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研究生： 蘇楠迪
Su, Nan-Ti
論文名稱： 控制ZIFs/silicate材料中ZIFs晶體尺度與CO2吸附之研究
Control on ZIFs Crystal Size in the ZIFs/silicate for CO2 Adsorption
指導教授： 林弘萍
Lin, Hong-Ping
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 90
中文關鍵詞： 氣體擴散 、晶體大小 、金屬矽酸鹽 、ZIFs/矽酸鹽 、二氧化碳吸附劑
外文關鍵詞： diffusion-limit, crystal size, metal-silicate, ZIFs/silicate, CO2 adsorption capability
相關次數： 點閱：152  下載：16 
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    • 本論文主要是以控制ZIFs crystals的顆粒大小為目標，讓ZIFs crystals的粒徑在次微米或奈米的尺度，降低氣體在微孔材料的擴散限制，因此本研究利用metal-silicate為原料：當metal-silicate與配位基存在於適當的反應環境下，配位基會從metal-silicate中溶出金屬離子，並藉由孔洞氧化矽結構的存在，讓ZIFs crystals傾向藉由異相成核的方式生成，促使ZIFs crystals在原位生長和限制ZIFs crystals的顆粒大小，進而控制ZIFs crystals的顆粒和提高其分散性，增加ZIFs/silicate的均一度，提高二氧化碳的吸附效率，使ZIFs/silicate成為優良的二氧化碳吸附劑。
    製作Zn-silicate前驅物是採取異相成核法的概念，在pH8.0和水熱溫度為100oC的水熱反應條件下來達成Zn(OH)2與SiO2之間的重組，接著將Zn-silicate與2-methylimidazole在乙醇中進行迴流，藉此來促進2-methylimidazole與Zn2+螯合，生成具有高表面積(約500 m2 g-1)和熱穩定性佳(約450oC)的ZIF-8/silicate，而在ZIF-8/silicate中的ZIF-8 crystals大小約240 nm、呈現高的結晶度，製作的ZIF-8/silicate具有高二氧化碳的吸附力(0.530 mmol g-1)。
    以相同的合成法製作Co-silicate前驅物，只是需要調高反應溶液至pH9.0才能達成Co(OH)2與SiO2之間的重組，接著將Co-silicate與Benzimidazole在乙醇中進行迴流，就能形成高熱穩定性的ZIF-9/silicate，其ZIF-9 crystals具有強的結晶度，製作的ZIF-9/silicate具有高二氧化碳的吸附力(0.448 mmol g-1)；若將Co-silicate與2-methylimidazole在水中室溫下反應，就會形成ZIF-67/silicate，其對二氧化碳的吸附力為0.439 mmol g-1。

    To decrease diffusion-limit in microporous ZIFs crystals, the crystal size of ZIFs should be reduced to submicron- or nano-sized dimension. For this purpose, we use metal-silicate as metal ions precursor and imidazolate as linkers to prepare the ZIFs/silicate. To synthesize the ZIFs/silicate, an appropriate amount of wet metal-silicate was directly added into imidazolate solution, and then refluxed. In the presence of the silicate, the resulted ZIF-8 crystals size is about 240 nm, ZIF-9 crystals size is about 2 μm and ZIF-67 crystals size is about 60 nm. The ZIF-8/silicate has high surface area (the BET surface area ~ 500 m2 g-1) and high thermal stability (decomposition temperature ~ 450oC under N2 and air). The ZIF-9/silicate has high thermal stability as same as ZIF-8/silicate. Because of the low Co/Si mole ratio in the ZIF-67/silicate sample with high surface area and high thermal stability, the signal of ZIF-67 crystals is hard to be identified. All of these ZIFs/silicate demonstrate large CO2 adsorption capability, around 0.530 mmol g-1 at STP for ZIF-8/silicate, 0.448 mmol g-1 at STP for ZIF-9/silicate and 0.395 mmol g-1 at STP for ZIF-67/silicate at 60oC.

    第一章 緒論 1 1.1 孔洞材料的定義 1 1.2 有機金屬架構的介紹(2) 1 1.3 沸石咪唑酯架構的介紹 2 1.3.1 形成方式 4 1.3.2 孔徑分布 7 1.3.3 合成方法(8) 8 1.4 觸媒合成方法 14 1.5 二氧化碳的基本性質 16 第二章 實驗部分 18 2.1 化學藥品 18 2.2 實驗步驟 19 2.2.1 ZIF-8/silicate 19 2.2.2 ZIF-9/silicate 20 2.2.3 ZIF-67/silicate 21 2.3 儀器鑑定分析 22 2.3.1 掃描式電子顯微鏡(Scanning Electron Microscopy；SEM) 22 2.3.2 穿透式電子顯微鏡(Transmission Electron Microscopy；TEM) 22 2.3.3 熱重分析儀(Thermogravimetry Analysis；TGA) 23 2.3.4 全反射紅外光譜法(Attenuated Total Reflectance；ATR) 24 2.3.5 X-射線粉末繞射光譜(Powder X-Ray Diffraction，XRD) 24 2.3.6 氣體吸附行為的測量 25 第三章 Controlling on ZIF-8 crystal size 32 3.1 研究動機 32 3.2 不同的前處理是否能合成ZIF-8/silicate 33 3.3 ZIF-8/silicate完成反應的時間 35 3.4 最佳化的MeIm/Zn莫耳比例來合成ZIF-8/silicate 36 3.5 不同的氧化矽與Zn2+的結合度會影響ZIF-8/silicate的生成 37 3.6 Zn-silicate的合成法對ZIF-8/silicate的影響 41 3.7 Zn-silicate與ZIF-8/silicate的關係 43 3.8 ZIF-8/silicate的合成溫度 44 3.9 調整Zn/Si莫耳比例來增加ZIF-8 crystals的分散性和顆粒大小 45 3.10 利用反應濃度來控制ZIF-8 crystals的大小 46 3.11 ZIF-8/silicate母液回收再利用 47 3.12 CO2測試 49 第四章 Controlling on ZIF-9 and ZIF-67 crystal size 53 4.1 controlling on ZIF-9 crystal size 53 4.1.1 研究動機 53 4.1.2 Co-silicate的合成法對ZIF-9/silicate的影響 54 4.1.3 調動Co-silicate的pH值來調整Co(OH)2與氧化矽的結合度 57 4.1.4 改變氧化矽來增加ZIF-9 crystals的分散性 59 4.1.5 不同反應pH值的ZIF-9/silicate差異 60 4.1.6 以水取代有機溶劑來合成ZIF-9/silicate 62 4.1.7 最佳化的bIm/Co莫耳比例來合成ZIF-9/silicate 63 4.1.8 ZIF-9/silicate的合成溫度 64 4.1.9 更換金屬源來調控ZIF-9/silicate上ZIF-9 crystals的大小 64 4.1.10 調整Co/Si莫耳比例來增加ZIF-9 crystals的分散性和顆粒大小 65 4.1.11 ZIF-9/silicate母液回收再利用 66 4.1.12 CO2測試 67 4.2 controlling on ZIF-67 crystal size 71 4.2.1 動機 71 4.2.2 最佳化的MeIm/Co莫耳比例來合成ZIF-67/silicate 71 4.2.3 調整Co/Si莫耳比例來改善濾液中有鹼性的Co2+存在 74 4.2.4 改變氧化矽來增加ZIF-67 crystals的分散性 75 4.2.5 以水取代有機溶劑來合成ZIF-67/silicate 76 4.2.6 ZIF-67/silicate的合成溫度 77 4.2.7 ZIF-67/silicate完成反應的時間 78 4.2.8 ZIF-67/silicate母液回收再利用 79 4.2.9 CO2測試 80 第五章 總結 84 參考文獻 86

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