本研究旨在開發一系列新型供體-受體（Donor-Acceptor， D-A）型共價有機骨架（COFs）。基於前期以 PMDA 為受體之 PI COF-201 研究基礎，本研究策略性地導入具廣泛共軛結構與高電子密度之蜜勒胺（Melem）作為電子供體並以均苯四甲酸二酐 (PMDA)作為電子供體。此富電子與缺電子單體之結合，成功建構出具強烈分子內偶極矩之骨架，有效促進分子內的電荷傳輸，並進而抑制光生載子之複合率。而在材料製備上，本研究分別採用了直接熱縮合法（direct thermal condensation）與溶劑熱法（solvothermal method）進行合成。為深入探討聚合行為對材料特性之影響，除了以等莫耳比例（Equimolar）進行合成外，亦嘗試調控起始物莫耳比例（PMDA : Melem = 1 : 2 與 2 : 1），以探討不同結構參數對材料性能之影響。迄今為止，將此類新型供受體（D-A）型共價有機框架（COFs）材料應用於光催化領域的相關文獻仍鮮有報導，突顯了本研究在該領域的高度新穎性與學術價值。而在應用方面，本研究建立亞甲基藍（MB）與甲基橙（MO）之光催化降解模型，並輔以 MB 之等溫吸附實驗，全面評估材料之應用潛力。實驗結果顯示，在 300 W 氙燈（Xe lamp）光源照射下，本研究合成之系列材料對不同電荷的目標染料皆展現出良好的光催化活性。在陽離子染料亞甲基藍（MB）的降解體系中，以 PI COF PM-1 (P1M1) 表現最佳，僅需光照 30 分鐘其降解率即可達 90.6 %；而在陰離子染料甲基橙（MO）的降解測試中，則以 PI COF PM-2 (P2M1) 表現最優，光照 60 分鐘之降解率高達 95.6 %。;This study aims to develop a series of novel donor-acceptor (D-A) covalent organic frameworks (COFs). Building upon previous research on COF-201 utilizing pyromellitic dianhydride (PMDA) as the acceptor， this work strategically introduces melem — a monomer possessing an extended conjugated structure and high electron density — as the electron donor. The combination of these electron-rich and electron-deficient monomers successfully constructs a framework with a strong intramolecular dipole moment， thereby promoting efficient intramolecular charge transfer and suppressing the recombination of photogenerated charge carriers. For material preparation， direct thermal condensation and solvothermal methods were employed to synthesize the PI COF PM-1 and PI COF PM-2 series， respectively. To thoroughly investigate the impact of polymerization behavior on material properties， in addition to the equimolar synthesis， the molar ratios of the precursors (PMDA : melem = 1 : 2 and 2 : 1) were systematically adjusted to evaluate the influence of different structural parameters on material performance. To the best of our knowledge， the application of such novel melem-based D-A COFs in the photocatalytic field represents a highly pioneering endeavor. Photocatalytic degradation models for methylene blue (MB) and methyl orange (MO) were established， supplemented by MB adsorption isotherm experiments， to comprehensively evaluate the environmental remediation potential of these materials. Experimental results demonstrated that under 300 W Xe lamp irradiation， the synthesized frameworks exhibited efficient photocatalytic activities toward target dyes with different charges. Specifically， for the cationic dye MB degradation， PI COF PM-1 (P1M1) achieved the highest performance， reaching a degradation efficiency of 90.6 % within only 30 min of irradiation. Conversely， for the anionic dye MO degradation， PI COF PM-2 (P2M1) delivered the optimal performance， yielding a degradation efficiency as high as 95.6 % after 60 min of irradiation.
