本文選題：介孔材料 + 微介孔復合材料��； 參考：《吉林大學》2015年博士論文

【摘要】：微介孔復合材料是研究人員期待的理想孔材料。但是如何能夠將沸石具有介孔結構而又不犧牲掉沸石本身具有的高穩(wěn)定性和催化活性是我們面臨的一大難題。目前多級孔分子篩材料的研究主要集中在硅鋁酸鹽材料方面，而多級孔磷酸鋁、磷酸硅鋁材料的報道很少，我們選擇合成微介孔復合材料的磷酸鋁、磷酸硅鋁催化材料在材料的合成和制備領域屬于應用基礎研究的前沿，對其酸活性和穩(wěn)定性的增加其進行探索。 本文成功利用導向劑法，將沸石分子篩的導向劑MFI，β，Y和L的次級結構單元在堿性條件下與十六烷基三甲基氯化銨表面活性劑相互作用，分別制備了高度有序的微介孔復合磷酸鋁材料SAPOS （Al-JQW-5，Al-JQW-6，Al-JQW-7和Al-JQW-8）。與傳統(tǒng)介孔SAPO材料相比，多級孔Al-JQW的孔壁較厚。而且介孔骨架縮合程度好，所以綜上兩點該介孔材料具有較高的熱穩(wěn)定性。而且隨著導向劑引入多級孔Al-JQW具有弱酸和強酸兩種的酸活性中心且酸性較強，另外從各種沸石前體組裝各種Al-JQW樣品的酸度是不同的。酸性強度的順序如下：Al-JQW-5Al-JQW-6的Al-JQW-7的Al-JQW-8，其結果與異丙基苯的催化實驗中的轉化率相同，而且與以前研究中得知的沸石的酸性順序相一致，如下：MFI BEA Y L。 第二部分實驗，我們使用微孔SAPO-5導向劑為無機物種使用十六烷基三甲基氯化胺（CTAC）作為模板劑，利用超聲波進行預處理，，水熱條件下成功地將SAPO-5分子篩納米晶嵌入了高度有序的介孔孔壁內，合成了微介孔復合硅磷酸鋁分子篩SAPO-5-UW，結果表明以三乙胺和CTAC為雙模板可以合成出微介孔復合分子篩SAPO-5-UW，透射電鏡（TEM）照片顯示產(chǎn)物具非常高的有序度，由于增厚的孔壁使其穩(wěn)定性較好且產(chǎn)物具有中強酸中心和弱酸中心，在酸催化方面有潛在的應用價值。合成中超聲波的輔助作用大大提高介孔相的生成速度，很好地實現(xiàn)了反應物之間的均勻混合，促進固體新相的形成，是一種非常方便快捷，并且適合廣泛應用于納米材料的合成輔助手法。我們在合成步驟中改變通過超聲輔助的順序，將表面活性劑事先在超聲環(huán)境下溶解，再加入導向劑，進一步水熱晶化后所得到的是孔徑在15-20納米具有SAPO-5單晶孔壁的囊泡。這是非常理想的多級孔材料，可是遺憾的是材料中有一部分是無定型非孔磷酸鋁材料。 當前，中國的生態(tài)環(huán)境已經(jīng)嚴重受到化學物質的污染，常年的水污染與大氣霧霾直接影響了人體健康。環(huán)境污染控制與修復是環(huán)境化學領域當務之急的重大問題，在前兩章的孔材料合成當中，本文作者發(fā)現(xiàn)，需要消耗很多的無機原料才能夠合成復合孔材料，而且一般的微介孔復合材料的有序的和熱穩(wěn)定性都不是特別理想。因此，作者認為如何突破傳統(tǒng)方法和技術以制備微孔，介孔以及復合孔材料和提高反應產(chǎn)率是目前合成研究中的一個極富探索意義的科學問題。 于是作者第三部分實驗致力于尋找到一個廉價的天然主體框架，可以將少量的沸石的次級結構單元進駐到主體框架內再進一步晶化，從而得到有序的超高穩(wěn)定性的微介孔復合材料，作者發(fā)現(xiàn)很多種天然礦石適合這個想法，比如膨潤土，云母等等，本著環(huán)保節(jié)約的想法，以工業(yè)的鈉基膨潤土為介觀主體框架，只應用少量微孔沸石的導向劑就創(chuàng)新性地成功合成了高熱穩(wěn)定性的酸活性的微介孔復合有序介孔材料，AMC-ZSM-5，AMC-Beta和AMC-TEOS。經(jīng)過測試我們新合成的材料具有非常高的熱穩(wěn)定性，這主要原因來源于其穩(wěn)定的膨潤土框架作為了孔道的上下孔壁，還有一部分原因是由于導向劑的加入使其左右孔壁也部分晶化。而且導向劑的加入使新材料具有微孔性，和其相對應的沸石的酸性。更重要的是使用的化學無機原料很少，屬于綠色合成化學，而且膨潤土一般更多的應用在污水處理方面，所以我們合成的微介孔復合有序介孔材料AMC-ZSM-5，AMC-Beta從制備到應用都是環(huán)境用好的新材料。
[Abstract]:Micro mesoporous composite is an ideal porous material expected by researchers. However, how to make zeolite have mesoporous structure without sacrificing the high stability and catalytic activity of zeolite itself is a difficult problem for us. At present, the research of multistage porous molecular sieves is mainly concentrated on the aluminosilicate material and multistage Kong Lin. Aluminum phosphate, aluminosilicate phosphate materials are rarely reported. We choose to synthesize aluminum phosphate of micro mesoporous composite. The synthesis and preparation of silicon and aluminum phosphate is the frontier of application basic research, and the increase of its acid activity and stability is explored.
In this paper, a highly ordered micro mesoporous aluminum phosphate composite SAPOS (Al-JQW-5, Al-JQW-6, Al-JQW-7 and Al-JQW-8) was prepared by interacting with the secondary structural units of zeolite molecular sieves MFI, beta, Y and L with sixteen alkyl three methyl ammonium chloride surfactants in alkaline conditions. Compared with the material, the multilevel hole Al-JQW has a thicker hole wall, and the mesoporous skeleton is well condensed, so the mesoporous material has high thermal stability. And with the introduction of the multi-stage hole, the Al-JQW has two acid active centers with weak acid and strong acid, and the acid is stronger. In addition, a variety of Al-JQW samples are assembled from various kinds of zeolite precursors. The order of the degree of acid is different. The order of the acid strength is as follows: Al-JQW-8 of Al-JQW-7 of Al-JQW-5Al-JQW-6, the result is the same as that in the catalytic experiment of isopropyl benzene, and it is in accordance with the acid order of the zeolite known in the previous study, as follows: MFI BEA Y L.
In the second part, we use the microporous SAPO-5 guiding agent for inorganic species to use sixteen alkyl three methyl chloramines (CTAC) as templates and pretreat them by ultrasonic wave. The SAPO-5 molecular sieve nanocrystals are successfully embedded in the highly ordered mesoporous wall under hydrothermal conditions, and the micro mesoporous compound silicon phosphate aluminum molecular sieve SAPO-5- is synthesized. UW, the results show that the micro mesoporous composite molecular sieve SAPO-5-UW can be synthesized with three ethylamine and CTAC as a double template. The transmission electron microscope (TEM) photo shows that the product has very high order degree. Because of the thickened hole wall, it has good stability and the product has middle and strong acid center and weak acid center. It has potential application value in acid catalysis. The auxiliary effect of sound waves greatly improves the formation speed of mesoporous phase, realizes the uniform mixing between reactants, and promotes the formation of new solid phase. It is a very convenient and quick method to be used in the synthesis of nano materials. In the synthetic procedure, we change the order of ultrasonic aid to the surface activity. The agent was dissolved in the ultrasonic environment and added to the guiding agent. After the hydrothermal crystallization, the pore size of the pore wall of the SAPO-5 single crystal hole was obtained at 15-20 nanometers. This is a very ideal multistage pore material. Unfortunately, some of the materials are amorphous and nonporous aluminum phosphate.
At present, the ecological environment of China has been seriously polluted by chemical substances. The annual water pollution and haze haze directly affect human health. The control and repair of environmental pollution is a major problem in the field of environmental chemistry. In the first two chapters, the author found that a lot of inorganic materials need to be consumed. The composite porous materials can be synthesized, and the ordered and thermal stability of the ordinary mesoporous composites are not particularly ideal. Therefore, the author believes that how to break through traditional methods and techniques to prepare micropores, mesoporous and compound porous materials and increase the yield of the reaction is a very important scientific problem in the recent research.
The third part of the author's experiment is to find a cheap natural body frame, which can further crystallize a small number of secondary structure units of zeolite into the main frame to obtain ordered ultra-high stability micro mesoporous composites. The author finds that many kinds of natural ores are suitable for this idea, such as bentonite, Mica and so on, in accordance with the idea of environmental conservation, using the industrial sodium bentonite as the mesoscopic frame, only a small amount of microporous zeolite guide is used to successfully synthesize the acid active microporous composite ordered mesoporous materials with high thermal stability. AMC-ZSM-5, AMC-Beta and AMC-TEOS. have been tested for our newly synthesized materials. The main reason for the high thermal stability is that the stable bentonite frame is used as the upper and lower hole wall of the channel, and partly because of the addition of the guide agent to crystallize the wall of the left and right holes. Moreover, the addition of the guide agent makes the new material microporous, and the acidity of the corresponding zeolite. Inorganic materials are rare, green synthetic chemistry, and bentonite is generally more used in sewage treatment, so our synthetic mesoporous composite ordered mesoporous material AMC-ZSM-5, AMC-Beta from preparation to application are good new materials for environmental use.
【學位授予單位】：吉林大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TB33

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本文編號：1941935