一种经济环保地合成共价三嗪骨架的方法

doi:10.1016/S1872-2067(17)62771-2

催化学报 ›› 2017, Vol. 38 ›› Issue (3): 583-588.DOI: 10.1016/S1872-2067(17)62771-2

一种经济环保地合成共价三嗪骨架的方法

张玲^a,b, 刘学^b, 杨瑞霞^b, 黄年玉^a, 邓伟侨^b

a 三峡大学生物与制药学院湖北省天然产物研究与开发重点实验室, 湖北宜昌 443002;
b 中国科学院大连化学物理研究所分子反应动力学国家重点实验室, 辽宁大连 116023

收稿日期:2016-11-30 修回日期:2016-12-25 出版日期:2017-03-18 发布日期:2017-03-22
通讯作者: Wei-Qiao Deng
基金资助:
国家自然科学基金（21373202，21525315）.

Environmentally benign and economic synthesis of covalent triazine-based frameworks

Ling Zhang^a,b, Xue Liu^b, Rui-Xia Yang^b, Nian-Yu Huang^a, Wei-Qiao Deng^b

a Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, Hubei, China;
b State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2016-11-30 Revised:2016-12-25 Online:2017-03-18 Published:2017-03-22
Supported by:
This work was supported by the National Natural Science Foundation of China (21373202, 21525315).

摘要/Abstract

摘要：

近年来，共价有机骨架材料（COFs）由于具有非常好的热化学稳定性、高的孔隙率和比表面积以及可控的表面功能化，因而在气体存储、分离以及催化等领域拥有潜在的应用价值.共价三嗪骨架材料（CTFs）是一种特殊的新型共价有机骨架材料，它是采用廉价的芳香腈为原料，在熔融的ZnCl₂作用下，通过离子热聚合反应制成.本文选择不同的二溴代芳烃化合物，在无毒的K₄[Fe（CN）₆]·3H₂O和微量Pd（OAc）₂的作用下，通过氰基化反应合成相应的二氰基单体，二氰基单体再聚合获得共价三嗪骨架.
溴代芳烃氰基化转化为芳香氰基化合物的反应中，我们避免使用有毒的金属氰化物，用廉价无毒的K₄[Fe（CN）₆]·3H₂O来代替，并不作任何处理直接使用.同时，以Pd（OAc）₂为催化剂，不采用任何昂贵的配体，避免增加实验成本.我们选择1，4-二溴苯为底物，探索最佳的反应条件，包括催化剂用量、溶剂以及反应时间，以得到最高的转化率和产率，整个反应过程用GC-MS监测.然后，扩展底物有芳香杂环化合物2，6-二溴吡啶和多环芳烃1，4-二溴萘.上述三种溴代芳烃氰基化后分别得到对应的二氰基单体1，4-二氰基苯（DCB），2，6-二氰基吡啶（DCP）和1，4-二氰基萘（DCN）.二氰基单体再聚合获得共价三嗪骨架，依次为CTF_DCB，CTF_DCP和CTF_DCN.
对三种CTF的氮气吸附性能进行了测试，测得三种聚合物CTF_DCB，CTF_DCP和CTF_DCN的BET比表面积依次为2404，1650和780 m²/g.其中，比表面积最大的CTF_DCB拥有最大的微孔体积0.85 m³/g，比表面积最小的CTF_DCN的微孔体积也有0.52 m³/g.三种聚合物的孔径分别为0.57，0.45和0.54 nm.三种材料的CO₂吸附性能测试结果表明，拥有最高N₂吸附量的CTF_DCB在25和0℃下CO₂吸附量分别仅为148和99 mg/g，而N₂吸附量较小的CTF_DCP的CO₂吸附量反而高达225和154 mg/g，CTF_DCN为129和97 mg/g.这表明该类多孔材料的CO₂吸附性能不仅与孔体积和比表面积有关，也与材料中氮原子含量有很大关系.与其它CO₂吸附材料相比，这三种多孔材料的CO₂吸附处于一个较高水平.

关键词: 共价三嗪骨架, 芳基溴化物, 氰基化反应, 六氰合铁（II）酸钾, 醋酸钯

Abstract:

Covalent triazine-based frameworks (CTFs) are important microporous materials with a wide range of applications. Here, we demonstrate an environmentally benign and economic synthetic pathway to CTFs. The monomers used for CTFs, aromatic nitriles, were obtained by cyanation using nontoxic potassium hexacyanoferrate(II) in place of commonly used toxic cyanides. Then, the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride. A series of CTFs was synthesized, and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m²/g. Among the synthesized CTFs, CTF_DCP exhibited excellent CO₂ adsorption properties, with a CO₂ uptake of 225 mg/g at 0℃.

Key words: Covalent triazine-based framework, Aryl bromide, Cyanation, Potassium hexacyanoferrate(II), Palladium acetate

张玲, 刘学, 杨瑞霞, 黄年玉, 邓伟侨. 一种经济环保地合成共价三嗪骨架的方法[J]. 催化学报, 2017, 38(3): 583-588.

Ling Zhang, Xue Liu, Rui-Xia Yang, Nian-Yu Huang, Wei-Qiao Deng. Environmentally benign and economic synthesis of covalent triazine-based frameworks[J]. Chinese Journal of Catalysis, 2017, 38(3): 583-588.

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一种经济环保地合成共价三嗪骨架的方法

Environmentally benign and economic synthesis of covalent triazine-based frameworks

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