Page 131 - 《精细化工》2020年第5期

第 5 期 毛会玲，等: TEMPO 功能化共轭微孔聚合物作为高效醇催化氧化剂 ·981·

离子具强氧化性，快速将芳香醇氧化成对应的醛或 [2] GUO Z, LIU B, ZHANG Q H, et al. Recent advances in
heterogeneous selective oxidation catalysis for sustainable
酮。NO 2 可以通过终端氧化剂氧气将 NO 氧化实现 chemistry[J]. Chemical Society Reviews 2014, 43(10): 3480-3524.
[3] DEBLASE C, DICHTEL W. Moving beyond boron: The emergence
再生。 of new linkage chemistries in covalent organic frameworks[J].
Macromolecules, 2016, 49(15)：5297-5305.
[4] LIN G Q, DING H M, YUNA D Q, et al. A pyrene-based, fluorescent
three-dimensional covalent organic framework[J]. Journal of the
American Chemical Society, 2016, 138(10): 3302-3305.
[5] CHEN L, YANG Y, GUO Z Q, et al. Highly efficient activation of
molecular oxygen with nanoporous metalloporphyrin frameworks in
heterogeneous systems[J]. Advanced Materials, 2011, 23(28): 3149-
3154.
[6] KUHN P, ANTONIETTI M, THOMAS A. Porous, covalent
triazine-based frameworks prepared by lonothermal synthesis[J].
Angewandte Chemie International Edition, 2008, 47(18): 3450-3453.
[7] ALSBAIEE A, SMITH B, XIAO L, et al. Rapid removal of organic
micropollutants from water by a porous β-cyclodextrin polymer[J].
Nature, 2015, 529(7585): 190-194.
[8] DAS G, BISWAL B, KANDAMBETH S, et al. Chemical sensing in
two dimensional porous covalent organic nanosheets[J]. Chemical
Science, 2015, 6(7): 3931-3939.
[9] CHEN L, HONSHO Y, SEKI S, et al. Light-harvesting conjugated
microporous polymers: Rapid and highly efficient flow of light
energy with a porous polyphenylene framework as antenna[J].
Journal of the American Chemical Society, 2010, 132(19):
6742-6748.
[10] JIANG J, SU F, TREWIN A, et al. Conjugated microporous poly
(aryleneethynylene) networks[J]. Angewandte Chemie International
Edition, 2010, 119(45): 8728-8732.
[11] CHANG Sheng (常盛), YANG Shuzhen (杨述祯), YUE Huijuan (岳
慧娟), et al. Progress of application of nitrogen-oxygen radical
TEMPO in synthetic chemistry[J]. Chemical Reagents (化学试剂),
2019, 41(1): 28-34.
[12] LIU M X, ZHOU B L, ZHOU L, et al. Nitroxyl radical based
conjugated microporous polymers as heterogeneous catalysts for
selective aerobic alcohol oxidation[J]. Journal of Materials Chemistry
A, 2018, 6(21): 9860-9865.

[13] YANG Guanyu (杨贯羽), GUO Yanchun (郭彦春), WU Guanghui
图 5 CMP-4-(TEMPO) 2 催化氧化醇反应机理 (武光辉), et al. Nitrogen-oxygen free radical TEMPO: A highly
Fig. 5 Reaction mechanism of catalytic oxidation of efficient organic small molecule catalyst for the selective oxidation
of alcohols[J]. Progress in Chemical (化学进展), 2007, 19(11):
alcohol by CMP-4-(TEMPO) 2 1727-1735.
[14] HUANGFU Y , SUN Q, PAN S X, et al. Porous polymerized
3 结论 organocatalysts rationally synthesized from the corresponding vinyl-
functionalized monomers as efficient heterogeneous catalysts[J].
ACS Catalysis, 2015, 5(3): 1556-1559.
（1）采用有机骨架中嵌入催化活性位点策略， [15] MAO Huiling (毛会玲), WANG Chen (王晨), XUE Yun (薛云), et
al. Radical modified conjugated microporous polymers were applied
合成双 TEMPO 功能化有机单体 Br 2 -Ph-(TEMPO) 2 。 to selective oxidation of 5-HMF[J]. Journal of Molecular Catalysis
(分子催化), 2019, 33(3): 245-252.
将该有机单体与四面体构型的四（4-乙炔基苯）甲 [16] KANG N, PARK J H, CHOI J, et al. Nanoparticulate iron oxide
烷通过 Sonogashira 偶联反应合成出高密度 TEMPO tubes from microporous organic nanotubes as stable anode materials
for lithium ion batteries[J]. Angewandte Chemie International Edition,
自由基功能化共轭微孔聚合物 CMP-4-(TEMPO) 2 。 2012, 51 (27): 6626-6630.
[17] MU P, BAI W, ZHANG Z, et al. Robust aerogels based on conjugated
（2）CMP-4-(TEMPO) 2 由 1~2 μm 的微球和中空 microporous polymer nanotubes with exceptional mechanical
2
纳米管组成，具有较高的比表面积（486 m /g），含 strength for efficient solar steam generation[J]. Journal of Materials
Chemistry, 2018, 6(37): 18183-18190.
有微孔、介孔以及大孔复合孔，孔道含有丰富的 [18] VEERAKUMAR P, THANASEKARAN P, LU K, et al.
Computational studies of versatile heterogeneous palladium-catalyzed
TEMPO 自由基官能团。 suzuki, heck and sonogashira coupling reactions computational
（3）CMP-4-(TEMPO) 2 具有高密度 TEMPO 自 studies of versatile heterogeneous palladium-catalyzed suzuki, heck
and sonogashira coupling reactions[J]. ACS Sustainable Chemistry &
由基催化活性位点，可以将 5-HMF 以及各种苄醇和 Engineering, 2017, 5(10): 8475-8490.
[19] TEBBEN l, STUDER A. Nitroxides: Applications in synthesis and in
含 O、N、S 杂原子醇高效、高选择性地氧化成相应 polymer chemistry[J]. Angewandte Chemie International Edition
的醛。但是，CMP-4-(TEMPO) 2 循环性能较差，催 2011, 50 (22): 5034-5068.
[20] CHUNTANAPUM A, MATSUMURA Y. Formation of tarry material
化剂经 2 次循环利用后，对 5-HMF 的转化率降至 from 5-HMF in subcritical and supercritical water[J]. Industrial &
Engineering Chemistry Research, 2009, 48(22): 9837-9846.
50%左右。 [21] HE X J, SHEN Z L, MO W M, et al. TEMPO-tert-butyl nitrite: An
efficient catalytic system for aerobic oxidation of alcohols[J].
参考文献： Advanced Synthesis & Catalysis, 2009, 351 (1/2), 89-92.
[22] ZHUANG J L, LIU X Y, ZHANG Y, et al. Zr-metal-organic
[1] DHAKSHINAMOORTHY A, ALVARO M, GARCIA H. Aerobic frameworks featuring TEMPO radicals: Synergistic effect between
oxidation of benzylic alcohols catalyzed by metal organic frameworks TEMPO and hydrophilic Zr-node defects boosting aerobic oxidation of
assisted by TEMPO[J]. ACS Catalysis, 2011, 1(1): 48-53. alcohols[J]. ACS Appl Mater Interfaces, 2019, 11(3): 3034-3043.