摘要
本研究之工作目的為開發以氧化鎂作為活性中心之固體鹼觸媒製備技術與建立適用之材料分析平台和完整的反應測試系統，作為評估非勻相催化反應之活性表現。在第一部份中，我們以共沉澱法製備鎂鋁氧複合式觸媒作為環氧丙烷之開環醚化反應之應用，並針對固體鹼觸媒建立一套材料鑑定方法與反應器之架設。在第二部分中，我們以Zn-MOF (ZIF-8)作為前驅體材料、氧化鎂作為活性成分，運用初濕含浸法合成出不同化學組成與外觀形貌之MOF衍生混成式奈米結構，並結合第一部份所建立之材料鑑定平台與反應測試系統，應用於催化轉酯化與脫酸環化等反應上。
在材料鑑定方法上，我們使用X光繞射儀(XRD)、掃描電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)、比表面積與孔徑分析儀(BET)、化學吸附儀(TPD)、指示劑法(Hammett indicator)和感應耦合電漿發射光譜儀(ICP-OES)等分別對固體鹼觸媒進行晶相分析，外觀型態之觀察，表面鹼度分布、比表面積與孔徑大小之測量和觸媒中元素之分析，而其中又以鹼度分析對於鹼性催化之影響至關重要，由第一部份之研究成果顯示，我們可以透過調整前驅物中鎂鋁莫耳比之大小，來改變觸媒表面之酸鹼特性，此外，當鎂鋁莫耳比接近4-5之間時，觸媒具有最佳之活性及對應含量最多之中鹼基位。在第二部分之研究成果中，我們成功以初濕含浸法合成出兩種不同型態之MOF衍生Mg-Zn混成式奈米結構—(1)氧化鎂奈米粒子包覆於Zn-MOF奈米晶體團簇之孔洞結構中(MgO@Zn-MOF)；(2)氧化鎂奈米粒子均勻分散於Zn-MOF衍生之氧化鋅奈米粒子上(MgO@ZnO)，而由結果顯示，透過Zn-MOF作為前軀體材料，可以有效地控制活性成分於高溫下的晶體成長，使之形成極為細小的氧化鎂奈米晶粒(< 5 nm for MgO@Zn-MOF及 ≈10 nm for MgO@ZnO)於奈米結構中，且與直接液相合成法製備之Mg-Zn觸媒(41MgO/ZnO-400)相比，以MOF衍生之Mg-Zn混成式奈米結構不僅在比表面積上，有顯著之增加(最大可達1048.5 m2/g)，其表面之鹼度也有所成長(提高1.2倍)，此外，在活性測試方面，MgO@Zn-MOF與MgO@ZnO於低醇油比下(Methanol-to-oil molar ratio = 3)亦展現了高催化活性(產率分別為67.6%與73.3%)與極佳之操作穩定度。本研究以氧化鎂作為基底，透過添入不同種類與比例之前驅物開發出具有不同表面物化性質之複合式奈米觸媒，並配合即時之材料分析平台與反應系統來優化觸媒表面之鹼位分布，除此之外，我們也期望可以將此套研究方法應用於其他非匀相鹼催化反應中，作為高值化產品之開發，並以簡易之方式製備出兼具高催化活性與高度穩定性之複合式奈米觸媒。

Abstract
The objective of the study is to develop a facile route for preparation of MgO-based solid base catalysts and establish a complementary material characterization platform and a suitable activity test system. In the first part, we utilize a co-precipitation method to prepare Mg-Al-O composite catalyst for the application of the ring-opening etherification reaction of propylene oxide. In the second part, we employ the incipient wetness impregnation method to develop metal-organic framework (MOF)-derived Mg-Zn hybrid nanocatalysts for transesterfication of soybean oil to biodiesel.
X-ray diffractometer (XRD), Transmission Electron Microscope (TEM), Scanning Electron Microscope (SEM), Brunauer-Emmett-Teller analyzer (BET), chemisorption analyzer (TPD), indicator method (Hammett indicator) and, Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) are used complementarily for characterization of catalyst material. The results of the first part show that we can alter the acid-base characteristics of the catalyst surface by adjusting the molar ratio of the magnesium to aluminum in the precursor. When the molar ratio of Mg/Al is nearly between 4-5, the catalyst has the best activity corresponding to its highest amount of the medium basic sites. In the second part, we have successfully fabricated two types of metal-organic framework (MOF)-derived Mg-Zn hybrid nanostructure via a incipient wetness impregnation approach, (1) MgO nanoparticles encapsulated in Zn-based MOF (MgO@Zn-MOF) and (2) MgO nanoparticles uniformly decorated on ZnO nanoparticles derived from Zn-MOF (MgO@ZnO), respectively. The results show that ultrafine MgO nanoparticles (< 5 nm for MgO@Zn-MOF and ≈10 nm for MgO@ZnO) were successfully synthesized and homogeneously dispersed in the MOF-derived Mg-Zn hybrid nanostructures. Significant increases in the specific surface area (i.e., by a maximum of 2.1 times) were achievable by using MOF-based strategy comparing to the Mg-Zn catalyst prepared by a conventional solution-based approach. High 3-cycle stability and high yields of fatty acid methyl esters at a stoichiometric feed ratio 3 were both achievable, 67.6% and 73.3% by using MgO@Zn-MOF and MgO@ZnO as the catalysts, respectively. The work demonstrates a prototype study of utilizing MOF to develop high-performance basic nanocatalysts through fundamental understanding of material synthesis by design versus their corresponding activities. It is also expected that the research methods can be applied to various types of heterogeneous catalytic reactions.

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