本論文研究主題有：（1）在於如何快速且有效地進行中孔洞氧化矽分子篩的表面修飾反應，進而利用已修飾Al2O3-氧化矽分子篩應用於中孔洞碳材的合成；（2）開發及改善其他合成中孔洞碳材的製備方法。

在中孔洞氧化矽分子篩的表面修飾研究中，我們將初合成氧化矽材料直接進行金屬氧化物嫁接反應，在實驗過程中因界面活性劑存在於孔洞內部，可避免水氣儲存在孔洞中而引起金屬源與水氣進行縮合反應形成金屬氧化物顆粒的行為。且初合成氧化矽材料沒有經過560 ℃煅燒處理，其矽羥基(Si-OH)密度遠高於煅燒後的氧化矽材料，此方式有利金屬烷氧化合物（Al(i-OPr)3、Ti(n-OBu)4和VO(OPr)3）或金屬氯化物（AlCl3及FeCl3）在氧化矽表面的化學修飾反應，經修飾後的氧化矽材料在560 ℃煅燒後即形成金屬氧化物覆蓋於氧化矽表面之複合型中孔洞材料。

在中孔洞碳材的研究中，分別以酚醛樹脂及呋喃醇當作碳源，並針對這兩種碳源的性質，分別以不同的方法製備中孔洞碳材。在酚醛樹脂的部分，由於酚醛樹脂是本實驗室合成中孔洞碳材最主要的碳源，所以先前的作法大都是以乾式含浸方式將酚醛樹脂導入煅燒後的中孔洞氧化矽中，但是中孔洞氧化矽其晶格結構及孔洞尺寸會因高溫煅燒過程而隨之緊縮。所以我們利用了高分子混摻原理（Polymer Blending），利用乙醇將部分P123中性界面活性劑從初合成中孔洞氧化矽中萃取溶出，同時再導入酚醛樹脂進入中孔洞氧化矽孔洞。如此一來，中孔洞氧化矽的晶格結構及孔洞尺寸都可保留原有特性，經過1000 ℃碳化及移除無機模板後，其比表面積可達到1000 ~ 2000 m2g-1，孔體積約0.6~ 1.3 cm3g-1。另外，在呋喃醇的部分，由於呋喃醇是一種酸催化聚合的單體，所以我們以初濕含浸（Incipient wetness process）及乾式含浸兩種方式利用矽鋁酸鹽及純氧化矽固體酸的特性，去催化呋喃醇聚合形成聚呋喃醇樹脂，經過1000 ℃碳化及移除無機模板後，即可得到中孔洞碳材，其比表面積可達到1000~ 1700 m2g-1，孔體積約0.5~ 1.7 cm3g-1。

In this thesis, there are two major researching parts. 1. Chemical coating of metal oxides onto as-synthesized mesoporous silicas; 2. Synthesis of mesoporous carbons.

The first part is chemical coating of metal oxides onto the as-synthesized mesoporous silicas. The mesoporous silicas of high surface area, tunable pore size and large pore volume are desirable for catalytic processes involving large molecules. However, the amorphous silica framework of weak acidity hinders the applications in acidic-catalytic reactions. The mesoporous silicas as potential catalysts can be enhanced by a modification of their surface with other metal oxides. To increase the acidity, grafting Al2O3 onto mesoporous silica is a very promising method. In typical grafting processes, the calcined mesoporous silicas have been widely used. While, there exist two disadvantages in using calcined mesoporous silica: 1. The calcined mesoporous silica has high absorption capability for water, which can lead to a serious self-clustering of metal oxides. 2. Removal of surfactants is a time- and energy-consuming process and the surface silanol group density is considerably reduced during high-temperature calcinations. In this thesis, we proposed a new method to coat the metal oxides layer onto the mesoporous silica by directly refluxing the as-synthesized mesoporous silica in a 1-propanol solution of the metal alkoxide. After calcination, the metal oxide-coated mesoporous silicas with high surface area, large porosity were obtained.

In the second part, we used mesoporous silicas–SBA-15 as a solid template to prepare the mesoporous carbons – CMK-3 or CMK-5 by using phenol-formaldehyde resin or furfuryl alcohol as carbon source. When using phenol-formaldehyde resin, a simple impregnation in ethanol solution was perform to introduce the phenol-formaldehyde polymer into mesoporous silicas. Cuing at 100 oC, carbonization at 1000 oC and silica etching by HF solution gave the CMK-3 mesoporous carbon. A typical incipient-wetness process was used to fill the mesopores of the acidic Al2O3-coated or pure silica mesoporous silicas with the furfuryl alcohol. Due to the high acidity of the Al2O3-coated mesoporous, polymerization of the furfuryl alcohol was achieved at relatively lower (60–80 oC). In contrast, higher polymerizing temperature (100 oC) was required for the pure-silica mesoporous silicas. After pyrolysis at 1000 oC under N2 environment and silica removal by HF-etching, the CMK-3 mesoporous carbons were synthesized. With a careful control on the furfuryl alcohol content, the CMK-5 consisted of carbon tube were generated instead. These mesoporous carbons possess the properties of high surface area (1700~1000 m2g-1), and large volume (1.5~ 0.7 cm3g-1).

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