离子液体及金属有机骨架材料的制备与性能研究
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摘要
离子液体和金属有机骨架材料是近年来国内外备受关注的新型功能性材料,其在化学工程中的应用领域不断扩大。本文制备了咪唑基离子液体和咪唑酯金属有机骨架材料ZIF-7,采用量子力学计算与实验研究相结合的方法,探索了其在相变蓄热以及二氧化碳捕集方面的应用。
本文合成了[C4MIM]PF6、[C16MIM]PF6两种离子液体,并用其为微胶囊囊心,三聚氰胺-甲醛树脂作为囊壁材料,采用原位聚合法制备相变微胶囊,对离子液体作为芯材的微胶囊相变材料的合成进行了摸索。
对于存在熔化热文献数据的44种离子液体,分别用PM3量子化学半经验方法进行计算,得到其稳定构型及相应结构参数,建立了结构参数与熔化热问的定量相关模型,模型具有良好的关联和预测性能。
用差示扫描量热(DSC)法测定了两种成核剂存在情况下离子液体熔融-凝固过程的热特性,研究了成核剂的加入对其过冷度的影响。
本文对ZlFs化合物的合成过程进行了详细的实验研究,用XRD对合成的ZIF-7产品进行表征,考察了晶化时间、晶化浓度等因素对ZIFs化合物结晶度的影响。采用恒定容积法,测定了将ZIF-7加入到吸收剂碳酸二甲酯前后,对二氧化碳捕集性能的影响。结果发现在碳酸二甲酯中加入1.5wt%的ZIF-7后,低温下对吸收CO2具有强化作用,而在较高温度下则对解吸有强化作用,这种特性有利于CO：吸收和解吸循环过程的节能,展示了良好的应用潜力。
Ionic liquids and Metal-Organic Frameworks are new materials which have been the concern of the researchs at home and abroad.The use of them have been exploring increasingly.In this paper,a ionic liquid with dual functional imidazolyl and a ZIF-7 were prepared. Quantum-mechanical calculation was combined with experiment, and a new application field for phase change energy storage, absorption of CO2 is explored. This article has reported the preparation of [C4MIM]PF6、[C16MIM]PF6, and take them for core material. Melamine-formaldehyde resin as wall materials in-situ Polymerization of Microencapsulated Phase Change.Take ionic liquids as a core material of phase change microencapsulated materials have been exploring the synthesis.
The stable configuration and the corresponding parameter of 44 kinds ionic liquids that are in the existing melting heat literature have been optimized with quantum chemistry semi-empirical PM3 method in this paper. The mathematics models of quantitative characterization structural parameter and melting heat were established, the result indicates that models are good enough to exactly be a predicted function and a good correlation.
A determine has been made on the thermal properties of the melting and solidification process of ionic liquids by using differential scanning calorimeter (DSC).
This paper has carried out a detailed experiment to find out the methods to synthesize ZIF-7 compound. We synthesize different samples in different conditions and analyse their structures by XRD. We have investigated how the crystallization time and crystallization concentration affect the ZIF crystalline compounds by changing single variable.The solubility of CO2 in DMC with ZIF-7 were measured.The result shows that the solubility of CO2 in DMC with 1.5wt% ZIF-7 increases while gas pressure rises and decreases while temperature rises. It indicates that ZIF-7 has potential for absorption of CO2.
本文合成了[C4MIM]PF6、[C16MIM]PF6两种离子液体,并用其为微胶囊囊心,三聚氰胺-甲醛树脂作为囊壁材料,采用原位聚合法制备相变微胶囊,对离子液体作为芯材的微胶囊相变材料的合成进行了摸索。
对于存在熔化热文献数据的44种离子液体,分别用PM3量子化学半经验方法进行计算,得到其稳定构型及相应结构参数,建立了结构参数与熔化热问的定量相关模型,模型具有良好的关联和预测性能。
用差示扫描量热(DSC)法测定了两种成核剂存在情况下离子液体熔融-凝固过程的热特性,研究了成核剂的加入对其过冷度的影响。
本文对ZlFs化合物的合成过程进行了详细的实验研究,用XRD对合成的ZIF-7产品进行表征,考察了晶化时间、晶化浓度等因素对ZIFs化合物结晶度的影响。采用恒定容积法,测定了将ZIF-7加入到吸收剂碳酸二甲酯前后,对二氧化碳捕集性能的影响。结果发现在碳酸二甲酯中加入1.5wt%的ZIF-7后,低温下对吸收CO2具有强化作用,而在较高温度下则对解吸有强化作用,这种特性有利于CO：吸收和解吸循环过程的节能,展示了良好的应用潜力。
Ionic liquids and Metal-Organic Frameworks are new materials which have been the concern of the researchs at home and abroad.The use of them have been exploring increasingly.In this paper,a ionic liquid with dual functional imidazolyl and a ZIF-7 were prepared. Quantum-mechanical calculation was combined with experiment, and a new application field for phase change energy storage, absorption of CO2 is explored. This article has reported the preparation of [C4MIM]PF6、[C16MIM]PF6, and take them for core material. Melamine-formaldehyde resin as wall materials in-situ Polymerization of Microencapsulated Phase Change.Take ionic liquids as a core material of phase change microencapsulated materials have been exploring the synthesis.
The stable configuration and the corresponding parameter of 44 kinds ionic liquids that are in the existing melting heat literature have been optimized with quantum chemistry semi-empirical PM3 method in this paper. The mathematics models of quantitative characterization structural parameter and melting heat were established, the result indicates that models are good enough to exactly be a predicted function and a good correlation.
A determine has been made on the thermal properties of the melting and solidification process of ionic liquids by using differential scanning calorimeter (DSC).
This paper has carried out a detailed experiment to find out the methods to synthesize ZIF-7 compound. We synthesize different samples in different conditions and analyse their structures by XRD. We have investigated how the crystallization time and crystallization concentration affect the ZIF crystalline compounds by changing single variable.The solubility of CO2 in DMC with ZIF-7 were measured.The result shows that the solubility of CO2 in DMC with 1.5wt% ZIF-7 increases while gas pressure rises and decreases while temperature rises. It indicates that ZIF-7 has potential for absorption of CO2.
引文
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[3]Wasserscheid P, Keim W. Ionic liquids-news solution for transition metal catalysis[J]. Angew. Chem. Int. Ed.,2000,39:3773-3789
[4]Tait S, Osteryoung R A. Infrared study of ambient-temperature chloroaluminates as a function of melt acidity[J]. Inorg. Chem.,1984,23:4352-4360
[5]Wikes J S. A short history of ionic liquids-from molten salts to neoteric solvents[J]. Green Chem.,2002,4(2):73-80
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[7]Wikes J S, Levisky J A, Wilson R A. Dialkylimidazolium chloroaluminate melts:a new class of room-temperature ionic liquids for electrochemistry, spectroscopy, and synthesis[J]. Inorg. Chem.,1982,21(3):1263-1264
[8]Wikes J S, Zaworotko M J. Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J]. J. Chem. Soc, Chem. Commun.,1992, (13):965-966
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[10]Fuller J, Carlin R T, Osteryoung. The room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrafluoro-borate:electrochemical couples and physical properties[J]. Journal of the Electrochemical Society,1997,144 (11):3881-3886
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[12]Bonhote P, Dias A P, Papageorgiou N. Hydrophobic, highly conductive ambient-temperature molten salts[J]. Inorg. Chem.,1996,35(5):1168-1178
[13]Dzyuba S V, Bartsch R A. Influence of structural variations in 1-alkyl(aralkyl)-3-methylimidazolium hexafluorophosphates and bis(teifluoromethylsufonyl)imides on physical properties of the ionic liquids[J]. Chem. Phys. Chem.,2002,3(2):161-166
[14]Uarmbyic, Osteryoung R A. Latent Acidity in Buffered Chloroalu Minate Ionic Liquids [J]. Am Chem. Soc.,1994,116:2649-2650
[15]Abdul Sada A A K, Greenway A M, Seddon K R,. A fast atom bombardment mass spectrometric study of room-temperature 1-ethyl-3-methylimidazolium chloroaluminate (Ⅲ) ionic liquids[J]. Org Mass Spectrom,1993, (28):759-765
[16]Wasserscheid P, Keim W. An ionic liquid as Catalyst medium for stereo selective Hydrogenations of sorbic acid with ruthenium complexes[J]. Chem. Int. Ed.,2000(39): 3772-3789
[17]Freemantle M. Designer solvents[J]. Chem. Eng News,1998,30:32-34
[18]Renner R. Ionic liquids:An industrial cleanup solution[J]. Environ. Sci. Technol.,2001, 35(19):410A-413A
[19]Rogers R D, Seddon K. Ionic liquids-solvents of the future[J]? Science,2003,302(5646): 792-793
[20]张玉芬,乔聪震,张金昌,等.离子液体-环境友好的溶剂和催化剂[J].化学反应工程与工艺.2003,119(2)：164-170
[21]石家华,孙逊,杨春和,等.离子液体研究进展[J].化学通报,2002,(04)：243-250
[22]Martyn J E, Kenneth R S. Ionic liquids green solvents for the future[J]. Pure Appl Chem. 2000.72:1391-1405
[23]阎立峰,朱清时.离子液体及其在有机合成中应用[J].化学通报.2001,64(11)：673-679
[24]Blanchard L A, Hancu D, Beckman E J. Green processing using ionic liquids and CO2[J]. Nature,1999,399:28-29
[25]Uzagare M C, Sanghvi Y S, Salunkhe M M. Application of ionic liquid 1-methoxyethyl-3-methyl limidazolium methanesulfonate innucleoside chemistry [J]. Green Chem.2003,5:370-372
[26]文玉华,朱如曾,周富信,等.分子动力学模拟的主要技术[J].力学进展.2003,33(01)：65-73
[27]周健,朱宇,汪文川,等.超临界NaCl水溶液的分子动力学模拟[J].物理化学学报.2002,18(3)：207-212
[28]梅东海,李以圭,陆九芳.同核双原子分子流体液汽界面的分子动力学模拟研究[J].化工学报.1998,49(6)：662-670
[29]Meng Z, Dolle A, Carper W R. Gas phase model of an ionic liquid: semi-empirical and ab initio-bonding and molecular structure[J]. J. Molecular Structure (Theochem).2002,585:119-128
[30]Jones de A, Elvis S B, Hubert S. A force field for liquid state simulations on room temperature molten salts:1-ethyl-3-methylimidazolium tetrachloroaluminate[J]. J. Phys. Chem. B.2002,106(14):3546-3548
[31]Jones de A, Elvis S B, Hubert S. Computational study of room temperature molten salts composed by 1-alkyl-3-methylimidazolium cations Force-field proposal and validation[J]. J. Phys. Chem. B.2002,106 (51):13344-13351
[32]Liu Z P, Huang S P and Wang W C. A refined force field for molecular simulation of imidazolium-based ionic liquids[J]. J. Phys. Chem. B.2004,108(34):12978-12989
[33]Paulechka Y U, Kabo G J, Blokhin A V. Thermodynamic properties of 1-butyl-3-methylimidazolium hexafluorophosphate in the ideal gas state[J]. J. Chem. Eng. Date.2003,48(30):457-462
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