刚石结构的高比表面多孔材料.本文从2009年第1例PAFs材料、PAF-1的设计思想与定向合成出发,分别讲述了PAFs材料的结构设计、合成策略、性质应用,总结了基于正四面体基元的PAFs材料的研究进展,以期为合成高稳定性高比表面积的多孔材料提供一些思路.Porous aromatic frameworks（PAFs）,an important class of porous materials,have gained worldwide attentions and been greatly developed since the first PAF material PAF-1 was successfully designed and synthesized in 2009.More than 100 PAF materials with specific functionalities were synthesized and reported in the last decade.The high surface areas,light skeleton densities and high thermal and chemical stabilities make PAF materials good candidates in various applications,such as gas sorption and separation,catalysis,sensor and host-guest chemistry.The design of PAF-1 came from the structure of diamond,the most stable substance exiting in the nature at present.The carbon atoms in diamond are covalently bonded with four adjacent carbon atoms by sp3 hybridization to form tetrahedral units.This special structure makes diamond the hardest material.However,the short length of C–C bond results in a compact structure of diamond.Conceptually,if the C–C bonds were replaced with rigid linear units,the resulting material should not only retain the diamond structure but also present increasing internal surface area.By employing Ullmann coupling reaction of tetrakis（4-bromophenyl）methane,PAF-1 with ultrahigh surface area as well as high thermal and chemical stability was synthesized.The structural information of PAF-1 was obtained by various characterizations,which is consistent with P2 model structure simulated from diamond topology.Thus,tetrahedral building units are good candidates to construct PAFs with high surface area and high stabilities.Reticular chemistry was introduced into the design of porous materials in the end of 20 th century,and has been well developed and employed with the concept of topology.Via the bottom-up and top-down ways,PAF materials derived from tetrahedral units may possess diamond-like structure thus they would exhibit high thermal stabilities.By adjusting the length of linkages between tetrahedral units,PAFs with tunable pore sizes can be targeted synthesized,which might even extend to m

关 键 词：多孔芳香骨架 可控合成 拓扑 吸附 分离 催化 

分 类 号：TB383.4[一般工业技术—材料科学与工程]