本文選題：ZIF-8膜　切入點(diǎn)：中空纖維管　出處：《浙江大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：金屬有機(jī)框架(Metal Organic Frameworks, MOFs)是一類由金屬離子與有機(jī)配體形成的有機(jī)無機(jī)復(fù)合多孔材料,因其優(yōu)異的比表面積以及光學(xué)特性等功能,近幾年來一直都是研究的熱點(diǎn)。類沸石咪唑框架(Zeolitic Imidazolate Frameworks,ZIFs)作為MOFs的一個(gè)重要子類,是由過渡金屬(如Zn、In等)和含N的咪唑類有機(jī)物相互交聯(lián)形成的多孔材料,其骨架為類似沸石分子篩的空間網(wǎng)狀拓?fù)浣Y(jié)構(gòu),且具有極大的比表面積、特定的孔道結(jié)構(gòu)以及優(yōu)良的熱穩(wěn)定性和化學(xué)穩(wěn)定性,因而在膜材料研究領(lǐng)域具有非常廣闊的應(yīng)用前景。目前ZIFs膜的研究已經(jīng)經(jīng)歷一段高速的發(fā)展期,關(guān)于ZIFs成膜的研究層出不窮,然而主要是集中在片狀載體上成膜或者分散于有機(jī)物中形成的復(fù)合膜,需要借助復(fù)雜的載體改性或者添加粘結(jié)劑等手段,并且得到的膜層普遍較厚,氣體的通量不高,膜層性能受到制約,同時(shí)片狀載體不適合制作膜組件,也不利于ZIF-8膜的大規(guī)模工業(yè)化應(yīng)用。針對(duì)以上問題,本論文選用高孔隙率、大比表面積以及適合于工業(yè)化放大的氧化鋁中空纖維管作為載體,研究其表面制備ZIF-8膜的影響因素。以自制的氧化鋁中空纖維管作為載體,采用簡便的晶種浸涂法在載體表面涂覆晶種層,通過二次生長法制備得到ZIF-8膜。重點(diǎn)考察了晶種大小、合成時(shí)間、合成配方等因素對(duì)成膜的影響。實(shí)驗(yàn)結(jié)果表明,由于ZIF-8晶體溶解現(xiàn)象的存在,雖然納米級(jí)晶體的晶種層分布均勻,但晶體外表面積大,在合成過程中晶體溶解速度快,不能很好地起到成核位點(diǎn)的作用,未能得到連續(xù)的ZIF-8膜；而對(duì)于微米級(jí)的晶體,雖然晶種層不及納米晶體均勻,但是由于外表面積小,在合成過程中溶解速度慢,晶體能夠很好地發(fā)揮成核位點(diǎn)的作用,在短短的2小時(shí)內(nèi)就誘導(dǎo)形成了連續(xù)致密的膜層,膜層厚度僅為7μm, H2滲透速率高達(dá)6.07×10-6mol·Pa-1·s-1·m-2,而H2與N2的理想分離因子達(dá)到了10.52,遠(yuǎn)遠(yuǎn)超過其努森分離因子。在不同的合成時(shí)間下研究了納米晶種以及微米晶種誘導(dǎo)成膜的生長規(guī)律,為晶體溶解現(xiàn)象的存在提供證據(jù)。對(duì)比了不同合成配方中晶體溶解現(xiàn)象的存在情況,證明了含有甲酸鈉的合成液中均存在晶體溶解現(xiàn)象。首次采用載體熱處理與合成液預(yù)晶化相結(jié)合的方法,通過原位生長在氧化鋁中空纖維管上制備ZIF-8膜。其具體步驟是(1)將氧化鋁中空纖維管載體置于150℃的烘箱中加熱4.0 h以上；(2)配置摩爾組成為ZnCl2:meIm:HCOONa: CH30H=1:1.5:1:250的合成液,并置于100℃的烘箱中預(yù)晶化一定的時(shí)間；(3)使合成液冷卻后,將熱處理過的載體趁熱插入預(yù)晶化過的合成液中；(4)將合成釜置于100℃烘箱中完成晶化。研究了不同預(yù)晶化時(shí)間、合成時(shí)間以及載體熱處理對(duì)成膜的影響。結(jié)果表明：合成液預(yù)晶化1.5 h、合成時(shí)間為4.0 h的條件下,制備得到了膜層厚度為6μm的ZIF-8膜,氣體透過性能測(cè)試結(jié)果表明H2的滲透率達(dá)到了1.38×10-5mol·Pa-1·s-1·m-2,H2/N2的理想分離因子為5.27,超過其努森分離因子。
[Abstract]:Metal organic frameworks (Metal, Organic Frameworks, MOFs) is a kind of organic inorganic composite porous materials by metal ions and organic ligand, because of its excellent surface area and optical properties and other functions, in recent years has always been a hot research. (Zeolitic Imidazolate zeolite imidazolate frameworks Frameworks, ZIFs) as a an important subclass of MOFs, is composed of transition metal (Zn, In) porous materials and N containing imidazole organic cross-linking to form, its skeleton space mesh topology is similar to zeolite, and has a very large surface area, specific pore structure and excellent thermal stability and chemical stability, so it has very broad application prospects in the research field of membrane materials. At present the research of ZIFs film has experienced a rapid development period, the research on ZIFs film is mainly concentrated however emerge in an endless stream, The composite film in the sheet carrier or dispersed in organic form, need to use complex carrier modification or addition of binder and other means, and the film is generally thick, gas flux is not high, the film performance is restricted, and the sheet carrier is not suitable for making membrane, large-scale industrial application is not for the ZIF-8 film. To solve the above problems, this paper adopts high porosity, large surface area and suitable for alumina hollow fiber on the industrial pipe as the carrier, to study the influencing factors on the preparation of ZIF-8 film on the surface of the alumina. With self-made hollow fiber tube as the carrier, using simple seed dipping coating on the surface of the carrier the seed layer, the two growth were prepared. The ZIF-8 film focuses on seed size, synthesis time, effect of synthetic formula and other factors on the film. The experimental results show that the ZIF-8 crystal The dissolution phenomenon, although the nano crystal seed layer of uniform distribution, but the crystal appearance of large area, in the process of synthesis of crystal dissolution speed, can play very well to the nucleation sites, failed to get a continuous ZIF-8 film; and for micron crystal, although less than the seed layer nano crystal uniform, but because of the appearance of a small area, in the synthesis process, slow dissolution rate, crystal can play well the role of nucleation sites, the film formed by continuous dense in just 2 hours, the film thickness is only 7 m, the permeation rate of H2 is 6.07 * 10-6mol Pa-1. S-1, m-2, and the ideal separation factor H2 and N2 reached 10.52, far more than the Knudsen separation factor under different synthesis. In the study of nanocrystalline and microcrystalline film induced the growth of crystal dissolution phenomenon exists for comparative evidence. The presence of crystal dissolution phenomena of different synthetic formula, proved that the crystal dissolution phenomena are synthetic solution containing sodium formate. Carrier method of heat treatment and pre crystallization combination of synthetic fluid used for the first time, the growth in ZIF-8 film was prepared by in situ alumina hollow fiber tube. The specific steps are (1) oven alumina hollow fiber carrier in 150 DEG C in heating above 4 h; (2) the molar composition of the synthesis solution configuration ZnCl2:meIm:HCOONa: CH30H=1:1.5:1:250, and in the time of 100 DEG C in an oven for a pre crystallization; (3) the synthesis liquid cooled, carrier will heat treated while hot insert pre crystallization synthesis liquid the; (4) the synthesis reactor is put into 100 DEG C oven complete crystallization was studied. Different pre crystallization time, reaction time and the influence of heat treatment on the carrier film. The results show that the synthetic liquid pre crystallization synthesis of 1.5 h. Time is 4 h under the conditions of preparation of the ZIF-8 film thickness is 6 m, gas permeability test results show that the penetration rate of H2 reached 1.38 * 10-5mol - Pa-1 - S-1 - m-2, ideal separation factor of H2/N2 is 5.27, more than the Knudsen separation factor.

【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)】：TQ051.893

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