| 摘要: | 本研究開發了兩種高效異相催化劑系統，分別應用於和催化轉移氫化反應，為綠色化學合成提供新的技術路徑。第一部分，採用一鍋共縮合法成功製備了磺酸-羧酸雙官能基修飾的 KIT-6 中孔矽材料催化劑（K6SXCY 系列），應用於 1,6-己二醇與丙烯酸的選擇性酯化反應。透過 SAXS、BET、HRTEM、XPS、FTIR 等多重表徵技術確認材料具有完整的三維立方 Ia3d 結構和成功的官能基修飾。XPS 分析在 171.1 eV 處觀察到 SO₃H···HOOC 氫鍵作用峰，證實雙官能基間的協同效應。最佳催化劑 K6S10C5 在優化條件下（AA:HDO = 1:1.2，90°C，2.5 wt% 催化劑用量）可達到 99.97% 丙烯酸轉化率和 80.62% 單酯（HDA）選擇性。動力學研究顯示反應遵循擬一級動力學，表觀活化能為 73 kJ/mol。催化劑經五次重複使用後仍保持良好活性，展現優異的穩定性和可回收性。
第二部分研究中，主要是，利用超音波輔助浸漬還原法製備釕負載的 UiO-66-NH₂ 金屬有機骨架催化劑（Ru-UiO-66-NH₂系列），應用於糠醛催化轉移氫化制備糠醇。通過 WAXRD、BET、HRTEM、XPS 等技術確認釕奈米粒子高度分散（平均粒徑 1.8 nm）且 MOF 骨架結構穩定。最佳催化劑 3wt% Ru-UiO-66-NH₂ 在異丙醇中、105°C 條件下 30 分鐘內達到 76.9% 糠醛轉化率和 95.5% 糠醇選擇性，對應產率 73.4%，TOF 達 71.1 h⁻¹。XPS 和 FTIR 分析證實釕與胺基配位作用有效提升催化活性。
綜合而言，兩種催化劑系統分別在酸催化酯化和金屬催化氫化反應中展現高活性、高選擇性和良好穩定性，為綠色化學中高值化轉化與催化劑設計提供重要理論依據和應用潛力。
;This thesis presents a two-part study on the development of heterogeneous catalysts for selective organic transformations, with a focus on esterification and catalytic transfer hydrogenation (CTH) reactions.
In Part I, sulfonic–carboxylic acid bifunctional catalysts were synthesized on stereosymmetric Ia3d-type KIT-6 mesoporous silica via a one-pot co-condensation method. The resulting K6SXCY catalysts were thoroughly characterized by SAXS, BET, HRTEM, FTIR, and XPS, confirming the preservation of the ordered mesoporous structure and the successful incorporation of acid functionalities. Notably, XPS analysis revealed a hydrogen-bonding interaction signal (SO₃H···HOOC) at 171.1 eV, indicating a synergistic effect between the dual acid groups.
The optimized catalyst, K6S10C5, achieved 99.97% acrylic acid conversion and 80.62% monoester (HDA) selectivity under optimized conditions (AA:HDO = 1:1.2, 90 °C, 2.5 wt%). Kinetic studies showed pseudo-first-order reaction behavior with an apparent activation energy of 73 kJ·mol⁻¹. Under acrylic acid-rich conditions (AA:HDO = 2.2:1), the yield of the diester (HDDA) increased to 97.99%. The catalyst maintained excellent activity and selectivity over five reuse cycles, outperforming homogeneous systems in reusability and waste minimization.
In Part II, ruthenium nanoparticles were immobilized onto amino-functionalized UiO-66 MOFs via an ultrasound-assisted impregnation–reduction method. Characterizations by WAXRD, BET, HRTEM, FTIR, and XPS confirmed that the MOF structure was preserved and that Ru nanoparticles (~1.8 nm) were well dispersed and coordinated with –NH₂ groups on the framework.
The optimal 3 wt% Ru–UiO-66–NH₂ catalyst exhibited 76.9% furfural conversion and 95.5% selectivity toward furfuryl alcohol within 30 minutes at 105 °C in isopropanol, corresponding to a 73.4% yield and a turnover frequency (TOF) of 71.1 h⁻¹. The catalyst demonstrated excellent stability and selectivity, offering a promising platform for biomass valorization.
Collectively, the two catalyst systems highlight distinct structure–activity relationships for acid-catalyzed esterification and metal-catalyzed hydrogenation, providing valuable insights into catalyst design and green chemical transformations. |
