發(fā)布時(shí)間：2018-05-19 07:08

  本文選題：金屬-有機(jī)框架材料 + 膜�。� 參考：《浙江大學(xué)》2014年博士論文

【摘要】：金屬-有機(jī)框架材料(Metal-organic frameworks,簡稱MOFs)作為一種新型的多孔無機(jī)-有機(jī)雜化晶態(tài)材料,在氣體存儲(chǔ)與分離、發(fā)光、傳感等領(lǐng)域具有重大的應(yīng)用前景,并受到廣泛的關(guān)注。膜材料具有高效、節(jié)能、經(jīng)濟(jì)等特點(diǎn),而且還能將應(yīng)用范圍拓展到一些氣態(tài)介質(zhì)領(lǐng)域,如氣體膜分離、氣體傳感等。目前,MOF膜的研究還處于初始階段,針對連續(xù)密堆積的MOF膜的制備和后功能化修飾的研究還很少�；跉怏w分子與MOF膜孔徑的尺寸差異和氣體分子相互間的分子量差異,有時(shí)難以對尺寸和分子量相近的氣體實(shí)現(xiàn)較好的分離,因而利用氣體分子與MOF膜孔洞表面的官能團(tuán)之間不同的相互作用實(shí)現(xiàn)氣體的高效分離成為一種新的思路。MOFs材料在熒光探測領(lǐng)域的研究主要集中于粉體材料對液體中小分子、離子等的探測,這極大限制了對氣態(tài)介質(zhì)的熒光探測。同時(shí),發(fā)光MOF膜,尤其是具有優(yōu)異發(fā)光性能的、以稀土離子為發(fā)光中心的MOF膜的直接制備尚存在很大的挑戰(zhàn)。 針對以上問題,本文主要開展了金屬-有機(jī)框架膜的多方法制備、后功能化修飾以及性能研究：采用原位溶劑熱法分別在多孔陽極氧化鋁膜、多孔α氧化鋁陶瓷片以及Pt納米顆粒修飾的硅片上制備連續(xù)密堆積的MOF多晶膜,同時(shí)利用“雙銦源”的方法在ITO(氧化銦錫)玻璃上制備了MOF多晶膜；研究了孔洞表面帶有羧酸官能團(tuán)的MOFs粉末的氣體吸附分離性能和該類MOF多晶膜的氣體膜分離性能；采用稀土離子后功能化修飾的方法,獲得以稀土離子為發(fā)光中心的發(fā)光MOF膜；研究了發(fā)光膜對硫醇蒸氣、氧氣等的熒光探測性能,以及MOFs中稀土離子與有機(jī)配體之間不同的傳能過程對氧氣探測性能的影響。 采用溶劑熱法合成了一種具有大孔結(jié)構(gòu)的、孔洞表面羧酸基團(tuán)修飾的MOFs材料In3O(OH)(H2O)2[BTC]2(MIL-100(In), BTC=1,3,5-苯三甲酸)。研究表明,由于MIL-100(In)孔洞表面含有羧酸基團(tuán),MOFs與極化率較高的甲烷間的相互作用強(qiáng)于極化率較低的氮?dú)?室溫下甲烷的吸附量約為氮?dú)獾?.5倍,甲烷／氮?dú)獾奈竭x擇性約為1.8�；贛IL-100(In)粉末的氣體吸附分離性能的研究,采用原位溶劑熱生長法在多孔陽極氧化鋁膜和多孔a氧化鋁陶瓷片上制備了連續(xù)密堆積的MIL-100(In)多晶膜,并研究活化后的MOF多晶膜對甲烷與氮?dú)獾臍怏w膜分離性能。單組份氣體滲透實(shí)驗(yàn)表明,以多孔陽極氧化鋁膜為支撐的、約5μm厚的MOF多晶膜對甲烷和氮?dú)獾睦硐敕蛛x因子為3.38,甲烷滲透速率為0.81×10-6mol·m-2·s-1·Pa-1；以多孔α氧化鋁片為支撐的、約5μm厚的MOF多晶膜,對甲烷和氮?dú)獾睦硐敕蛛x因子為2.75,甲烷的滲透速率為1.32×10-6mol·m-2·s-1·pa-1。甲烷和氮?dú)馀cMOFs之間不同的相互作用強(qiáng)度使兩種氣體在MOFs中形成較大差異的表面擴(kuò)散速率,最終致使MOF多晶膜具有優(yōu)異的CH4/N2膜分離性能,為天然氣和煤層氣中的甲烷濃縮與提純提供了新途徑。同時(shí),從氣體在多孔膜中的表面擴(kuò)散機(jī)理的角度去選擇與制備孔洞表面具有官能團(tuán)修飾的MOFs分離膜的策略為設(shè)計(jì)與制備具有優(yōu)異分離性能的MOF膜提供了新的思路。 采用溶劑熱法在表面經(jīng)Pt納米顆粒修飾的硅片上成功制備了厚度范圍為0.3～4.5μm的連續(xù)MIL-100(In)多晶膜。探索MIL-100(In)膜的生長過程和生長機(jī)理,推測MOFs在高缺陷和高表面能的Pt納米顆粒表面更容易形核與生長,從而促進(jìn)膜的生長與制備。采用稀土離子后功能化修飾的方法制備了以稀土離子為發(fā)光中心的MIL-100(In)(?)Ln3+(Ln=Eu、Tb、Dy和Sm)多晶膜。研究表明稀土離子與MOFs孔洞中的末去質(zhì)子化的羧基發(fā)生配位作用,從而通過配體到稀土離子的傳能作用,使稀土離子發(fā)光得到敏化。經(jīng)活化的多孔MIL-100(In)(?)Eu3+發(fā)光膜對易揮發(fā)的1,2-乙二硫醇、正丁硫醇有較好的原位熒光探測性能。處于飽和蒸氣濃度的1,2-乙二硫醇和正丁硫醇能夠使MIL-100(In)=)Eu3+多晶膜分別發(fā)生約92%和94%的熒光淬滅。后修飾的方法為制備以稀土離子為發(fā)光中心的MOF膜提供了一種新的途徑,解決了稀土MOFs難以制備為發(fā)光膜的難題。同時(shí)MOF發(fā)光膜能夠直接實(shí)現(xiàn)原位熒光探測,排除非原位探測帶來的干擾。 采用“雙銦源”方法,在表面覆蓋氧化銦錫層的ITO玻璃上原位溶劑熱生長制備了三種以In3+為金屬離子的金屬-有機(jī)框架膜,In12O(OH)12[(OH)4·(H2O)5][BTC]6(MIL-96(In))、[(CH3)2NH2][In3O(BTC)2(H2O)3]2[In3(BTC)4](CPM-5)和MIL-100(In)多晶膜。以MIL-96(In)多晶膜為例研究了其在ITO玻璃基板上的生長過程與生長機(jī)理,研究表明ITO玻璃表面的氧化銦錫層為MIL-96(In)在表面形核與生長提供了一種銦離子的來源,從而促進(jìn)MOFs在表面的形核速率和生長速度。CPM-5為陰離子型金屬-有機(jī)框架材料,孔洞中含有可自由移動(dòng)的電平衡離子(CH3)2NH2+,因此實(shí)驗(yàn)采用離子交換后修飾的方法制備了含電平衡離子Tb3+的CPM-5(?)Tb3+發(fā)光膜。利用MIL-100(In)孔洞中含有未去質(zhì)子化的羧基,采用后修飾的方法引入能與羧基發(fā)生螯合配位作用的Tb3+制備MIL-100(In)(?)Tb3+發(fā)光膜�；贛OFs的多孔性特點(diǎn),研究了發(fā)光膜對氧氣的探測性能,并考察了Tb3+在兩種膜中不同的存在方式對氧氣探測性能的影響。研究表明兩種膜具有很好的氧氣探測性能,膜的發(fā)光強(qiáng)度與氧氣分壓間的Sterm-Volmer曲線呈現(xiàn)很好的線性關(guān)系。以分子內(nèi)能量轉(zhuǎn)移的方式敏化稀土離子發(fā)光的MIL-100(In)(?)Tb3+多晶膜比以分子間能量轉(zhuǎn)移的方式敏化稀土離子發(fā)光的CPM-5(?)Tb3+多晶膜具有更高的Sterm-Volmer淬滅常數(shù)KSV,即更高的靈敏度；并且由于MIL-100(In)(?)Tb3+比CPM-5(?)Tb3+具有更高的孔隙率,前者的膜具有更短的響應(yīng)時(shí)間和恢復(fù)時(shí)間。MIL-100(In)(?)Tb3+多晶膜的氧氣淬滅常數(shù)KSV最高約為14,對應(yīng)的響應(yīng)時(shí)間和恢復(fù)時(shí)間分別為4s和39s。稀土離子與有機(jī)配體間的能量傳遞過程對氧氣探測性能的影響的研究為制備具有高靈敏度和快響應(yīng)時(shí)間的MOF發(fā)光膜指引了方向。
[Abstract]:Metal-organic frameworks (MOFs), as a new type of porous inorganic organic hybrid crystalline material, has a great application prospect in the fields of gas storage and separation, luminescence, sensing and so on. It has been widely concerned. The membrane material has the characteristics of high efficiency, energy saving, economy and so on, and it can also extend the application scope. In some gaseous media, such as gas membrane separation, gas sensing, and so on. At present, the research of MOF film is still in the initial stage. There are few studies on the preparation and post functional modification of the continuous dense MOF membrane. The size difference between the pore size of gas molecules and the MOF membrane and the molecular weight difference between the gas subdivisions are sometimes difficult to be measured in size. A new way of separating gas from the interaction between gas molecules and the functional groups on the surface of the cavity surface of the MOF membrane becomes a new idea. The study of.MOFs materials in the field of fluorescence detection mainly focuses on the detection of small molecules, ions, and so on. The fluorescence detection of the gaseous medium is greatly limited. At the same time, the direct preparation of the luminescent MOF film, especially the MOF film with rare earth ions as the luminescent center, has great challenge.
In order to solve the above problems, this paper mainly carried out multi method preparation of metal organic frame membrane, post functionalized modification and performance study. In situ solvothermal method was used to prepare continuous dense MOF polycrystalline membrane on porous anodic alumina membrane, porous Al2O3 ceramic tablet and Pt nano particle modified silicon chip. The MOF polycrystalline membrane was prepared on ITO (indium tin oxide) glass by the method of indium source. The gas adsorption separation performance of the MOFs powder with carboxylic functional groups on the hole surface and the separation performance of the gas film in this kind of MOF polycrystalline membrane were studied. The luminescent MOF film with rare earth ions as the luminescent center was obtained by the method of functional modification after the rare earth ions. The detection performance of luminescence film for thiol vapor, oxygen and so on, as well as the influence of different energy transfer processes between rare earth ions and organic ligands in MOFs on the detection performance of oxygen are studied.
A kind of MOFs material In3O (OH) (MIL-100 (In), BTC=1,3,5- benzene three formic acid modified by the carboxylic acid group on the pore surface is synthesized by solvothermal method. The study shows that the interaction between the MIL-100 (In) hole surface contains carboxylic acid groups and the interaction between MOFs and high polar methane is stronger than that of low polarizability. The adsorption of methane at room temperature is about 2.5 times that of nitrogen, and the adsorption selectivity of methane / nitrogen is about 1.8. based on MIL-100 (In) powder. The in-situ solvent thermal growth method is used to prepare a continuous dense MIL-100 (In) polycrystalline membrane on porous anodic alumina membrane and porous a alumina ceramic. The performance of methane and nitrogen gas membrane was separated from the activated MOF polycrystalline membrane. The single component gas permeation experiment showed that the ideal separation factor of methane and nitrogen was 3.38 and the methane permeation rate was 0.81 x 10-6mol. M-2. S-1. Pa-1 with porous anodic alumina membrane supported by porous anodic alumina membrane, and the methane permeation rate was 0.81 x 10-6mol. M-2. S-1. Pa-1; porous Al2O3 was supported. The ideal separation factor of methane and nitrogen is 2.75, the ideal separation factor of methane and nitrogen is 2.75. The permeability rate of methane is 1.32 * 10-6mol. M-2. S-1. Pa-1. methane and the different interaction strength between nitrogen and MOFs, which makes the two different kinds of surface diffusion rate in MOFs, which eventually leads to the excellent CH4/N2 film of MOF polycrystalline membrane. The separation performance provides a new way for the concentration and purification of methane in natural gas and coalbed methane. At the same time, the strategy of selecting the MOFs separation membrane with functional group modification on the surface of the porous membrane from the surface diffusion mechanism of the gas in the porous membrane provides a new idea for the design and preparation of the MOF film with excellent separation performance.
Continuous MIL-100 (In) polycrystalline membrane with a thickness range of 0.3 to 4.5 u m was successfully prepared on the surface of Pt nanoparticles modified by solvothermal method. The growth process and growth mechanism of MIL-100 (In) films were explored. It is speculated that MOFs can be more easily nucleated and grown on the surface of Pt nanoparticles with high defects and high surface energy, thus promoting the growth of the membrane and the growth of the membrane. The polycrystalline films of MIL-100 (In) (?) (?) Ln3+ (Ln=Eu, Tb, Dy and Sm) with rare earth ions as the luminescent center were prepared by functional modification after rare earth ions. The study showed that the coordination of rare earth ions and the carboxylic groups of the terminal deprotonation in the pores of MOFs, through the transfer of the ligand to the rare earth ions, led to the luminescence of the rare earth ions. The activated porous MIL-100 (In) (?) Eu3+ luminescent film has a good in situ fluorescence detection performance for the volatile 1,2- B two thiol and n-butanol. The 1,2- two thiol and n-butanol at the saturated vapor concentration can make the MIL-100 (In) =) Eu3+ polycrystalline membrane about 92% and 94% fluorescence quenching respectively. The rare earth ions provide a new way for the MOF film of the luminescent center, which solves the difficult problem that the rare earth MOFs is difficult to prepare as a luminescent film. At the same time, the MOF luminescent film can directly detect the fluorescence in situ and eliminate the interference from the non in situ detection.
Three kinds of metal organic frame membranes, In12O (OH) 12[(OH) 4. (H2O) 5][BTC]6 (MIL-96 (In)), In12O (OH) 12[(OH) 4. (MIL-96) and polycrystalline membrane, are prepared by the "double indium source" method in situ solvothermal growth on the ITO glass covered with indium tin oxide layer. The growth process and growth mechanism on the ITO glass substrate have been studied. The study shows that the indium tin oxide layer on the surface of ITO glass is MIL-96 (In), which provides a source of indium ions in the surface nucleation and growth, thus promoting the nucleation rate and growth speed of MOFs on the surface of the MOFs as an anionic organic frame material and the hole in the hole. There is an electrically balanced ion (CH3) 2NH2+ that can be freely moved, so the CPM-5 (?) Tb3+ luminescence film of an electrically balanced ion Tb3+ is prepared by the method of post exchange modification. MIL-100 (In) Kong Dongzhong contains an unprotonated carboxyl group, and the post modification method is used to prepare MIL-100 (In) with a Tb3+ that can chelate the carboxyl group. Tb3+ luminescence film. Based on the characteristics of the porous properties of MOFs, the detection performance of the luminescent film on oxygen is studied, and the effect of different modes of existence of Tb3+ on the oxygen detection performance in the two kinds of membranes is investigated. The study shows that the two films have good oxygen detection performance, and the Sterm-Volmer curves between the luminescence intensity and the oxygen partial pressure of the membrane are very good. The MIL-100 (In) (?) Tb3+ polycrystalline membrane sensitized by the intramolecular energy transfer method has a higher Sterm-Volmer quenching constant KSV, or higher sensitivity, than the CPM-5 (?) Tb3+ polycrystalline membrane sensitized by the intermolecular energy transfer method; and because MIL-100 (In) Tb3+ is CPM-5 (?) Tb3+. With higher porosity, the former film has shorter response time and recovery time, the oxygen quenching constant KSV of.MIL-100 (In) Tb3+ polycrystalline membrane is about 14. The corresponding response time and recovery time are the study of the influence of the energy transfer process between the 4S and 39s. rare earth ions and the organic ligands on the oxygen detection performance. The MOF light-emitting film with high sensitivity and fast response time has guided the way.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TB383.2

【參考文獻(xiàn)】

相關(guān)博士學(xué)位論文 前1條

1 張鳳;金屬有機(jī)骨架膜的制備與性能研究[D];吉林大學(xué);2013年

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