具高比例羧酸官能化之中孔洞材料於染料吸附及奈米金屬顆粒製備之應用

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研究生：	張惟捷 Wei-chieh Chang
論文名稱：	具高比例羧酸官能化之中孔洞材料於染料吸附及奈米金屬顆粒製備之應用 Direct Synthesis of Mesoporous Organosilicas Functionalized with Carboxylic Acid Groups: Study on Dye Adsorption and Fabrication of Metal (Ag, Pt) Nanoparticles
指導教授：	高憲明 Hsien-ming Kao
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	188
中文關鍵詞：	中孔洞材料、亞甲基藍、奈米金屬、羧酸官能基
相關次數：	點閱：7 下載：0
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本篇論文主要合成兩種羧酸官能化之中孔洞材料，並分別探討羧酸官能化之中孔洞材料吸附染料亞甲基藍能力分析和吸附金屬離子加以還原成金屬奈米顆粒兩大部分。
第一部分是利用非離子型界面活性劑F127做為模板，並利用1,3,5-trimethylbenzene (TMB)當作擴孔劑，再以tetraethyl orthosilicate (TEOS) 和carboxyethylsilanetriol sodium salt (CES)為共同矽源在酸性條件下合成孔洞大小約9-11 nm的具羧酸官能基中孔洞材料FTC-x；之後再利用該材料吸附亞甲基藍染料，最高可達 374 mg/g，並且在重覆使用上有很好的表現。
第二部分是利用非離子型界面活性劑Brij 76為模板，利用1,2-bis(triethoxysilyl) ethane (BTEE) 和CES為共同矽源，合成具乙烷和羧酸官能基的雙官能基中孔洞材料EC-x，其中羧酸官能基含量最高可達85%；再利用該材料吸附銀、鉑兩種金屬離子，並利用熱還原法將金屬離子還原成金屬粒子，在製備金屬粒子的過程中因受到孔洞大小的空間限制及羧酸官能基的影響有效控制金屬顆粒大小約3-4 nm鉑金屬與4-6 nm銀金屬。

Here we report two projects,based one-pot synthesis of mesoporous organosilicas functionalized with carboxylic acid group. In the first project, well-order cubic mesoporous silicas FDU-12 functionalized with various contents of carboxylic acid groups were successfully synthesized via co-condensation of tetraethyl orthosilicate (TEOS) and carboxyethylsilanetriol sodium salt (CES) under acidic conditions using Pluronic F127 triblock copolymer as template, FTC-x (x refers to the [CES/(TEOS+CES)] molar ratio). The maximum loading of CES contents into the pore wall without degrading the Fm3m mesostructure was up to 50% (base on silicon).The cage size distrubutions 9-11 nm were obtained. In this study, a variefy of techniques was adopted to charaterize the FTC-x materials, including powder X-ray diffraction, nitrogen sorption measurement, 13C CP-MAS NMR, 29Si MAS NMR, fourier transform infrared spectrometer, thermogravimetric analyzer and transmission electron microscopy. And we used FTC-x to adsorp the dye, Methylene blue. The adsorption process was carefully studied with various systematic factors, including the loading amount of CES, the quanity of methylene blue, pH of adsorption system and the reuse ability.

The aim of the second project was to synthesize high order ethane-briged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid groups, up to 85%, EC-x (x refers to the [CES/(BTEE+CES)] molar ratio). In the study, many techniques were used to charaterize the EC-x materials just like FTC-x. Preparation of Ag and Pt nanoparticles is important application in EC-x. TEM was employed to observe the metal particles distrubution in EC-x, caculate the metal particles’s size from wide-angle XRD with Scherrer Formula and control the particles’s size by EC-x.

第一章    緒論    1
1-1中孔洞分子篩材料    1
1-2界面活性劑與矽酸鹽性質    5
1-2-1界面活性劑的種類    5
1-2-2微胞的形成與結構    7
1-2-3界面活性劑與矽酸鹽的交互作用31,33,34,48    10
1-3中孔洞表面修飾官能基    18
1-4相關文獻回顧    20
1-4-1 具羧酸官能基中孔洞材料發展    21
1-4-2中孔洞材料FDU-12合成與介紹    27
1-4-3中孔洞材料吸附染料的發展應用    28
1-4-4中孔洞材料吸附金屬的發展應用    30
1-5研究動機與目的    35
第二章    實驗部分    36
2-1實驗藥品    36
2-2實驗步驟    37
2-2-1合成具羧酸官能基的FTC-x與EC-x    37
2-2-2以硫酸裂解模版    40
2-2-3以鹽酸去除矽源之乙氧基    41
2-2-5利用酸鹼滴定鑑定孔洞材料的酸當量    41
2-2-6比較FTC-x除水前除水後之Solid State NMR實驗    41
2-2-7亞甲基藍檢量線配製    42
2-2-8利用FTC-x吸附最大量亞甲基藍實驗    42
2-2-9利用FTC-x在不同時間吸附亞甲基藍實驗    43
2-2-10利用FTC-x在不同pH值下吸附亞甲基藍實驗    44
2-2-11比較FTC-x物理混合與化學混合差異實驗1    44
2-2-12 FTC-x重覆使用性實驗    45
2-2-13利用EC-x吸附鉑金屬實驗    46
2-2-14利用EC-x吸附銀金屬實驗    46
2-3實驗設備    47
2-3-1實驗合成設備    47
2-3-2實驗鑑定設備    47
2-4鑑定儀器之原理    49
2-4-1同步輻射中心光束線(National Synchrotron Radiation Research Center)    49
2-4-2 X射線粉末繞射(Powder X-Ray Diffractometer, XRD)    51
2-4-3氮氣吸附脫附儀(Accelerated surface area and porosimetry system)    52
2-4-4熱重分析儀(Thermogravimetric Analyzer)    57
2-4-5固態核磁共振儀(Solid State Nuclear Magnetic Resonance)    58
2-4-6穿透式電子顯微鏡(Transmission Electron Microscope)    68
2-4-7傅立葉紅外線吸收光譜儀(Fourier Transform Infrared Spectrometer)    70
2-4-8紫外光/可見光光譜儀(UV-Vis Spectrometer)    72
2-4-9感應偶合電漿質譜分析儀 (Inductively Coupled Plasma-Mass )    76
2-4-10 掃描式電子顯微鏡(Scanning Electron Microscope)    77
第三章    結果與討論    78
3-1合成不同比例的FTC-x鑑定    78
3-1-1中孔洞材料FTC-x之XRD鑑定    78
3-1-2中孔洞材料FTC-x之氮氣吸脫附鑑定    81
3-1-3中孔洞材料FTC-x之FT-IR紅外線光譜鑑定    85
3-1-4中孔洞材料FTC-x之13C CP/MAS NMR鑑定    87
3-1-5中孔洞材料FTC-x之29Si MAS NMR鑑定    89
3-1-6中孔洞材料FTC-x之1H MAS NMR鑑定    92
3-1-7中孔洞材料FTC-x之13C{1H} HETCOR NMR鑑定    93
3-1-8中孔洞材料FTC-x之熱重分析鑑定    95
3-1-9中孔洞材料FTC-x之TEM鑑定    97
3-1-10中孔洞材料FTC-x之SEM鑑定    99
3-1-11中孔洞材料FTC-x之酸鹼滴定    100
3-2利用FTC-x吸附染料亞甲基藍應用    101
3-2-1 亞甲基藍UV光譜及檢量線    102
3-2-2中孔洞材料FTC-x對亞甲基藍最大吸附量結果    103
3-2-3 FTC-x在不同時間吸附亞甲基藍結果    105
3-2-4 FTC-x在不同pH值吸附亞甲基藍結果    106
3-2-5等溫吸附模式及動力學吸附結果    107
3-2-6利用FTC-x重覆使用能力    113
3-2-7比較FTC-x物理混合與化學混合    114
3-3合成不同比例的EC-x鑑定    115
3-3-1中孔洞材料EC-x之XRD鑑定    115
3-3-2中孔洞材料EC-x之氮氣吸脫附鑑定    119
3-3-3中孔洞材料EC-x之FT-IR紅外線光譜鑑定    122
3-3-4中孔洞材料EC-x之13C CP/MAS NMR鑑定    124
3-3-5中孔洞材料EC-x之29Si MAS NMR鑑定    126
3-3-6中孔洞材料EC-x之酸鹼滴定    129
3-3-7中孔洞材料EC-x之熱重分析鑑定    131
3-3-8中孔洞材料EC-x之SEM鑑定    133
3-3-9中孔洞材料EC-x之TEM鑑定    135
3-4利用EC-x吸附鉑、銀金屬應用    137
3-4-1中孔洞材料EC-x吸附鉑、銀金屬TEM結果    137
3-4-2中孔洞材料EC-x吸附鉑、銀金屬XRD結果    139
3-4-3中孔洞材料EC-x吸附鉑、銀金屬ICP/MAS結果    142
第四章結論    143
參考文獻    144
附錄    154
合成具羧酸官能基之S16C-x    154
實驗步驟    154
鑑定結果    156
XRD鑑定    156
氮氣等溫吸脫附結果    158
紅外線光譜結果    162
掃描式電子顯微鏡結果    164
穿透式電子顯微鏡結果    166
固態核磁共振光譜結果    168
熱重分析結果    170

 
圖目錄
圖1- 1M41S系列中孔洞分子篩15,16,27    3
圖1- 2 SBA-15的XRD與TEM圖譜36    4
圖1- 3 界面活性劑CTMABr親水端頭基與疏水端長碳鏈示意圖    5
圖1- 4 表面張力與界面活性劑對微胞排列之影響43    8
圖1- 5 界面活性劑堆積參數示意圖    9
圖1- 6不同pH值下氧化矽的水解聚合相對速率49,50    12
圖1- 7界面活性劑與矽源合成路徑圖27    13
圖1- 8 中孔洞材料合成反應機構27 (a)真實液晶相反應機制(TLCT)    15
圖1- 9 Monnier提出MCM-41以電荷密度相稱的形成機制51    17
圖1- 10 Firouzi等人利用(A)濃度30%形成六方堆積的 CTAB界面活性劑水溶液與(B)濃度6.8%形成微胞的CTAB水溶液所測的2H NMR52    17
圖1- 11合成機制圖 (a)後修飾法 (b)直接合成法    18
圖1- 12後修飾法修飾硫醇官能基53    19
圖1- 13利用共聚合之直接合成法57    19
圖1- 14 中孔洞發展前期材料鑑定開發後期材料應用    21
圖1- 15氰基水解成羧酸官能基紅外線光譜圖75    22
圖1- 16第一次利用直接合成法合出羧酸官能基中孔洞材料84    23
圖1- 17 (A)x-COOH-SBA-15之XRD圖：x= (a) 0, (b) 20, (c) 30, (d) 40, (e) 50, (f) 60及(B) 50-COOH-SBA-15 TEM圖85。    24
圖1- 18 proximal-C-A-SBA-15 & maximum-C-A-SBA-15合成圖77    25
圖1- 19 COOH-Bz-x之TEM圖:(a) COOH-Bz-40 之孔道圖,    26
圖1- 20 COOH-ES-x之SBA-15 TEM，x=(A)20(B)60(C)70(D)8073。    27
圖1- 21 FDU-12 不同溫度鍛燒之(A)氮氣吸脫附圖 (B)TEM圖    28
圖1- 22利用SBA-15 (a)吸附不同染料及(b)吸附過程為擬二級吸附10    29
圖1- 23 TPTAC-SBA-15養成金鉑金屬奈米顆粒92    31
圖1- 24為 2% wt 金屬 /SBA-15 TEM 圖93：(a) Pd/SBA-15，(b) Pt/SBA-15，(c) Au/SBA-15，(d) Ag/SBA-15。    32
圖1- 25 SBA-15包覆鉑離子流程圖94    32
圖1- 26 Ag/KIT-6 (a) 和 (b)為SEM圖(c) 和 (d) 為TEM 圖95    33
圖1- 27 奈米金屬線合成示意圖96    33
圖1- 28 SBA-15-COOH/Cu (a)TEM圖(b)顆粒大小分佈圖97    34
圖1- 29 金奈米粒子在不同濃度或中孔材料上養成5    34
圖2- 1 FTC-x初反應流程示意圖。    38
圖2- 2FTC-x流酸迴流示意圖。    40
圖2- 3 吸附MB最大量示意圖    43
圖2- 4 不同時間吸附MB示意圖    43
圖2- 5 同步輻射光產生示意圖。    50
圖2- 6 新竹國家同步輻射中心同步加速器示意圖    50
圖2- 7  X射線繞射示意圖。    51
圖2- 8在固體上等溫吸附的六種類型102    54
圖2- 9 IUPAC 提出的四種遲滯迴路曲線106    56
圖2- 10 TGA 基本構造儀器示意圖。    58
圖2- 11 氫原子在靜磁場中的能量分裂。    61
圖2- 12魔角旋轉之磁場與樣品相對位置圖。    66
圖2- 13  Si NMR訊號T群和Q群分子示意圖    67
圖2- 14交叉極化脈衝程序示意圖。    68
圖2- 15 穿透式電子顯微鏡結構示意圖    69
圖2- 16 分子振動類型圖。    71
圖2- 17 電子能階及躍遷示意圖    72
圖2- 18 紫外光可見光光譜儀 (a)單光徑型、(b)空間間隔式雙光徑型及  (c)時間分隔式雙光徑型。    75
圖2- 19原子放射光譜儀的組成如圖所示109    76
圖3- 1 as FTC-x移除模板前XRD繞射圖譜：    80
圖3- 2 FTC-x 移除模板後之XRD繞射圖譜    80
圖3- 3 FTC-x 之氮氣等溫吸脫附曲線圖：    83
圖3- 4 FTC-x之 FT-IR 光譜圖：    86
圖3- 5 CES分子和所對應在13C NMR之化學位移    87
圖3- 6 FTC-10 界面活性劑未移除乾淨 13C CP/MAS NMR 光譜    88
圖3- 7FTC-x 之 13C CP/MAS NMR 光譜圖：    88
圖3- 8 FTC-x 之 29Si MAS NMR 光譜圖：    90
圖3- 9 FTC-50 之 1H MAS NMR 光譜圖: (a)除水前、(b)除水後    92
圖3- 10 FTC-50 之 13C{1H} HETCOR NMR 光譜圖    94
圖3- 11 FTC-30 移除模板前後熱重分析(a)TGA圖；(b)DTA圖    95
圖3- 12 FTC-x 移除模板後熱重分析(a)TGA圖；(b)DTA圖    96
圖3- 13 FTC-x 之TEM圖    98
圖3- 14 FTC-x 移除模板後SEM圖    99
圖3- 15 FTC-x 酸鹼滴定曲線圖x= (a)20 (b)40。    100
圖3- 16亞甲基藍分子結構式。    101
圖3- 17亞甲基藍(a)UV吸收光譜、(b)檢量線。    102
圖3- 18 FTC-x吸附亞甲基藍最大量長條圖    104
圖3- 19 FTC-x在不同時間下吸附亞甲基藍    105
圖3- 20 FTC-30在不同pH下吸附亞甲基藍(a)長條圖(b)UV光譜    106
圖3- 21 FTC-x吸附亞甲基藍統整圖。    109
圖3- 22 FTC-x吸附亞甲基藍log qe對 log Ce作圖。    110
圖3- 23 FTC-x吸附亞甲基藍Ce/qe對Ce作圖。    110
圖3- 24 (a)FTC-x不同時間吸附MB (b)Pseudo-second order圖    112
圖3- 25 FTC-30重覆吸附性長條圖。    113
圖3- 26 寬角度XRD比較物理混合與化學混合。    114
圖3- 27 EC-x 移除模板前之XRD圖譜：x＝(a) 0%, (b) 10%, (c) 20%, (d) 30%, (e) 40%, (f) 50%, (g) 60%, (h) 70%, (i) 80%, (j) 85%。    117
圖3- 28 EC-x 移除模板後之XRD圖譜：x＝(a) 0%, (b) 10%, (c) 20%, (d) 30%, (e) 40%, (f) 50, (g) 60%, (h) 70%, (i) 80%, (j) 85%。    118
圖3- 29 EC-90 移除模板後之XRD圖譜(a)水熱2天(b)水熱5天    118
圖3- 30 EC-x 移除模板後氮氣等溫吸脫附圖：x＝(a) 0%, (b) 10%, (c) 20%, (d) 30%, (e) 40%, (f) 50, (g) 60%, (h) 70%, (i) 80%, (j) 85%。    121
圖3- 31 EC-x 移除模板後紅外線光譜圖：x＝(a) 0%, (b) 10%, (c) 20%, (d) 30%, (e) 40%, (f) 50, (g) 60%, (h) 70%, (i) 80%。    123
圖3- 32 EC-x 移除模板後13C CP/MAS NMR光譜圖：    125
圖3- 33 EC-x 移除模板後29Si MAS NMR光譜圖：    128
圖3- 34 EC-x 滴定曲線圖：x＝(a) 20%, (b) 40%, (c) 60%, (d) 80%。    130
圖3- 35 EC-x移除模板後熱重分析圖：x＝(a) 0%, (b) 20%, (c) 40%, (d) 50%, (e)60%, (f)80%。    132
圖3- 36 EC-x之SEM圖：    134
圖3- 37 EC-x TEM圖：x= (a)40, (b) 60, (c) 80,左為孔洞右為孔道    136
圖3- 38 EC-x (A) 銀奈米顆粒 (B)鉑奈米顆粒TEM圖：    138
圖3- 39 EC-x (A) 銀奈米顆粒 (B)鉑奈米顆粒寬角度XRD圖：    140
圖3- 40 EC-x (A) 銀奈米顆粒 (B)鉑奈米顆粒小角度XRD圖：    141

 
表目錄
表1- 1界面活性劑堆積參數與微胞結構、代表材料    9
表2- 1實驗藥品整理表    36
表2- 2 FTC-x樣品反應列表    38
表2- 3 EC-X 之樣品反應列表。    39
表2- 4 一些常見核種的性質。    60
表3- 1 FTC-x 之孔洞性質分佈表。    84
表3- 2 FTC-x 之 Tm 與 Qn 比例。    91
表3- 3 FTC-x 之當量點及酸當量數據表。    100
表3- 4 FTC-x 對亞甲基藍最大吸附量統計表。    104
表3- 5 FTC-x 吸附亞甲基藍等溫模式參數。    111
表3- 6 FTC-x 吸附亞甲基藍動力學吸附參數。    112
表3- 7 EC-x 孔洞性質分析表。    120
表3- 8 EC-x 29Si MAS NMR中，TE(BTEE)和TC(CES)比例    127
表3- 9 EC-x 當量點和酸當量數據表    129
表3-10 EC-x 吸附銀、鉑金屬顆粒大小    140
表3- 11 EC-x 吸附銀、鉑金屬離子之殘餘液ICP/MAS結果分析    142

                                

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