本文選題：金屬有機(jī)框架物　切入點(diǎn)：膜　出處：《浙江大學(xué)》2015年碩士論文

【摘要】：金屬有機(jī)框架物(Metal-organic frameworks, MOFs)作為一種新型的多孔材料,具有極大的比表面積、可調(diào)控的孔洞尺寸和形狀、骨架易被化學(xué)修飾,結(jié)構(gòu)豐富等優(yōu)點(diǎn),在氣體存儲(chǔ)、氣體吸附分離、傳感、催化、藥物釋放等領(lǐng)域都有廣闊的應(yīng)用前景。將MOFs以膜的形式制備在硅片、多孔氧化鋁、高分子膜等基底上,不僅高效經(jīng)濟(jì)適應(yīng)未來(lái)的工業(yè)化生產(chǎn),更能拓展其應(yīng)用。但目前MOF膜的研究還出于發(fā)展期,連續(xù)致密的MOF膜的制備仍存在挑戰(zhàn),如致密性不好、反應(yīng)能耗高、時(shí)間長(zhǎng),有機(jī)溶劑毒性大等,制約了性能的提高和生產(chǎn)的大規(guī)�；�。同時(shí),大多數(shù)MOFs都是在溶液中合成并形核長(zhǎng)大,形核過程的對(duì)晶體形貌、尺寸以及薄膜質(zhì)量等都有著重要影響,但鮮有針對(duì)此過程的研究。關(guān)于MOFs晶體和薄膜制備過程中添加劑對(duì)最終晶體形貌和性能影響的研究還處于初級(jí)階段,尚沒有明確的機(jī)理解釋。針對(duì)以上問題,本文開展了利用表面帶正電、活性高的銅基納米材料制備金屬有機(jī)框架物的研究。取得的主要?jiǎng)?chuàng)新性成果如下：1.采用氫氧化銅納米線作為銅源,通過“水浴加熱反應(yīng)-冷卻結(jié)晶”的方法制備出特殊的MOP-18管狀晶體。通過控制冷卻速率調(diào)節(jié)了晶體尺寸大小和形貌。研究了氨水作為添加劑在反應(yīng)體系中的作用：對(duì)含羧酸的有機(jī)配體去質(zhì)子化,促進(jìn)氫氧化銅納米線和有機(jī)配體配位形成MOP-18；在冷卻結(jié)晶過程中,促成“擴(kuò)散驅(qū)動(dòng)不穩(wěn)定”,使最終形成了管狀晶體。2.利用氫氧化銅納米線膜,通過室溫溶液反應(yīng)法,在氨和有機(jī)配體5-十二烷氧基間苯二甲酸摩爾比1：2,5-十二烷氧基間苯二甲酸濃度22 mmol/L左右的條件下,首次制備出連續(xù)的MOP-18膜。3.采用氧化銅納米片作為銅源,以室溫?cái)嚢璺磻?yīng)的方法在均苯三甲酸的乙醇／水溶液(vol乙醇：水=1：1)中快速制備出HKUST-1粉末。4.將氧化銅納米片制備成膜,室溫靜置于添加了甲酸鈉的、均苯三甲酸的水和乙醇溶液中,得到了連續(xù)致密的HKUST-1膜。采用不同溶劑進(jìn)行反應(yīng)發(fā)現(xiàn),DMF和水均不適合,水和乙醇混合溶劑最優(yōu)。同時(shí),研究了甲酸鈉作為添加劑對(duì)成膜的影響：由于對(duì)晶體表面有機(jī)配體有去質(zhì)子化作用,提高反應(yīng)程度,促使完全反應(yīng)形成純HKUST-1膜；提高晶體之間的互生,使膜更加致密；甲酸鈉添加量的增加會(huì)顯著提高反應(yīng)速率。溶液中均苯三甲酸的最優(yōu)濃度為5-10 mmol/L。在優(yōu)化條件下得到的HKUST-1膜的理想分離因子分別是H2/CH4=2.90, H2/N2=3.61, H2/CO2=4.24,表現(xiàn)為基于努森擴(kuò)散的氣體選擇性分離。
[Abstract]:Metal organic frameworks (Metal-organic, frameworks, MOFs) as a new type of porous material has great specific surface area, adjustable pore size and shape, the skeleton is easily modified, the structure of the advantages of rich in gas storage, gas adsorption and separation, sensing, catalysis, drug release and other fields have used broad prospects. The MOFs in the form of a film prepared on the silicon wafer, porous alumina, polymer film on substrate, not only efficient economy to adapt to industrial production in the future, it can expand its application. But at present the research of MOF film is in the period of development, continuous and compact MOF film preparation is still a challenge, such as dense bad reaction, high energy consumption, long time, organic solvent toxicity, which improve the large-scale production and performance. At the same time, because most of the MOFs in the solution synthesis and nucleation, nucleation process on crystal morphology, size And the film quality have a significant impact, but few studies in this process. The research on MOFs crystal and film preparation process, effects of additives on crystal morphology and properties of the final is still at the primary stage, there is no clear explanation of the mechanism. To solve the above problems, this paper carried out the research by the positively charged surface, copper base the preparation of nano materials of metal organic framework with high activity. The main contributions of this dissertation are as follows: 1. using copper hydroxide nanowires as copper source, preparation method by water bath heating and cooling crystallization reaction "to prepare MOP-18 tubular crystal special. By controlling the cooling rate of adjusting the size and morphology of crystal size was studied. Ammonia as additives in the reaction system in the role of organic ligands containing carboxylic acid deprotonation, promote copper hydroxide nanowires and organic ligands to form MOP-18; in the cold But in the process of crystallization, to promote the "diffusion driven instability", which eventually formed tubular crystals using.2. hydroxide nanowires film by reaction method at room temperature conditions in solution, ammonia and organic ligands 5- twelve alkoxy benzene two formic acid twelve mol ratio 1:2,5- alkoxy benzene two formic acid concentration of about 22 mmol/L under for the first time, the preparation of MOP-18 film by.3. continuous copper oxide nano sheets as copper source, ethanol / water solution with stirring at room temperature in all three formic acid (Vol ethanol: water =1:1) fast preparation of HKUST-1 powder.4. copper oxide nanosheets were prepared by the film, at room temperature in addition the sodium formate, all three formic acid water and ethanol solution, the continuous and compact HKUST-1 film. With different solvent reaction, and DMF are not suitable for water, water and ethanol mixed solvent. The optimal at the same time, the study of sodium formate as Tim Effect of additive on film: due to the deprotonation of the organic ligand crystal surface, improve the reaction degree, to completely formed by reaction of pure HKUST-1 film; improve the crystal between alternate, makes the film more compact; sodium formate additions will significantly improve the reaction rate. The optimal solution of ideal separation factor is the concentration of benzene three formic acid HKUST-1 film with 5-10 mmol/L. obtained at optimized conditions were H2/CH4=2.90, H2/N2=3.61, H2/CO2=4.24, is based on the selectivity of Knudsen diffusion separation.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.4

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本文編號(hào)：1694245