博碩士論文 973406004 詳細資訊




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姓名 林玲珠(Ling-Chu Lin)  查詢紙本館藏   畢業系所 環境工程研究所
論文名稱 表面改質之多孔洞吸附介質對特定污染物吸附之研究
(Formation of functionalized mesoporous silicas and factors affecting adsorption of heavy metal from aqueous solution)
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摘要(中) 一般多孔性吸附介質孔洞常具備大小分佈不均、比表面積不夠高,且對特定金屬無選擇性等缺失。本研究透過不同條件合成多孔洞吸附材料,並藉由改變不同改質影響因子,如水分子效應、溶劑效應、官能基濃度及種類等,以瞭解各項影響因子對官能基於多孔洞材料鍵結率之影響,藉此探討多孔性介質之孔洞大小、比表面積變化、表面結構之差異、官能基之鍵結量多寡與不同改質方法於混合液中對特定金屬 (Hg2+、Ag+) 之選擇性吸附效果,以達到合成對特定重金屬吸附能力良好之吸附介質,解決對環境有害之重金屬污染問題。
改質前後之多孔性吸附介質分別以TGA、EA、BET、FTIR、13C NMR、及SEM等儀器進行表面特性鑑定,探討不同影響因子及官能基對吸附介質特性之影響。經BET表面鑑定,改質前C9及C16孔徑分別為2.43nm及3.18nm比表面積為981.65m2/g及1,013.28m2/g。改質前吸附等溫線為第IV型,改質後因孔洞為官能基所阻塞,而轉變為第II型,類似非孔洞材料。由13C NMR及FT-IR可以確認本研究已成功將巰基、氨基及氰基等官能基接枝於多孔洞吸附介質表面,其中以孔洞大小及水份含量影響接枝率最大。EA鑑定結果,官能基覆蓋率亦相當高,平均鍵結率可高達2.0 mmol SH/g,其中又以C9-SAnC (11.37%; 3.55 mmol SH/g) 最高。
本研究對Hg2+的吸附量以C16-SHC最高,達126.58 mg/g (0.63mmol/g)。Hg2+/S莫耳比以C16-SHC的0.62為最高,其次為C16-SAnC的0.44。經評估各項影響影響因子,以溶劑之影響最為重要,其次為孔徑大小,C16-SHC吸附介質表面官能基以單層鍵結之型態居多,其飽和吸附量為其他多孔性吸附介質所無法比擬。對Ag+離子所進行之吸附實驗結果,除了C9-LHT吸附量最少為71.94 mg/g (0.67 mmol/g)外,其餘多孔洞吸附介質吸附量均大於1.0 m mol/g,尤其以C16-SHT之吸附量更高達250.00 mg/g (2.32mmol/g),遠大於目前文獻發表的任何多孔性吸附劑之吸附量。以Freundlich 模式擬合較Langmuir模式更適合用來描述未改質C9及C16之吸附行為,且改質後之多孔洞吸附劑較適合以Langmuir模式來描述吸附Ag+、Hg2+離子之吸附平衡等溫線,而改質後多孔洞吸附劑對Ag+之吸附動力模式則以擬二階擬合最為合適。
本研究不論是於何種改質條件下進行改質,改質後多孔洞吸附介質對Hg2+及Ag+離子吸附量均較未改質增加百倍以上。顯示本研究所開發的合成及改質方法能夠成功合成對特定金屬具極高親和力的多孔性吸附介質,而吸附Hg2+或Ag+之改質多孔洞吸附劑後續亦能被應用於抑菌及環境衛生等方面。
摘要(英) Mesoporous materials lack for uniform pore-size distribution, ordered pore structure, and high surface area. Meosporous materials are also less selectivity toward heavy metal adsorption. This study described the effective synthesis of mesoporous materials by altering different synthesis parameters. Subsequently, the synthesized mesoporous materials were functionalized under different controlling factors, such as water effect, solvent effect, different functional groups and concentration of functional group to enhance the adsorption capacity toward metal ions such as Hg2+ and Ag+. In the same time, the effects of changing pore size, surface area, and morphology of the mesoporous material were also evaluated in this studied.
The before and after functionalized mesoporous materials were characterized by TGA, EA, BET, SEM, FT-IR, and 13C NMR to verify the effect of the controlling factors on the functionalized mesoporous material. The C9 and C16 had surface area of 981.62 m2/g and 1013.28 m2/g; pore size of 2.43nm and 3.18nm, respectively. The BET isotherms curve for the unmodified samples were typical type IV. The BET isotherms curve for functionalized samples, which might be caused by blocking pore channel, had been changed to type II. The characteristic FT-IR, and 13C NMR results showed that the functional group had been grafted to the surface of mesoporous successfully. The most important controlling factors for grafting density were pore size and water effect. The EA results showed that the amount of functional group grafted to the surface of mesoporous material were relatively high. The average density was 2.0 mmol SH/g, and C9-SAnC sample had the highest grafting amount (11.37%, 3.55mmol SH/g). The Freundlich model better described the unmodied samples adsorption behavior. However, the adsorption behaviors of the functionalized samples were better delineated by Langmuir model. The pseudo second order fitted the Ag+ adsorption kinetic model better.
The adsorption experiments results showed that the C16-SHC had the highest Hg2+ adsorption capacity of 126.58 mg/g (0.63mmol/g). The C16-SHC had the highest Hg2+/S molar ratio of 0.62. The C16-SAnC came in second of 0.44. The factors influence the adsorption capacity the most were solvent effect, and pore size. The average Ag+ adsorption capacity was 1.0 mmol/g. The C16-SHT had the highest adsorption capacity of 250.00 mg/g (2.32mmol/g). The C9-LHT had the lowest adsorption capacity 71.94 mg/g (0.67 mmol/g). The results were higher than those of other researchers’.
The adsorption capacity of functionalized mesoporous materials under all control factors were enhanced by two orders. This study developed the synthesis and functionalization method with high affinity toward adsorbing heavy metal successfully. The functionalized mesoporous material can be reused as bacteria inhibitor after adsorbing Hg2+ and Ag+ ions.
關鍵字(中) ★ 多孔性吸附介質
★ 影響因子
★ 改質
★ 表面鑑定
★ 吸附
★ 聚合作用
關鍵字(英) ★ mesoporous materials
★ control factor
★ functionalization
★ surface characterization
★ adsorption capacity
★ polymerization
論文目次 目 錄
目次 頁次
目錄……………………………………………………..................……............. I
圖目錄………………………………………....................................................... V
表目錄………………………………………......................……………............. IX

第一章 前言…………………………………………......................................... 1

1-1 研究緣起…………………………………………………................…... 1
1-2 研究目的與內容…………………................................................……... 4
第二章 文獻回顧…………………………………………......................……... 6

2-1 多孔性吸附介質發展……………………………….…....................….. 6
2-1-1 FSM-16 簡介………………….….. …..............................….. 8
2-1-2 PCH 簡介………………………………....................……….. 9
2-1-3 SBA-15簡介………………………………………................ 9
2-2 多孔性吸附介質特性……………………………................................... 10
2-2-1 合成多孔性吸附介質之途徑及方法………………………… 10
2-2-1-1 合成途徑………………………........................................... 10
2-2-1-2 合成方法………………………........................................... 12
2-2-2 合成多孔性吸附介質之形成機制…………………………… 13
2-3 多孔性吸附介質之表面改質………………………….............……….. 15
2-3-1 表面改質反應機制……………......…...................................... 17
2-3-2 多孔性吸附介質表面改質之方法……………………............ 18
2-3-3 官能基鍵結量之影響因子探討……………………................ 23
2-4 表面改質後之多孔性吸附介質的應用……………................………... 29
2-5 重金屬污染……………………….....……………………….................. 31
2-5-1 重金屬來源與危害………………………......……………….. 31
2-5-2 去除重金屬之方法……............................................................ 33
2-6 吸附理論……................ ……................ ……......................................... 35
2-6-1 等溫吸附線…….............……................…............................... 37
2-6-2 遲滯現象……...............……...............…….............................. 41
2-6-3 等溫吸附模式……...............……...............……...................... 44
第三章 研究方法………………………...........……………………………… 47

3-1 研究內容與流程……………………..............…......................………... 47
3-2 實驗材料…………………......................................…............................. 52
3-3 實驗設備與儀器………………............................................................... 53
3-3-1 實驗設備.................................................................................... 53
3-3-2 實驗儀器.................................................................................... 54
3-3-2-1 儀器簡介………………………………………................... 54
3-3-2-2 儀器原理………………………………………................... 57
3-4 多孔性吸附介質合成實驗....................................................................... 61
3-4-1 有機模板條件實驗.................................................................... 61
3-4-2 水熱合成條件實驗.................................................................... 62
3-4-2-1 加熱時間條件實驗……………………………................... 62
3-4-2-2 水熱溫度條件實驗…………………………....................... 62
3-4-3 移除模板條件實驗.................................................................... 63
3-4-4 過濾與乾燥方法實驗................................................................ 63
3-4-5 pH控制實驗……………………………………….................. 64
3-5 多孔性吸附介質改質實驗…………………………............................... 68
3-5-1 改質方法S(Stir)........................................................................ 69
3-5-2 改質方法 R(reflux)................................................................... 69
3-5-3 改質方法 D(Dean-Stark).......................................................... 70
3-6 表面改質覆蓋率計算…………………................................................... 73
3-7 重金屬吸附實驗………………………………………........................... 74
3-8 改質後表面鑑定………………………………………........................... 75
3-9 吸附速率及平衡曲線之量測及分析………………………………...… 76
第四章 初步結果與討論……………………………………............................. 77

4-1 合成多孔性吸附介質………………....................................................... 77
4-1-1 不同有機模板之影響..........................................…………….. 77
4-1-2 其他不同合成條件之影響........................................................ 82
4-1-3 X光繞射光譜(XRD)............................…….....................….... 86
4-2 官能基鍵結量…………………….……………...................................... 87
4-2-1 熱重分析 (TGA)…………………........................................... 87
4-2-1-1 水分子效應………………………………........................... 87
4-2-1-2 溶劑效應………………………………………................... 89
4-2-1-3 濃度效應………………………………………................... 91
4-2-1-4 移除模板方法………………………………....................... 93
4-2-2 元素分析 (EA) …………………………................................. 96
4-2-2-1 水分子效應…………………………………....................... 96
4-2-2-2 溶劑效應………………………………………................... 97
4-2-2-3 官能基濃度效應………………………………................... 99
4-2-2-4 去除模板方法…………………………………................... 100
4-2-2-5 官能基種類………………………………........................... 100
4-2-2-6 改質方法………………………………………................... 102
4-3 改質後多孔洞吸附介質表面型態…………………………….......….... 104
4-3-1 氮氣恆溫氣態吸附(BET)..........................................………… 104
4-3-1-1 水分子效應……………………………………................... 104
4-3-1-2 溶劑效應………………………………………................... 107
4-3-1-3 濃度效應………………………………………................... 109
4-3-1-4 去除模板方法………………………………….................. 111
4-3-2 掃描式電子顯微鏡 (SEM) ……………………….................. 114
4-3-2-1 水分子及溶劑效應………………………........................... 114
4-3-2-2 去除模板方法………………………………....................... 115
4-3-2-3 濃度效應………………………………………................... 117
4-4 官能基表面特性之鑑定………….......................................................... 119
4-4-1 紅外光譜 (FTIR) 分析......................................................…. 119
4-4-1-1 水分子效應…………………………………………......... 121
4-4-1-2 官能基種類…………………………………………......... 122
4-4-1-3 官能基濃度…………………………………………......... 123
4-4-1-4 有機模板去除方法………………………………………. 125
4-4-2 固態核磁共振光譜儀 (Solid State NMR)................……….... 126
4-5 重金屬吸附實驗………………………………………........................... 128
4-5-1 Hg2+吸附量………………………………………..................... 128
4-5-1-1 改質前之最大吸附量…………………………................... 128
4-5-1-2 水分子及溶劑效應………………………........................... 130
4-5-1-3 孔洞效應………………………………………................... 135
4-5-2 Ag+吸附量………………………………………..................... 140
4-5-2-1 改質前之最大吸附量……………………………............... 140
4-5-2-2 水分子效應………………………………........................... 142
4-5-2-3 孔洞效應………………………………………................... 146
4-5-2-4 不同官能基……………………………………................... 151
4-5-2-5 不同改質方法…………………………………................... 153
4-5-3 其他重金屬…………………………………............................. 155
4-6 吸附現象探討………………………………………………………...… 157
4-6-1 吸附平衡等溫線……………………………………………… 157
4-6-1-1 改質前多孔洞吸附劑吸附模式………………………..… 157
4-6-1-2 改質後多孔洞吸附模式………………………………..…. 158
4-6-2 吸附動力學……………………………………………………. 160

第五章 結論與建議.………………………………………………......……...... 166

5-1 結論………………………………………………………....................... 166
5-2 建議……………………………………………………................……... 168
參考文獻……………………………………………………………................... 169

圖 目 錄
目次 頁次
圖2-1 MCM系列結構示意圖……………………......................................... 7
圖2-2 Fold Sheet Mechanism...................................................................... 8
圖2-3 PCH 結構............................................................................................. 9
圖2-4 不同型式之矽酸鹽/溶劑交界面,虛線表示H-鍵結反應................... 10
圖2-5 多孔性吸附介質之形成機制示意圖................................................... 15
圖2-6 後修飾法之反應方程式....................................................................... 17
圖2-7 後修飾法之反應機制流程圖............................................................... 17
圖2-8 改質實驗各階段反應化學結構示意圖............................................... 18
圖2-9 共凝結及後修飾法中孔洞改質示意圖............................................... 19
圖2-10 有機官能基分布狀態(共凝結法)示意圖............................................ 20
圖2-11 溶劑置換法局部未移除之模板之官能基鍵結示意圖....................... 20
圖2-12 後修飾表面改質之示意圖................................................................... 21
圖2-13 MPTMS於多孔洞材料表面反應機制(a)對SiO2表面的表面脫水;(b)在溶劑中的自我聚合............................................................ 25
圖2-14 不同溶劑與表面矽烷基交互作用型態(a) 氫鍵結;(b) 凡得瓦力作用;(c) 離子交互作用。.................................................................... 27
圖2-15 不同MPTMS濃度於二氧化矽表面形成MPTMS層之結構及表面型態示意圖(a) 5 × 10-3 M, (b) 2 × 10-2 M, (b) 4 × 10-2 M………… 28
圖2-16 等溫吸附線之基本形態....................................................................... 38
圖2-17 孔洞結構吸/脫附現象示意圖.............................................................. 42
圖2-18 四種典型遲滯曲線示意圖…………………...……………………… 42
圖3-1 合成實驗架構圖................................................................................... 50
圖3-2 改質流程圖........................................................................................... 51
圖3-3 合成多孔性吸附介質流程圖............................................................... 65
圖3-4 合成多孔性吸附介質流程圖............................................................... 66
圖3-5 (a) MPTS水分子存在單層, 和(b)水分子存在MPTS多層形成示意圖和巰基之間的相互作用............................................................... 68
圖3-6 改質方法 SAn 流程圖........................................................................ 69
圖3-7 改質方法 R 流程圖............................................................................ 70
圖3-8 改質方法 D 流程圖............................................................................ 71
圖3-9 吸附實驗流程圖................................................................................... 74
圖3-10 多孔洞表面修飾偶合及交聯示意圖................................................... 75
圖4-1 ZC16之氮氣等溫吸附曲線................................................................. 80
圖4-2 ZC14之氮氣等溫吸附曲線................................................................. 80
圖4-3 ZC12之氮氣等溫吸附曲線................................................................. 80
圖4-4 ZC9之氮氣等溫吸附曲線................................................................... 80
圖4-5 ZC1系列之BJH累積孔洞分佈圖...................................................... 81
圖4-6 ZC1系列之BJH孔洞分佈圖.............................................................. 82
圖4-7 ZC9-155、7 系列之氮氣等溫吸附曲線.............................................. 84
圖4-8 ZC9-155、7 系列之BJH 孔洞分佈圖.............................................. 84
圖4-9 ZC16 之XRD 圖譜............................................................................. 86
圖4-10 熱重分析曲線:水分子效應............................................................... 88
圖4-11 熱重分析曲線:溶劑效應................................................................... 90
圖4-12 熱重分析曲線:濃度效應................................................................... 92
圖4-13 熱重分析曲線:移除模板方式........................................................... 94
圖4-14 改質前後BET 圖--水分子效應(a) C9 (b) C16 (c) C9-SAnT、(d) C16-SAnT(e) C9-SHT (f) C16-SHT..................................................... 106
圖4-15 BET 圖—溶劑效應(a) C9-SAnC (b) C16-SAnC (c) C9-SHC (d) C16-SHC............................................................................................... 108
圖4-16 BET 圖—濃度效應(a) C9-LAnT (b) C16-LAnT (c) C9-LHT(d)C16
-LHT...................................................................................................... 110
圖4-17 BET 圖—去除模板方法(a) C9-E (b) C16-E (c) C9-ES (d) C16-ES.. 112
圖4-18 未改質之 SEM 圖;倍率分別為 (a) (b) 1000、(c) (d) 10,000........ 114
圖4-19 SEM 圖--溶劑及水分子效應(a) C9-SAnT (b) C16-SAnT (c) C9-SAnC (d) C16-SAnC(e) C9-SHC (f) C16-SHC,倍率為5000…. 116
圖4-20 SEM 圖—溶劑萃取模板(a) C9-E (b) C16-E (c) C9-SE、(d) C16-SE,倍率為5000.......................................................................... 117
圖4-21 SEM 圖—濃度效應(a) C9- LHT (b) C16- LHT (c) C9- LAnT、 (d) C16- LAnT,倍率為5000.................................................................... 118
圖4-22 FTIR 光譜圖 (a) C9-106 (b) C16......................................... 120
圖4-23 (a) C9水分子效應FTIR光譜圖;(b) C16 水分子效應FTIR光譜圖........................................................................................................... 121
圖4-24 氨基與巰基FTIR光譜圖 (a) C9 (b) C16........................................... 123
圖4-25 官能基濃度FTIR光譜圖 (a) C9 (b) C16.......................................... 124
圖4-26 有機模板移除方法FTIR 光譜圖 (a) C9 (b) C16.............................. 125
圖4-28 C9-SAnC 13C NMR光譜圖.................................................................. 127
圖4-29 C16-SAnC 13C NMR光譜圖...………………………………………. 127
圖4-30 未改質之Hg2+等溫吸附曲線............................................................... 129
圖4-31 氯仿為溶劑改質之Hg2+等溫吸附曲線(a) C9, (b)C16....................... 131
圖4-32 甲苯為溶劑改質之Hg2+等溫吸附曲線(a) C9, (b)C16……………... 132
圖4-33 低官能基濃度改質之Hg2+等溫吸附曲線(a) C9, (b)C16.................. 134
圖4-34 氯仿為溶劑添加水改質之Hg2+等溫吸附曲線……………………... 136
圖4-35 氯仿為溶劑未添加水改質之Hg2+等溫吸附曲線............................... 136
圖4-36 甲苯為溶劑添加水改質之Hg2+等溫吸附曲線................................... 137
圖4-37 甲苯為溶劑未添加水改質之Hg2+等溫吸附曲線………………….. 137
圖4-38 低官能基濃度添加水改質之Hg2+等溫吸附曲線.............................. 138
圖4-39 低官能基濃度未添加水改質之Hg2+等溫吸附曲線………………... 138
圖4-40 未改質吸附Hg2+之等溫吸附曲線…….………………...………….. 141
圖4-41 氯仿為溶劑改質之Ag+等溫吸附曲線(a) C9, (b)C16......................... 143
圖4-42 甲苯為溶劑改質之Ag+等溫吸附曲線(a) C9;(b)C16.................... 144
圖4-43 低官能基濃度改質之Ag +等溫吸附曲線(a) C9;(b)C16.................. 146
圖4-44 以氯仿為溶劑添加水改質之Ag+等溫吸附曲線…………………... 148
圖4-45 以氯仿為溶劑未添加水改質之Ag+等溫吸附曲線……………….... 148
圖4-46 以甲苯為溶劑未添加水改質之Ag+等溫吸附曲線……………….... 149
圖4-47 以甲苯為溶劑添加水改質之Ag+等溫吸附曲線..……………..…… 149
圖4-48 低官能基濃度添加水改質之Ag+等溫吸附曲線............................... 150
圖4-49 低官能基濃度未添加水改質之Ag+等溫吸附曲線........................... 150
圖4-50 氨基官能基未添加水改質吸附Ag+之等溫吸附曲線....…………… 152
圖4-51 Ag+離子顆粒內擴散模式關係圖(a)C9,(b)C16...................... 163
圖4-52 Ag+離子擬一階模式關係圖(a)C9,(b)C16.............................. 164
圖4-53 Ag+離子擬二階模式關係圖(a)C9,(b)C16.............................. 165

表 目 錄
目次 頁次
表2-1 多孔性材料孔洞大小分類………………........................................... 6
表2-2 有機矽烷對矽酸鹽表面進行修飾方法比較....................................... 22
表2-3 全球排放重金屬趨勢 (1000 metric tonnes/year)................................ 31
表2-4 重金屬在各產業界來源....................................................................... 32
表2-5 物理吸附與化學吸附之比較............................................................... 36
表3-1 改質劑代號表....................................................................................... 48
表3-2 不同改質方法及條件之樣品編號表................................................... 49
表3-3 實驗藥品材料理化特性表................................................................... 52
表3-4 不同波數下有機官能基....................................................................... 55
表3-5 合成多孔性吸附介質之合成條件....................................................... 67
表3-6 改質劑之基本特性表.......................................... ................................ 72
表4-1 ZC1系列樣品之表面積和孔洞大小................................................... 81
表4-2 合成多孔性吸附劑之比表面積及孔洞大小....................................... 85
表4-3 水分子效應--各溫度區間樣品損失百分比彙整表............................. 89
表4-4 溶劑相關化學特性彙整表................................................................... 91
表4-5 溶劑效應--各溫度區間樣品損失百分比彙整表................................. 92
表4-6 濃度效應--各溫度區間樣品損失百分比彙整表................................ 93
表4-7 移除模板方式--各溫度區間樣品損失百分比彙整表........................ 95
表4-8 熱重分析各溫度區間樣品損失百分比彙整表................................... 95
表4-9 元素分析結果彙整表—水分子效應................................................... 97
表4-10 元素分析結果彙整表—溶劑效應....................................................... 98
表4-11 元素分析結果彙整表—官能基濃度效應........................................... 99
表4-12 元素分析結果彙整表—去除模板方法............................................... 100
表4-13 元素分析結果彙整表—官能基種類效應........................................... 101
表4-14 元素分析結果彙整表—官能基種類效應........................................... 102
表4-15 元素分析結果總彙整表....................................................................... 103
表4-16 水分子效應改質前後樣品之表面積、孔洞體積和孔洞大小............ 107
表4-17 溶劑效應樣品之表面積、孔洞體積和孔洞大小............................... 109
表4-18 濃度效應樣品之表面積、孔洞體積和孔洞大小............................... 111
表4-19 去除模板方式樣品之表面積、孔洞體積和孔洞大小....................... 113
表4-20 溶劑效應樣品之表面積、孔洞體積和孔洞大小................................ 113
表4-21 多孔洞矽表面氫氧基IR波峰位置...................................................... 120
表4-22 Hg2+ 之等溫吸附模式參數.................................................................. 130
表4-23 Hg2+之等溫吸附模式參數—水分子效應............................................ 135
表4-24 Hg2+之等溫吸附模式參數—孔洞效應................................................ 139
表4-25 Ag+之等溫吸附模式參數..................................................................... 141
表4-26 Ag+之等溫吸附模式參數—水分子效應............................................. 147
表4-27 孔洞效應之Ag+最大吸附量與官能基鍵結量.................................... 151
表4-28 不同官能基之Ag+最大吸附量與官能基鍵結量................................ 153
表4-29 改質方法之Ag+最大吸附量與官能基鍵結量.................................... 154
表4-30 不同吸附劑改質對不同重金屬吸附比較表....................................... 156
表4-31 Hg2+之等溫吸附平衡模式參數............................................................ 158
表4-32 Hg2+之等溫吸附平衡模式參數……….............................................. 159
表4-33 Ag+之等溫吸附模式參數..................................................................... 160
表4-34 Ag+離子顆粒內擴散模式相關參數……............................................. 163
表4-35 Ag+擬一階模式相關參數..................................................................... 164
表4-36 Ag+擬二階模式相關參數..................................................................... 165
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指導教授 李俊福(Jiunn-Fwu Lee) 審核日期 2013-1-29
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