兩性離子液體的自組裝結(jié)構(gòu)及其功能化研究
發(fā)布時間：2018-08-08 10:54
【摘要】：經(jīng)過多年的發(fā)展,離子液體不再被僅僅看作是"綠色溶劑"。研究人員開始針對特定的應(yīng)用,有目的性地設(shè)計離子液體的陰、陽離子結(jié)構(gòu)。一系列新型離子液體被設(shè)計合成出來,包括手性離子液體、磁性離子液體、氨基酸離子液體、金屬配位離子液體以及具有氧化還原活性的離子液體等,極大地拓展了離子液體的應(yīng)用范圍。同時,為了改善傳統(tǒng)離子液體的缺陷,多種新型的離子液體衍生結(jié)構(gòu)也引起了研究人員的廣泛關(guān)注,比如兩性離子液體、聚離子液體等。關(guān)于離子液體有序分子聚集體的研究經(jīng)過近十年的快速發(fā)展,研究方向也不再僅僅局限于發(fā)現(xiàn)新的聚集體形貌,而是更加關(guān)注如何將離子液體獨特的物理化學(xué)性質(zhì)與有序分子聚集體的結(jié)構(gòu)、尺寸效應(yīng)相結(jié)合。一方面,基于離子液體的可設(shè)計性,將具有不同功能基團(tuán)的離子液體引入到分子有序聚集體中,是實現(xiàn)有序分子聚集體功能化的有效途徑。另一方面,得益于有序聚集體的結(jié)構(gòu)效應(yīng)和尺寸效應(yīng),也進(jìn)一步拓展了離子液體的應(yīng)用。本論文以離子液體的可設(shè)計性為基礎(chǔ),設(shè)計合成了多種具有特定功能的兩性離子液體以及聚離子液體,系統(tǒng)研究了離子液體結(jié)構(gòu)變化對其聚集體結(jié)構(gòu)和功能的影響。開展了以下四部分的工作:1.鋰離子傳導(dǎo)離子液體液晶的構(gòu)筑。采用兩性離子液體結(jié)構(gòu),通過咪唑兩性離子(3-(1-Dodecyl-3-imidazolio)propanesulfonate,C12IPS)與鋰鹽(LiTFSI)"中和"的方法,合成了含有鋰離子的室溫離子液體[C12IPS][LiTFSI]。C12IPS與LiTFSI室溫時均為固體粉末,等摩爾混合后,根據(jù)軟硬酸堿理論軟親軟、硬親硬的原則,兩性離子中的咪唑陽離子會優(yōu)先與TFSI-陰離子相互作用,從而使體系的晶格能顯著降低,形成室溫離子液體。由于兩性離子整體呈電中性,其在電場中并不遷移,因而可以實現(xiàn)鋰離子的選擇性傳輸。由于C12IPS具有典型的雙親分子結(jié)構(gòu),隨著[C12IPS][LiTFSI]/H20體系中離子液體濃度的不斷增大,觀察到了由蠕蟲狀膠束到六角液晶相、Ia3d雙連續(xù)立方液晶相以及層狀液晶相的轉(zhuǎn)變。采用POM、SAXS、流變等表征方法系統(tǒng)研究溫度和濃度對這種離子液體液晶相行為的影響,并以此為基礎(chǔ)探究了液晶微觀結(jié)構(gòu)對其電導(dǎo)率和傳導(dǎo)機理的影響。結(jié)果表明,液晶有序微觀結(jié)構(gòu)的引入顯著提高了鋰離子的傳輸效率,所有液晶樣品的電導(dǎo)率都呈現(xiàn)出明顯的結(jié)構(gòu)依賴性。其中,Ia3d雙連續(xù)立方液晶由于具有三維連續(xù)離子通道,與其他液晶相態(tài)相比電導(dǎo)率更高,離子傳導(dǎo)過程的表觀活化能更低。2.質(zhì)子傳導(dǎo)液晶體系的構(gòu)筑。在上一部分工作的基礎(chǔ)上,進(jìn)一步探索了兩性離子液體結(jié)構(gòu)變化對其聚集體形貌和功能的調(diào)控作用,構(gòu)筑了質(zhì)子傳導(dǎo)液晶體系。合成了一系列不同烷基鏈長的咪唑兩性離子(CnIPS,n=12,14,16),并通過與不同取代基結(jié)構(gòu)的磺酸(CH3SO3H,C6H5SO3H,CF3SO3H)"中和"的方法合成了一系列含有質(zhì)子的離子液體,探究了抗衡離子結(jié)構(gòu)變化和烷基鏈長對離子液體的物理化學(xué)性質(zhì)以及聚集行為的影響。其中[C12IpS][CH3SO3H]呈現(xiàn)出最豐富的相行為。這種雙親性離子液體可以在水溶液中自組裝形成六角相和Pm3n立方相結(jié)構(gòu)的質(zhì)子傳導(dǎo)液晶。采用POM和SAXS系統(tǒng)研究了這種離子液體參與構(gòu)筑的液晶體系的相行為并計算了相關(guān)機構(gòu)參數(shù),并以此為基礎(chǔ)探究了液晶微觀結(jié)構(gòu)對其電導(dǎo)率和傳導(dǎo)機理的影響。液晶有序微觀結(jié)構(gòu)的引入顯著提高了其電導(dǎo)率,并促成了質(zhì)子傳導(dǎo)由擴(kuò)散機理向跳躍機理的轉(zhuǎn)變,同時也觀察到了基于液晶相變過程的溫度響應(yīng)性質(zhì)子傳導(dǎo)行為。3.聚離子液體微觀有序陰離子傳導(dǎo)膜的構(gòu)筑。設(shè)計合成了一系列不同烷基鏈長的可聚合咪唑離子液體(3-n-alkyl-1-vinylimidazoliumbromide,CnVIMBr)。借助于這種離子液體的雙親性,構(gòu)筑了可聚合的六角液晶相和層狀液晶相,通過液晶原位光聚合的方法制備了自支持的聚離子液體膜。聚離子液體膜中液晶微觀結(jié)構(gòu)的保留通過SAXS、POM和SEM表征得到了確認(rèn)。雖然在C12VIMBr/H20的二元體系中只觀察到了六角和層狀液晶相,我們在嘗試過多種不同種類的添加劑之后,發(fā)現(xiàn)適量對二甲苯的加入可以在C12VIMBr/H20體系中誘導(dǎo)產(chǎn)生可聚合的Im3m雙連續(xù)立方液晶相,從而首次成功制備了具有雙連續(xù)立方液晶相結(jié)構(gòu)的陰離子傳導(dǎo)膜。對保留有六角、層狀和立方液晶微觀結(jié)構(gòu)的陰離子傳導(dǎo)膜的電導(dǎo)率、溶脹率和堿穩(wěn)定性等測試表明,液晶結(jié)構(gòu)的引入有效改善了其綜合性能,與沒有液晶結(jié)構(gòu)的對照組相比,具有液晶相結(jié)構(gòu)的陰離子傳導(dǎo)膜在實現(xiàn)高電導(dǎo)率的同時保持了極低的溶脹率。特別是具有Im3m雙連續(xù)立方液晶微觀結(jié)構(gòu)的陰離子傳導(dǎo)膜,借助于三維連續(xù)的氫鍵網(wǎng)絡(luò)促成了其氫氧根離子傳導(dǎo)由擴(kuò)散機理向跳躍機理的轉(zhuǎn)變。4.兩性離子軟模板制備貴金屬納米材料。受兩性離子液體結(jié)構(gòu)特點的啟發(fā),通過兩性離子與貴金屬前驅(qū)體離子之間的靜電相互作用,構(gòu)筑了抗衡離子為貴金屬前驅(qū)體離子的有序分子聚集體。通過分步還原法控制反應(yīng)速率,實現(xiàn)了以有序分子聚集體為模板的軟模板法制備貴金屬納米材料。在第一節(jié)中,合成了一種分子尾鏈末端帶有羥基的咪唑兩性離子,借助于羥基之間的氫鍵作用,在不加任何添加劑的情況下,這種兩性離子與等摩爾的HAuC14在水中可以自組裝形成多室囊泡。由于羥基具有一定的還原性,在體系中觀察到了以囊泡雙分子層為模板的金納米片的自還原過程,并進(jìn)一步通過兩步還原法實現(xiàn)了囊泡到球狀金納米顆粒的形態(tài)復(fù)制。在第二節(jié)中,通過調(diào)節(jié)兩性離子中的陽離子結(jié)構(gòu),成功得到了抗衡離子為AuCl4-,PtCl62-PdCl42-的蠕蟲狀膠束體系。并以蠕蟲膠束為模板得到了形貌規(guī)整的金、鉑、鈀及其合金的納米線網(wǎng)絡(luò)結(jié)構(gòu)。證明了雙親分子有序聚集體作為軟模板結(jié)構(gòu)易于調(diào)控和普適性的特點。
[Abstract]:After years of development, ionic liquids are no longer regarded as only "green solvents". Researchers have begun to purposefully design the anion and cation structure of ionic liquids for specific applications. A series of new ionic liquids have been designed and synthesized, including chiral ionic liquids, magnetic ionic liquids, amino acid ionic liquids and metal coordination. Subliquid and ionic liquid with redox activity have greatly expanded the application range of ionic liquids. At the same time, in order to improve the defects of traditional ionic liquids, a variety of new ionic liquid derivatization structures have attracted the attention of researchers, such as amphoteric liquid, polyionic liquids, etc.. On ionic liquids order. After nearly ten years of rapid development of molecular aggregation, the research direction is not only limited to the discovery of new aggregates, but more concerned with how to combine the unique physical and chemical properties of ionic liquids with the structure and size effect of ordered molecules. The ionic liquids of the same functional groups are introduced into the molecular ordered aggregates, which are an effective way to realize the functionalization of ordered molecules. On the other hand, the application of ionic liquids is further expanded thanks to the structural and dimensional effects of ordered aggregates. This paper is based on the design of ionic liquids and has been designed and synthesized. The effects of the structural changes of ionic liquids on the structure and function of the polymer were systematically investigated. The following four parts were carried out: 1. the construction of liquid crystal of lithium ion conduction ion liquid liquid crystal, amphoteric ionic liquid structure, and imidazole amphoteric ions (3- (1-Dodecyl-3-imidaz) Olio) Propanesulfonate, C12IPS) and the method of "Neutralization" with lithium salt (LiTFSI), synthesis of a room temperature ionic liquid containing lithium ion, [C12IPS][LiTFSI].C12IPS and LiTFSI at room temperature, are solid powders. After isormole mixing, the imidazole cations in the amphoteric ions will give priority to TFSI- detachment according to the softness and hardness principle of the theory of soft and hard acid and alkali. The lattice energy of the system is significantly reduced and the room temperature ionic liquid is formed. Because the amphoteric ion is neutral in the whole, it does not migrate in the electric field, and thus the selective transfer of lithium ion can be realized. Since C12IPS has a typical parent molecular structure, the ionic liquid concentration in the C12IPS][LiTFSI]/H20 system does not. The transition from vermicular micelle to six angle liquid crystal phase, Ia3d double continuous cubic liquid crystal phase and lamellar liquid crystal phase were observed. The influence of temperature and concentration on the liquid crystal phase behavior of this ionic liquid was systematically studied by means of POM, SAXS, rheology and so on. The results show that the introduction of the ordered microstructures of the liquid crystal significantly improves the transmission efficiency of the lithium ion, and the conductivity of all the liquid crystal samples shows a distinct structural dependence. In this case, the Ia3d double continuous cubic liquid crystal has a higher conductivity compared with the other liquid crystalline phase because of the three dimensional continuous ion channel, and the ion conduction process is higher than that of other liquid crystalline phase states. The structure of the.2. proton conducting liquid crystal system with apparent activation energy is lower. On the basis of the previous work, the regulation of the structure change of the amphoteric ionic liquid to its aggregate morphology and function is further explored. The proton conducting liquid crystal system is constructed. A series of CnIPS, n=12,14,16, which are different alkyl chain long, are synthesized. A series of ionic liquids containing protons were synthesized by the neutralization method of sulfonic acid (CH3SO3H, C6H5SO3H, CF3SO3H) with different substituent groups. The effects of the changes in the structure and the length of the alkyl chain on the physical and chemical properties of the ionic liquids and the aggregation behavior of the ionic liquids were investigated. Among them, [C12IpS][CH3SO3H] showed the most abundant phase behavior. A two parent ionic liquid can be self assembled in a aqueous solution to form a proton conducting liquid crystal with six angular phases and a Pm3n cubic phase structure. The phase behavior of the liquid crystal system constructed by this ionic liquid is studied by POM and SAXS systems, and the parameters of the related mechanism are calculated. The conductivity of the liquid crystal ordered microstructures was greatly improved, and the transformation of proton conduction from the diffusion mechanism to the jumping mechanism was promoted. At the same time, the structure of the micro ordered anion conduction membrane of the.3. polyionic liquid based on the temperature responsive proton conduction behavior of the liquid crystal phase transition process was also observed. A series of polymerizable imidazole ionic liquids (3-n-alkyl-1-vinylimidazoliumbromide, CnVIMBr) with different alkyl chain lengths were used to construct a polymerizable six angle liquid crystal phase and lamellar liquid crystal phase. A self supported polyionic liquid film was prepared by the method of liquid crystal in situ polymerization. Liquid membrane in polyionic liquid membrane was prepared. The retention of crystal microstructure was confirmed by the characterization of SAXS, POM and SEM. Although only six angles and lamellar liquid crystals were observed in the two element system of C12VIMBr/H20, we found that a proper amount of para xylene could be induced to produce polymerizable Im3m double connections in the C12VIMBr/H20 system after a variety of different kinds of additives were tried. The anion conducting membrane with a double continuous cubic liquid crystal phase structure was successfully prepared for the first time, and the conductivity, swelling rate and alkali stability of the anion conducting membrane with six angle, layered and cubic liquid crystal microstructures were tested. The results showed that the introduction of liquid crystal structure improved its comprehensive performance and no liquid crystal. Compared with the structure of the control group, the anion conduction membrane with the liquid crystal phase structure keeps a very low swelling rate while realizing high conductivity. Especially, the anion conduction membrane with the Im3m double continuous cubic liquid crystal microstructure has contributed to the mechanism of the hydrogen oxygen radical ion conduction from the diffusion mechanism to the hopping mechanism by the three-dimensional continuous hydrogen bond network. The.4. amphoteric ion soft template is used to prepare the noble metal nanomaterials. Inspired by the structure characteristics of the amphoteric ionic liquid, the ordered molecular aggregates are constructed by the electrostatic interaction between the amphoteric ions and the noble metal precursor ions. The reaction rate is controlled by the stepwise reduction method. In the first section, a kind of imidazole amphoteric ion with hydroxyl group was synthesized in the first section. With the aid of hydrogen bonding between hydroxyl groups, the amphoteric ions and isomole HAuC14 can be self assembled in water without any additives. As the hydroxyl group has a certain reducibility, the self reduction process of the gold nanoscale with the bimolecular layer of the vesicle is observed in the system, and the form of the spherical gold nanoparticles is replicated by the two step reduction method. In the second section, the cationic structure in the amphoteric ion is successfully regulated. The worm like micelle system with a counterion of AuCl4- and PtCl62-PdCl42- was obtained. The morphology of gold, platinum, palladium and its alloy nanowires was obtained by using worm micelle as a template. It was proved that the ordered aggregation of parent molecules was easy to regulate and universality as a soft template.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O645.1
，
本文編號：2171575
[Abstract]:After years of development, ionic liquids are no longer regarded as only "green solvents". Researchers have begun to purposefully design the anion and cation structure of ionic liquids for specific applications. A series of new ionic liquids have been designed and synthesized, including chiral ionic liquids, magnetic ionic liquids, amino acid ionic liquids and metal coordination. Subliquid and ionic liquid with redox activity have greatly expanded the application range of ionic liquids. At the same time, in order to improve the defects of traditional ionic liquids, a variety of new ionic liquid derivatization structures have attracted the attention of researchers, such as amphoteric liquid, polyionic liquids, etc.. On ionic liquids order. After nearly ten years of rapid development of molecular aggregation, the research direction is not only limited to the discovery of new aggregates, but more concerned with how to combine the unique physical and chemical properties of ionic liquids with the structure and size effect of ordered molecules. The ionic liquids of the same functional groups are introduced into the molecular ordered aggregates, which are an effective way to realize the functionalization of ordered molecules. On the other hand, the application of ionic liquids is further expanded thanks to the structural and dimensional effects of ordered aggregates. This paper is based on the design of ionic liquids and has been designed and synthesized. The effects of the structural changes of ionic liquids on the structure and function of the polymer were systematically investigated. The following four parts were carried out: 1. the construction of liquid crystal of lithium ion conduction ion liquid liquid crystal, amphoteric ionic liquid structure, and imidazole amphoteric ions (3- (1-Dodecyl-3-imidaz) Olio) Propanesulfonate, C12IPS) and the method of "Neutralization" with lithium salt (LiTFSI), synthesis of a room temperature ionic liquid containing lithium ion, [C12IPS][LiTFSI].C12IPS and LiTFSI at room temperature, are solid powders. After isormole mixing, the imidazole cations in the amphoteric ions will give priority to TFSI- detachment according to the softness and hardness principle of the theory of soft and hard acid and alkali. The lattice energy of the system is significantly reduced and the room temperature ionic liquid is formed. Because the amphoteric ion is neutral in the whole, it does not migrate in the electric field, and thus the selective transfer of lithium ion can be realized. Since C12IPS has a typical parent molecular structure, the ionic liquid concentration in the C12IPS][LiTFSI]/H20 system does not. The transition from vermicular micelle to six angle liquid crystal phase, Ia3d double continuous cubic liquid crystal phase and lamellar liquid crystal phase were observed. The influence of temperature and concentration on the liquid crystal phase behavior of this ionic liquid was systematically studied by means of POM, SAXS, rheology and so on. The results show that the introduction of the ordered microstructures of the liquid crystal significantly improves the transmission efficiency of the lithium ion, and the conductivity of all the liquid crystal samples shows a distinct structural dependence. In this case, the Ia3d double continuous cubic liquid crystal has a higher conductivity compared with the other liquid crystalline phase because of the three dimensional continuous ion channel, and the ion conduction process is higher than that of other liquid crystalline phase states. The structure of the.2. proton conducting liquid crystal system with apparent activation energy is lower. On the basis of the previous work, the regulation of the structure change of the amphoteric ionic liquid to its aggregate morphology and function is further explored. The proton conducting liquid crystal system is constructed. A series of CnIPS, n=12,14,16, which are different alkyl chain long, are synthesized. A series of ionic liquids containing protons were synthesized by the neutralization method of sulfonic acid (CH3SO3H, C6H5SO3H, CF3SO3H) with different substituent groups. The effects of the changes in the structure and the length of the alkyl chain on the physical and chemical properties of the ionic liquids and the aggregation behavior of the ionic liquids were investigated. Among them, [C12IpS][CH3SO3H] showed the most abundant phase behavior. A two parent ionic liquid can be self assembled in a aqueous solution to form a proton conducting liquid crystal with six angular phases and a Pm3n cubic phase structure. The phase behavior of the liquid crystal system constructed by this ionic liquid is studied by POM and SAXS systems, and the parameters of the related mechanism are calculated. The conductivity of the liquid crystal ordered microstructures was greatly improved, and the transformation of proton conduction from the diffusion mechanism to the jumping mechanism was promoted. At the same time, the structure of the micro ordered anion conduction membrane of the.3. polyionic liquid based on the temperature responsive proton conduction behavior of the liquid crystal phase transition process was also observed. A series of polymerizable imidazole ionic liquids (3-n-alkyl-1-vinylimidazoliumbromide, CnVIMBr) with different alkyl chain lengths were used to construct a polymerizable six angle liquid crystal phase and lamellar liquid crystal phase. A self supported polyionic liquid film was prepared by the method of liquid crystal in situ polymerization. Liquid membrane in polyionic liquid membrane was prepared. The retention of crystal microstructure was confirmed by the characterization of SAXS, POM and SEM. Although only six angles and lamellar liquid crystals were observed in the two element system of C12VIMBr/H20, we found that a proper amount of para xylene could be induced to produce polymerizable Im3m double connections in the C12VIMBr/H20 system after a variety of different kinds of additives were tried. The anion conducting membrane with a double continuous cubic liquid crystal phase structure was successfully prepared for the first time, and the conductivity, swelling rate and alkali stability of the anion conducting membrane with six angle, layered and cubic liquid crystal microstructures were tested. The results showed that the introduction of liquid crystal structure improved its comprehensive performance and no liquid crystal. Compared with the structure of the control group, the anion conduction membrane with the liquid crystal phase structure keeps a very low swelling rate while realizing high conductivity. Especially, the anion conduction membrane with the Im3m double continuous cubic liquid crystal microstructure has contributed to the mechanism of the hydrogen oxygen radical ion conduction from the diffusion mechanism to the hopping mechanism by the three-dimensional continuous hydrogen bond network. The.4. amphoteric ion soft template is used to prepare the noble metal nanomaterials. Inspired by the structure characteristics of the amphoteric ionic liquid, the ordered molecular aggregates are constructed by the electrostatic interaction between the amphoteric ions and the noble metal precursor ions. The reaction rate is controlled by the stepwise reduction method. In the first section, a kind of imidazole amphoteric ion with hydroxyl group was synthesized in the first section. With the aid of hydrogen bonding between hydroxyl groups, the amphoteric ions and isomole HAuC14 can be self assembled in water without any additives. As the hydroxyl group has a certain reducibility, the self reduction process of the gold nanoscale with the bimolecular layer of the vesicle is observed in the system, and the form of the spherical gold nanoparticles is replicated by the two step reduction method. In the second section, the cationic structure in the amphoteric ion is successfully regulated. The worm like micelle system with a counterion of AuCl4- and PtCl62-PdCl42- was obtained. The morphology of gold, platinum, palladium and its alloy nanowires was obtained by using worm micelle as a template. It was proved that the ordered aggregation of parent molecules was easy to regulate and universality as a soft template.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O645.1
，
本文編號：2171575
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