离子热合成沸石分子筛:技术特性、研究进展与应用前景

doi:10.16085/j.issn.1000-6613.2015.06.001

摘要/Abstract

摘要： 离子热法是一种以离子液体或低共熔物为反应介质、在低挥发性的离子态反应环境中合成沸石分子筛的方法。离子热合成可在接近常压下进行, 因此不但能够克服常规液相合成体系高压带来的操作困难, 而且为分子筛合成机理研究提供了便利, 同时便于与微波等电磁技术耦合。本文总结了离子热法在沸石分子筛材料合成及机理研究方面取得的进展。通过调变反应介质种类、反应物组成、晶化条件以及添加氟或有机胺等可以得到不同组成、结构的沸石分子筛产物以及AlPO、SAPO分子筛膜;在离子热合成过程中, 离子液体和低共熔物的阳离子、有机胺或铵盐、金属阳离子等能够独立或协同起到结构导向作用。预期离子热法可为分子筛器件的放大生产提供一条灵活、方便的途径。

关键词: 离子热合成, 分子筛, 结晶, 膜, 微波化学, 溶剂效应

Abstract: Ionothermal synthesis is a method that uses either ionic liquid (IL) or deep eutectic solvent (DES) as reaction medium to synthesize zeolitic molecular sieves. The reaction environment of ionothermal synthesis is ionic and extremely low volatile. This is due to the inherent characteristics of IL/DES, as well as their isolation-deactivation effect on molecular reactants via hydrogen bonds. Compared with hydro/solvothermal routes, the most significant property of ionothermal synthesis is that it can take place at ambient pressure with few safety risks. This property brings convenience to in situ studies, and benefits the application of microwave heating to the synthesis of molecular sieves. Moreover, great flexibility is shown in ionothermal synthesis. By alternating reaction medium, reactant composition and crystallization condition, zeolitic products with various compositions and structures can be ionothermally synthesized. In the past decade, fruitful results have been obtained with respect to both the synthesis of zeolitic materials and the study of formation mechanisms of molecular sieves. Ionothermal synthesis has been proven as a promising method to prepare zeolitic phosphates. More than 20 zeolite framework types of zeolitic phosphates have been ionothermally synthesized until now. Some of these zeolitic phosphates, such as CoAPO-SIV and AlPO-CLO, have never been obtained from traditional systems. Under ionothermal conditions, a variety of zeolite films and membranes, such as AlPO, SAPO and metal-organic framework, have been prepared via the in situ method or the substrate surface conversion method. The substrate surface conversion method can be applied to preparing AlPO membranes on porous Al₂O₃, which is used as both substrate and aluminium source. This method inhibits the crystallization of molecular sieves in the liquid phase, avoids the influence of species diffusion on membrane formation, and benefits the formation of membranes with high quality. Under ionothermal conditions, various species, such as the cations of IL/DES, the additive amines/ammonium cations and the metal cations, have potential structure directing ability. The complex cations, which are formed by amine molecules and IL/DES cations via hydrogen bonds, can also play the role of structure directing agent. Compared with molecular solvents, IL and DES have little disturbance to the structure directing process during the formation of molecular sieves. Considering its fascinating features, ionothermal synthesis would be a rational choice for the industrial preparation of zeolite-based devices.

Key words: ionothermal synthesis, molecular sieves, crystallization, membranes, microwave chemistry, solvent effect

中图分类号:

田志坚, 刘浩. 离子热合成沸石分子筛:技术特性、研究进展与应用前景[J]. 化工进展, 2015, 34(06): 1501-1510.

TIAN Zhijian, LIU Hao. Ionothermal synthesis of zeolitic molecular sieves:Properties, progress and prospect[J]. Chemical Industry and Engineering Progree, 2015, 34(06): 1501-1510.

参考文献

[1] Cooper E R, Andrews C D, Wheatley P S, et al. Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues[J]. Nature, 2004, 430(7003):1012-1016.
[2] Taubert A, Li Z H. Inorganic materials from ionic liquids[J]. Dalton Trans., 2007(7):723-727.
[3] Parnham E R, Morris R E. Ionothermal synthesis of zeolites, metal-organic frameworks, and inorganic-organic hybrids[J]. Acc. Chem. Res., 2007, 40(10):1005-1013.
[4] Morris R E. Ionothermal synthesis-Ionic liquids as functional solvents in the preparation of crystalline materials[J]. Chem. Commun., 2009, 21:2990-2998. DOI:10.1039/B902611H.
[5] Ma Z, Yu J H, Dai S. Preparation of inorganic materials using ionic liquids[J]. Adv. Mater., 2010, 22(2):261-285.
[6] Freudenmann D, Wolf S, Wolff M, et al. Ionic liquids:New perspectives for inorganic synthesis?[J]. Angew. Chem. Int. Ed., 2011, 50(47):11050-11060.
[7] 王亚松, 徐云鹏, 田志坚, 等. 离子热法合成分子筛的研究进展[J]. 催化学报, 2012, 33(1):39-50.
[8] 顾彦龙, 石峰, 邓友全. 室温离子液体:一类新型的软介质和功能材料[J]. 科学通报, 2004, 49(6):515-521.
[9] Weingärtner H. Understanding ionic liquids at the molecular level:Facts, problems, and controversies[J]. Angew. Chem. Int. Ed., 2008, 47:654-670.
[10] 韦露, 樊友军. 低共熔溶剂及其应用研究进展[J]. 化学通报:印刷版, 2011, 74(4):333-339.
[11] Abbott A P, Capper G, Davies D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chem. Commun., 2003, 1:70-71. DOI:10.1039/B210714G.
[12] Ma H J, Tian Z J, Xu R S, et al. Effect of water on the ionothermal synthesis of molecular sieves[J]. J. Am. Chem. Soc., 2008, 130(26):8120-8121.
[13] Cammarata L, Kazarian S G, Salter P A, et al. Molecular states of water in room temperature ionic liquids[J]. Phys. Chem. Chem. Phys., 2001, 3(23):5192-5200.
[14] Hanke C G, Lynden-Bell R M. A simulation study of water-dialkylimidazolium ionic liquid mixtures[J]. J. Phys. Chem. B, 2003, 107(39):10873-10878.
[15] Danten Y, Cabaço M I, Besnard M. Interaction of water highly diluted in 1-alkyl-3-methyl imidazolium ionic liquids with the PF₆^- and BF₄^- anions[J]. J. Phys. Chem. A, 2009, 113(12):2873-2889.
[16] Cai R, Liu Y, Gu S, et al. Ambient pressure dry-gel conversion method for zeolite MFI synthesis using ionic liquid and microwave heating[J]. J. Am. Chem. Soc., 2010, 132(37):12776-12777.
[17] Wragg D S, Slawin A M Z, Morris R E. The role of added water in the ionothermal synthesis of microporous aluminium phosphates[J]. Solid State Sci., 2009, 11(2):411-416.
[18] Drylie E A, Wragg D S, Parnham E R, et al. Ionothermal synthesis of unusual choline-templated cobalt aluminophosphates[J]. Angew. Chem. Int. Ed., 2007, 46(41):7839-7843.
[19] Liu H, Tian Z J, Gies H, et al. Mn²⁺ cation-directed ionothermal synthesis of an open-framework fluorinated aluminium phosphite-phosphate[J]. RSC Adv., 2014, 4(55):29310-29313.
[20] Wang L, Xu Y P, Wei Y, et al. Structure-directing role of amines in the ionothermal synthesis[J]. J. Am. Chem. Soc., 2006, 128(23):7432-7433.
[21] 舒静, 任丽丽, 张铁珍, 等. 微波辐射在催化剂制备中的应用[J]. 化工进展, 2008, 27(3):352-357.
[22] Xu Y P, Tian Z J, Wang S J, et al. Microwave-enhanced ionothermal synthesis of aluminophosphate molecular sieves[J]. Angew. Chem. Int. Ed., 2006, 45(24):3965-3970.
[23] Taulelle F, Haouas M, Gerardin C, et al. NMR of microporous compounds:From in situ reactions to solid paving[J]. Colloids Surf. A, 1999, 158(1-2):299-311.
[24] Xu R S, Zhang W P, Guan J, et al. New insights into the role of amines in the synthesis of molecular sieves in ionic liquids[J]. Chem. Eur. J., 2009, 15(21):5348-5354.
[25] Xu R S, Shi X C, Zhang W P, et al. Cooperative structure-directing effect in the synthesis of aluminophosphate molecular sieves in ionic liquids[J]. Phys. Chem. Chem. Phys., 2010, 12(10):2443-2449.
[26] Wragg D S, Byrne P J, Giriat G, et al. In situ comparison of ionothermal kinetics under microwave and conventional heating[J]. J. Phys. Chem. C, 2009, 113(48):20553-20558.
[27] Ma H J, Xu R S, You W S, et al. Ionothermal synthesis of gallophosphate molecular sieves in 1-alkyl-3-methyl imidazolium bromide ionic liquids[J]. Microporous Mesoporous Mater., 2009, 120(13):278-284.
[28] Wei Y, Tian Z J, Gies H, et al. Ionothermal synthesis of an aluminophosphate molecular sieve with 20-ring pore openings[J]. Angew. Chem. Int. Ed., 2010, 49(31):5367-5370.
[29] Ng E P, Sekhon S S, Mintova S. Discrete MnAlPO-5 nanocrystals synthesized by an ionothermal approach[J]. Chem. Commun., 2009(13):1661-1663. DOI:10.1039/B820883B.
[30] Bieniok A, Brendel U, Sereni P, et al. Raman spectroscopy and crystal structure investigation of solvo- and ionothermally prepared microporous metal-aluminophosphates with the laumontite framework structure[J]. Z. Kristallogr., 2013, 228(8):374-381.
[31] Yonemoto B T, Lin Z J, Jiao F. A general synthetic method for MPO₄ (M = Co, Fe, Mn) frameworks using deep-eutectic solvents[J]. Chem. Commun., 2012, 48(73):9132-9134.
[32] Parnham E R, Morris R E. The ionothermal synthesis of cobalt aluminophosphate zeolite frameworks[J]. J. Am. Chem. Soc., 2006, 128(7):2204-2205.
[33] Carvalho M M, Ruotolo L A M, Fernandez-Felisbino R. Synthesis of aluminophosphate by the ionothermal method using factorial design[J]. Microporous Mesoporous Mater., 2013, 165:163-167.
[34] Liu L, Li X P, Xu H, et al. Template control in ionothermal synthesis of aluminophosphate microporous materials[J]. Dalton Trans., 2009(47):10418-10421. DOI:10.1039/B820883B.
[35] Parnham E R, Morris R E. 1-Alkyl-3-methyl imidazolium bromide ionic liquids in the ionothermal synthesis of aluminium phosphate molecular sieves[J]. Chem. Mater., 2006, 18(20):4882-4887.
[36] Pei R Y, Tian Z J, Wei Y, et al. Ionothermal synthesis of AlPO₄-34 molecular sieves using heterocyclic aromatic amine as the structure directing agent[J]. Mater. Lett., 2010, 64(21):2384-2387.
[37] Liu L, Kong Y, Xu H, et al. Ionothermal synthesis of a three-dimensional zinc phosphate with DFT topology using unstable deep-eutectic solvent as template-delivery agent[J]. Microporous Mesoporous Mater., 2008, 115(3):624-628.
[38] Liu L, Wragg D S, Zhang H Y, et al. Ionothermal synthesis, structure and characterization of three-dimensional zinc phosphates[J]. Dalton Trans., 2009(34):6715-6718. DOI:10.1039/b906934h.
[39] Fayad E J, Bats N, Kirschhock C E A, et al. A rational approach to the ionothermal synthesis of an AlPO₄ molecular sieve with an LTA-type framework[J]. Angew. Chem. Int. Ed., 2010, 49(27):4585-4588.
[40] 裴仁彦, 徐云鹏, 魏莹, 等. 有机胺在离子热合成LTA型磷酸铝分子筛中的助模板作用[J]. 催化学报, 2010, 31(8):1083-1089.
[41] Zhao X H, Kang C X, Wang H, et al. Ionothermal synthesis of FeAlPO-16 molecular sieve by microwave irradiation in eutectic mixture[J]. J. Porous Mater., 2011, 18(5):615-621.
[42] Han L J, Wang Y B, Li C X, et al. Simple and safe synthesis of microporous aluminophosphate molecular sieves by inothermal approach[J]. AIChE J., 2008, 54(1):280-288.
[43] Ng E P, Itani L, Sekhon S S, et al. Micro- to macroscopic observations of MnAlPO-5 nanocrystal growth in ionic-liquid media[J]. Chem. Eur. J., 2010, 16(43):12890-12897.
[44] Khoo D Y, Kok W M, Mukti R R, et al. Ionothermal approach for synthesizing AlPO-5 with hexagonal thin-plate morphology influenced by various parameters at ambient pressure[J]. Solid State Sci., 2013, 25:63-69.
[45] Shi Y W, Liu G Z, Wang L, et al. Ionothermal synthesis of phase pure AlPO₄-5 using a series of tri-substituted imidazolium bromides[J]. Microporous Mesoporous Mater., 2014, 193:1-6.
[46] Griffin J M, Clark L, Seymour V R, et al. Ionothermal ¹⁷O enrichment of oxides using microlitre quantities of labelled water[J]. Chem. Sci., 2012, 3(7):2293-2300.
[47] 王少君, 侯蕾, 徐云鹏, 等. 铝源前驱体对离子热法合成磷酸铝分子筛的影响[J]. 过程工程学报, 2008, 8(1):93-96.
[48] 裴仁彦. 离子热法合成分子筛结构导向作用的研究[D]. 大连:中国科学院大连化学物理研究所, 2010.
[49] Lohmeier S J. Synthese und Charakterisierung von in ionischen Flüssigkeiten hergestellten Aluminiumphosphaten[D]. Hannover:Gottfried Wilhelm Leibniz Universität Hannover, 2011.
[50] Li D W, Xu Y P, Wang Y S, et al. Ionothermal syntheses and characterizations of cobalt-substituted extra-large pore aluminophosphate molecular sieves with -CLO topology[J]. Microporous Mesoporous Mater., 2014, 198:153-160.
[51] Wang L, Xu Y P, Wang B C, et al. Ionothermal synthesis of magnesium-containing aluminophosphate molecular sieves and their catalytic performance[J]. Chem. Eur. J., 2008, 14(34):10551-10555.
[52] Zhao X H, Chen J, Sun Z P, et al. Formation mechanism and catalytic application of hierarchical structured FeAlPO-5 molecular sieve by microwave-assisted ionothermal synthesis[J]. Microporous Mesoporous Mater., 2013, 182:8-15.
[53] Zhao X H, Sun Z P, Zhu Z Q, et al. Evaluation of iron-containing aluminophosphate molecular sieve catalysts prepared by different methods for phenol hydroxylation[J]. Catal. Lett., 2013, 143(7):657-665.
[54] 马英冲, 徐云鹏, 王少君, 等. 室温离子液体中合成方钠石的研究[J]. 高等学校化学学报, 2006, 27(4):739-741.
[55] 马英冲, 王少君, 宋宇, 等. 离子热合成微球方钠石[J]. 无机化学学报, 2010, 26(11):1923-1926.
[56] Wheatley P S, Allan P K, Teat S J, et al. Task specific ionic liquids for the ionothermal synthesis of siliceous zeolites[J]. Chem. Sci., 2010, 1(4):483-487.
[57] McLeary E E, Jansen J C, Kapteijn F. Zeolite based films, membranes and membrane reactors:Progress and prospects[J]. Microporous Mesoporous Mater., 2006, 90(1-3):198-220.
[58] Lew C M, Cai R, Yan Y S. Zeolite thin films:From computer chips to space stations[J]. Acc. Chem. Res., 2009, 43(2):210-219.
[59] Gascon J, Kapteijn F, Zornoza B, et al. Practical approach to zeolitic membranes and coatings:State of the art, opportunities, barriers, and future perspectives[J]. Chem. Mater., 2012, 24(15):2829-2844.
[60] 李永生, 王金渠, 郭树才. 沸石膜的合成最新进展[J]. 化工进展, 2001, 20(2):42-47.
[61] 张延风, 许中强, 陈庆龄. 分子筛膜制备技术[J]. 化工进展, 2002, 21(4):270-274.
[62] Cai R, Sun M W, Chen Z W, et al. Ionothermal synthesis of oriented zeolite AEL films and their application as corrosion-resistant coatings[J]. Angew. Chem. Int. Ed., 2008, 47(3):525-528.
[63] 田志坚, 厉晓蕾, 李科达, 等. 一种多孔氧化铝载体支撑的ZIF-8膜的制备方法:中国, 201310136268.3[P]. 2014-10-22.
[64] Li K D, Tian Z J, Li X L, et al. Ionothermal synthesis of aluminophosphate molecular sieve membranes through substrate surface conversion[J]. Angew. Chem. Int. Ed., 2012, 51(18):4397-4400.
[65] 李科达, 厉晓蕾, 王亚松, 等. 离子热法合成AEL磷酸铝分子筛膜及其机理研究[J]. 化学学报, 2013, 71(4):573-578.
[66] 李科达. 离子热合成磷酸铝分子筛膜的研究[D]. 大连:中国科学院大连化学物理研究所, 2013.
[67] 李激扬, 于吉红, 徐如人. 微孔化合物生成中的结构导向与模板作用[J]. 无机化学学报, 2004, 20(1):1-16.
[68] Morris R E, Weigel S J. The synthesis of molecular sieves from non-aqueous solvents[J]. Chem. Soc. Rev., 1997, 26(4):309-317.
[69] Corma A, Davis M E. Issues in the synthesis of crystalline molecular sieves:Towards the crystallization of low framework-density structures[J]. Chem. Phys. Chem., 2004, 5(3):304-313.
[70] Parnham E R, Morris R E. Ionothermal synthesis using a hydrophobic ionic liquid as solvent in the preparation of a novel aluminophosphate chain structure[J]. J. Mater. Chem., 2006, 16(37):3682-3684.
[71] Martineau C, Bouchevreau B, Tian Z J, et al. Beyond the limits of X-ray powder diffraction:Description of the nonperiodic subnetworks in aluminophosphate-cloverite by NMR crystallography[J]. Chem. Mater., 2011, 23(21):4799-4809.
[72] Pei R Y, Wei Y, Li K D, et al. Mixed template effect adjusted by amine concentration in ionothermal synthesis of molecular sieves[J]. Dalton Trans., 2010, 39(6):1441-1443.
[73] 李臻, 陈静, 夏春谷. 离子液体的工业应用研究进展[J]. 化工进展, 2012, 31(10):2113-2123, 2182.
[74] Noack M, Kölsch P, Schäfer R, et al. Molecular sieve membranes for industrial application:Problems, progress, solutions[J]. Chem. Eng. Technol., 2002, 25(3):221-230.