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研究生： 張溫文
Zhang, Wen-Wen
論文名稱： 40-環鋁鋅亞磷酸鹽的模板置換探索及催化性能研究
Template Exchange Exploration and Catalytic Property Study for 40-Membered Ring Aluminum Zincophosphite
指導教授： 王素蘭
Wang, Sue-Lein
口試委員: 黃暄益
Huang, Hsuan-Yi
林嘉和
Lin, Chia-Her
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： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 183
中文關鍵詞： 鋁鋅亞磷酸鹽 、模板置換 、二氧化碳環加成 、還氧丙烷 、NTHU-13 、碳酸丙烯酯
外文關鍵詞： Aluminum Zincophosphite, Template Exchange, Carbon dioxide catalysis, propylene oxide, NTHU-13, propylene carbonate
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    • 本論文研究目標主要是開發無機孔洞骨架物質在二氧化碳固定化的應用性。首先運用離子交換提升孔隙率的原理，將40R-NTHU-13(Al)(以下簡稱40R(Al))孔洞中所填充的模板離子，從長碳鏈的辛基銨(n-octlyammonium)換成短碳鏈的半胱銨(cysteammonium)；其次利用半胱銨具有的硫醇官能基進行銀奈米粒子的負載製作複合材料。最後對兩類修飾過的40R(Al)，分別研究其在環氧丙烷與二氧化碳的環加成反應中作為異相催化劑的效果。
    藉由熱重分析儀確認模板離子置換的比例與粉末X光繞射測量置換後樣品的結構穩定性，結果顯示約33%的辛基銨被置換成半胱銨為最佳置換條件，在後續將此樣品稱為40R-SH；40R(Al)固體表面原先呈現疏水性質，40R-SH則變為親水性。在77 K氮氣與196 K二氧化碳氣體吸附分析中，40R-SH展示出比40R(Al)相對高的吸附量：吸附量分別提升52 %與54 %，驗證了置換短鏈模板提升孔隙率的想法。此外，由電子顯微鏡影像分析亦證實奈米銀粒子能均勻附載在40R-SH上而得到40R-SH-Ag複合材料。
    40R(Al)骨架的建構單元分成ABC三種，C單元中的六配位鋅金屬中心的被證實是一個催化活性位點，可在二氧化碳與環氧丙烷環加成反應過程中提供環氧丙烷分子附著。因此進一步將鋅金屬中心部分摻雜鎂離子，再進行模板置換可得40R(Al)@Mg-SH。針對上述所有材料研究其催化效率：在80 ℃/1.36 MPa CO2的實驗條件下，對比文獻中其他晶性孔洞材料，40R(Al)所表現的催化效果TOF值(348.9 h-1)為最高；接著比較40R-SH與40R-SH-Ag，都發現具有因為結構修飾所貢獻的催化效果提升，尤其是當反應溫度是室溫時效果更明顯，最佳的催化效率則是由40R(Al)@Mg-SH所展現的30 %效率提升。
    此論文研究結果顯示40(Al)結構可修飾作為二氧化碳與環氧丙烷環加成反應的異相催化劑，開創了第一個金屬亞磷酸鹽孔洞結構在二氧化碳固定化之應用的首例。

    The goal of this thesis is to explore the application of inorganic nanoporous materials as the heterogeneous catalysts for the cycloaddition reaction of CO2 and epoxide, namely CO2 fixation. The template exchange was conducted on the aluminium zincophosphite with 40R channels (denoted by 40R(Al)) to replace the template, octylammonium (OA), with a smaller cysteammonium (CA) to enhance the porosity. The thiol functional group of CA in template-exchanged sample was utilized for Ag nanoparticles loading to prepare a nanocomposite. The efficiency of these functionalized materials as catalysts was evaluated.
    In the second chapter, several template-exchange conditions were examined by the concentration gradient of CA to give products which are characterized by TGA、EA and PXRD analysis. The results show the product of the optimized condition, which the integrity of structure sustained, was that near 33 % of OA exchanged by CA. The template exchange also resulted in the elevated porosity of template-exchanged sample (denoted by 40R-SH) compared to 40R(Al), evidenced by the enhancement of the adsorption capacity, 52 % for N2 and 54 % for CO2, respectively. More interestingly, the hydrophobic surface of 40R(Al) attributed to the long alkyl chain of OA was altered during the template exchange process. The surface of 40R-SH became hydrophilic, revealed by contact angle measurements, also an indication of the successful template exchange. Furthermore, we succeeded in loading silver nanoparticles with 1.8 nm particles size on 40R-SH, denoted by 40R-SH-Ag, which would be useful for further applications.
    It was perceived that block C, a structural building unit of 40R(Al), is an active site for the epoxide molecules to bind in the cycloaddition. Therefore, the Zn centers of block C were doped with Mg centers, which have shown catalytic activity in CO2 fixation. Followed by the template exchange, a sample named 40R(Al)Mg-SH was produced. By comparing the catalysis efficiencies of 40R(Al) and the crystalline porous materials in the literature, 40R(Al) showed the highest TOF value (348.9 h-1) in 80℃/1.36 MPa CO2 condition. The enhancements of catalysis efficiencies of 40R-SH and 40R-SH-Ag were observed especially at low temperature (i.e. R.T.). Remarkably, 40R(Al)@Mg-SH surpassed all the above-mentioned cases with a TOF value raised by 30 % relative to 40R(Al) in the same condition.
    In conclusion, 40R(Al) have shown viable post-modification and practical applications as the heterogeneous catalyst for the cycloaddition reaction of CO2 and epoxide and also been the first case of metal phosphites in CO2 fixation.

    目錄 第一章 緒論 1-1 背景簡介-------------------------------1 1-2 論文研究目標與成果摘要------------------8 1-3 水熱合成法簡介-------------------------11 1-4 藥品一覽表-----------------------------14 1-5 鑑定方法-------------------------------15 1-5-1 單晶X-ray繞射與結構分析---------------16 1-5-2 粉末X-ray繞射分析(PXRD)--------------20 1-5-3 熱重分析儀(TGA)----------------------21 1-5-4 元素分析(EA)-------------------------22 1-5-5高性能液相層析串聯質譜儀(HPLC- MS)-----23 1-5-6感應耦合電漿質譜儀(ICP-MS)-------------24 1-5-7高解析電子能譜儀(HR-XPS)---------------25 1-5-8穿透式電子顯微鏡(TEM)------------------26 1-5-9掃描式電子顯微鏡(SEM)------------------27 1-5-10 氣體吸脫附分析儀---------------------28 1-5-11 500 MHz核磁共振儀(500 MHz NMR)------32 1-6 參考文獻-------------------------------33 第二章 40員環鋁鋅亞磷酸鹽模板置換研究 2-1 背景簡介-------------------------------36 2-2 實驗部分-------------------------------47 2-3 化合物的鑑定及分析----------------------50 2-3-1單晶X光繞射(SXRD)與結構解析------------50 2-3-2粉末X光繞射分析(PXRD)------------------51 2-3-3熱穩定分析-----------------------------55 2-3-4 模板置換量分析------------------------62 2-3-5 樣品形貌分析--------------------------65 2-4 結果與討論------------------------------71 2-4-1 結構描述------------------------------71 2-4-2 性質討論------------------------------73 2-5 結論------------------------------------82 2-7 參考文獻--------------------------------83 第三章 40員環鋁鋅亞磷酸鹽於CO2催化性質研究 3-1 背景簡介--------------------------------85 3-2 實驗部分--------------------------------92 3-3 結果與討論------------------------------95 3-3-1 Block C催化能力與機制------------------95 3-3-2 40R(Al)應用於CO2環加成催化-------------99 3-3-3 共催化劑劑量探討----------------------100 3-3-4 反應溫度探討--------------------------102 3-3-5 40R(Al)催化循環測試-------------------104 3-3-6 修飾後40R(Al)的催化比較---------------105 3-3-7 NTHU-13催化整理-----------------------110 3-5 結論-----------------------------------116 3-6 參考文獻-------------------------------118 第四章 總結--------------------------------120 附錄一 : 晶體數據列表 附錄二 : CO2催化反應之1H-NMR圖譜 附錄三 : 文獻中的CO2催化效果

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