多孔有機聚合物(POPs)因其孔隙率、比表面積高，且具有優異的化學及熱穩定性，在各種應用方面展現了極大的潛力，例如氣體儲存與吸附、化學傳感器、能量存儲等等。本論文的第一部分將提到吾人透過鈴木偶聯及薗頭耦合反應，成功合成三種噻蒽基共軛微孔聚合物(CMPs)，即Bz-Th-CMP、TPA-Th-CMP及P-Th-CMP。這些共軛微孔聚合物材料展現了高比表面積及優良熱穩定性，且在恆電流充放電(GCD)實驗中，顯示出在電流密度0.5 A g-1時， P-Th-CMP具有高達217 F g-1的電容值。此外，將P-Th-CMP應用作鋰硫電池的陰極材料，在0.2 C的充放電循環條件下，第一圈表現出高達1319 mA h g-1的電容值，在充放電循環100圈後仍保有高達913 mA h g-1的電容值。
　　在第二部分中，吾人透過傅-克反應，成功合成兩種超交聯微孔聚合物(HCPs)，即Fe-Bi-HCP及An-Bi-HCP。這些超交聯微孔聚合物結構中具有共軛π電子和雜原子的芳環，且有高達898 m2 g−1的比表面積，促使吾人探索他們的二氧化碳吸附及碘吸收特性。在室溫時，Fe-Bi-HCP及An-Bi-HCP具有1.64和1.24 mmol g-1的二氧化碳吸附量。而在含碘的環己烷溶液中，Fe-Bi-HCP及An-Bi-HCP具有54.7%和37.8%的碘捕捉率，且碘釋放效率高達85.1和88.6%，使這些材料具有作為可逆碘吸附劑的潛力。

Porous Organic Polymers (POPs) have been showcased outstanding potential in many applications, including gas storage, adsorption, chemo-sensors, energy storage and conversion, attributing to their superior inherent porosity, high surface area and superior stability. In the first part of our work, we report three thianthrene-based conjugated microporous polymers (CMPs) －Bz-Th, TPA-Th, and P-Th-CMPs－through Suzuki reaction and Sonogashira reaction. These CMP materials demonstrated exceptional heat stability and high surface areas. According to galvanostatic charge/discharge experiment, the P-Th-CMP has a high specific capacitance of 217 F g−1 at the current density of 0.5 A g-1. Furthermore, the performance on the cathode of lithium–sulfur battery was also investigated. Our P-Th-CMP cathode exhibited a discharge capacity of 1319 mA h g-1 at the initial cycling, and a high specific capacity of 913 mA h g-1 at 0.2 C after 100 cycles.
In the second part, we report two hyper-crosslinked polymers (HCPs) －Fe-Bi-HCP and An-Bi-HCP－through Friedel crafts reaction. These HCPs contain aromatic rings with conjugated π-electrons and heteroatoms, and show the high surface area reaching up to 898 m2 g−1, which have prompted us to explore their CO2 uptake and iodine capture properties. At room temperature, the CO2 capacities of the Fe-Bi-HCP and An-Bi-HCP were 1.64 and 1.24 mmol g-1, respectively. As for iodine capture efficiency, Fe-Bi-HCP and An-Bi-HCP could remove 54.7 and 37.8% of iodine in iodine/cyclohexane solution. Moreover, the desorption efficiency of Fe-Bi-HCP and An-Bi-HCP were up to 85.1 and 88.6%, which make these materials suitable for reversible iodine uptake adsorbents.

論文審定書 i
誌謝 iii
摘要 iv
Abstract v
Content vi
Figure Captions ix
Table Captions xiv
Scheme Captions xv
Chapter 1 Introduction 1
1-1 Porous Materials 1
1-2 Conjugated Microporous Polymers, CMPs 2
1-2-1 Suzuki Coupling Reaction 4
1-2-2 Sonogashira Reaction 4
1-3 Hypercrosslinked Polymers, HCPs 4
Chapter 2 Literature Review 6
2-1 Adsorption Theory 6
2-2 Electrochemical Measurement Method 10
2-3 Supercapacitors 16
2-3-1 Introduction of Supercapacitors 16
2-3-2 Electric Double-Layer Capacitor, EDLC 18
2-3-3 Pseudocapacitors 18
2-3-3 Porous Organic Polymers Applied as Supercapacitor Electrodes 19
2-4 Lithium–Sulfur (Li–S) Batteries 20
2-4-1 Introduction of Lithium–Sulfur Batteries 20
2-4-2 Electrochemistry of Lithium–Sulfur Batteries 22
2-4-3 Porous Organic Polymers Applied as Lithium–Sulfur Battery Electrodes 24
2-5 CO2 Uptake 25
2-6 Iodine Capture 26
2-6-1 Introduction of Iodine Capture 26
2-6-2 Porous Organic Polymers Applied as Iodine Adsorbents 26
Chapter 3 Motivation and Objectives 28
Chapter 4 Experimental Section 30
4-1 Materials 30
4-2 Characterization 30
4-3 Part 1 32
4-3-1 Synthesis of Th-Br2 32
4-3-2 Synthesis of Bz-3BO 33
4-3-3 Synthesis of TPA-Br3 33
4-3-4 Synthesis of TPA-3BO 34
4-3-5 Synthesis of P-T 35
4-3-6 Synthesis of Bz-Th-CMP 36
4-3-7 Synthesis of TPA-Th-CMP 36
4-3-8 Synthesis of P-Th-CMP 37
4-3-9 Preparation of S@P-Th-CMP 38
4-3-10 Fabrication of Coin Cell 38
4-4 Part 2 40
4-4-1 Synthesis of FDI 40
4-4-2 Synthesis of ADI 40
4-4-3 Synthesis of Fe-Bi-HCP 41
4-4-4 Synthesis of An-Bi-HCP 41
Chapter 5 Results and Discussion 42
5-1 Part 1 42
5-1-1 Synthesis and Characterization of Th-CMPs 42
5-1-2 Elemental Analyses 57
5-1-3 Thermal Stability Analyses 58
5-1-4 X-Ray Diffraction Analyses 59
5-1-5 Surface Area and Porosity Analyses 59
5-1-6 Electron Microscopic Analyses 61
5-1-7 Electrochemical Analyses 62
5-1-8 Application for Lithium–Sulfur Battery 70
5-2 Part 2 77
5-2-1 Synthesis and Characterization of Bi-HCPs 77
5-2-2 Thermal Stability Analyses 84
5-2-3 Surface Area and Porosity Analyses 85
5-2-4 Electron Microscopic Analyses 86
5-2-5 Electrochemical Analyses 87
5-2-6 CO2 Uptake Capacity Analyses 91
5-2-7 Iodine Uptake Capacity Analyses 92
Chapter 6 Conclusions 96
References 98

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