本文選題：透射電子顯微分析 + 電子衍射斷層術(shù)�。� 參考：《吉林大學(xué)》2015年博士論文

【摘要】：隨著材料科學(xué)的發(fā)展,材料種類(lèi)也越來(lái)越豐富,微孔材料因?yàn)榫哂写蟮谋缺砻娣e、分子選擇性等優(yōu)點(diǎn),而被廣泛應(yīng)用于氣體吸附與分離、離子交換以及催化等領(lǐng)域。但一種材料是否有應(yīng)用價(jià)值、有多大的應(yīng)用前景,與其結(jié)構(gòu)性質(zhì)是緊密相關(guān)的,因此對(duì)材料的結(jié)構(gòu)進(jìn)行研究有著十分重要的意義。微孔材料根據(jù)其結(jié)晶性劃分,包含了無(wú)定形的微孔材料(如活性炭、PAF等)已及結(jié)晶的微孔材料(如分子篩、金屬-有機(jī)骨架材料等)。無(wú)定形材料由于在原子量級(jí)為無(wú)序排列或者為短程有序,因此很難用一個(gè)確切的結(jié)構(gòu)模型來(lái)描述,因此我們研究的重點(diǎn)是結(jié)晶微孔材料的結(jié)構(gòu)問(wèn)題。傳統(tǒng)的研究晶體結(jié)構(gòu)的主要手段有:單晶X-射線衍射法(SXRD)、粉末X-射線衍射法(PXRD)以及透射電子顯微分析(TEM)等三種方法。本論文主要運(yùn)用透射電子顯微學(xué)方法來(lái)研究沸石分子篩(Zeolite)和金屬-有機(jī)骨架材料(Metal-Organic Frameworks,MOFs)的結(jié)構(gòu)問(wèn)題,特別是利用一種全新的透射電子顯微分析技術(shù)——三維電子衍射斷層重構(gòu)(Electron Diffraction Tomography,EDT)技術(shù)來(lái)解析分子篩和金屬-有機(jī)骨架材料的結(jié)構(gòu)。本文主要包含以下幾個(gè)部分:第一章是緒論部分,概述了微孔材料和透射電子顯微鏡的發(fā)展歷史,簡(jiǎn)單介紹了傳統(tǒng)的透射電子顯微學(xué)的應(yīng)用以及取得的成果,并重點(diǎn)講述了三維電子衍射斷層技術(shù)(EDT)的發(fā)展背景、工作原理。另外,也對(duì)三維電子衍射斷層重構(gòu)的研究工具——RED軟件做了詳細(xì)介紹等。第二章,主要介紹了傳統(tǒng)的透射電子顯微學(xué)在沸石分子篩材料的結(jié)構(gòu)研究中的應(yīng)用。首先,我們利用高分辨透射電子顯微術(shù)(High Resolution Transmission Electron Microscopy,HRTEM)研究了A相富集Beta分子篩中的A、B相層錯(cuò)共生的缺陷問(wèn)題。并在原子級(jí)層面分析了其A、B相的堆積方式,計(jì)算了不同樣品顆粒中A相所占的比例。其次,我們研究了多級(jí)孔Beta分子篩材料的孔壁結(jié)晶情況,以及樣品整體的結(jié)晶性,并證明了該樣品顆粒整體上是高度有序的結(jié)晶微介孔復(fù)合材料。最后,我們還研究了多級(jí)孔ZSM-5分子篩樣品顆粒的結(jié)晶狀況,以及構(gòu)成樣品顆粒的納米片的生長(zhǎng)取向問(wèn)題。第三章,主要探索了EDT技術(shù)在MOFs材料的結(jié)構(gòu)分析中應(yīng)用的可行性。目前,利用EDT技術(shù)解析分子篩結(jié)構(gòu)已經(jīng)有了大量報(bào)道,但利用EDT技術(shù)來(lái)解析MOFs材料的結(jié)構(gòu)尚未有報(bào)道,因此我們計(jì)劃將EDT技術(shù)拓展到MOFs材料的結(jié)構(gòu)解析領(lǐng)域。金屬鋯的MOFs具有著良好的穩(wěn)定性,而Ui O-66便是其中的典型代表。Ui O-66具有粒徑尺寸均一(一般在100-300nm)、穩(wěn)定性良好,因此很適合用EDT技術(shù)來(lái)嘗試解析它的結(jié)構(gòu)。我們?cè)谟肊DT方法獲得Ui O-66的骨架結(jié)構(gòu)之后,將其與HRTEM直接“觀察”得到的結(jié)果進(jìn)行了比較,發(fā)現(xiàn)兩者是吻合的,最后我們又將其與PXRD精修得到的結(jié)構(gòu)的原子位置進(jìn)行了比較,發(fā)現(xiàn)RED方法獲得結(jié)果與PXRD結(jié)果的原子位置坐標(biāo)基本相同,僅有一個(gè)氧原子(O2)的位置坐標(biāo)有較大的偏差(0.35?),其他原子的位置坐標(biāo)偏差均小于0.1?。這說(shuō)明EDT技術(shù)應(yīng)用于金屬-有機(jī)骨架材料的結(jié)構(gòu)解析是可行的。第四章,我們主要應(yīng)用了EDT技術(shù)來(lái)研究了MOFs材料——JUC-32的端基氧原子。材料端基原子(或原子團(tuán))的性質(zhì)在很大程度上決定了材料的物理化學(xué)性質(zhì),因此對(duì)材料端基原子的研究具有重要的意義。隨著透射電子顯微技術(shù)的進(jìn)步,特別是球差校正電鏡的出現(xiàn),利用透射電子顯微鏡直接“觀察”到金屬氧化物中的氧原子已經(jīng)實(shí)現(xiàn)。但想要“觀察”到氧原子就需要很高的放大倍率,此時(shí)單位面積電子輻照劑量也非常高,對(duì)樣品損傷也十分嚴(yán)重,因此利用球差校正電鏡只能研究在電子束輻照下非常穩(wěn)定的材料。而絕大多數(shù)MOFs材料在電子束作用下都很不穩(wěn)定,因而很難用球差校正電鏡直接“觀察”來(lái)研究。而利用其他電子顯微學(xué)方法來(lái)研究MOFs材料的端基原子的文獻(xiàn)也鮮有報(bào)道,因此利用EDT技術(shù)來(lái)研究確定JUC-32端基氧原子位置就有著十分重要的意義。第五章,我們利用EDT技術(shù)成功解析了一種新型磷鋁分子篩PST-6的結(jié)構(gòu)骨架,并將其結(jié)果與HRTEM照片分析的結(jié)果進(jìn)行了對(duì)比,發(fā)現(xiàn)兩者是基本吻合的,再次證明了三維電子衍射斷層重構(gòu)技術(shù)可以廣泛應(yīng)用于復(fù)雜分子篩的結(jié)構(gòu)解析�？偨Y(jié),本論文討論了傳統(tǒng)透射電子顯微學(xué)在材料結(jié)構(gòu)研究中的應(yīng)用,將EDT技術(shù)對(duì)比傳統(tǒng)的結(jié)構(gòu)解析方法的做了對(duì)比,探討了EDT技術(shù)在MOF材料的結(jié)構(gòu)解析中的運(yùn)用的可行性,最后我們利用EDT技術(shù)成功解析了結(jié)構(gòu)未知的磷鋁分子篩PST-6的骨架結(jié)構(gòu)。我們的研究工作為EDT技術(shù)的進(jìn)一步完善和發(fā)展做出了積極的貢獻(xiàn)。也為電子顯微學(xué)方法在材料結(jié)構(gòu)研究中的應(yīng)用與推廣產(chǎn)生了極大的促進(jìn)作用。
[Abstract]:With the development of material science, the variety of materials is becoming more and more rich. Microporous materials have been widely used in the fields of gas adsorption and separation, ion exchange and catalysis because of the advantages of large specific surface area and molecular selectivity. However, whether a material has application value or not has many applications and is closely related to its structure and properties. Therefore, it is of great significance to study the structure of materials. According to their crystallization, microporous materials include amorphous microporous materials (such as activated charcoal, PAF, etc.) and crystallized microporous materials (such as molecular sieves, metal organic skeleton materials, etc.). Amorphous materials are arranged in order of order in order of order, or for short range. Therefore, it is difficult to describe the structure of a precise structural model, so the focus of our research is the structure of crystalline microporous materials. The main means to study the crystal structure are three methods, such as single crystal X- ray diffraction (SXRD), powder X- ray diffraction (PXRD) and transmission electron microanalysis (TEM). This paper is mainly used in this paper. Transmission electron microscopy is used to study the structural problems of zeolite molecular sieves (Zeolite) and metal organic framework materials (Metal-Organic Frameworks, MOFs), especially for the analysis of molecular sieves and gold using a new transmission electron microscopic analysis technique, three dimensional electron diffraction fault reconstruction (Electron Diffraction Tomography, EDT) technology. The structure of the genera organic skeleton material. This article mainly contains the following parts: the first chapter is the introduction, summarizing the development history of microporous materials and transmission electron microscopy, briefly introducing the application and achievements of traditional transmission electron microscopy, and focusing on the development background of the three-dimensional electron diffraction tomography (EDT). The second chapter, the second chapter, mainly introduces the application of traditional transmission electron microscopy in the structure study of zeolite molecular sieve materials. First, we use High Resolution Transmission Elec (high resolution transmissive electron microscopy). Tron Microscopy, HRTEM) studied the defects of A and B phase dislocation in Beta molecular sieves enriched by A phase, and analyzed the accumulation mode of A and B phase at the atomic level and calculated the proportion of A phase in different sample particles. Secondly, we studied the pore wall crystallization of multistage pore Beta molecular sieves and the crystallization of the sample as a whole. It is proved that the sample particles are highly ordered crystalline micro mesoporous composites on the whole. Finally, we also studied the crystallization of the sample particles of the multistage ZSM-5 molecular sieve and the growth orientation of the nanoscale particles that constitute the sample particles. The third chapter mainly explored the application of EDT in the structural analysis of MOFs materials. At present, there have been a lot of reports on the analysis of molecular sieve structure using EDT technology, but it is not reported that using EDT technology to analyze the structure of MOFs materials has not been reported. Therefore, we plan to extend the EDT technology to the domain of structural analysis of MOFs materials. The MOFs of metal zirconium has good stability, and Ui O-66 is a typical.Ui O-66. The size of the particle size is uniform (generally in 100-300nm) and has good stability, so it is very suitable to use EDT technology to try to analyze its structure. After we use the EDT method to obtain the skeleton structure of Ui O-66, we compare the results with the results obtained directly from the HRTEM "observation", and find that they are in good agreement with the PXRD. Finally, we also refined it with the PXRD. The atomic position of the structure is compared. It is found that the results obtained by the RED method are basically the same as the atomic position coordinates of the PXRD results. The position coordinates of only one oxygen atom (O2) have a larger deviation (0.35?) and the position coordinates of other atoms are less than 0.1? This indicates that the EDT technology is applied to the structural analysis of the metal organic skeleton materials. It is feasible. In the fourth chapter, we mainly use EDT technology to study the MOFs material, the terminal oxygen atom of JUC-32. The properties of the end group atom (or atomic mass) determine the physical and chemical properties of the material to a great extent. Therefore, it is of great importance to the study of the end group atom of the material. Especially for the appearance of spherical aberration correction electron microscopy, the oxygen atom in metal oxide has been realized by transmission electron microscope directly. But the need to "observe" the oxygen atom needs a high magnification. At this time the radiation dose per unit area is very high and the damage to the sample is very serious, so the spherical aberration correction is used. Electron microscopy can only study very stable materials irradiated by electron beams, and most of the MOFs materials are very unstable under the action of electron beams. Therefore, it is difficult to use the spherical aberration correction electron microscopy to direct "observation". And the literature of the end group of MOFs materials by other electron microscopy methods is rarely reported, so the use of EDT Technology It is of great significance to study and determine the position of the JUC-32 terminal radical oxygen atom. In the fifth chapter, we have successfully analyzed the structural skeleton of a new type of phosphorus aluminum molecular sieve PST-6 using EDT technology, and compared the results with the results of the HRTEM photo analysis. The layer reconstruction technique can be widely used in the structural analysis of complex molecular sieves. In this paper, the application of traditional transmission electron microscopy in the study of material structure is discussed. The comparison of EDT technology to traditional structural analytical methods is made, and the feasibility of using EDT technology in the structural analysis of MOF materials is discussed. Finally, we benefit The framework of the unknown structure of phosphorus and aluminum molecular sieve PST-6 is successfully analyzed by EDT technology. Our research work has made a positive contribution to the further improvement and development of EDT technology. It also has a great promoting effect on the application and popularization of electron microscopy in the study of material structure.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TB303

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