本研究主要是以陽離子界面活性劑(cetyltrimethylammonium
bromide，CTAB)為有機分子模板，四氯化錫(hydrous tin chloride，
SnCl4
.5H2O)為無機前驅物，NH3(aq)為酸鹼值之調整劑，在室溫下合成
具有中孔結構之二氧化錫。其中改變的變因有：合成環境之酸鹼度，
界面活性劑與無機前驅物之比例(S/I ratio)，靜置時間(Aging time)以及
不同之添加順序。
由X 光繞射(XRD)結果顯示，中孔結構之形成，主要取決於混合
溶液之pH 值，而與CTAB(aq)，SnCl4(aq)及NH3(aq)混合之順序無關，在
CTAB 對SnCl4 莫耳比R=0.2，0.5，1 之溶液中，pH<1 時會合成出一
有機-無機複合之結晶相，阻礙含錫前驅物之水解與縮合，也間接阻
礙中孔結構之形成。當pH=2~5 時，中孔結構之繞射峰漸趨明顯，而
pH>7 時可穩定合成具備中孔結構之粉末。
另外由R=0.01 之鹼性混合液，亦可合成出中孔結構之粉末，證
實有機、無機分子之集體合作過程，無需經過膠柱及六角狀柱列之階
段，因CTAB(aq)之濃度遠低於形成膠柱所需之臨界濃度(10wt％)。而
由R=10(CTAB=5g，SnCl4=0.5g)之鹼性溶液合成之產物僅發現膠柱而
無中孔結構，顯示無機物數量不足時，就算CTAB 形成膠柱，亦無法
合成二氧化錫之中孔結構。
根據中孔結構合成之模型，在製程中界面活性劑離子(S+)，無機
前驅物離子(I+)及緩衝離子(X-)，藉靜電力吸引，以S+X-I+之聯結行集
體合作而造成中孔結構。而由CTAB(aq)添加NH3(aq)時之量測顯示pH
值急速上升，證實CTA+OH-之聯結不存在，故X-可能是存在溶液中
之Br-或Cl-，而非OH-。
最後，本研究所得之中孔結構高溫穩定性欠佳，在500 /2h ℃ r &#28997;
燒後全部瓦解，其穩定性尚有待大力改進。

In this research, cetyltrimethylammonium bromide (CTAB) is used
as organic template and hydrous tin chloride (SnCl4) is used as inorganic
precursor to prepare mesostructured SnO2 powder. The synthesis is
carried out in the room temperature using NH3(aq) as pH-modifier. The
changing variables in the synthesis process include: the mixing sequence
of CTAB(aq), SnCl4(aq) and NH3(aq), the molar ratio of CTAB/SnCl4 (R), the
pH value of the mixture and the aging time of the mixture.
The X-ray diffraction (XRD) results show that the pH value of the
mixture is the determining factor for the successful synthesis of
mesoporous powder. On the other hand, the mixing sequence is of no
consequence on the formation of the mesostructure. For solutions of
pH<1 and R=0.2, 0.5 or 1, a crystalline phase of organic-inorganic
complex is found in the final products, which hinders the hydrolysis and
condensation of the inorganic precursor and hence the formation of
mesoporous structure. For powders derived from the solutions of pH=2~5,
the diffraction peak of mesoporous structure appears and becomes more
intense with increasing pH value. For solutions of pH>7, mesoporous
powders are obtained constantly.
As mesoporous powder is also obtained from solution of R=0.01, it
is concluded that the formation of surfactant cylinders and the
subsequently packed hexagonal arrays are not fulfilled during the
cooperation assembly process of organic and inorganic moleculars
because the concentration of CTAB is far below the critical concentration
for rod micelle (~10wt0/0).
On the other hand, surfactant rod micelles instead of mesoporous
structure is found in the powder derived from the basic solution of R=10
(CTAB: 5 g, SnCl4: 0.5 g). This implies that in spite of the formation of
CTAB rod micelles, the mesostructured SnO2 powder can not be obtained
without sufficient amount of Sn-precursor .
According to the model of mesostructure synthesis, in current work,
surfactant ions (S+), inorganic ions (I+) and counter ions (X-) are
connected in the form of S+X-I+ through the electrostatic attraction and
their cooperation assembly results in mesoporous structure. As pH valueincreases instantly as NH3(aq) is added into CTAB(aq), it is concluded that
CTA+OH- does not exist and X- is Br- or Cl- instead of OH-.
Finally, the mesostructure obtained in this work collapse after a
calcination of 5000C for two hours. Therefore, a great deal needs to be
done to improve the thermal stability in the future.

I
目錄.I
表目錄..........................................................................................................................III
圖目錄..........................................................................................................................IV
第一章前言................................................................................................................1
第二章文獻回顧..........................................................................................................6
§2.1 二氧化錫之晶體結構及應用.......................................................................6
§2.2 界面活性劑簡介...........................................................................................7
§2.3 超分子液晶模板機制之簡介.......................................................................8
§2.4 以超分子模板構築之中孔結構(Supramolecular-templated mesostructure)
..............................................................................................................................10
§2.5 中孔結構二氧化錫.....................................................................................12
§2.6 偏光顯微鏡之簡介.....................................................................................13
第三章、實驗步驟與方法..........................................................................................17
§ 3.1 實驗藥品....................................................................................................17
§ 3.2 先期工作....................................................................................................17
3.2.1 CTA-OH 之檢測.................................................................................17
3.2.2 不同濃度SnCl4(aq)之pH 值變化......................................................18
3.2.3 靜置時間(Aging Time)對產物結構的影響......................................18
3.2.4 以HCl 為pH 值調整劑之嘗試........................................................18
3.2.5 以甲醯胺為pH 值調整劑之嘗試.....................................................19
3.2.6 R=10 及R=0.01 之對比實驗.............................................................19
§ 3.3 中孔結構二氧化錫之製備.........................................................................20
3.3.1 (C+S)+N--[即(CTAB(aq)+SnCl4(aq))+NH3(aq)] 順序： .....................20
3.3.2 (C+N)+S--[即(CTAB(aq)+NH3(aq))+SnCl4(aq)] 順序： .....................21
3.3.3 (S+N)+C--[即(SnCl4(aq)+NH3(aq))+ CTAB(aq)] 順序： ....................21
3.3.4 &#28997;燒....................................................................................................21
§ 3.4 中孔結構之鑑定.........................................................................................22
3.4.1 偏光顯微鏡(Polarized Optical Microscopy).....................................22
3.4.2 X 光繞射儀(X-Ray Diffractometry) ..................................................22
3.4.3 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) .............23
§ 4.1 先期工作之實驗結果................................................................................28
4.1.1 CTA-OH 之檢測結果.........................................................................28
4.1.2 不同SnCl4(aq)濃度之pH 值變化結果................................................28
4.1.3 靜置時間對結構型態的影響結果....................................................28
4.1.4 以HCl 為pH 值調整劑之結果........................................................29
4.1.5 以甲醯胺為pH 值調整劑之結果.....................................................29
II
4.1.6 R=10 及R=0.01 之對比實驗結果.....................................................30
§4.2 中孔結構二氧化錫之合成結果.................................................................30
4.2.1 (C+S)+N 順序，R=0.2 之pH 系列X 光繞射結果..........................30
4.2.2 (C+S)+N 順序，R=0.5 之pH 系列X 光繞射結果..........................30
4.2.3 (C+S)+N 順序，R=1 之pH 系列X 光繞射結果.............................31
4.2.4 (C+N)+S 順序，不同R 值之pH 系列X 光繞射結果....................31
4.2.5 (S+N)+C 順序，不同R 值之pH 系列X 光繞射結果....................32
4.2.6 &#28997;燒後樣品之X 光繞射結果...........................................................32
§4.3 偏光顯微鏡結果.........................................................................................33
§4.4 掃描式電子顯微鏡(SEM)結果..................................................................34
§4.5 穿透式電子顯微鏡(TEM)之結果.............................................................35
第五章討論..............................................................................................................70
§5.1 溶液pH 值對中孔結構之影響..................................................................70
§5.2 I+離子之確認...............................................................................................71
§5.3 X-離子之辨別..............................................................................................72
§5.4 靜置時間(Aging Time)對中孔結構的影響...............................................72
§5.5 混合順序的影響.........................................................................................73
§5.6 界面活性劑與無機前驅物混合比例的影響.............................................74
§5.7 以HCl(aq)及甲醯胺為pH 調整劑之影響..................................................75
§5.8 顯微鏡之分析.............................................................................................77
第六章結論................................................................................................................81
第七章未來之研究方向............................................................................................82
參考文獻......................................................................................................................83
附錄一..........................................................................................................................87
附錄二..........................................................................................................................88
附錄三..........................................................................................................................90
附錄四之一..................................................................................................................91
附錄四之二..................................................................................................................93
附錄五..........................................................................................................................94
附錄六..........................................................................................................................95
III
表目錄
表3- 1 實驗所用之藥品資料表................................................................................17
表4- 1 氨水添加量與CTAB(aq)之pH 值的變化關係................................................36
表4- 2 不同SnCl4(aq)濃度之pH 值變化結果............................................................36
IV
圖目錄
圖2- 1 二氧化錫的結晶構造圖...............................................................................14
圖2- 2 界面活性劑之分子結構................................................................................15
圖2- 3 CTAB 之分子結構圖......................................................................................15
圖2- 4 液晶模板之形成機制....................................................................................15
圖2- 5 中孔結構之形成機制....................................................................................16
圖2- 6 偏光顯微鏡之簡單原理圖............................................................................16
圖3- 1 (C+S)+N 混合順序之實驗流程圖................................................................25
圖3- 2 (C+N)+S 混合順序之實驗流程圖................................................................26
圖3- 3 (S+N)+C 混合順序之實驗流程圖................................................................27
圖4- 1 氨水添加量與CTAB(aq)pH 值的變化關係...................................................37
圖4- 2 以電腦模擬CTA-OH 之檢測結果..............................................................37
圖4- 3 不同SnCl4(aq)濃度其pH 值變化結果...........................................................38
圖4- 4 (S+N)+C，R=0.1 分別靜置6 小時及168 小時樣品之XRD 繞射圖........38
圖4- 5 HCl 作為pH 值調整劑所得樣品之低角度X 光繞射圖..............................39
圖4- 6 HCl 作為pH 值調整劑所得樣品之高角度X 光繞射圖..............................39
圖4- 7 Formamide 作為pH 值調整劑所得樣品之低角度X 光繞射圖...................40
圖4- 8 Formamide 作為pH 值調整劑所得樣品之高角度X 光繞射圖...................40
圖4- 9 Formamide 樣品&#28997;燒500℃後之X 光繞射結果........................................41
圖4- 10 R=10 及R=0.01 之對比實驗低角度X 光繞射結果.................................41
圖4- 11 R=10 及R=0.01 之對比實驗高角度X 光繞射結果..................................42
圖4- 12 (C+S)+N 順序，R=0.2 系列樣品之低角度X 光繞射圖..........................42
圖4- 13 (C+S)+N 順序，R=0.2 系列樣品之高角度X 光繞射圖..........................43
圖4- 14 (C+S)+N 順序，R=0.5 系列樣品之低角度X 光繞射圖..........................43
圖4- 15 (C+S)+N 順序，R=0.5 系列樣品之高角度X 光繞射圖.........................44
圖4- 16 (C+S)+N 順序，R=1 系列樣品之低角度X 光繞射圖.............................44
圖4- 17 (C+S)+N 順序，R=1 系列樣品之高角度X 光繞射圖.............................45
圖4- 18 (C+N)+S 順序，R=0.2 系列樣品之低角度X 光繞射圖..........................45
圖4- 19 (C+N)+S 順序，R=0.2 系列樣品之高角度X 光繞射圖..........................46
圖4- 20 (C+N)+S 順序，R=0.5 系列樣品之低角度X 光繞射圖..........................46
圖4- 21 (C+N)+S 順序，R=0.5 系列樣品之高角度X 光繞射圖..........................47
圖4- 22 (C+N)+S 順序，R=1 系列樣品之低角度X 光繞射圖.............................47
圖4- 23 (C+N)+S 順序，R=1 系列樣品之高角度X 光繞射圖.............................48
圖4- 24 (S+N)+Ｃ順序，R=0.2 系列樣品之低角度X 光繞射圖..........................48
圖4- 25 (S+N)+Ｃ順序，R=0.2 系列樣品之高角度X 光繞射圖..........................49
圖4- 26 (S+N)+Ｃ順序，R=0.5 系列樣品之低角度X 光繞射圖..........................49
圖4- 27 (S+N)+Ｃ順序，R=0.5 系列樣品之高角度X 光繞射圖..........................50
圖4- 28 (S+N)+Ｃ順序，R=1 系列樣品之低角度X 光繞射圖.............................50
圖4- 29 (S+N)+Ｃ順序，R=1 系列樣品之高角度X 光繞射圖.............................51
圖4- 30 (C+N)+S R=0.2 系列樣品&#28997;燒500℃之低角度X 光繞射圖...................51
圖4- 31 (C+N)+S R=0.2 系列樣品&#28997;燒500℃之高角度X 光繞射圖...................52
圖4-32 (a) S+C 溶液靜置一天之偏光顯微鏡照V
圖4-32 (b) S+C 溶液靜置一天之偏光顯微鏡照片(沒放λ 板) ...........................53
圖4-33 (a) S+C 溶液靜置兩天之偏光顯微鏡照片..................................................54
圖4-33 (b) S+C 溶液靜置兩天之偏光顯微鏡照片(沒放λ 板) ...........................54
圖4-34 S+C 溶液靜置三天之偏光顯微鏡照片(沒放λ 板) ..............................55
圖4-35 (a) S+N 溶液靜置一天之偏光顯微鏡照片.................................................55
圖4-35 (b) S+N 溶液靜置一天之偏光顯微鏡照片(沒放λ 板) ..........................56
圖4-36 (a) S+N 溶液靜置兩天之偏光顯微鏡照片.................................................56
圖4-36 (b) S+N 溶液靜置兩天之偏光顯微鏡照片(沒放λ 板) ...........................57
圖4-37 (a) (C+N)+S 樣品，靜置一天之偏光顯微鏡結果......................................57
圖4-37 (b) (C+N)+S 樣品，靜置一天之偏光顯微鏡結果(沒放λ 板)................58
圖4-38 (a) (C+N)+S 樣品，靜置兩天之偏光顯微鏡結果......................................58
圖4-38 (b) (C+N)+S 樣品，靜置兩天之偏光顯微鏡結果(沒放λ 板)................59
圖4-39 (a) (C+N)+S，R=0.2，pH=0.94 樣品之偏光顯微鏡結果..........................59
圖4-39 (b) (C+N)+S，R=0.2，pH=4.42 樣品之偏光顯微鏡結果.........................60
圖4-39 (c) (C+N)+S，R=0.2，pH=9.52 樣品之偏光顯微鏡結果..........................60
圖4-40 (a) (S+N)+C，R=10，pH=9.75 樣品之偏光顯微鏡結果...........................61
圖4-40 (b) (S+N)+C，R=0.01，pH=10.16 樣品之偏光顯微鏡結果.....................61
圖4-41 (a) (C+S)+HCl，R=0.2，pH=0.53 樣品之偏光顯微鏡結果......................62
圖4-41 (b) (C+S)+N，R=0.2，pH=0.88 樣品之偏光顯微鏡結果.........................62
圖4-42 (C+N)+S，R=0.2，pH=0.94 樣品之SEM 結果......................................63
圖4-43 (C+N)+S，R=0.2，pH=4.13 樣品之SEM 結果......................................63
圖4-44 (C+N)+S，R=0.2，pH=7.58 樣品之SEM 結果......................................64
圖4-45 (C+N)+S，R=0.2，pH=8.55 樣品之SEM 結果......................................64
圖4-46 (C+N)+S，R=0.2，pH=8.93 樣品之SEM 結果......................................65
圖4-47 (a) (C+S)+N，R=0.2，pH=0.88 樣品之明視野(BF)圖..............................66
圖4-47 (b) (C+S)+N，R=0.2，pH=0.88 樣品之繞射圖.........................................67
圖4-48 (a) (C+S)+N，R=0.5，pH=8.58 樣品之明視野(BF)圖..............................68
圖4-48 (b) (C+S)+N，R=0.5，pH=8.58 樣品之繞射圖.........................................69
圖5- 1 XRD patterns of the synthesized products (a) Sn-CNS ................................80
圖5- 2 Two possible pathways for the LCT mechanism............................................80片..................................................53

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