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研究生： 林冠文
Lin, Guan-Wen
論文名稱： 以四吡啶基卟吩合成金屬有機結構物之製備、鑑定與應用
Synthesis, characterization, and application of tetrapyridylporphine-based metal-organic framework
指導教授： 許梅娟
Syu, Mei-Jywan
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 77
中文關鍵詞： 二氧化碳 、金屬有機結構物 、卟吩
外文關鍵詞： carbon dioxide, metal-organic framework, porphine
相關次數： 點閱：318  下載：0 
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    • 隨著工業與科技的發展，人類大量排放的二氧化碳被視為溫室效應惡化最主要原因，尋找有效的除碳材料以減少大氣中的二氧化碳，成為重要的課題。以金屬離子與有機配體配位而成的金屬有機結構物 (metal-organic frameworks, MOFs)，為高孔洞性、具有可撓性的可設計性的孔洞材料，可使用其作為儲存與催化二氧化碳的應用；針對金屬有機結構物之合成與材料鑑定為本研究的主題。
    本研究使用卟吩 (porphine) 衍生物TPyP (5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine)) 與鈷離子以溶劑加熱法進行配位化學反應，合成金屬有機結構物。合成的材料以FT-IR (Fourier-transform infrared spectrometer) 與UV/Vis spectrophotometer (ultraviolet/visible spectrophotometer) 驗證配位化學反應的發生；以SEM (scanning electron microscope)、XRD (X-ray diffraction analyzer) 與氣體吸附儀測定材料的基本性質；以TGA analyzer (thermogravimetric analyzer) 估算鈷離子與TPyP組成比例；並以二氧化碳吸附測試與化學吸附儀評估二氧化碳應用的可行性。
    由FT-IR鍵結分析可證實TPyP與鈷離子發生配位化學反應並形成配位共價鍵結；從TGA估算出鈷元素與TPyP組成比例約為1.3:1.0，推測其形成延續性的結構物；從UV/Vis光譜圖中，反應前後主要吸收峰發生藍位移，說明鈷離子螯合於TPyP中心，使TPyP去質子化並形成配位共價鍵結，使結構更加對稱。由SEM可得知晶體呈現規則的六角柱狀；由XRD圖說明合成出的材料具有良好的結晶性質。材料的BET surface area大約為357368 m2/g，Langmuir surface area大約為472488 m2/g；另外，二氧化碳吸附量為56.9 cm3/g，二氧化碳化學吸附量為0.44 mmol/g CoTPyP STP (19 mg/g CoTPyP STP)，顯示材料對於二氧化碳具有化學吸附能力，預期加入適當的犧牲劑作為提供電子轉移的媒介，即可作為二氧化碳還原觸媒應用。
    本研究亦有使用TPBi (2,2',2'-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole))分別與鈷離子、銅離子以溶劑加熱法進行配位化學反應，嘗試合成金屬有機結構物；雖推測其鍵結皆形成，但無良好結果。推測是因為TPBi具有較大的立體障礙，導致配位鍵結受到較大的干擾，預期如能於反應中加入適當的第二種有機配體或選用其他有機配體，將有助於鍵結與結構形成。

    Metal-organic frameworks (MOFs), also called porous coordination polymers (PCPs). They are porosity materials with molecular pore size. They possess special chemical sites and have fine tunability by precise design. In this research, we synthesized CoTPyP and discussed the potential for application on the adsorption of carbon dioxide. CoTPyP was synthesized by solvothermal synthesis with cobalt(II) acetate tetrahydrate as the metal precursor and tetra(4-pyridyl)-porphine (TPyP) as the organic ligand. The MOF was confirmed by Fourier-transform infrared spectrometer (FT-IR) and ultraviolet/visible spectrophotometer (UV/Vis spectophotometer). The surface morphology of CoTPyP is hexagonal from the scanning electron microscope (SEM) images. CoTPyP owns good crystallinity which can be inspected from X-ray diffraction analyzer (XRD). The ratio of cobalt and TPyP in CoTPyP was estimated to be approximately 1.3:1.0 by thermogravimetric analyzer (TGA analyzer). For CoTPyP, the BET surface area was about 357368 m2/g, the Langmuir surface area was around 472488 m2/g and the carbon dioxide uptake capacity was 56.9 cm3/g, respectively. Thermal stability of CoTPyP is up to 200oC. The water & light stability was good.

    目錄 中文摘要 I Extended Abstract II 誌謝 V 目錄 VI 表目錄 IX 圖目錄 X 第一章 緒論 1 1-1 前言 1 1-1-1 金屬有機結構物 (Metal-organic frameworks, MOFs) 1 1-1-2 溫室氣體 (Greenhouse gas) 1 1-1-3 研究動機與目的 2 第二章 文獻回顧 3 2-1 金屬有機結構物 3 2-1-1 金屬有機結構物組成要件 [5,6] 3 2-1-2 金屬有機結構物組成方式 [12] 5 2-2 金屬有機結構物之合成方法 [13,14] 7 2-2-1 傳統溶劑加熱法 (Conventional solvothermal synthesis) [15,16] 7 2-2-2 微波溶劑加熱法 (Microwave-assisted solvothermal synthesis) 8 2-2-3 超音波化學合成法 (Sonochemical synthesis) 8 2-2-4 電化學合成法 (Electrochemical synthesis synthesis) 9 2-2-5 溶劑乾燥法 (Solvent evaporation synthesis) 9 2-2-6 液相磊晶法 (Liquid phase epitaxy or layer by layer method) 10 2-2-7 機械力化學合成法 (Mechanochemical synthesis) 10 2-2-8 離子加熱法 (Ionothermal synthesis) 11 2-2-9 微流體合成法 (Microfluidic synthesis) [24] 11 2-2-10 異相溶劑沉積法 (Heterogeneous solution deposition) 12 2-3 金屬有機結構物應用 12 2-3-1 氣體儲存 (Gas storage) 12 2-3-1-1 氫氣儲存 [25] 12 2-3-1-2 二氧化碳儲存 [29] 13 2-3-2 分離純化 (Separation and purification) 15 2-3-3 感測 (Sensor) 15 2-3-4 藥物載體 (Drug delivery) [36] 17 2-3-5 催化 (Catalysis) [41] 18 2-3-5-1 有機催化反應 18 2-3-5-2 二氧化碳還原催化 20 第三章 實驗方法、材料與儀器 23 3-1 金屬有機結構物CoTPyP之合成 23 3-1-1 金屬有機結構物CoTPyP網狀結構之粗產物 23 3-1-2 金屬有機結構物CoTPyP之再結晶 23 3-1-3 合成溶劑對CoTPyP網狀結構之影響 23 3-2 金屬有機結構物CoTPBi之合成 24 3-3 金屬有機結構物CuTPBi之合成 24 3-4 分析儀器與原理簡介 25 3-4-1 紫外/可見光光譜儀 (Ultraviolet/visible spectrophotometer, UV/Vis) 25 3-4-2 傅立葉轉換紅外線光譜儀 (Fourier-transform infrared spectrometer, FT-IR) 25 3-4-3 掃描式電子顯微鏡 (Scanning electron microscope, SEM) 26 3-4-4 X射線繞射儀 (X-ray diffraction, XRD) 26 3-4-5 熱重分析儀 (Thermogravimetric analyzer, TGA) 26 3-4-6 表面積及奈米孔徑分析儀 (Surface area and porosimetry analyzer) 27 3-4-7 全自動化學吸附儀 (Fully automated chemisorption analyzer) 27 3-5 實驗藥品 28 3-6 實驗儀器 29 第四章 結果與討論 30 4-1 金屬有機結構物之合成 30 4-2 各項儀器測定 32 4-2-1 傅立葉轉換紅外線 (FT-IR) 之官能基分析 32 4-2-2 紫外/可見光 (UV/Vis) 光譜儀之吸光度測定 35 4-2-3 熱重分析 36 4-2-4 SEM影像之表面形態分析 38 4-2-5 XRD之結晶性分析 42 4-2-6 氣體吸附儀對合成材料之吸附孔洞分析 45 4-2-7 CoTPyP之二氧化碳化學吸附測量 49 4-3 穩定性測試 50 4-3-1 熱穩定測試 50 4-3-2 水與光穩定性測試 52 4-4 合成溶劑對CoTPyP網狀結構之影響 53 4-4-1 以chloroform為合成溶劑 53 4-4-2 以DMSO為合成溶劑 56 4-5 以有機配體TPBi進行金屬有機結構物之合成研究 61 4-5-1 金屬有機結構物CoTPBi之合成 61 4-5-2 金屬有機結構物CuTPBi之合成 66 第五章 結論 71 參考文獻 72   表目錄 表2-3-1 金屬有機結構物於光催化二氧化碳之無氫還原應用 21 表4-2-1 CoTPyP粗產物與再結晶產物重量損失及估算之成份組成莫爾比 37 表4-2-2 較長與較短反應時間所得的結晶物表面形態與尺寸大小整理比較 40 表4-2-3 粗產物與再結晶產物孔洞分析資料 47 表4-2-4 CoTPyP粗產物與PCN-88二氧化碳吸附比較 48 表4-2-5 CoTPyP粗產物之二氧化碳化學吸附分析資料 49 表4-4-1 不同溶劑合成之CoTPyP產物的分析資料 59 表4-5-1 CoTPBi之孔洞分析資料 65 表4-5-2 CuTPBi之孔洞分析資料 69   圖目錄 圖1-1-1 有機金屬結構之應用 [2] 1 圖1-1-2 每年與金屬有機結構物相關文獻發表數量 (1990–2015) [4] 2 圖2-1-1 價殼層電子對互斥理論 (Valence shell electron-pair repulsion, VSEPR) 簡圖 3 圖2-1-2 金屬有機結構物中常見之有機化合物形式 [6] 4 圖2-1-3 常見界面活性劑 5 圖2-1-4 同形相容金屬/有機金屬有機結構物組成 [12] 6 圖2-1-5 核殼金屬有機結構物組成 [12] 7 圖2-1-6 賓分子金屬有機結構物組成 [12] 7 圖2-2-1 微波溶劑加熱法示意圖 [13] 8 圖2-2-2 超音波化學合成法示意圖 [13] 9 圖2-2-3 電化學合成法示意圖 [13] 9 圖2-2-4 噴霧乾燥法。(a) 噴霧乾燥合成法與表面張力影響示意圖；(b) 晶體聚集成中空球體 [19] 10 圖2-2-5 液相磊晶法示意圖 [20] 10 圖2-2-6 機械力化學合成法示意圖 [13] 11 圖2-2-7 離子加熱法示意圖 [13] 11 圖2-2-8 微流體合成法示意圖 [24] 12 圖2-3-1 NU-100。(a) 有機配體結構式；(b) 金屬有機結構物示意圖 [28] 13 圖2-3-2 SMTs之延伸結構研究。(a) PCN-88之合成與結構示意圖；(b) 二氧化碳、氮氣與甲烷之恆溫吸附曲線 [30] 14 圖2-3-3 不同鋯離子為主的金屬有機結構物。(a) NU-1000結構圖；(b) SALI-n之二氧化碳吸附模擬圖 [31] 14 圖2-3-4 ZIF-300、ZIF-301與ZIF-302於CO2/N2於乾溼混合氣中對二氧化碳專一吸附結果 [32] 15 圖2-3-5 Zn-JAST-1隨著吸附不同分子而改變結構 [34] 16 圖2-3-6 NCP-1合成與改質示意圖 [39] 17 圖2-3-7 MIL-101(Fe) 作為藥物載體示意圖 [40] 18 圖2-3-8 IRMOF-3LIr與Uio-66-NH2LIr與其應用催化反應 [42] 19 圖2-3-9 Pd@IRMOF-3。(a) 組成示意圖；(b) 應用催化反應 [43] 19 圖2-3-10 利用POM-MOF催化hydrogen sulfide轉換成octasulfur [44] 20 圖 2-3-11 以卟啉衍生物為有機配體之研究。(a) Pd-MOF催化反應；(b) SnIV-MOF光催化反應 [45] 20 圖3-1-1 CoTPyP網狀結構示意圖 24 圖4-1-1 有機配體TPyP。(a) TPyP結構示意圖；(b) TPyP之UV/Vis光譜圖 31 圖4-1-2 反應前後與再結晶後溶液。(a) 反應前；(b) 反應後；(c) 再結晶後 31 圖4-1-3 TPyP與產物粉末。(a) TPyP；(b) CoTPyP粗產物；(c) CoTPyP再結晶產物 31 圖4-2-1 TPyP之FT-IR圖譜 33 圖4-2-2 水分子與二氧化碳對FT-IR圖譜影響。(a) 盡量避免汙染之樣品；(b) 受水分子汙染之樣品；(c) 受二氧化碳污染之樣品 33 圖4-2-3 鈷離子配位於TPyP結構中心之反應示意圖 34 圖4-2-4 CoTPyP粗產物與再結晶產物FT-IR圖譜。(a) CoTPyPy再結晶產物；(b) CoTPyP粗產物；(c) TPyP；(d) cobalt(II) acetate tetrahydrate 34 圖4-2-5 反應前後與CoTPyP純化前後之UV/Vis光譜圖比較。 (a) 300-700 nm 區間；(b) 400-430 nm 區間 35 圖4-2-6 反應前驅物與CoTPyP粗產物之熱重分析結果 37 圖4-2-7 CoTPyP純化前後之熱重分析結果 37 圖4-2-8 CoTPyP粗產物之SEM圖像。晶體形態為六角柱 (a) x 5 k, (b) x 20 k；部分晶體於六角柱端點有聚集現象 (c) x 5 k, (d) x 20 k；較長反應時間 (e) x 5 k, (f) x 20 k 39 圖4-2-9 CoTPyP不同再結晶之靜置時間後之SEM圖像。短時間再結晶之後 (a) x 5 k, (b) x 20 k；長時間再結晶之後 (c) x 5 k, (d) x 20 k 40 圖4-2-10 CoTPyP增量反應之SEM圖像。粗產物 (a) x 5 k, (b) x 20 k；再結晶產物 (c) x 5 k, (d) x 20 k；非使用基板之粗產物樣品 (e) x 5 k, (f) x 20 k 41 圖4-2-11 CoTPyP與反應起始物之XRD圖。(a) 再結晶產物；(b) 粗產物；(c) TPyP；(d) cobalt(II) acetate tetrahydrate 43 圖4-2-12 不同反應時間之粗產物與再結晶產物之XRD圖。(a) 較長時間之再結晶產物；(b) 較長時間之粗產物；(c) 較短時間之再結晶產物；(d) 較短時間之粗產物 43 圖4-2-13 靜置不同時間之CoTPyP再結晶產物之XRD圖。(a) 靜置較久時間；(b) 靜置較短時間；(c) 粗產物 44 圖4-2-14 CoTPyP增量反應前後之粗產物與再結晶產物之XRD圖。(a) 增量後之再結晶產物；(b) 增量後之粗產物；(c) 增量前之再結晶產物；(d) 增量前之粗產物 44 圖4-2-15 六種主要等溫吸脫附線模型 [61] 45 圖4-2-16 CoTPyP粗產物之等溫吸脫附曲線 46 圖4-2-17 CoTPyP粗產物之孔徑分布曲線 46 圖4-2-18 CoTPyP再結晶產物之等溫吸脫附曲線 47 圖4-2-19 CoTPyP再結晶產物之孔徑分布曲線 47 圖4-2-20 CoTPyP粗產物之二氧化碳等溫吸脫附曲線 48 圖4-2-21 CoTPyP粗產物之二氧化碳化學吸附測量 49 圖4-3-1 CoTPyP粗產物熱穩定性測試之XRD圖。(a) as-synthesized；(b) 200oC； (c) 300oC；(d) 400oC 50 圖4-3-2 CoTPyP粗產物熱穩定性測試之SEM圖。as-synthesized (a) x 5 k, (b) x 20 k；200oC (c) x 5 k, (d) x 20 k；300oC (e) x 5 k, (f) x 20 k；400oC (g) x 5 k, (h) x 20 k 51 圖4-3-3 CoTPyP粗產物水與光穩定性測試之XRD圖。(a) 測試前；(b) 測試後 52 圖4-3-4 CoTPyP粗產物水與光穩定性測試之SEM圖。測試前 (a) x 5 k, (b) x 20 k；測試後 (c) x 5 k, (d) x 20 k 53 圖4-4-1 以chloroform合成之粗產物與再結晶產物FT-IR比較圖。(a) 再結晶產物；(b) 粗產物；(c) TPyP；(d) cobalt(II) acetate tetrahydrate 54 圖4-4-2 以chloroform合成之粗產物與再結晶產物熱重分析結果 55 圖4-4-3 以chloroform合成CoTPyP之XRD比較圖。(a) 再結晶產物；(b) 粗產物；(c) 以DMF合成之粗產物 55 圖4-4-4 以不同溶劑合成之粗產物與再結晶產物SEM比較圖。(a) 以chloroform合成之粗產物 (x 5 k)；(b) 以chloroform合成之再結晶產物 (x 5 k)；(c) 以DMF合成之粗產物 (x 5 k)；(d) 以DMF合成之再結晶產物 (x 5 k) 56 圖4-4-5 以DMSO合成之粗產物與再結晶產物FT-IR比較圖。(a) 再結晶產物；(b) 粗產物；(c) TPyP；(d) cobalt(II) acetate tetrahydrate 57 圖4-4-6 以DMSO合成之粗產物與再結晶產物熱重分析結果 58 圖4-4-7 以DMSO合成CoTPyP之XRD比較圖。(a) 再結晶產物；(b) 粗產物；(c) 以DMF合成之粗產物 58 圖4-4-8 以不同溶劑合成之粗產物與再結晶產物SEM比較圖。(a) 以DMSO合成之粗產物 (x 5 k)；(b) 以DMSO合成之再結晶產物 (x 5 k)；(c) 以DMF合成之粗產物 (x 5 k)；(d) 以DMF合成之再結晶產物 (x 5 k) 59 圖4-4-9 以不同溶劑合成之CoTPyP產物的等溫吸脫附曲線。黑色曲線為以DMF合成之再結晶產物；紅色曲線為以DMF合成之粗產物；藍色曲線為以chloroform合成之再結晶產物；綠色曲線為以DMSO合成之再結晶產物 60 圖4-4-10 不同溶劑合成之CoTPyP產物的孔徑分布曲線 60 圖4-5-1 有機配體TPBi。(a) 化合物結構；(b) FT-IR圖譜 61 圖4-5-2 TPBi與CoTPBi粉末。(a) TPBi；(b) CoTPBi 62 圖4-5-3 反應前後之UV/Vis光譜圖比較 62 圖4-5-4 CoTPBi之FT-IR圖譜。(a) CoTPBi；(b) TPBi/cobalt(II) acetate tetrahydrate；(c) TPBi；(d) cobalt(II) acetate tetrahydrate 63 圖4-5-5 反應前驅物與CoTPBi之熱重分析結果 63 圖4-5-6 CoTPBi與反應起始物之XRD圖。(a) CoTPBi；(b) TPBi；(c) cobalt(II) acetate tetrahydrate 64 圖4-5-7 CoTPBi之SEM圖像。(a) x 5 k, (b) x 20 k 64 圖4-5-8 CoTPBi之等溫吸脫附曲線 65 圖4-5-9 CoTPBi之孔徑分布曲線 65 圖4-5-10 TPBi與CuTPBi粉末。(a) TPBi；(b) CuTPBi 66 圖4-5-11 反應前後之UV/Vis光譜圖比較。(a) 260-700 nm 區間；(b) 260-340 nm 區間 67 圖4-5-12 CuTPBi之FT-IR圖譜。(a) CuTPBi；(b) TPBi/copper(II) chloride dihydrate；(c) TPBi；(d) copper(II) chloride dihydrate 67 圖4-5-13 反應前驅物與CuTPBi之熱重分析結果 68 圖4-5-14 CuTPBi與反應起始物之XRD圖。(a) CuTPBi；(b) TPBi；(c) copper(II) chloride dihydrate 68 圖4-5-15 CuTPBi之SEM圖像。(a) x 5 k, (b) x 20 k 69 圖4-5-16 CuTPBi之等溫吸脫附曲線 69 圖4-5-17 CuTPBi之孔徑分布曲線 70

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