凝胶法制备介孔氧化锆.DOC

以三嵌段兩性共聚物輔助溶膠–凝膠法製備介孔氧化鋯 Preparation and characterization of mesoporous zirconia with a surfactant-mediated method 研究生：賴俊良 Lai, Jun-Liang 指導教授：張莉毓 Teoh, Lay-Gaik 【摘要】 自從Mobil 公司在1992 年發表MCM-41 開始，介孔材料所具有的高比表面積、均勻孔洞大小和可控制孔洞大小等特性，是近年來相當引人注目的研究領域之ㄧ。本研究是利用三嵌段兩性共聚物作為天然模板，ZrOCl2?8H2O、YCl3?6H2O為反應前驅物，以模板輔助溶膠–凝膠法製備高比表面積的介孔氧化鋯與介孔釔安定氧化鋯(YSZ)。實驗是以熱重分析、X-ray 繞射分析、穿透式電子顯微鏡及氮氣吸附/脫附曲線分析該材料之微結構及比表面積，並探討各種合成因素例如改變三嵌段兩性共聚物濃度與煆燒溫度、釔(Yttrium)添加量及前驅物中添加水量對介孔氧化鋯與介孔YSZ 之結構影響。 實驗結果顯示，使用三嵌段兩性共聚物(F108)的添加量為1.5 g，煆燒溫度500 oC，可合成出比表面積約為67.92 m2/g、孔洞直徑約為69.77 ? 的介孔氧化鋯。當Yttrium 添加量從0YSZ 改變至12YSZ 時，經煆燒溫度500 oC，其比表面積會從67.92 m2/g 增加至128.33 m2/g，孔徑從69.77 ? 縮小至62.73 ?。經由X-ray 繞射分析可知在反應系統中水濃度的含量不會影響氧化鋯之結晶相，可合成單一立方晶相的介孔YSZ，而由BET 分析顯示其比表面積隨著水取代量越多則越小，以Yttrium 添加量為12YSZ 經煆燒溫度500 oC 為例，水取代量從0 wt% ~ 50 wt% 時，其比表面積會從128.33 m2/g 縮小至109.85 m2/g，平均孔徑從62.73 關鍵字：氧化鋯、釔安定氧化鋯、溶膠–凝膠法、三嵌段兩性共聚物 【Abstract】 Since the mesoporous molecular sieves such as MCM-41, first reported by Mobil scientists in 1992, mesoporous materials have attracted particular attention because they usually show higher surface area, regular pore size and tunable pore structures compared with nanocrystalline materials. In this study, the mesoporous ZrO2 and Yttrium-Stabilized Zirconia(YSZ) were prepared by sol-gel process and the synthesis was accomplished by using block copolymer as the template, and ZrOCl2?8H2O, YCl3?6H2O as the inorganic precursor. TGA, XRD, TEM and N2 adsorption-desorption isotherms were used to characterize the microstructure of the samples. We adjusted the experimental parameters such as the concentration of block copolymer, calcination temperatures, molar ratio of Yttrium to Zirconium, and additive of water to investigate their effects on the structure of mesoporous ZrO2 and YSZ. In this study, using 1.5g F108 block copolymer as the template, the mesoporous ZrO2 exhibits a high BET surface area of 67.92 m2/g and an average pore size of 69.77 ? after calcined at 500 oC. The addition of Yttrium increased from 0YSZ to 12