TEMPO功能化锆基MOFs的合成及醇催化氧化性能  

Synthesis and alcohol catalytic properties of TEMPO functionalized Zr-based MOFs

作　　者：庄金亮 刘湘粤 杜嬛[3] ZHUANG Jin-liang;LIU Xiang-yue;DU Xuan(Key Laboratory of Functional Materials and Chemistry of Guizhou Province,School of Chemistry and Materials,Guizhou Normal University,Guiyang 550001,China;College of Chemistry,Fuzhou University,Fuzhou 350108,China;Key Laboratory of Green Process and Engineering,CAS,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[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,贵阳550001 [2]福州大学化学学院,福州350108 [3]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

出　　处：《材料工程》2020年第10期169-175,共7页Journal of Materials Engineering

基　　金：国家自然科学基金(21861013);贵州省科技厅基金项目(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);贵州省教育厅普通高等学校科技拔尖人才支持计划(黔教合KY字[2017]063)。

摘　　要：采用有机骨架分子侧链嫁接有机小分子催化基团策略,合成出TEMPO自由基功能化的三联苯二羧酸有机配体H2tpdc-TEMPO。利用醋酸为调节剂,H2tpdc-TEMPO与ZrOCl2溶剂热反应可获得TEMPO功能化的UiO-68-TEMPO纳米晶体。UiO-68-TEMPO为单分散八面体形貌纳米晶体,尺寸在800-1200 nm之间,BET比表面积高达1320 m^2/g,固态电子顺磁共振谱(EPR)谱证明UiO-68-TEMPO骨架含有大量TEMPO自由基。UiO-68-TEMPO纳米晶体可将各种芳香一级醇、二级醇和杂原子醇高效、高选择性氧化成相应的醇或者酮。UiO-68-TEMPO纳米晶体可重复使用4次仍保持75%以上的催化效率。最后,提出了UiO-68-TEMPO催化氧化苯甲醇的机理,即TBN作为助催化剂产生NO2/NO氧化还原对,实现了O2将TEMPO自由基氧化为鎓氧正离子,最终实现苯甲醇氧化成苯甲醛。A strategy based on grafting organocatalytic units as side-chain on the organic linkers,a TEMPO radical decorated terphenyl-dicarboxylic acid linker was synthesized.By employing acetic acid as modulator,TEMPO radical decorated UiO-68-TEMPO nanocrystals were synthesized by using H2tpdc-TEMPO as organic linker and ZrOCl2 as metal source under solvothermal conditions.UiO-68-TEMPO are monodispersed nanocrystals with side in the range of 800-1200 nm,with high BET areas(up to 1320 m^2/g),and contain a large number of TEMPO radicals as evidenced by solid-state EPR spectrum.UiO-68-TEMPO nanocrystals enable selective oxidation of a broad range of alcohols,including primary aromatic alcohols,secondary aromatic alcohols,and heterogeneous atomic alcohols,with high efficiency and selectivity.The catalytic activity of UiO-68-TEMPO nanocrystals remains 75% after catalysis for four cycles.Finally,a plausible catalytic mechanism for the oxidation of benzyl alcohol by UiO-68-TEMPO was proposed,that is the TBN co-catalyst produces NO2/NO redox mediator,which enables the oxidation of TEMPO radicals to oxoammonium cations by O2,and finally oxidize benzyl alcohol to benzaldehyde.

关 键 词：多孔材料 锆基金属-有机骨架化合物 有机小分子催化剂 自由基 醇氧化 

分 类 号：O611.4[理学—无机化学] O643.322[理学—化学]