含磷多孔有机聚合物的合成及其在多相催化中的应用

doi:10.16085/j.issn.1000-6613.2020-1924

摘要/Abstract

摘要：

含磷多孔有机聚合物不仅具有发达的孔隙和表面结构，还具有很强的可调变性和可修饰性，在多相催化中有着广泛的应用前景。目前还没有概述含磷多孔有机聚合物的制备及其在多相催化中应用的综述，本文对该领域近十年来的研究进展进行了归纳和梳理。指出含磷多孔有机聚合物的合成方法发展十分迅速，包括偶联缩聚、锂盐参与的缩聚、Friedel-Crafts缩聚、溶剂热烯烃聚合、Scholl缩聚、酚醛聚合、醛胺缩合、聚吡喃盐的磷代以及多段式聚合等。基于其骨架中含有大量膦配体，含磷多孔有机聚合物能负载一系列金属化合物制成负载型金属纳米颗粒催化剂，甚至单原子或单位点金属催化剂。表明聚合物基催化剂中，膦配体不仅能诱导金属在聚合物中均匀分布，并且在调控金属的表面电子性质和位阻性质等方面发挥重要作用，进而对催化剂的活性和选择性产生影响。

关键词: 多孔有机聚合物, 膦配体, 催化剂, 多相催化

Abstract:

Phosphorus-containing porous organic polymers with a flexible porous structure, high surface area, and diversified modification potential show a promising prospect in heterogeneous catalysis. For the lack of review on the preparation of phosphorus-containing porous organic polymers and their applications in heterogeneous catalysis, herein, we retrospect their developments and advances in the past decade. Phosphorus-containing porous organic polymers have a great progress in preparation, including coupling polycondensation, organolithiation route, Friedel-Crafts polycondensation, solvothermal olefin polymerization, scholl polycondensation, phenolic polymerization, aldimine condensation, phosphating of poly-pyrylium salts, and multi-stage polymerization, etc. Due to the excellent coordination ability of phosphorus-containing porous organic polymers, metal nanoparticle or even metal single-atom (or single-site) catalysts can be prepared by loading these polymers with different metal species. In phosphorus-containing porous organic polymers based catalytic systems, phosphorus can not only induce the distribution of metal species but also modify their electronic and steric properties, thus they can regulate the activity and selectivity of catalysts.

Key words: porous organic polymers, phosphines, catalyst, heterogeneous catalysis

中图分类号:

吴淼江, 孙鹏, 李福伟. 含磷多孔有机聚合物的合成及其在多相催化中的应用[J]. 化工进展, 2021, 40(4): 1983-2004.

WU Miaojiang, SUN Peng, LI Fuwei. Synthesis of phosphorus-containing porous organic polymers and their applications in heterogeneous catalysis[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1983-2004.

图/表 28

参考文献 110

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单体组成^①	S/V(S_后/V_后)^②	孔径^③	金属	催化反应	参考文献
Heck偶联缩聚
a1/b1=1/1 a2/b1=1/1	318/0.239 684/0.342	0~2nm	钯	Suzuki-Miyaura偶联反应	[27]
a3/b2=1.0/1.1	554/0.959	0~10nm	钯	硝基芳烃、α,β-不饱和酮的加氢反应	[28]
Sonogashira-Hagihara偶联缩聚
a4/b3=1/1 a4/b4=1/1 a4/b5=0.75/1.0 a4/b6=0.75/1.0	391/0.56 407/0.36 474/1.00 509/0.88	0~5nm 0~5nm 0~5nm 0~5nm	钌铱	β-酮酯化合物的不对称氢化反应喹哪啶不对称氢化反应	[29]
Suzuki-Miyaura偶联缩聚
a5/b7=1/2	(354/—)	0~7nm	钯	Suzuki-Miyaura偶联反应	[30]
a6/b7=1.17/1.76	72.4/—	0~10nm	无	光催化析氢反应	[31]
Yamamoto偶联缩聚
a8	650/—(114/—)	0~6nm	钯无	Suzuki偶联反应环氧化物和CO₂生成环碳酸酯的反应	[32]
a5 a7	1284/1.11 1353/1.07	0~4nm 0~4nm	钯	Suzuki偶联反应	[33]

单体组成^①	S/V(S_后/V_后)^②	孔径^③	金属	催化反应	参考文献
Heck偶联缩聚
a1/b1=1/1 a2/b1=1/1	318/0.239 684/0.342	0~2nm	钯	Suzuki-Miyaura偶联反应	[27]
a3/b2=1.0/1.1	554/0.959	0~10nm	钯	硝基芳烃、α,β-不饱和酮的加氢反应	[28]
Sonogashira-Hagihara偶联缩聚
a4/b3=1/1 a4/b4=1/1 a4/b5=0.75/1.0 a4/b6=0.75/1.0	391/0.56 407/0.36 474/1.00 509/0.88	0~5nm 0~5nm 0~5nm 0~5nm	钌铱	β-酮酯化合物的不对称氢化反应喹哪啶不对称氢化反应	[29]
Suzuki-Miyaura偶联缩聚
a5/b7=1/2	(354/—)	0~7nm	钯	Suzuki-Miyaura偶联反应	[30]
a6/b7=1.17/1.76	72.4/—	0~10nm	无	光催化析氢反应	[31]
Yamamoto偶联缩聚
a8	650/—(114/—)	0~6nm	钯无	Suzuki偶联反应环氧化物和CO₂生成环碳酸酯的反应	[32]
a5 a7	1284/1.11 1353/1.07	0~4nm 0~4nm	钯	Suzuki偶联反应	[33]

单体组成^①	S/V(S_后/V_后)^②	孔径^③	金属	催化反应	参考文献
a9/b8=16.7/25	646/—	—	钯铑	环己酮与异丙醇的氢转移反应	[35]
a9/b8=13.0/20.0	135/0.04(58/0.009)	—	钯	1,3-丁二烯的调聚反应	[36]
a9/b8=12.7/20 a10/b8=9.75/20 a11/b8=7.15/20	150/— 33/— 42/—	—	钌	甲酸分解反应	[37]
a10/b9=1/1	469/0.475	0~180nm	钌	CO₂加氢合成N,N-二甲基甲酰胺的反应	[38]

单体组成^①	S/V(S_后/V_后)^②	孔径^③	金属	催化反应	参考文献
a9/b8=16.7/25	646/—	—	钯铑	环己酮与异丙醇的氢转移反应	[35]
a9/b8=13.0/20.0	135/0.04(58/0.009)	—	钯	1,3-丁二烯的调聚反应	[36]
a9/b8=12.7/20 a10/b8=9.75/20 a11/b8=7.15/20	150/— 33/— 42/—	—	钌	甲酸分解反应	[37]
a10/b9=1/1	469/0.475	0~180nm	钌	CO₂加氢合成N,N-二甲基甲酰胺的反应	[38]

单体组成^①	S/V(S_后/V_后)^②	孔径^③	金属	催化反应	参考文献
a12/b10/c1=1/1/3	1036/—(1025/1.5)	0~100nm	钯钯	Suzuki-Miyaura偶联反应氯化苄的Suzuki-Miyaura偶联	[41] [42]
a12/b10/c1=1/1/3	993/0.12(916/1.18)	0~100nm	钌	芳基酮、NH₄OAc和DMF的环化反应；重氮二羰基化合物和烯烃的环加成反应	[43]
a12/b10/c1=1/1/2 a12/b11/c1=1/1/2 a12/b12/c1=3/1/6 a12/b13/c1=3/1/6	(723/0.92) (524/0.66) (672/0.70) (549/0.84)	0~20nm	铑	氢甲酰化反应	[44]
a13/b12/c1=1/2/8	350/0.438	0~100nm	无	对硝基苯酚的还原反应	[45]
a14/b15/c1=1/1/3	282/—(59/—)	0~10nm	钌	硝基芳烃的还原	[46]
a12/c3=2/3 a15/c3=2/3	788/—(608/—) 491/—(466/—)	0~2nm	金	对硝基苯酚的还原反应	[47]
a12/b14/c1=1/1/2	20/0.06(18/0.05)	—	银	末端炔烃与二氧化碳的羧基化反应	[48]
a16/b10/c1=1/20/60	702/0.546	0~10nm	钯	Suzuki-Miyaura偶联反应芳基卤化物和芳基硼酸酯的自偶联反应	[49]
a17/b10/c1=1/40/120	810/0.52	0~14nm	钌	甲酸制氢反应	[50]
a18/c2(Solvent) a19/c2(Solvent) a20/c2(Solvent)	300/0.203 20/0.12 49/0.07	2.2nm 1.7nm 5.9nm	钌金	苯甲醇的胺化反应炔烃水合反应；苯胺与苯乙炔的氢胺化反应	[52]