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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭淑芬(Soofin Cheng) | |
dc.contributor.author | Guan-Ping Chen | en |
dc.contributor.author | 陳冠萍 | zh_TW |
dc.date.accessioned | 2021-06-15T16:18:38Z | - |
dc.date.available | 2020-08-20 | |
dc.date.copyright | 2015-08-20 | |
dc.date.issued | 2015 | |
dc.date.submitted | 2015-08-17 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/52561 | - |
dc.description.abstract | 本研究主要是以一步合成法來製備含不同胺基官能基(diamine-、PholNH-、triamine-、PholNNH-、guanidine-、NH2-及MeNH-)之扁平狀SBA-15分子篩,使用tetraethylorthosilicate (TEOS) 作為矽源且以非離子型界面活性劑P123 (EO20PO70EO20)當作模板,在酸性條件下加入適量的ZrOCl2•8H2O來合成出二維孔洞結構p6mm的扁平狀介孔分子篩SBA-15。藉由In situ small-angle X-ray scattering找出不同胺基官能基於TEOS預水解的最佳化時間約為2小時,之後再加入胺基官能基對介孔分子篩的自組裝的干擾最小,而能製備出具有規則排列的骨架結構及孔洞大小相當一致的含胺基官能基介孔SBA-15材料。所得材料經由XRD、N2 adsorption-desorption isotherm、TGA、SEM、FT-IR、Solid state NMR等技術鑑定,可得知所合成出含不同胺基官能基的材料擁有很好的二維介孔結構、比表面積可達600 m2/g以上、孔徑分布相當集中、維持扁平狀形貌且證實胺基官能基有鑲嵌在二氧化矽的骨架中。接著,將一價銅離子(Cu+)引入含胺基官能基扁平狀SBA-15內,利用ICP-MS、XPS與XAS等技術鑑定觸媒中銅的相對含量與氧化態。主要探討配位基數目的多寡與有無半安定配位基 (hemilabile ligand) 的形成及配位基鹼性強度對催化苯乙炔自身耦合氧化加成反應的影響,以空氣作為氧化劑且在室溫下進行反應1 h後,產率即可高達90%以上且選擇率幾乎可達100%。此外,也針對鹼性添加物質進行一系列研究並發現不同鹼添加物對催化速率有極大的影響。更設計出觸媒中不僅含銅錯合物又具有強鹼性而形成協同效應,不須額外再加入Piperidine等鹼添加物質也能有相當好的催化活性與重複使用率。 | zh_TW |
dc.description.abstract | SBA-15 mesoporous silica materials with short mesochannels were functionalized with various amino-groups, including NH2-, MeNH-, PholNH, PholNNH-, diamine-, triamine-, guanidine- groups through one-pot co-condensation of tetraethylorthosilicate (TEOS) and amino-containing trimethoxysilane in the presence of P123 as pore-directing agent and appropriate amount of Zr(IV) ions. In situ X-ray scattering was used to find out the optimal prehydrolysis period of TEOS to be around 2 h prior to the addition of the amino-functional groups, in order to prepare platelet SBA-15 materials with well-ordered p6mm pore structure and narrowly distributed pore sizes. The resultant materials were characterized by XRD, N2 sorption isotherm, TGA, SEM, FT-IR, Solid NMR. Cu(I) was anchored with amino-functionalized SBA-15 through complexation, and the resultant Cu-amine-SBA-15-p was examined as the catalysts in the oxidative homocoupling of phenylacetylene at room temperature with air as the oxidant. With organic base as the additive, the yield and selectivity of 1,4-diphenyl-1,3-butadiyne were roughly up to 90% and nearly 100%, respectively. Furthermore, different kinds of base additives were found to have enormous influence on the rates of the reaction. Efforts were made to replace the liquid base additives by designing a Cu-catalyst with strong-basicity groups in order to have a synergistic effect and achieve reusability of the catalysts. | en |
dc.description.provenance | Made available in DSpace on 2021-06-15T16:18:38Z (GMT). No. of bitstreams: 1 ntu-104-R02223107-1.pdf: 8457824 bytes, checksum: ab1d6b08229616f6b70c04904536c68c (MD5) Previous issue date: 2015 | en |
dc.description.tableofcontents | 謝誌 I
摘要 II Abstract III 目錄 IV 表目錄 VIII 圖目錄 X Scheme XIX 第1章 緒論 1 1-1催化劑的發展 1 1-2介孔材料的介紹 2 1-2-1 M41S 的介紹-以鹼式法合成介孔型分子篩 2 1-2-2 SBA-15 的介紹-以酸式法合成介孔型分子篩 5 1-3界面活性劑及自我組裝(Self-Assembly) 9 1-3-1臨界微胞濃度之影響因子 12 1-3-2矽酸鹽與界面活性劑之作用 14 1-4具短孔道形貌之介孔 SBA-15 材料的介紹 16 1-4-1加入少量的Zr(IV)所形成扁平狀SBA-15自組裝的機制探討 18 1-5介孔材料的有機官能基化 19 1-6銅觸媒於催化反應的應用 23 1-6-1應用於末端炔(苯乙炔)自身耦合反應之觸媒 24 1-6-2末端炔(苯乙炔)自身耦合反應DFT模擬機制[66] 26 1-7 研究動機與目標 31 第2章 實驗部分 32 2-1 化學藥品 32 2-2 材料製備 33 2-2-1探討diamine-官能基於不同TEOS預水解時間加入對扁平SBA-15之影響 33 2-2-2 N-(2-hydroxybenzyl)-3-aminopropyltrimethoxysilane 的合成(以PholNH-表示) 33 2-2-3 N1-(2-aminoethyl)-N2-(2-hydroxylbenzyl)-3-aminopropyltri- methoxysilane 的合成(以PholNNH-表示) 34 2-2-4 Guanidinetrimethoxysilane (Cl)之合成 (以guanidine-表示) 35 2-2-5不同負載量之胺基官能基修飾於超短孔道之扁平狀介孔SBA-15的製備 36 2-2-6 活化觸媒前驅物 37 2-2-7含銅觸媒之製備 37 2-3鑑定材料之儀器與方法 38 2-3-1 X光粉末繞射 ( Powder X-ray Diffraction, XRD ) 38 2-3-2 氮氣吸附-脫附等溫曲線 ( N2 Adsorption-desorption Isotherm) 38 2-3-3掃描式電子顯微鏡 ( Scanning Electron Microscopy, SEM ) 41 2-3-4元素分析儀 (Elemental Analyzer, EA) 41 2-3-5熱重分析 ( Thermogravimetric Analysis, TGA ) 41 2-3-6霍氏紅外線光譜儀 ( Fluorier Transform Infrared Spectroscopy, FT-IR ) 41 2-3-7固態核磁共振光譜儀 ( Solid-state Nuclear Magnetic Resonance, SNMR ) 41 2-3-8誘導耦合電漿質譜儀 ( Inductively Coupled Plasma/Mass spectroscopy, ICP-MS ) 42 2-3-9 X光光電子能譜 ( X-ray Photoelectron Spectroscopy, XPS ) 42 2-3-10 X光吸收光譜 ( X-ray Absorption Spectroscopy, XAS ) 42 2-3-11 紫外光-可見光譜儀 ( UV-VIS reflectance spectroscopy, UV-Vis ) 43 2-4催化反應 44 2-4-1苯乙炔自身耦合氧化加成反應 44 2-4-2反應物及產物之定量分析 44 第3章 結果與討論 45 3-1探討diamine-官能基於不同TEOS預水解時間加入對扁平SBA-15之影響 45 3-1-1-a In situ-SAXS 45 3-1-1-b XRD 47 3-1-2 –HRSEM 47 3-1-3 –N2 Absorption/Desorption Isotherm 49 3-1-4 – 29Si-NMR 50 3-2 N-(2-hydroxybenzyl)-3-aminopropyltrimethoxysilane 的合成鑑定(以PholNH-表示) - 1H-NMR 51 3-3 N1-(2-aminoethyl)-N2-(2-hydroxylbenzyl)-3-aminopropyltri- methoxysilane 的合成(以PholNNH-表示) - 1H-NMR 53 3-4 guanidinetrimethoxysilane(Cl)的合成鑑定 55 3-5不同負載量之胺基官能基修飾於扁平狀型態與超短孔道之介孔SBA-15 56 3-5-1含胺基官能基之扁平狀介孔SBA-15之鑑定---XRD 56 3-5-2含胺基官能基之扁平狀介孔SBA-15之鑑定---HRSEM 63 3-5-3含胺基官能基之扁平狀介孔SBA-15之鑑定---N2 sorption isotherm 69 3-5-4含胺基官能基之扁平狀介孔SBA-15之鑑定---熱重分析 (TGA) 83 3-5-5含胺基官能基之扁平狀介孔SBA-15之鑑定---600 MHz 13C CP-MAS NMR 87 3-5-6含胺基官能基之扁平狀介孔SBA-15之鑑定---600 MHz 29Si NMR 92 3-6含銅觸媒的製備與鑑定結果 96 3-6-1含銅觸媒之製備 96 3-6-2含銅觸媒之鑑定(定性分析)---FT-IR 98 3-6-3含銅觸媒之鑑定(定性分析)---X光吸收光譜(XAS) 104 3-6-4含銅觸媒之鑑定(半定量分析)---X光光電子能譜(XPS) 108 3-6-5含不同胺基官能基的含銅異相觸媒之ICP-MS測定 116 3-7進行苯乙炔自身耦合氧化加成反應之催化 119 3-7-1含有鹼添加物的條件下,探討含不同胺基官能基之銅觸媒催化活性 119 3-7-2在無添加鹼性物質的條件下,探討含不同胺基官能基之銅觸媒催化活性 136 3-7-3探討載體形貌的改變對苯乙炔自身耦合反應的影響 145 3-7-4再生觸媒之催化活性 148 3-7-5以In situ UV-Vis偵測苯乙炔自身耦合反應過程 150 3-8異相銅觸媒應用於苯乙炔自身耦合氧化性加成反應之催化機制推導 152 3-8-1 Piperidine促進劑的存在下,催化機制的推導 152 3-8-2不加入任何鹼物質的條件下,催化機制的推導 154 3-8-3不加入任何鹼物質的條件下,針對Cu-10%-guanidine-p (Cu/F.G ~ 0.6)催化機制的推導 156 第4章 結論 158 第5章 參考文獻 162 | |
dc.language.iso | zh-TW | |
dc.title | 應用含Cu (I)-胺基之介孔 SBA-15在空氣下催化苯乙炔自身氧化耦合加成反應 | zh_TW |
dc.title | Application of Cu (I) Containing Amino-functionalized SBA-15 in Catalytic Oxidative Homocoupling of Phenylacetylene under Air | en |
dc.type | Thesis | |
dc.date.schoolyear | 103-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 牟中原(Chung-Yuan Mou),蔡蘊明(Yeun-Min Tsai),邱靜雯(Ching-Wen Chiu) | |
dc.subject.keyword | 含胺基之SBA-15,扁平狀形貌,預水解,末端炔之自身耦合反應,銅觸媒, | zh_TW |
dc.subject.keyword | Amino-functionalized SBA-15,Platelet morphology,Prehydrolysis,Homocoupling of terminal alkynes,Cu-catalyst, | en |
dc.relation.page | 165 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2015-08-17 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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