論文中分為二個部份，第一部份是沸石經 NH4F 氟化處理後，利用 NMR
技術來研究探討，第二部份為中孔洞材料 SBA-1 植入胺基官能基，利用 XRD
等溫氮氣吸脫附及 29Si MAS NMR 來研究官能基對孔洞結構的影響。
首先在沸石 HY 方面，在經過 NH4F 處理後，可在 27Al MAS NMR 觀察
到四配位的鋁會脫離骨架而形成骨架外的六配位鋁化物，對應 19F MAS NMR
則位於 -141 ppm 乃是屬於 (NH4)3AlF6 化合物。在這篇論文中，主要發現到的
是，反應溫度為 80 度在 FNH4F/AlHY = 3 於 19F MAS NMR 則是觀察到訊號峰
為 -173 ppm 和其側峰 -182 ppm，並且經由 27Al/19F 2D HETCOR NMR 交錯訊
號得到 50 ppm 為骨架鋁的訊號峰，可能氟離子跟骨架鋁進行反應，使得氟離
子鍵結在骨架中的鋁，形成四配位氟鋁化合物。
而在 FNH4F/AlHY = 4，經由27Al MAS NMR 結果為位於 -20 ppm 至 -70 ppm
有極寬之訊號產生，對應於 19F MAS NMR 則是觀察到兩個訊號峰，分別處於
-151 及 -166 ppm，經過鑑定後確定為 NH4AlF4 化合物，而該訊號的產生需在
NH4F 反應劑量為 FNH4F/AlHY = 4 或者反應溫度需提高到攝氏 100 度且
FNH4F/AlHY 降低到 2 就可得到 NH4AlF4。另外 HY 和 NH4F 在溫度 25oC 下反
應時，並且反應時間維持 3 小時，主要由 27Al NMR 上得知，主要訊號峰為 -1
ppm，並且由 19F NMR 得知反應物分佈位置為 -143 至 -153 ppm，可能氟鋁化
合物為 Al(O5F)、Al(O4F2) 與 AlF3
.nH2O。
第二部份是以四乙氧基矽酸鹽 (TEOS) 與胺丙烷基三甲氧基矽烷 (APTMS)
為共同矽源，使用十六烷基三乙基溴化銨 (C16TEABr) 作為主要模板試劑，以
直接合成具有胺基官能基的中孔洞材料，在移除模板後，得到的中孔洞材料仍
具有 SBA-1 的結構存在。
藉由改變不同的合成溫度及不同矽源，探討對於合成具有胺基官能基之
SBA-1 的結構影響，在 XRD 的結果中可以發現胺基官能基對結構的影響，藉由固態核磁共振之 13C 及 29Si MAS NMR 可以得知胺基官能基在骨架中的含量。

The thesis is divided into two parts. Studies on fluorination of zeolites HY and
amine functionalization of mesoporous materials.
First, HY samples treated with NH4F (FNH4F/AlHY = 3) at 80oC, 27Al NMR
revealed that tetrahedral aluminum was at 60 ppm from the zeolitic framework and
some extraframework aluminum was also observed. The corresponding 19F NMR
showed a dominant peak at -173 ppm with a shoulder at -182 ppm. Interestingly,
these fluorinated species were associated with tetrahedral framework Al at 50 ppm,
as revealed by 27Al/19F 2D HETCOR NMR for the first time. This observation
implies that these fluorinated species are possibly due to the framework Al-F species.
For HY samples treated with NH4F at 100oC, on the other hand, a broad powder
pattern spreading from -20 ppm to -70 ppm due to the NH4AlF4 crystalline phase is
observed for the cases of FNH4F/AlHY ≥ 2. The NH4AlF4 crystalline phase observed
exhibited two 19F resonance peaks at -151 ppm and -166 ppm, which are assigned to
the fluorine atoms in the terminal Al-F and bridging Al-F-Al group, respectively.
Different aluminum fluoro-complexes after dealumination were detected. First, for
NH4F treated HY, that tetrahedral aluminum was expelled from the zeolitic
framework, resulting in the formation of (NH4)3AlF6, which was evident from the
peak at -1 ppm in the 27Al MAS NMR and at -141 ppm in the 19F MAS NMR.
In the second part of thesis, direct synthesis of well-ordered cubic mesoporous
silicas SBA-1 with amino functionality group were direct-synthesized of containing
simultaneously tetrathoxysilane (TEOS) and 3-aminopropyltrimethoxsilane (APTMS)
and has been synthesized by cetyltriethylammonium bromide (CTEABr) under
strongly acidic conditions.
The materials obtained were characterized by variety of techniques including
power X-ray diffraction (XRD),nitrogen sorption measurements, scanning electron
microscopy (SEM), and thernmogravimetric analysis (TGA). Qualitative evidence of
present of chemically atteched amino group moieties was provided by solid-state 13C
and 29Si MAS NMR.

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