臺灣博碩士論文加值系統

類沸石咪唑酯框架(ZIF)是一種具有發展性的材料應用於膜的氣體分離，在我們的研究中，藉由核延續法以核-殼的結構將ZIF-8與ZIF-67結合而形成ZIF-67@ZIF-8，相較於ZIF-67，ZIF-67@ZIF-8展現出高比表面積、氣體吸附以及熱穩定性，將ZIF填充物加入6FDA-DAM搭配適當的溶劑去製備混合基材薄膜。為了瞭解核-殼結構的氣體分離機制，薄膜的製備占很重要的角色來獲得無缺陷的複合膜，包括膠體溶液、priming method與熱處理。均勻散佈的核-殼沸石咪唑酯框架複合膜提供氣體擴散更多的微孔的通道，氣體擴散的結果指出複合膜擁有非凡的氫氣通透性以及微小地增加對於氮氣與甲烷的選擇性，最好性能的核-殼沸石咪唑酯框架複核膜超越了氫氣與甲烷的2008羅伯森上限，核-層類沸石咪唑酯框架複核膜的現象不只適用於玻璃高分子，也適用於橡膠高分子。

Zeolitic imidazolate framework (ZIF) is a promising material in membrane technology for gas separation. In our work, ZIF-8 and ZIF-67 were synthesized in the form of core-shell structure (ZIF-67@ZIF-8) by the seed mediated growth method. ZIF-67@ZIF-8 nanocrystals present higher surface area, gas uptake and thermal stability in comparison with the core (ZIF-67). ZIF fillers were added into 6FDA-DAM with the proper solvent to fabricate mixed matrix membranes (MMMs). In order to realize the mechanism of the core-shell structure, the preparation of membrane plays an important role to obtain defect-free nanocomposite by the colloidal solution, priming method and annealing treatment. The well-dispersed core-shell ZIFs nanocomposites provide more microporous pathways for gas separation. The result of MMMs demonstrates a remarkable hydrogen permeability and the slight enhancement of selectivities against N2 and CH4. The highest performance of ZIF-67@ZIF-8 MMM surpasses the 2008 Robeson’s upper bound for H2/CH4. This effect of core-shell structure can be observed in glassy as well as rubbery polymer.

摘要 ……………………………………………………………………………………..i
Abstract ……………………………………………………………………………………ii
Acknowledgement iv
List of Figures vii
List of Tables ix
Chapter 1 Background 1
1-1 Introduction 1
1-2 Review of Relevant Literature 5
1-3 Motivation 14
Chapter 2 Experimental 15
2-1 Materials and Reagents 15
2-2 Instruments 15
2-3 Instrument Analysis and Identification 16
2-3-1 Scanning Electron Microscopy 16
2-3-2 Transmission Electron Microscopy 17
2-3-3 Energy-Dispersive X-ray Spectroscopy 17
2-3-4 X-ray Diffraction 18
2-3-5 Thermogravimetric Analysis 19
2-3-6 Fourier-Transform Infrared spectroscopy 19
2-3-7 Gel Permeation Chromatography 19
2-3-8 Micropore Size and Surface Area Analysis 20
2-3-9 Nanomechanical characterization 21
2-3-10 Single Gas Separation System 21
2-4 Experiment Methods 23
2-4-1 Synthesis of Zeolitic Imidazolate Framework 23
2-4-2 Synthesis of Neat 6FDA-DAM 24
2-4-3 Fabrication of Mixed Matrixed Membranes 25
2-4-4 Gas permeation measurements 26
Chapter 3 Result and Discussion 28
3-1 Characteristics of ZIF-67 and ZIF-67@ZIF-8 Particles 28
3-1-1 X-ray Diffraction of ZIFs 28
3-1-2 Morphology of ZIFs 29
3-1-3 Sorption Analysis of ZIFs 31
3-1-4 Thermogravimetric Analysis of ZIFs 33
3-1-5 Dispersion in solvents 35
3-2 Characteristics of 6FDA-DAM 37
3-2-1 FTIR Spectra and GPC of 6FDA-DAM 37
3-3 Characteristics of ZIFs/6FDA-DAM Mixed Matrix Membranes 39
3-3-1 The Morphology of Mixed Matrix Membrane 39
3-3-2 XRD pattern of ZIFs/6FDA-DAM MMMs 43
3-3-3 FTIR Spectra of ZIFs/6FDA-DAM MMMs 44
3-3-4 Thermogravimetric Analysis of ZIFs/6FDA-DAM MMMs 45
3-3-5 Mechanical property of ZIFs/6FDA-DAM MMMs 47
3-4 Gas Separation Performance of ZIFs/6FDA-DAM MMMs 49
Chapter 4 Conclusions 60
Chapter 5 Future Work 61
Reference 62

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