| 自由基修饰共轭微孔聚合物应用于5-羟甲基糠醛选择性氧化 |
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| 引用本文： | 毛会玲,王晨,薛云,晏秘,申妍铭,程琥,庄金亮.自由基修饰共轭微孔聚合物应用于5-羟甲基糠醛选择性氧化[J].分子催化,2019,33(3):245-252. |
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| 作者姓名： | 毛会玲 王晨 薛云 晏秘 申妍铭 程琥 庄金亮 |
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| 作者单位： | 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,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,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,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,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,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,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 |
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| 基金项目： | 国家自然科学基金（21861013）；贵州省科技厅重点基金项目（黔科合基础[2016]1413）；贵州省科技计划项目（黔科合平台人才[2018]5769号）；贵州省教育厅基金项目（黔教合KY字[2017]063） |
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| 摘 要： | 采用有机单体侧链嫁接2，2，6，6-四甲基哌啶氧自由基（2，2，6，6-tetramethylpiperidineoxyl，TEMPO）的策略将TEMPO嫁接到2，5-二溴苯甲酸侧链，并与四（4-乙炔基苯）甲烷通过Sonogashira偶联反应，构筑TEMPO自由基功能化共轭微孔聚合物CMP-4-TEMPO.利用核磁共振谱（NMR）、扫描电子显微镜（SEM）、粉末X-射线衍射（XRD）红外吸收光谱（FT-IR）和电子顺磁共振谱（EPR）等技术研究了所合成单体及CMP形貌和结构.催化性能测试结果表明CMP-4-TEMPO可将5-羟甲基糠醛（5-HMF）高效、高选择性氧化成高附加值2，5-二甲酰基呋喃（2，5-DFF）.CMP-4-TEMPO催化剂循环利用10次仍保持较高的转化率.提出了CMP-4-TEMPO中形成TEMPO氧正离子是实现5-HMF转化为2，5-DEF的催化氧化机理.CMP-4-TEMPO有望成为各种醇高效、高选择性氧化以及可循环利用的异相催化剂.
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| 关 键 词： | 多孔材料 共轭微孔聚合物 醇氧化 TEMPO自由基 5-羟甲基糠醛 |
| 收稿时间： | 2019/4/22 0:00:00 |
| 修稿时间： | 2019/5/23 0:00:00 |
Synthesis of Radical Decorated Conjugated Microporous Polymers for Selective Oxidation of 5-Hydroxymethylfurfural |
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| MAO Hui-ling,WANG Chen,XUE Yun,YAN Mi,SHEN Yan-ming,CHENG Hu and ZHUANG Jin-liang.Synthesis of Radical Decorated Conjugated Microporous Polymers for Selective Oxidation of 5-Hydroxymethylfurfural[J].Journal of Molecular Catalysis (China),2019,33(3):245-252. |
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| Authors: | MAO Hui-ling WANG Chen XUE Yun YAN Mi SHEN Yan-ming CHENG Hu and ZHUANG Jin-liang |
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| Institution: | Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China,Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China,Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China,Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China,Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China,Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China and Guizhou Normal University, School of Chemistry and Materials, Key Laboratory of Functional Materials and Chemistry of Guizhou Province, Guiyang 550001, China |
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| Abstract: | By appending 2,2,6,6-tetramethylpiperidineoxyl (TEMPO) radicals into 2,5-dibromobenoic acid, and further reacted with tetrakis(4-ethynylphenyl)methane, resulting the formation of TEMPO radical decorated conjugated microporous polymers (CMPs), named CMP-4-TEMPO. The chemical composition and structural information of the corresponding monomer and final polymers are characterized by NMR, SEM, XRD, and EPR spectra. CMP-4-TEMPO is able to catalyze to conversion of 5-Hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (2,5-DEF) with high conversion and selective in ten runs. A heterogeneous catalytic mechanism with regard to the formation of TEMPO oxoammonium is proposed. CMP-4-TEMPO is expected to be highly active and reusable heterogeneous catalyst for a broad range of alcohols. |
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| Keywords: | porous materials conjugated microporous polymers alcohol oxidation TEMPO radicals 5-Hydroxymethylfurfural |
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