超交联多孔离子聚合物的研究进展

doi:10.16085/j.issn.1000-6613.2019-1707

摘要/Abstract

摘要：

超交联多孔离子聚合物（hyper-crosslinked porous ionic polymers，HCPiPs）是一类兼具多孔结构、大比表面积、高电荷密度的新型离子有机功能材料，具有制备方式多样、条件温和、易于功能化等特点，在气体捕集/存储、分离、催化、能源环境等方面取得了显著成绩。本文综述了HCPiPs的基本合成原理和方法，系统总结了含离子单体的一步交联法、交联-离子化同步合成法、后修饰法3种制备HCPiPs常用方法的优缺点，以及近年来在气体捕集与分离、异相催化、能量存储与转化、污染物吸附分离等领域的研究进展，并对今后的发展进行了展望，指出了加强HCPiPs的孔结构和活性位点的设计及调控、解决HCPiPs的功能离子的含量与比表面积相互矛盾的问题以及制备各种新型功能性HCPiPs以不断拓展其在催化和电池等领域的应用三个主要研究方向。

关键词: 超交联多孔离子聚合物, 固载离子液体, CO₂捕集, 吸附, 分离, 催化

Abstract:

Hyper-crosslinked porous ionic polymers (HCPiPs) are a series of novel ionic organic functional materials with porous structure, large specific surface area and high charge density. Due to the advantages of mild reaction conditions, diverse preparation methods and easy functionalization, HCPiPs have made remarkable achievements in gas capture/storage, separation, catalysis, and energy storage ＆ conversion in recent years. An overview of recent progress in the basic synthesis principles and strategies, as well as its application in the fields of gas capture/separation, heterogeneous catalysis, electrochemical energy storage, pollutant adsorption, etc., were presented. In addition, the key technical barriers on current HCPiPs preparation processes, one-step crosslinking, crosslinking-ionizing synchronous synthesis and post-modification were discussed, such as limited specific surface areas and total pore volumes, low charge density and uneven distribution, poor catalyst stability and efficiency. It was pointed out that further synthesis strategies should be focused on the design of proper pore structure and active site, content of functional ions and specific surface area, development of various new functional HCPiPs so as to expand its application fields.

Key words: hyper-crosslinked porous ionic polymers, immobilized ionic liquid, CO₂ capture, adsorption, separation, catalysis

中图分类号:

O631.5

项小燕, 罗小燕, 裴宝有, 赵朝阳, 丘荣星, 陈晓燕, 李佳然, 张子姮, 马瑞勋, 林金清. 超交联多孔离子聚合物的研究进展[J]. 化工进展, 2020, 39(8): 3110-3123.

Xiaoyan XIANG, Xiaoyan LUO, Baoyou PEI, Zhaoyang ZHAO, Rongxing QIU, Xiaoyan CHEN, Jiaran LI, Ziheng ZHANG, Ruixun MA, Jinqing LIN. Research progresses on hyper-crosslinked porous ionic polymers[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3110-3123.

参考文献

1	WU J L, XU F, LI S M, et al. Porous polymers as multifunctional material platforms toward task-specific applications[J]. Advanced Materials, 2019, 31(4): 1802922.
2	CUI C Z, CAO Z, ZHANG S P, et al. Application of a novel diol-based porous organic polymer to the determination of trace-level tetracyclines in water[J]. Analytical Methods, 2019, 11: 2473-2481.
3	MOURADZADEGUN A, GANJALI M R, MOSTAFAVI M A. Design and synthesis of a magnetic hierarchical porous organic polymer: a new platform in heterogeneous phase-transfer catalysis[J]. Applied Organometallic Chemistry, 2018, 32(4): e4214.
4	DAS S, HEASMAN P, BEN T, et al. Porous organic materials: strategic design and structure-function correlation[J]. Chemical Reviews, 2017, 117(3): 1515-1563.
5	TAN L X, TAN B E. Hypercrosslinked porous polymer materials: design, synthesis, and applications[J]. Chemical Society Reviews, 2017, 46: 3322-3356.
6	HOU S S, RAZZAQUE S, TAN B E. Effects of synthesis methodology on microporous organic hypercrosslinked polymers with respect to structural porosity, gas uptake performance and fluorescence properties[J]. Polymer Chemistry, 2019, 10: 1299-1311.
7	KRAMER S, BENNEDSEN N R, KEGNAES S. Porous organic polymers containing active metal centers as catalysts for synthetic organic chemistry[J]. ACS Catalysis, 2018, 8(8): 6961-6982.
8	XIE Y Q, LIANG J, FU Y W, et al. Hypercrosslinked mesoporous poly (ionic liquid)s with high ionic density for efficient CO₂ capture and conversion into cyclic carbonate[J]. Journal of Materials Chemistry A, 2018, 6: 6660-6666.
9	ZHANG W, MEI Y, WU P, et al. Highly tunable periodic imidazole-based mesoporous polymers as cooperative catalysts for efficient carbon dioxide fixation[J]. Catalysis Science & Technology, 2019, 9: 1030-1038.
10	LIANG X P, HU P, ZHANG H Y, et al. Hypercrosslinked strong anion-exchange polymers for selective extraction of fluoroquinolones in milk samples[J]. Journal of Pharmaceutical and Biomedical Analysis, 2019, 166: 379-386.
11	CHEN G J, ZHANG Y D, XU J Y, et al. Imidazolium-based ionic porous hybrid polymers with POSS-derived silanols for efficient heterogeneous catalytic CO₂ conversion under mild conditions[J]. Chemical Engineering Journal, 2020, 381: 122765.
12	CHENG M, JIANG J J, WANG J, et al. Highly salt resistant polymer supported ionic liquid adsorbent for ultrahigh capacity removal of p-nitrophenol from water[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(9): 8195-8205.
13	FONTANALS N, MARCE R M, BORRULL F. Handbooks in separation science[M]. USA：Elseviser，2020: 55-82.
14	ZHENG X, CHEN F F, ZHANG X W, et al. Ionic liquid grafted polyamide 6 as porous membrane materials: enhanced water flux and heavy metal adsorption[J]. Applied Surface Science, 2019, 481: 1435-1441.
15	XU Z X, ZHAO Y L, WANG P Y, et al. Extraction of Pt(Ⅳ), Pt(Ⅱ), and Pd(Ⅱ) from acidic chloride media using imidazolium-based task-specific polymeric ionic liquid[J]. Industrial & Engineering Chemistry Research, 2019, 58(5): 1779-1786.
16	ZHENG X, DING X, GUAN J P, et al. Ionic liquid-grafted polyamide 6 by radiation-induced grafting: new strategy to prepare covalently bonded ion-containing polymers and their application as functional fibers[J]. ACS Applied Materials & Interfaces, 2019, 11(5): 5462-5475.
17	LIU L L, GUO F Y, XU J, et al. Adsorption-enhanced oxidative desulfurization by a task-specific pyridinium-based porous ionic polymer[J]. Fuel, 2019, 244: 439-446.
18	NAYEBI R, TARIGH G, SHEMIRANI F. Porous ionic liquid polymer: a reusable adsorbent with broad operating pH range for speciation of nitrate and nitrite[J]. Scientific Reports, 2019, 9(1)：11130-11140.
19	WANG H, SHI H F, YE W P, et al. Amorphous ionic polymers with color-tunable ultralong organic phosphorescence[J]. Angewandte Chemie: International Edition, 2019, 131(52): 18952-118958.
20	LIU F, GU Y Q, ZHAO P H, et al. Cooperative conversion of CO₂ to cyclic carbonates in dual-ionic ammonium salts catalytic medium at ambient temperature[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(6): 5940-5945.
21	ZHANG Q, ZHANG S B, LI S H. Novel functional organic network containing quaternary phosphonium and tertiary phosphorus[J]. Macromolecules, 2012, 45: 2981-2988.
22	FISCHER S, SCHIMANOWITZ A, DAWSON R, et al. Cationic microporous polymer networks by polymerisation of weakly coordinating cations with CO₂ storage ability[J]. Journal of Materials Chemistry A, 2014, 2: 11825-11829.
23	SU Y Q, WANG Y X, LI X J, et al. Imidazolium-based porous organic polymers: anion exchange driven capture and luminescent probe of Cr₂[J]. ACS Applied Materials & Interfaces, 2016, 8: 18904-18911.
24	WANG J Q, YANG J G W, YI G S, et al. Phosphonium salt incorporated hypercrosslinked porous polymers for CO₂capture and conversion[J]. Chemical Communications, 2015, 51: 15708-15711.
25	SUO X, XIA L, YANG Q W, et al. Synthesis of anion-functionalized mesoporous poly(ionic liquid)s via a microphase separation-hypercrosslinking strategy: highly efficient adsorbents for bioactive molecules[J]. Journal of Materials Chemistry A, 2017, 5: 14114-14123.
26	HU X M, CHEN Q, SUI Z Y, et al. Triazatriangulenium-based porous organic polymers for carbon dioxide capture[J]. RSC Advances, 2015, 5: 90135-90143.
27	李侦慷. 离子液体超交联聚合物的合成及气体分离性能研究[D]. 杭州: 浙江大学，2017.
27	LI Z K. The synthesis of ionic liquid-based hypercrosslinked polymers and their application in the gas separations[D]. Hangzhou: Zhejiang University, 2017.
28	CHO H C, LEE H S, CHUN J, et al. Tubular microporous organic networks bearing imidazolium salts and their catalytic CO₂conversion to cyclic carbonates[J]. Chemical Communications, 2011, 47: 917-919.
29	BUYUKCAKIR O, JE S H, CHOI D S, et al. Porous ationic polymers: the impact of counteranions and charges on CO₂ capture and conversion[J]. Chemical Communications, 2016, 52: 934-937.
30	FISHER S, SCHMIDT J, STRAUCH P, et al. An anionic microporous polymer network prepared by the polymerization of weakly coordinating anions[J]. Angewandte Chemie： International Edition, 2013, 52(46): 12174-12178.
31	ZHAO H, WANG Y, WANG R H. In situ formation of well-dispersed palladium nanoparticles immobilized in imidazolium-based organic ionic polymers[J]. Chemical Communications, 2014, 50: 10871-10874.
32	YUAN Y, SUN F X, LI L, et al. Porous aromatic frameworks with anion-templated pore apertures serving as polymeric sieves[J]. Nature Communications, 2014, 5: 4260-4267.
33	MITRA S, KANDAMBETH S, BISWAL B P, et al. Self-exfoliated guanidinium-based ionic covalent organic nanosheets(iCONs）[J]. Journal of the American Chemical Society, 2016, 138: 2823-2828.
34	HUANG N, WANG P, ADDICOAT M A, et al. Ionic covalent organic frameworks: design of a charged interface aligned on 1D channel walls and its unusual electrostatic functions[J]. Angewandte Chemie: International Edition, 2017, 56(18): 4982-4986.
35	ZHANG P F, JIANG X G, WAN S, et al. Charged porous polymers using a solid C—O cross-coupling reaction[J]. Chemistry: a European Journal, 2015, 21(37): 12866-12870.
36	ZHANG P F, QIAO Z A, JIANG X G, et al. Nanoporous ionic organic networks: stabilizing and supporting gold nanoparticles for catalysis[J]. Nano letters, 2015, 15: 823-828.
37	CHEN G J, ZHOU Y, WANG X C, et al. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers[J]. Scientific Reports, 2015, 5: 11236-11250.
38	KIM K, BUYUKCAKIR O, COSKUN A. Diazapyrenium-based porous cationic polymers for colorimetric amine sensing and capture from CO₂ scrubbing conditions[J]. RSC Advances, 2016, 6: 77406-77409.
39	RAJA A R, YAVUZ C T. Charge induced formation of crystalline network polymers[J]. RSC Advances, 2014, 4: 59779-59784.
40	LI J, JIA D G, GUO Z J, et al. Imidazolinium based porous hypercrosslinked ionic polymers for efficient CO₂ capture and fixation with epoxides[J]. Green Chemistry, 2017, 19: 2675-2686.
41	HAO S, LIU Y C, SHANG C N, et al. CO₂ adsorption and catalytic application of imidazole ionic liquid functionalized porous organic polymers[J]. Polymer Chemistry, 2017, 8: 1833-1839.
42	WANG J Q, YANG J G W, YI G S, et al. Imidazolium salt-modified porous hypercrosslinked polymers for synergistic CO₂capture and conversion[J]. Chemical Communications, 2015, 51:12076-12079.
43	HAN S, FENG Y L, ZHANG F, et al. Metal-phosphide-containing porous carbons derived from an ionic-polymer framework and applied as highly effificient electrochemical catalysts for water splitting[J]. Advanced Functional Materials, 2015, 25: 3899-3906.
44	LIU F J, WANG L, SUN Q, et al. Transesterification catalyzed by ionic liquids on superhydrophobic mesoporous polymers: heterogeneous catalysts that are faster than homogeneous catalysts[J]. Journal of the American Chemical Society, 2012, 34(41): 16948-16950.
45	ZHAO W X, ZHANG F, YANG L Y, et al. Anionic porous polymers with tunable structures and catalytic properties[J]. Journal of Materials Chemistry A, 2016, 4: 15162-15168.
46	LU W G, YUAN D Q, SCULLEY J, et al. Sulfonate-grafted porous polymer networks for preferential CO₂ adsorption at low pressure[J]. Journal of the American Chemical Society, 2011, 133: 18126-18129.
47	MA H P, HAO R, ZOU X Q, et al. Post-metalation of porous aromatic frameworks for highly efficient carbon capture from CO₂+N₂ and CH₄+N₂ mixtures[J]. Polymer Chemistry, 2013, 5(1): 144-152.
48	DENG G Y, WANG Z G. Hierarchical porous phenolic resin and its supported Pd-catalyst for Suzuki-Miyaura reactions in water medium[J]. Macromolecular Rapid Communications, 2018, 39(3):1700618.
49	GU C, HUANG N, CHEN Y C, et al. Porous organic polymer films with tunable work functions and selective hole and electron flows for energy conversions[J]. Angewandte Chemie: International Edition, 2016, 55: 3049-3053.
50	YU W, ZHOU M H, WANG T Q, et al. “Click chemistry” mediated functional microporous organic nanotube networks for heterogeneous catalysis[J]. Organic Letters, 2017, 19(21): 5776-5779.
51	PUTHIARAJ P, RAVI S, YU K, et al. CO₂ adsorption and conversion into cyclic carbonates over a porous ZnBr₂-grafted N-heterocyclic carbene-based aromatic polymer[J]. Applied Catalysis B: Environmental, 2019, 251: 195-205.
52	XU S, WENG Z H, TAN J, et al. Hierarchically structured porous organic polymer microspheres with built-in Fe₃O₄ supraparticles: construction of dual-level pores for Pt-catalyzed enantioselective hydrogenation[J]. Polymer Chemistry, 2015, 6(15): 2892-2899.
53	LI X C, ZHANG Y Z, WANG C Y, et al. Redox-active triazatruxene-based conjugated microporous polymers for high-performance supercapacitors[J]. Chemical Science, 2017, 8(4): 2959-2965.
54	PAN H, CHENG Z B, XIAO Z B, et al. Lithium-sulfur batteries: the fusion of imidazolium-based ionic polymer and carbon nanotubes: one type of new heteroatom-doped carbon precursors for high-performance lithium-sulfur batteries[J]. Advanced Functional Materials, 2017, 27(44): 1703936.
55	ZHAO W X, ZHUANG X D, WU D Q, et al. Boron-π-nitrogen-based conjugated porous polymers with multi-functions[J]. Journal of Materials Chemistry A, 2013, 1: 13878-13884.
56	YANG R X, WANG T T, DENG W Q. Extraordinary capability for water treatment achieved by a perfluorous conjugated microporous polymer[J]. Scientific Reports, 2015, 5: 10155.
57	XIANG Z H, CAO D P, WANG W C, et al. Postsynthetic lithium modifification of covalent-organic polymers for enhancing hydrogen and carbon dioxide storage[J]. The Journal of Physical Chemistry?C, 2012, 116(9): 5974-5980.
58	DANI A, CROCELLA V, MAGISTRIS C, et al. Click-based porous cationic polymers for enhanced carbon dioxide capture[J]. Journal of Materials Chemistry A, 2017, 5: 572-583.
59	LUO Y L, LI B Y, WANG W, et al. Hypercrosslinked aromatic heterocyclic microporous polymers: a new class of highly selective CO₂ capturing materials[J]. Advanced Materials, 2012, 24(42): 5703-5707.
60	杨宵, 刘晶, 胡建波. 氢气在共价有机骨架材料中的吸附机理[J]. 化工学报, 2015, 66(7):186-192.
60	YANG X, LIU J, HU J B. Adsorption mechanism of H₂ on covalent organic frameworks[J]. CIESC Journal, 2015, 66(7): 186-192.
61	SUN Q, JIN Y Y, AGUILA B, et al. Porous ionic polymers as a robust and efficient platform for capture and chemical fixation of atmospheric CO₂[J]. ChemSusChem, 2017, 10(6): 1160-1165.
62	LUO R C, CHEN Y J, HE Q, et al. Metallosalen-based ionic porous polymers as bifunctional catalysts for the conversion of CO₂ into valuable chemicals[J]. ChemSusChem, 2017, 10(7): 1526-1533.
63	ZHANG P F, LI M T, YANG B L, et al. Polymerized ionic networks with high charge density: quasi-solid electrolytes in lithium-metal batteries[J]. Advanced Materials, 2015, 27(48):8088-8094.
64	WANG L X, DING J J, SUN S, et al. Viologen-hypercrosslinked ionic porous polymer films as active layers for electronic and energy storage devices[J]. Advanced Materials Interfaces, 2018, 5(10):1701679.
65	刘丽露, 吴凡, 李泓，等. 硫化物固态电解质电化学稳定性研究进展[J]. 硅酸盐学报, 2019, 47(10): 1367-1385.
65	LIU L L, WU F, LI H, et al. Advances in electrochemical stability of sulfide solid-state electrolyte[J]. Journal of the Chinese Ceramic Society, 2019, 47(10): 1367-1385.
66	REN Y Y, ZHANG J D, GUO J N, et al. Porous poly(ionic liquid) membranes as efficient and recyclable absorbents for heavy metal ions[J]. Macromolecular Rapid Communications, 2017, 38(14): 1700151.
67	ZHAO G X, HUANG X B, TANG Z W, et al. Polymer-based nanocomposites for heavy metal ions removal from aqueous solution: a review[J]. Polymer Chemistry, 2018, 9: 3562-3582.
68	YUAN Y, SUN F X, ZHANG F, et al. Targeted synthesis of porous aromatic frameworks and their composites for versatile, facile, efficacious, and durable antibacterial polymer coatings[J]. Advanced Materials, 2013, 25(45): 6619-6624.
69	JIANG K, FEI T, ZHANG T. Humidity sensing properties of LiCl-loaded porous polymers with good stability and rapid response and recovery[J]. Sensors and Actuators B: Chemical, 2014, 199(6): 1-6.
70	FEI T, JIANG K, LIU S, et al. Humidity sensors based on Li-loaded nanoporous polymers[J]. Sensors & Actuators B: Chemical, 2014, 190(1): 523-528.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[7]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[8]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[9]	李世霖, 胡景泽, 王毅霖, 王庆吉, 邵磊. 电渗析分离提取高值组分的研究进展[J]. 化工进展, 2023, 42(S1): 420-429.
[10]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[11]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[12]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[13]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[14]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[15]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.