DSpace community: 化學研究所

利用機械力球磨法和原位合成策略封裝奈米金屬與酵素之應用研究;Encapsulation of Nanometals and Enzymes via Mechanochemistry and De Novo Synthesis Approaches

Fri, 06 Mar 2026 10:22:59 GMT

title: 利用機械力球磨法和原位合成策略封裝奈米金屬與酵素之應用研究;Encapsulation of Nanometals and Enzymes via Mechanochemistry and De Novo Synthesis Approaches abstract: 本篇論文分成兩部分：二氧化碳（Carbon dioxide, CO2）大量排放，已成為導致全球暖化及溫室效應日益嚴重的主要原因之一。為減緩氣候變遷影響，如何有效捕捉與轉化二氧化碳成為當前研究的重點課題。目前工業上普遍使用的二氧化碳吸附劑如單乙醇胺（Monoethanolamine, MEA）和三乙醇胺（Triethanolamine, TEA），雖然具備一定的吸附效果，但因其再生能耗高、腐蝕性強及環境友善性不足等缺點，限制了其實際應用。近年來，金屬有機骨架材料（Metal-Organic Frameworks, MOFs）因其高比表面積及孔洞可調性，成為具有潛力的新興二氧化碳吸附材料。在眾多的MOFs材料中，MOF-74具有一維孔洞結構和未配位的活性位點，能與二氧化碳形成較強的相互作用，進而增強吸附和擴散效率。然而，單純的物理吸附難以實現高效的利用。因此引入酶催化轉化的概念，將甲酸脫氫酶（Formate Dehydrogenase, FDH）結合MOF-74，形成一種生物複合材料不僅能有效吸附二氧化碳，還能催化二氧化碳還原生成具經濟價值的甲酸。本研究中參考本實驗室於2015年基於酵素固定化概念，研發出創新的原位溫和水相合成法，成功將過氧化氫酶（Catalase, CAT）封裝於ZIF-90中。透過MOF孔洞結構，使基質順利進入催化位點，同時防止大分子蛋白酶的水解作用，提升酵素穩定性與活性。2021年，本實驗室進一步改良技術，於室溫下以溫和水相系統快速合成Zn-MOF-74並同時封裝酵素，顯著提升固定化酵素的活性。在此基礎上進一步將甲酸脫氫酶封裝於Zn-MOF-74中，利用其優異的二氧化碳吸附能力及14 Å大孔道結構，增加菸鹼醯胺腺嘌呤二核苷酸（Nicotinamide adenine dinucleotide, NADH）與二氧化碳的擴散能力，提升二氧化碳還原成甲酸的效率。為進一步增強吸附性能，將金屬中心由Zn改為Co，並也成功把酵素封裝於Co-MOF-74之中，因其Co²⁺具有空的3d軌道，能夠更容易與CO₂形成配位，進一步加強CO₂的吸附。有效增強二氧化碳捕集及催化轉化效率。實驗結果顯示，甲酸脫氫酶和Co-MOF-74組成的複合生物材料在CO₂吸附及甲酸生成上，均優於Zn-MOF-74，展現其在溫室氣體轉化應用中的潛力。本論文第二部分著重於開發一套具高效率與通用性的機械力輔助封裝技術(Mechanochemical, LAG) ，成功將奈米金屬粒子封裝於金屬有機框架中，實現特定尺寸與晶面之奈米金屬催化劑的快速製備。傳統奈米金屬因具高表面能，極易在反應過程中發生團聚與粒徑成長，進而導致催化活性下降與回收困難。本研究藉由MOFs具備高度有序孔洞與框架結構的特性，不僅有效隔離金屬奈米粒子、抑制其團聚，亦大幅提升其結構穩定性與重複使用能力。考量不同晶面在催化選擇性與反應活性上所展現之顯著差異，本研究進一步採用球磨法成功封裝具特定晶面之奈米金屬，並透過MOFs提供的保護環境，在高溫或酸性等嚴苛條件下仍可維持其原始晶面結構，保留其優異的催化功能。而且MOF材料所具有之分子篩選性孔徑亦有助於反應物選擇性進入，有效提升催化反應之產率與選擇性。與傳統合成方法水熱合成需24小時或是兩步驟球磨程序耗時約6.5小時相比，本研究所建立之封裝方法具備顯著的時間與流程優勢，可於單一步驟且僅需約5分鐘內完成奈米金屬與MOF前驅物的反應與包覆過程。此策略大幅簡化操作流程並提高反應效率，展現其作為快速、穩定且可控制製備異相奈米催化劑平台的可行性與實用潛力。 ;This thesis is divided into two main parts: Massive CO₂ emissions are a major driver of global warming and the greenhouse effect. To address climate change, efficient CO₂ capture and conversion have become a research priority. While industrial absorbents like monoethanolamine (MEA) and triethanolamine (TEA) are effective, they suffer from high regeneration costs, corrosiveness, and poor environmental compatibility. Metal-Organic Frameworks (MOFs), particularly MOF-74, offer promising alternatives due to their high surface area, tunable pores, and unsaturated metal sites that enhance CO₂ adsorption and diffusion. However, physical adsorption alone limits practical utility. To increase CO₂’s value, this study integrates formate dehydrogenase (FDH) with MOF-74 to form a bio-composite that not only captures CO₂ but also catalyzes its reduction to formic acid—a commercially valuable product. In 2015, we reported an innovative in situ method to encapsulate catalase (CAT) within ZIF-90 under mild, aqueous, room-temperature conditions. The porous MOF structure permitted substrate access while protecting the enzyme from hydrolysis, enhancing stability and activity. In 2021, we refined this approach to rapidly synthesize Zn-MOF-74 under similar conditions, enabling simultaneous enzyme encapsulation and significantly improving catalytic performance. Building on our 2015 study, we encapsulated formate dehydrogenase (FDH) into Zn-MOF-74. Its strong CO₂ adsorption and 14 Å channels enhanced the diffusion of NADH and CO₂, improving formic acid production. To further boost adsorption, Zn was replaced with Co, and FDH was successfully encapsulated into Co-MOF-74. The Co²⁺ ions, with empty 3d orbitals, provided stronger CO₂ coordination. As a result, the FDH@Co-MOF-74 bio-composite outperformed the Zn-based counterpart in both CO₂ capture and conversion, showing strong potential for greenhouse gas mitigation. The second part of this study presents a rapid and versatile mechanochemical strategy for synthesizing MOF-based nanocomposites containing metal nanoparticles (NPs) with controlled sizes and exposed crystal facets. Metal NPs typically suffer from aggregation due to high surface energy, reducing catalytic activity and complicating recovery. Utilizing the ordered porous structure of MOFs, this method prevents NP aggregation and enhances their stability and reusability. Recognizing the importance of crystal facets in catalytic performance, facet-controlled NPs were encapsulated via ball milling. The MOF framework protects these facets under harsh conditions (e.g., high temperature, acidity), preserving catalytic activity. Additionally, the molecular sieving effect of MOFs improves substrate selectivity by controlling reactant diffusion. Compared to conventional hydrothermal (24 h) or two-step milling (6.5 h) methods, this one-step encapsulation completes in just 5 minutes, offering significant advantages in speed and simplicity. This strategy provides a robust, efficient, and scalable platform for fabricating heterogeneous catalysts.

立體對稱Ia3d-KIT-6磺酸-羧酸雙活性位點丙烯酸酯催化及面心立方UiO-66糠醛選擇性氫化研究;Development of Ia3d Cubic Symmetry KIT-6 Supported Bifunctional Catalysts for Acrylate Esterification and Face-Centered Cubic UiO-66 for Biomass-Derived Furfural Hydrogenation

Fri, 06 Mar 2026 10:22:48 GMT

title: 立體對稱Ia3d-KIT-6磺酸-羧酸雙活性位點丙烯酸酯催化及面心立方UiO-66糠醛選擇性氫化研究;Development of Ia3d Cubic Symmetry KIT-6 Supported Bifunctional Catalysts for Acrylate Esterification and Face-Centered Cubic UiO-66 for Biomass-Derived Furfural Hydrogenation abstract: 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.

亞硝鎓離子與苯乙酮合成2-氧代-2-苯基乙烷-1,1-二基二乙酸酯之反應研究

Fri, 06 Mar 2026 10:22:39 GMT

title: 亞硝鎓離子與苯乙酮合成2-氧代-2-苯基乙烷-1,1-二基二乙酸酯之反應研究 abstract: 本篇論文為苯乙酮 (acetophenone) 與四氟硼酸亞硝鎓 (nitrosonium tetrafluoroborate, NOBF4) 在酸性條件下於苯乙酮的α位置進行氧化生成2-氧代-2-苯基乙烷-1,1-二基二乙酸酯 (2-oxo-2-phenylethane-1,1-diyl diacetate)，以下簡稱α-酮二乙酸酯 (a-keto diacetate)。反應機制之研究顯示：在酸性條件下，亞硝鎓離子(nitrosonium ion, NO¬+)，與苯乙酮的烯醇互變異構體 (acetophenone enol) 會生成異腈羥胺基苯乙酮 (isonitrosoacetophenone) 後，與醋酸或水進行水解取代反應，得到α-酮二乙酸酯。此方法條件溫和且反應試劑容易取得，我們利用此方法製備出 23種2-氧代-2-苯基乙烷-1,1-二基二乙酸酯衍生物，最高產率可達 91 %，期望此方法未來可以廣泛地應用於製備這類型的化合物。 ;In this study, we report the oxidation of α-position of acetophenones with nitrosonium tetrafluoroborate (NOBF4) under acidic conditions (trifluoroacetic acid/acetic acid) to afford 2-oxo-2-phenylethane-1,1-diyl diacetates. After our mechanistic study, the reaction mechanism was proposed: under the acidic condition, nitrosonium ion (NO+) reacts with the enol tautomer of acetophenone to generate isonitrosoacetophenone as the reaction intermediate. Isonitrosoacetophenone subsequently undergoes an acetic acid or water–mediated hydrolysis-like transformation to yield the α-keto diacetate. This method features mild reaction conditions and employs readily available reagents. We successfully synthesized 23 α-keto diacetates with yields of up to 91 %. We anticipate that this method will find broad application in the field of this α-keto diacetate synthesis chemistry

合成用於染料敏化太陽能電池之光致變色釕亞碸錯合物;Synthesis of Photochromic Ruthenium Sulfoxide Complexes for Dye-Sensitized Solar Cells

Fri, 06 Mar 2026 10:22:30 GMT

title: 合成用於染料敏化太陽能電池之光致變色釕亞碸錯合物;Synthesis of Photochromic Ruthenium Sulfoxide Complexes for Dye-Sensitized Solar Cells abstract: 光致變色分子可藉由光照來改變染料結構與吸收特性進而改變顏色，在外界刺激下可變回原本的顏色，此類分子組裝成DSC可能具有光致變色的特性，可以應用在建築上。本研究以iPr-pyso (2-(propane-2-sulfinylmethyl)-pyridine) 作為釕錯合物的輔助配位基，合成出含Ru-S=O變色單元的化合物PC-Na、PC-Cl及PC-NCS。以配位能力較強的分子(如: DMSO)作為測量光致變色性質的溶劑，在照光後原本輔助配位基會被溶劑分子置換而失去光致變色的能力，故溶劑選擇配位能力較弱之MeOH。在濃度為1⨯10-4 M的MeOH溶液中，經由太陽光模擬器的光源(照射至樣品功率為100 mW/cm2) 照射後，PC-Na在照光1分鐘內變色明顯，從橘色變成深紅色，變色原因可能與配位點從(Ru-S=O)變成(Ru-O=S)有關；放置暗處1天後顏色則從深紅色變回橘色，變色原因可能是配位點從(Ru-O=S)變回(Ru-S=O)；PC-NCS需要照光至8分鐘，顏色從橘色變深紅色，變色可能的原因除了與配位點從(Ru-S=O)變成(Ru-O=S)外，也涉及到配位基(NCS-)的斷裂；PC-Cl的顏色則需要照光至20分鐘，才從淡褐色變較深的褐色，變色可能的原因為Cl-的斷裂，PC-NCS和PC-Cl在暗處顏色皆變不回去。其中變色後較吸收可逆性較高的染料為PC-Na，PC-Na在1次循環後與未照光的吸收度差值為6%，光致變色的反應可進行2次以上，將PC-Na組裝成元件後，光電轉換效率為2.91%，照光20分鐘後可增加至3.62%，靜置在暗處會減少為2.82%。;Photochromic molecules can undergo structural and absorption changes upon light irradiation, resulting in a color change, and can revert to their original color when exposed to external stimuli. When such molecules are assembled into DSCs, they may exhibit photochromic properties and can be applied in architecture. In this study, iPr-pyso (2-(propane-2-sulfinylmethyl)-pyridine) was used as an ancillary ligand for ruthenium complexes to synthesize compounds PC-Na, PC-Cl, and PC-NCS containing Ru–S=O photochromic units. When a strong coordinating solvent (e.g., DMSO) is used to measure photochromic properties, the ancillary ligand is replaced by solvent molecules upon irradiation, leading to the loss of photochromic ability. Therefore, MeOH, a weaker coordinating solvent, was chosen. In a 1⨯10⁻⁴ M MeOH solution, under irradiation from a solar simulator (100 mW/cm² at the sample), PC-Na exhibited a distinct color change within 1 minute, shifting from orange to dark red. The color change may be related to the coordination site switching from (Ru–S=O) to (Ru–O=S). When left in the dark for 1 day, the color reverted from dark red to orange, possibly due to the coordination site switching back from (Ru–O=S) to (Ru–S=O). PC-NCS required 8 minutes of irradiation for its color to change from orange to dark red, likely due not only to the coordination site change (Ru–S=O → Ru–O=S) but also to the dissociation of the NCS⁻ ligand. PC-Cl required 20 minutes of irradiation for its color to change from light brown to darker brown, which may be attributed to Cl⁻ dissociation. Unlike PC-Na, both PC-NCS and PC-Cl did not revert to their original colors in the dark. Among these, PC-Na exhibited the highest reversibility in absorption after coloration, with only a 6% difference in absorbance between the irradiated and non-irradiated states after one cycle. The photochromic reaction could proceed for more than two cycles. When PC-Na was assembled into a device, its power conversion efficiency was 2.91%, which increased to 3.62% after 20 minutes of irradiation, but decreased to 2.82% after being left in the dark.