| 摘要: | 有序中孔洞材料在吸附、分離、催化和能量儲存的優異表現，吸引了各界的高度關注。中孔洞矽材擁有高表面積、大孔洞體積及可調孔徑（2-50奈米）的優勢。計畫的第一部分首先利用合成各式中孔洞矽材及其表面具官能基之類似物，透過濕式含浸和熱還原方法將金屬/雙金屬奈米顆粒擔載於中孔洞矽材，然後將這類奈米觸媒應用於各式反應的催化反應，如硝基芳烴的氫化反應、二氧化碳的加氫反應、硼烷氨的產氫反應等。 計畫的第二部分為合成有序中孔洞碳材和富含氮的中孔洞碳材，並應用於能量儲存，CMK系列有序中孔洞碳材是利用中孔洞矽材作為模板和蔗糖作為碳化前驅物的奈米模鑄法合成，或使用軟模板法直接合成中孔洞碳材。另外也會利用三聚氰胺-尿素-甲醛作為碳氮的來源，合成富含氮的中孔洞碳材，並擔載金屬氧化物而進行鋰/鈉離子電池的陽極性能測試。 計畫的第三部分為透過各式化學製備法合成含金屬及金屬氧化物奈米顆粒的MOFs(金屬有機骨架材料)及其衍生碳材料。利用MOFs的兩個子類為M-MOF-74和ZIFs及其碳衍生物，作為穩定或擔載金屬奈米顆粒的的基本擔體系統。最後，透過直接熱解法將矽奈米顆粒擔載於M-MOF-74和ZIFs衍生碳材料，將評估這些材料作為反應催化劑和鋰/鈉離子電池陽極的性能。 ;Ordered mesoporous materials have attracted a wide range of interests due to their promising applications in adsorption, separation, catalysis and energy storage. Among the ordered mesoporous materials, ordered mesoporous silicas and ordered mesoporous carbons have shown great potentials in many areas of modern science and technology. Ordered mesoporous silicas are considered as promising materials due to their high surface area, large pore volumes and tunable pore sizes (2-50 nm). The design, synthesis and modification of ordered mesoporous silicas are still a challenge considering their role in different applications. In the first part of our proposal, a variety of ordered mesoporous silicas, namely SBA-1, SBA-15, SBA-16, FDU-12, KIT-5, KIT-6 and their organic functionalized analogues will be synthesized. These functionalized ordered mesoporous silicas will be used in adsorption and separation of molecules. Meanwhile, mesoporous silicas with large pores will be synthesized for immobilization of large biomolecules. In addition, metal/bimetallic nanoparticles (Ni, Co, Ag, Pt, Pd, Cu, Ru, etc.) encapsulated ordered mesoporous silicas will be synthesized by wet impregnation followed by thermal reduction. These metal encapsulated ordered mesoporous silicas will be used as catalysts for various reactions, such as hydrogenation of nitroarenes, CO2 hydrogenation, hydrogen generation from ammonia borane, hydrogenation of aromatic aldehydes, aerobic oxidation of alcohols, oxidation of cyclohexanol, oxidation of styrene to benzaldehyde, etc. In the second part of our proposal, ordered mesoporous carbons and nitrogen-rich ordered mesoporous carbons will be synthesized for energy storage application. The CMK series (CMK-5/CMK-8/CMK-9) ordered mesoporous carbons will be synthesized by the nanocasting method using SBA-15 and KIT-6 silica templates and sucrose as carbon precursor. Different metal precursors will infiltrate into CMK-5/CMK-8/CMK-9 ordered mesoporous carbons to obtain metal or metal oxide nanoparticles encapsulated mesoporous carbons. Metal oxide nanoparticles embedded ordered mesoporous carbons will also be synthesized by the direct self-assembly method (soft-templating) by using Pluronic F127, resol and metal precursors. Moreover, nitrogen-rich ordered mesoporous carbons will be synthesized by using silica hard templates, such as SBA-15 and KIT-6, and melamine-urea-formaldehyde resins. These nitrogen-rich ordered mesoporous carbons will be further modified by encapsulating metal/metal oxide nanoparticles inside the mesopores. All these materials will be investigated as anodes for lithium and sodium-ion batteries. Meanwhile, they will be also tested for various catalytic reactions. In the third part of our proposal, metal-organic frameworks (MOFs), MOFs-derived carbons, metal/metal oxide nanoparticles doped MOFs and MOFs-derived carbons will be synthesized by hydrothermal, solvothermal and sonochemical methods. The modification of MOFs with different ligands or metal centers can generate a whole bunch of multivariate MOFs. Two sub-classes of MOFs, namely M-MOF-74 and ZIFs with their carbon derivatives will be employed as the fundamental support systems for the stabilization or encapsulation of metal NPs. In addition, transition metal and metal oxide nanoparticles doped MOFs- and ZIFs-derived N-doped mesoporous carbons will be synthesized. Finally, silicon nanoparticles encapsulated in M-MOF-74 and ZIFs-derived carbonaceous supports will be synthesized through a direct pyrolysis method. The performances of these materials as catalysts for catalytic reactions and as anodes for lithium and sodium-ion batteries will be evaluated. |
