近幾年來的碳材一直都是很熱門的研究領域，由於它的應用領域廣泛且都是與生活上息息相關。在此研究中利用兩種不同的ABA型嵌段共聚物分別為Poly(ε-Caprolactone)-b-Poly(Ethylene Glycol)-b-Poly(ε-Caprolactone)(PCL-b-PEO-b-PCL)及Poly(Lactide)-b-Poly(Ethylene Glycol)-b-Poly(Lactide)(PLA-b-PEO-b-PLA) 作為模板，個別與作為碳源的鹼性酚醛樹酯(Resol)進行混摻，透過揮發誘導自組裝(Evaporation Induced Self-Assembly, EISA)後加熱固化，最後以鍛燒的方式移除模板得到大中孔洞的碳材。透過小角度X光散射(Small-Angle X-ray Scatting, SAXS)以及穿透式電子顯微鏡(Transmission Electron Microscopy, TEM)對碳材的結構及形貌做鑑定，利用比表面積分析儀(BET)檢測大中孔碳材的比表面積以及氮氣吸脫附測試，並且進行二氧化碳捕捉能力和電化學之分析。製備出的大中孔碳材之比表面積為609.7 m2/g，孔徑平均約53.7 nm，在273 K下進行的二氧化碳捕捉達6.19 mmol/g，電化學測試中掃描速率5 mV/s時電容值為120 F/g，且經由5000次的循環測試仍保留90 %的電容量。

　　Carbon materials is a hot research in recent years, because of its wide range of application and close to our life. In this study, we used two kinds ABA type block copolymers as template respectively, Poly(ε-Caprolactone)-b-Poly(Ethylene Glycol)-b-Poly(ε-Caprolactone) (PCL-b-PEO-b-PCL) and Poly(Lactide)-b-Poly(Ethylene Glycol)-b-Poly(Lactide)(PLA-b-PEO-b-PLA), and blend with phenolic resin(Resol), curing after blending by evaporation induced self-assembly(EISA). Finally, remove the templated by thermal treatment to obtain the large mesoporous carbon. The structure and characterization of large mesoporous carbon identified by small-angle X-ray scatting(SAXS) and transmission electron microscopy(TEM), specific surface area and nitrogen adsorption isotherm measured by BET analysis. And application properties of the large mesoporous carbon, we check by carbon dioxide capture and electrochemical measurement.
　　The prepared large mesoporous carbon has a specific surface area 609.7m2/g, pore size 53.7 nm, carbon dioxide capture capacity of 6.19mmol/g at 273K, and the capacitance is 120F/g, the cycle test showed efficient stabilities with 90% retentions after 5000 times.

論文審定書 i
致謝 ii
摘要 iii
Abstract iv
目錄 v
表目錄 x
圖目錄 viii
第一章 緒論 1
1.1前言 1
1.2研究動機 3
第二章 理論與文獻回顧 4
2.1嵌段共聚物(Block Copolymer) 4
2.2揮發誘導自組裝(Evaporation Induced Self-Assembly, EISA) 5
2.3氫鍵作用力(Hydrogen Bond Interaction) 6
2.4反應導致微觀相分離(Reaction-Induced Microphase Separation. RIMPS) 7
2.5等溫吸附曲線(Adsorption Isotherm) 8
第三章 實驗方法及步驟 12
3.1 實驗內容 12
3.1.1 合成大中孔洞碳材 12
3.1.2 電化學測試 12
3.2 使用藥品 13
3.3 樣品製備 14
3.3.1合成嵌段共聚物Poly(ε-Caprolactone)-b-Poly(Ethylene Glycol)-b-Poly(ε-Caprolactone) 14
3.3.2合成嵌段共聚物Poly(Lactide)-b-Poly(Ethylene Glycol)-b-Poly(Lactide) 15
3.3.3 合成鹼性酚醛樹酯(Resol) 16
3.3.4 利用PCL-b-PEO-b-PCL及PLA-b-PEO-b-PLA與鹼性酚醛樹酯(Resol)合成中孔洞碳材 17
3.4 使用儀器 18
3.4.1氫核磁共振分析儀(Nuclear Magnetic Resonance, NMR)型號：UNITY INOVA-200 18
3.4.2傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR)型號：Bruker Tensor-27 19
3.4.3 凝膠滲透層析儀(Gel Permeation Chromatography, GPC)型號：Jasco-980 19
3.4.4熱重分析儀(Thermal Gravimetric Analyzer, TGA)型號：TA Q-50 20
3.4.5小角度X光散射儀(Small Angle X-ray Scattering, SAXS)型號：Bruker AXS VANTEC-2000 20
3.4.6微差掃描熱卡儀(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 21
3.4.7穿透式電子顯微鏡(Transmission Electron Microscope, TEM)型號：JEOL-2100 21
3.4.8比表面積分析儀(Specific Surface Area & Pore Size Distribution Analyzer, BET)型號：ASAP 2020 22
3.4.9 場發射型掃描式電子顯微鏡(Field-Emission Scanning Electron Microscope, FE-SEM)型號：JEOL-6330 22
3.4.10微光致螢光/拉曼光譜儀(Micro Raman/PL + cold stage) 型號：HORIBA HR800 23
3.4.11 電化學工作站(Electrochemical Workstation) 型號：Zahner Zennium　E 23
第四章 結果與討論 24
4.1利用PCL-b-PEO-b-PCL為模板製備大中孔洞碳材之分析 24
4.1.1嵌段共聚物PCL-b-PEO-b-PCL鑑定 24
4.1.2熱重分析儀(TGA)分析 25
4.1.3微分掃描熱卡儀(DSC)分析 26
4.1.4傅立葉轉換紅外線光譜儀(FTIR)分析 27
4.1.5大中孔洞碳材鍛燒前後小角度X光散射(SAXS)之分析 29
4.1.6大中孔洞碳材穿透式電子顯微鏡(TEM)之分析 30
4.1.7大中孔洞碳材掃描式電子顯微鏡(SEM)分析 32
4.1.8大中孔洞碳材比表面積分析儀(BET)分析 34
4.2利用PLA-b-PEO-b-PLA製備大中孔洞碳材之分析 36
4.2.1嵌段共聚物PLA-b-PEO-b-PLA之鑑定 36
4.2.2熱重分析儀(TGA)之Tm分析 37
4.2.3微分掃描熱卡儀(DSC)分析 38
4.2.4傅立葉轉換紅外線光譜儀(FTIR)分析 39
4.2.5以PLA-b-PEO-b-PLA為模板中孔洞碳材之分析 40
4.2.6大中孔洞碳材穿透式電子顯微鏡(TEM)之分析 41
4.2.7大中孔洞碳材掃描式電子顯微鏡(SEM)分析 43
4.2.8大中孔洞碳材比表面積分析儀(BET)分析 44
4.3大中孔洞碳材應用之分析 46
4.3.1 石墨化程度分析 46
4.3.2 二氧化碳吸附能力 48
4.3.3 電化學測試 50
第五章 結論 53
第六章 參考文獻 54
圖目錄
Figure 2. 1 Phase diagram of block copolymer microphase separation 4
Figure 2. 2 Scheme of Evaporation-Induced Self-Assembly 21 5
Figure2. 3 The IUPAC classification of adsorption isotherms showing both the adsorption desorption pathways 25 8
Figure 2. 4 The IUPAC classification of hysteresis 25 10
Figure 3. 1 Scheme of prepared large mesoporous carbon…………………………….12
Figure 3. 2 Scheme of synthesis of poly(ε-carprolactone)-b-poly(ethylene glycol)-b-poly(ε-Caprolactone) 14
Figure 3. 3 Scheme of synthesis of poly(lactide)-b-poly(ethylene glycol)-b-poly(lactide) 15
Figure 3. 4 Scheme of synthesis of phenolic resin (Resol type) 16

Figure 4. 1 1H NMR spectra of PCL-b-PEO-b-PCL 24
Figure 4. 2 Characterization of blending of PCL-b-PEO-b-PCL with resol 25
Figure 4. 3 DSC curves of resol % after curing (a)cooling (b)heating 26
Figure 4. 4 FTIR spectra recorded at room temperature displaying the 28
Figure 4. 5 SAXS patterns of large mesoporous phenolic resin with various resol concentration (a) before remove template (b) remove template 29
Figure 4. 6 TEM images of large mesoporous carbon, percentage of phenolic resin 31
Figure 4. 7 FESEM images of large mesoporous carbon (a-b) top view (c-d) cross-section 32
Figure 4. 8 Percent of pore size by FE-SEM (a) schematic diagram (b) statistical diagram 33
Figure 4. 9 BET analysis images of large mesoporous (a) N2 adsorption/desorption isotherms with various Resol % (b) pore size distribution curve with various Resol % 35
Figure 4. 10 1H NMR spectra of PLA-b-PEO-b-PLA 36
Figure 4. 11 Characterization of blending of PLA-b-PEO-b-PLA with resol 37
Figure 4. 12 DSC curves of resol % after curing (a)cooling (b)heating 38
Figure 4. 13 FTIR spectra recorded at room temperature displaying the 39
Figure 4. 14 SAXS patterns of large mesoporous phenolic resin with various resol concentration (a) before remove template (b) remove template 40
Figure 4. 15 TEM images of large mesoporous phenolic resins, percentage of phenolic resin (a) 70% (b) 60% (c) 50% (d) 40% 42
Figure 4. 16 FE-SEM images of large mesoporous carbon (a)6k (b)15k 43
Figure 4. 17 BET analysis images of large mesoporous (a) N2 adsorption/desorption isotherms with various Resol % (b) pore size distribution curve with various Resol % 45
Figure 4. 18 Raman spectra of large mesoporous carbon using templated 47
Figure 4. 19 CO2 capture property at 273K of large mesoporous carbon 49
Figure 4. 20 CO2 capture property at 298K of large mesoporous carbon 49
Figure 4. 21 Electrochemical performance of different system and using three-electrode cell: cyclic voltammograms at different scan rate in 1.0 M KCl. 51
Figure 4. 22 Electrochemical performance of different system when scan rate increase 52
Figure 4.23 Cycling performance of different system 52


表目錄
Table 4. 1 Pore size distributed table of large mesoporous templated using PCL-b-PEO-b-PCL from TEM image 30
Table 4. 3 Pore size distributed table of large mesoporous templated using PLA-b-PEO-b-PLA from TEM image 41
Table 4. 4 Properties of large mesoporous templated using PLA-b-PEO-b-PLA 44
Table 4. 5 Characteristic peaks and area ratio of different templates 47
Table 4.6 Blending resol 60% of pore size distributed table of large mesoporous templated using different templated from TEM image 48

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