欢迎访问过程工程学报, 今天是

过程工程学报 ›› 2020, Vol. 20 ›› Issue (5): 576-582.DOI: 10.12034/j.issn.1009-606X.219264

• 过程与工艺 • 上一篇    下一篇

有机单体空间构型对共轭微孔聚合物催化性能的影响

王 晨1， 毛会玲1， 程 琥1， 杜 嬛2*， 连小兵3*， 庄金亮1*   

  1. 1. 贵州师范大学化学与材料科学学院，贵州省功能材料化学重点实验室，贵州 贵阳 550001 2. 中国科学院过程工程研究所中国科学院绿色过程与工程重点实验室，北京 100190 3. 泉州师范学院化学工程系，福建 泉州 362000
  • 收稿日期:2019-08-03 修回日期:2019-10-08 出版日期:2020-05-22 发布日期:2020-05-18
  • 通讯作者: 庄金亮 jlzhuang@xmu.edu.cn
  • 基金资助:
    Magnéli相亚氧化钛的可控制备、微结构与性能基础研究;贵州省科技厅重点基金项目;贵州省科技计划项目;贵州省教育厅拔尖人才支持计划

Geometric effects of organic monomers on catalytic activity of conjugated microporous polymers

Chen WANG1, Huiling MAO1, Hu CHENG1, Xuan DU2*, Xiaobing LIAN3*, Jinliang ZHUANG1*   

  1. 1. School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guizhou Normal University, Guiyang, Guizhou 550001, China 2. Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 3. Department of Chemical Engineering, Quanzhou Normal University, Quanzhou, Fujian 362000, China
  • Received:2019-08-03 Revised:2019-10-08 Online:2020-05-22 Published:2020-05-18

PDF

摘要： 以TEMPO自由基功能化2,5-二溴-N-(2,2,6,6-四甲基哌啶)苯甲酰胺为有机单体，与平面三角构型(D3h对称性)的1,3,5-三乙炔苯和四面体构型(Td对称性)的四(4-乙炔基苯)甲烷分别通过Sonogashira-Hagihara偶联反应获得CMP-3-TEMPO和CMP-4-TEMPO。扫描电子显微镜照片(SEM)显示两种TEMPO功能化CMPs形貌上有显著差异，CMP-3-TEMPO为不规则的棒状和块状微米聚合物，CMP-4-TEMPO为尺寸较均一的微米球聚合物。固态电子顺磁共振谱(EPR)证明了CMP-3-TEMPO和CMP-4-TEMPO均含有TEMPO自由基。两种CMPs催化剂均可将5-羟甲基糠醛(5-HMF)选择性催化氧化成2,5-二甲酰基呋喃(2,5-DFF)，但在催化效率和循环利用率方面存在显著差异。有机配体的空间立体构型对CMPs的形貌和催化性能有重要影响，选择具有空间立体构型的有机单体，所合成的CMP-4-TEMPO具有更稳定的结构，催化循环性能更优异。

关键词: TEMPO自由基, Sonogashira-Hagihara偶联反应, 共轭微孔聚合物, 异相催化, 5-羟甲基呋喃

Abstract: Conjugated microporous polymers (CMPs) exhibit extended p-conjugated frameworks, and are typically built from aromatic organic building blocks. CMPs decorated with functional groups are of particular interest in catalysis because these functional groups can serve as potential catalytic sites. Despite great efforts have been devoted to the synthesis of functionalized CMPs, there is still much room for the development of functionalized CMPs with stable and accessible catalytic sites. Two TEMPO (2,2,6,6-tetramethylpiperidinyloxy) decorated conjugated microporous polymers (CMPs), named CMP-3-TEMPO and CMP-4-TEMPO by Sonogashira-Hagihara coupling reaction were synthesized in this work. A TEMPO radical appended 2,5-dibromo-N-(2,2,6,6-tetramethylpiperidinyloxy)benzamide serving as a build block and reacted with 1,3,5-triethynylbenzene (trigonal planar, D3h symmetry) and tetrakis(4-ethynylphenyl)methane (tetrahedron geometry, Td symmetry), to form CMP-3-TEMPO and CMP-4-TEMPO, respectively. The as-synthesized CMP-3-TEMPO and CMP-4-TEMPO were characterized by SEM, PXRD, FT-IR, and EPR spectroscopy. Moreover, the catalytic activity of CMP-3-TEMPO and CMP-4-TEMPO toward the selective oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (2,5-DEF) were investigated. Importantly, the results indicated that the geometry of organic monomers played a key factor for the morphology and catalytic activity of CMPs. CMP-3-TEMPO consisted of micro-chunks and micro-rods, while CMP-4-TEMPO exhibited microspheres with uniform sites in the range of 2~3 ?m. Catalytic performances indicated that both TEMPO-CMPs enabled the selective oxidation of alcohols to their corresponding aldehydes with high efficiency. However, the stability and reusability of CMP-4-TEMPO was much better than CMP-3-TEMPO, which can be attributed to specific geometry of the corresponding organic monomers. It is anticipated that our findings could provide useful information for the design and synthesis of functionalized CMPs.

Key words: TEMPO radicals, Sonogashira-Hagihara coupling, conjugated microporous polymers, heterocatalysis, 5-Hydroxymethylfurfural