臺灣博碩士論文加值系統

本論文主要使用金屬有機骨架(Metal-Organic Frameworks,MOFs)與高分子複合進行碘分子氣體和揮發性有機汙染物的吸附移除。
論文第一部分首先將多種MOFs進行對氣相中碘分子氣體的吸附，進一步將金屬有機骨架ZIF-8與高分子polyethersulfone (PES)依不同比例混摻製備成的混和基質膜(Mixture-Matrix Membranes, MMMs)去進行碘分子氣體的吸附移除實驗。在性質鑑定上，分別以粉末X-ray繞射(PXRD)鑑定混摻後的混和基質膜與原始的有機金屬骨架其繞射圖譜結構差異，場發射式掃描電子顯微鏡(FE-SEM)進行薄膜表面和側面的觀察，熱失重分析鑑定薄膜的熱穩定性。實驗結果表明，成功製備具有ZIF-8晶相的混和機質膜ZIF-8@PES，且ZIF-8的混摻比高達40%wt，同時擁有1387.6 mg/g碘分子氣體的吸附量，相較於原始ZIF-8粉末提升了接近60%的吸附效果。
論文第二部分主要探討熱處理後的MOFs對有機揮發性汙染物的吸附實驗，在400 oC到550 oC的環境下進行MOFs的熱處理後，以粉末X-ray繞射(PXRD)鑑定其結構，並進行粉體對VOCs的吸附實驗。再利用靜電紡絲將MOFs與高分子PAN進行混合後紡絲，將所得之纖維複合材去進行附懸浮顆粒(PM)和有機揮發性汙染物(VOCs)的捕抓研究。實驗結果表明，熱處理後的MOFs在不同的有機揮發性汙染物上有選擇性的吸附效果，例如，ZIF-8進行450 oC的熱處理後對乙酸乙酯(3415.9 mg/g)和四氫呋喃(3398.9 mg/g)有較優異的吸附效果，而進行500 oC的熱處理後則對甲苯(4714.8 mg/g)和乙醇(5147.5 mg/g)有更優異的吸附效果。而纖維複合材吸附方面，Membrane D在吸附0.5m (PM 0.5)懸浮顆粒也高達了99.93%的移除效果，對甲苯和乙醇也有顯著的吸附效果，分別為29181.8 mg/g和12065.8 mg/g。

This paper mainly uses Metal-Organic Frameworks (MOFs) for the adsorption of iodine molecular gases and volatile organic compounds.
In the first part, a variety of MOFs were firstly adsorbed to the iodine molecular gas in the gas phase, and the metal-organic frameworks ZIF-8 and the polymer polyethersulfone (PES) were mixed in different proportions to prepare a Mixture-Matrix Membranes(MMMs) were used to perform adsorption removal experiments on iodine molecular gas. In the identification of the properties, powder X-ray diffraction (PXRD) was used to identify the difference in the diffraction pattern between the mixture-matrix membranes and the original metal-organic frameworks, and the field-emission scanning electron microscope (FE-SEM) was used for observating the film’s surface and side, thermogravimetric analysis to identify the thermal stability of the film. The experimental results show that the mixture-matrix membrane ZIF-8@PES with ZIF-8 crystal phase is successfully prepared, and the mixing ratio of ZIF-8 is as high as 40%wt, and the adsorption amount of 1387.6 mg/g iodine molecular gas is obtained. Nearly 60% adsorption is improved compared to the original ZIF-8 powder.
The second part of the paper is mainly discusses the capture of organic volatile compounds by heat-treated MOFs. After heat treatment of MOFs in the environment of 400 °C to 550 °C, the structure is identified by powder X-ray diffraction (PXRD). The adsorption experiments of powder on VOCs were carried out. The MOFs were mixed with the polymer PAN by electrospinning and then spun. The obtained fiber composites were subjected to the capture of particulate matter (PM) and volatile organic compounds (VOCs). The experimental results show that the heat treatment MOFs have selective adsorption effects on different volatile organic compounds. For example, ZIF-8 is heat treated at 450 oC for ethyl acetate (3415.9mg/g) and tetrahydrofuran (3398.9mg/g) has an excellent adsorption effect, and after heat treatment at 500 oC, it has better adsorption effect on toluene (4714.8 mg/g) and ethanol (5147.5 mg/g). In terms of fiber composite adsorption, Membrane D also adsorbed 0.5m (PM 0.5) remove effusion up to 99.93%, and also had significant adsorption effects on toluene and ethanol, respectively 29181.8 mg/g and 12065.8 mg/ g.

目錄
摘要 I
Abstract III
目錄 V
圖目錄 XI
表目錄 XVI
第一章 緒論 1
1-1 MOFs 介紹 1
1-1-1 MIL-68 3
1-1-2 ZIF-8 5
1-1-3 CAU-10 7
1-1-4 A520 8
1-2 碘 9
1-3 混和基質膜 14
1-4 有機揮發汙染物 (VOCs) 17
1-5 研究動機 24
第二章 藥品與鑑定方法 28
2-1 實驗藥品 28
2-2 儀器型號及鑑定方法 34
2-2-1 粉末X-射線繞射儀 （PXRD） 34
2-2-2 表面積及孔徑分析儀 35
2-2-3 熱重分析儀 （TGA） 36
2-2-4 場發射式掃描電子顯微鏡(FE-SEM) 36
2-2-5 靜電紡絲 37
第三章 MOF/PES MMMs吸附碘蒸氣之探討 38
3-1 MOFs合成與混合基質膜的製備 39
3-1-1 MOF合成 39
3-1-2 MOF純化 41
3-1-3 濕式膜與乾式膜的製備 42
3-1-4 不同混摻比混合基質膜的製備 43
3-2 粉末X-ray繞射分析(PXRD) 46
3-2-1 MOF的X-ray繞射分析(PXRD) 46
3-2-2 濕式膜與乾式膜的X-ray繞射分析(PXRD) 51
3-2-3 不同混摻比混合基質膜的X-ray繞射分析 53
3-3場發射式掃描電子顯微鏡(FE-SEM) 54
3-3-1濕式膜與乾式膜的場發射式掃描電子顯微鏡 54
3-3-2不同混摻比混合基質膜的場發射式掃描電子顯微鏡 55
3-4熱重分析儀 （TGA） 58
3-5 碘分子氣體吸附實驗 59
3-5-1 MOF對碘分子氣體的吸附實驗 59
3-5-2 濕式膜與乾式膜對碘分子氣體的吸附實驗 63
3-5-3 不同混摻比混合基質膜對碘分子氣體的吸附實驗 65
3-6 結論 67
第四章 MOFs複合吸附材吸附揮發性有機化合物(VOCs)之探討 68
4-1 MOFs的熱處理與混合吸附材的製備 71
4-1-1 MOFs的熱處理 71
4-1-2複合材的製備 74
4-2 粉末X-ray繞射分析(PXRD) 75
4-2-1 熱處理後的ZIF-8 75
4-2-2 熱處理後的MIL-68(Al) 76
4-2-3 熱處理後的CAU-10 77
4-2-4 熱處理後的A520 78
4-3 熱處理後的MOFs對揮發性有機汙染物的吸附 79
4-3-1 實驗方式 79
4-3-2 對揮發性有機化合物(VOCs)的吸附結果 81
4-4 纖維複合材吸附揮發性有機化合物(VOCs)之探討 84
4-4-1 實驗裝置 84
4-4-2 對揮發性有機化合物(VOCs)的吸附結果 85
4-5 結論 86
第五章 結論 87
參考文獻 88
附錄A 比表面積與孔徑分析儀 94
附錄B 熱處理MOFs對碘分子氣體的吸附 101
附錄C 熱處理MOFs的水穩定性 103
附錄D 複合材吸附懸浮顆粒(PM)之探討 105
D-1 實驗裝置 106
D-2 對懸浮顆粒(PM)的吸附結果 107
附錄E ZIF-8和PES d.之熱重分析 108






圖目錄
圖1-1 金屬與有機配位基自組裝示意圖58 1
圖1-2 Yaghi等人用不同配位基合成等結構MOFs示意圖55 2
圖1-3 MOFs具多種應用性8 3
圖1-4 MIL-68(Al)結構的PXRD圖12 4
圖1-5 MIL-68結構圖(左)與其無機鏈跟配位基的配位方式(右) 12 5
圖1-6 M-IM-M (1)與沸石(2)的 bridging angles 相近13 5
圖1-7 ZIF系列的X-ray繞射結構13 6
圖1-8 ZIF-8的籠狀孔洞結構13 6
圖1-9 CAU-10-X 示意圖53 7
圖1-10 A520 示意圖57 8
圖1-11 含銀MOR捕獲碘的示意圖14 10
圖1-12 ZIF-8吸附前後PXRD圖譜15 11
圖1-13 ZIF-8中碘吸附型態15 11
圖1-14 捕抓前後樣品顏色差異15 11
圖1-15 實驗裝置示意圖16 12
圖1-16 捕抓前後HKUST-1的PXRD圖16 13
圖1-17 HKUST-1中碘吸附型態16 13
圖1-18薄膜製備流程示意圖47 15
圖1-19 a)由各種MOF產生的獨立式MMM（≈1×1 cm 2）。b）照片證明大面積的HKUST-1，UiO-66和MIL-53（Fe）MMM（≈3×5 cm 2）具有對機械應力的彈性並且易於處理。47 15
圖1-20 以UiO-66形成的獨立式MMM進行染料分離實驗47 16
圖3-1 聚醚砜polyethersulfone (PES)結構 38
圖3-2 乾式膜與濕式膜的製備流程示意圖47 43
圖3-3 ZIF-8@PES外觀 45
圖3-4 ZIF-8的PXRD圖 46
圖3-5 HKUST-1的PXRD圖 47
圖3-6 MIL-68(Al)的PXRD圖 48
圖3-7 A520的PXRD圖 49
圖3-8 CAU-10的PXRD圖 50
圖3-9兩種製成的混合機質膜的PXRD圖 51
圖3-10 ZIF-8 w.的PXRD圖 52
圖3-11 ZIF-8@PES的PXRD圖 53
圖3-12 ZIF-8@PES w.(a)和ZIF-8@PES d.(b)表面之SEM 55
圖3-13 ZIF-8@PES不同MOF混摻比之表面SEM與SEM-EDS SEM: (a) 10%；(b) 20%；(c) 30%；(d) 40% SEM-EDX: (e) 10%；(f) 20%；(g) 30%；(h) 40% 57
圖3-14 ZIF-8@PES不同MOF混摻比之側面SEM (a) 10%；(b) 20%；(c) 30%；(d) 40% 58
圖3-15 ZIF-8@PES 熱失重曲線圖 59
圖3-16碘蒸氣捕抓實驗裝置圖 60
圖3-17 MOF捕抓I2的吸附結果 61
圖3-18捕抓後的的樣品 62
圖3-19碘蒸氣捕抓實驗裝置圖 63
圖3-20碘蒸氣吸附曲線圖 64
圖3-21 ZIF-8@PES d.(a)和ZIF-8@PES w.(b)吸附後之薄膜外觀 65
圖3-22碘蒸氣吸附曲線圖 66
圖4-1 HKUST-1的化學處理實驗49 69
圖4-2氮氣吸脫附曲圖50 70
圖4-3 zeta電位曲線圖50 70
圖4-4高溫管狀鍛燒爐 72
圖4-5 MOFs的熱處理後的外觀 (a) ZIF-8 (b) MIL-68(Al) (c) CAU-10 (d) A520 73
圖4-6 ZIF-8熱處理後的PXRD圖 75
圖4-7 MIL-68(Al)熱處理後的PXRD圖 76
圖4-8 CAU-10熱處理後的PXRD圖 77
圖4-9 A520熱處理後的PXRD圖 78
圖4-10實驗裝置 80
圖4-11吸附揮發性有機化合物實驗裝置 84
圖A-1氮氣吸附等溫線圖 98
圖A-2孔徑分佈圖 100
圖B-1熱處理後MOFs捕抓I2的吸附結果 102
圖C-1結構水穩定性測試 (X-ray繞射分析) 104
圖D-1捕抓懸浮顆粒實驗裝置 106
圖D-2捕抓懸浮顆粒實驗結果 107
圖E-1 ZIF-8(上)和PSE d.(下)的熱失重曲線圖 109


表目錄
表1-1典型VOC的來源和健康影響51 19
表1-2活性碳在典型VOC蒸氣吸附中的應用51 22
表3-1不同MOF混摻比配製方法 44
表3-2 MOF捕抓碘蒸氣實驗數據整理 61
表4-1 MOFs熱處理後的材料命名 72
表4-2前驅液配置與複合材名稱 74
表4-3揮發性有機化合物的吸附結果 81
表4-4纖維複合材對揮發性有機化合物(VOCs)的吸附結果 86
表A-1 MOFs 的比表面積與孔洞大小 95
表C-1水穩定性測試前後重量和重量損失 104

(1)Hermes, S.; Schro¨der, F.; Amirjalayer, S.; Schmid, R.; Fischer, R. A. J. Mater. Chem., 2006, 16, 2464
(2)Li, H.; Eddaoudi, M.; O´Keeffe, M.; Yaghi, O. M. Nature, 1999, 402, 276
(3)Saha, D.; Deng, S. Tsinghua. Sci. Technol., 2010, 15, 363
(4)Liang, C.; Shi, Z.-L.; He, C.-T. ; Tan, J.; Zhou, H.-D.; Zhou, H.-L.; Lee, Y.; Zhang, Y.-B. J. Am. Chem. Soc., 2017, 139 (38), pp 13300–13303
(5)Rodriguesa, M. A.; Ribeirob, J. D. S.; Costab, E. D. S.; Mirandab, J. L. D.; Ferraza, H. C. J. Sep. A. Pu. Tec., 2018,192 491–500
(6)Bakuru, V. R.; Kalidindi S. B. J. Chem. A. Eu.,2017
(7)Chernikova, V.; Yassine, P.; Shekhah, O.;Eddaoudi, M.; Salama, K. N. J. Mater. Chem. A, 2018, 6, 5550-5554
(8)Ren, J.;Dyosiba, X.;Musyoka, N. M.;Langmi, H. H.;Mathe, M.;Liao, S. Coord. Chem. Rev., 2017, 352, 187–219
(9)Rallapalli, P.; Prasanth, K. P.; Patil , D.;Somani, R. S.; Jasra, R. V.; Bajaj,H. C. J. Porous Mater 2011, 18, 205.
(10)Barthelet, K; Marrot, J.; Férey, G.; Riou, D. Chem. Commun. 2004, 520
(11)Volkringer, C.; Meddouri, M.; Loiseau, T.; Guillou, N.; Marrot, J.; Fe´rey, G.; Haouas, M.; Taulelle F.; Audebrand, N.; Latroche, M. Inorg. Chem., 2008, 47, 24
(12)Fateeva, A.; Horcajada, P.; Devic, T.; Serre, C.; Marrot, J.; Grenèche, J. M.; Morcrette, M.; Tarascon, J. M.; Maurin, G., Férey, G. Eur. J. Inorg. Chem. 2010, 3789
(13)Kyo, S.; Zheng, N.; Adrien, P.; Jae, Y.; Rudan, H.;Fernando, J.;Uribe, R.; Hee, K.; Michael, O.;Omar, M. PNAS, 2006,103(27),10186-10191
(14)Karena, W.; Peter, J.;Tina, M. J. Am. Chem. Soc., 2010, 132, 8897–8899,9,8897
(15)Dorina, F.; Mark, A.; Karena, W.;Peter, J.;Jeffery, A.;Paul, S.; Tina, M. J. Am. Chem. Soc. 2011, 133, 12398–12401
(16)Dorina, F.; Karena, W.; Mark, A.;Jeffery, A.;Paul, S.;Haiyan, Z.;Peter, J.;Tina, M. Chem. Mater., 2013, 25 (13), 2591–2596
(17)Kaiqiong, Q.;Lixian, Y.;Junmin, L.;Peitao, W.;Yi, Y.;Daiqi, Y.;Liming, W. Atmos. Environ., 2014 , 86 , 102-112
(18)Patnaik, P. John Wiley & Sons, Inc, New Jersey US (2007)
(19) Qian, Q.;Gong, C.; Zhang, Z.; Yuan, G. Adsorption, 2015 ,21, 333-341
(20)McInnes, G. Atmospheric Emission Inventory Guidebook: A Joint Emep/corinair Production, EC
(21)Li, Y.;Lee, C.;Gullett, B. Carbon, 2002 , 40 , 65-72
(22)Singh, H.;Tabazadeh, A.;Evans, M.;Field, B.;Jacob, D.;Sachse, G.;Crawford, J.;Shetter, R.;Brune, W. Geophys. Res. Lett., 2003 ,30
(23) Mitsui, T.;Tsutsui, K.;Matsui, T. ;Kikuchi, R.;Eguchi, K. Appl. Catal. B: Environ., 2008, 78 , 158-165
(24) Klett, C.;Duten, X.;Tieng, S.;Touchard, S.;Jestin, P.;Hassouni, K. ;Vega-González, A. J. Hazard. Mater., 2004 , 279, 356-364
(25)Lovelock, J. Nature, 1975, 256 , 193-194
(26)Broadgate, W.;Liss, P.;Penkett, S. Geophys. Res. Lett., 1997 ,24 , 2675-2678
(27)Singh, H.;Tabazadeh, A.;Evans, M.;Field, B. ;Jacob, D.;Sachse, G.;Crawford, J.;Shetter, R.;Brune, W. Geophys. Res. Lett., 2003 ,30
(28)Li, L.;Song, J.;Yao, X.;Huang, G.;Liu, Z.;Tang, L. J. Cent. South Univ., 2012, 19, 3530-3539
(29)Delage, F.;Pré, P.;Le Cloirec, P. Environ. Sci. Technol., 2000, 34 , 4816-4821
(30)Oh, K.;Park, D.;Kim, S.;Park, S. Korean J. Chem. Eng., 2010, 27 , 632-638
(31)Wang, C.;Chang, K.;Chung, T.;Wu, H. J. Chem. Eng. Data, 2004, 49 , 527-531
(32)Yu, F.; Luo, L.;Grevillot, G. J. Chem. Eng. Data, 2002, 47, 467-473
(33)Oh, K.;Park, D.;Kim, S.;Park, S. Korean J. Chem. Eng., 2010, 27, 632-638
(34)Delage, F.;Pré, P.;Le, C. P. Environ. Sci. Technol., 2000, 34, 4816-4821
(35)Cardoso, B.;Mestre, A.;Carvalho, A.;Pires, J. Ind. Eng. Chem. Res., 2008, 47, 5841-5846
(36)Borkar, C.;Tomar, D.;Gumma, S. J. Chem. Eng. Data, 2010, 55, 1640-1644
(37)Oh, K.;Park, D.;Kim, S.;Park, S. Korean J. Chem. Eng., 2010, 27, 632-638
(38)Delage, F.;Pré, P.;Le, C. P. Environ. Sci. Technol., 2000, 34, 4816-4821
(39)Wang, C.;Chung, T.;Huang, C.;Wu, H. J. Chem. Eng. Data, 2005, 50, 811-816
(40)Yu, F.; Luo, L.;Grevillot, G. J. Chem. Eng. Data, 2002, 47, 467-473
(41)Delage, F.;Pré, P.;Le, C. P. Environ. Sci. Technol., 2000, 34, 4816-4821
(42)Wang, C.;Chung, T.;Huang, C.;Wu, H. J. Chem. Eng. Data, 2005, 50, 811-816
(43)Oh, K.;Park, D.;Kim, S.;Park, S. Korean J. Chem. Eng., 2010, 27, 632-638
(44)Wang, C.;Chung, T.;Huang, C.;Wu, H. J. Chem. Eng. Data, 2005, 50, 811-816
(45)Cardoso, B.;Mestr,e A.;Carvalh,o A.;Pires, J. Ind. Eng. Chem. Res., 2008, 47, 5841-5846
(46)Li, L.;Liu, S.;Liu, J. J. Hazard. Mater., 2011, 192 ,683-690
(47)Michael, S.; Jr, D.;Cohen, M. Angew. Chem. Int. Ed., 2015, 54, 9029 –9032
(48)Deng, Y.;Chen, J.;Chang, G.;Liao, K.;Tung, K.;Price, W.;Yamauchi, Y.;Wu, K. Angew. Chem. Int. Ed. 2016, 55, 12793 –12796
(49)Yan, X.;Komarneni, S.; Zhang, Z.;Yan, Z. Microporous Mesoporous Mater., 2014, 183, 69–73
(50)Abbasi, Z.;Shamsaeia, E.;Leonga, S.-K.;Ladewig, B.;Zhanga, X.; Wang, H. Microporous Mesoporous Mater., 2016, 236, 28−37
(51)Zhang, X.;Gao, B.;Creamer, A. E.;Cao, C.; Li, Y. J. Hazard. Mater. , 2017, 338, 102–123
(52)免費圖庫 http://90sheji.com/
(53)Reinsch, H.; Monique, A.; Gil, B.;Marszalek, B.; Verbiest, T.; Vos, D.; Stock, N. Chem. Mater. 2013, 25, 17−26
(54)Kuroda, R. J.; Yoshida, Nakamura, A.; Nishikiori, S. I. CrystEngComm ,2009, 11, 427.
(55)Deng, H.; Grunder, S.; Cordova, K. E.; Valente, C.; Furukawa, H.; Hmadeh, M.; Gandara, F.; Whalley, A. C.; Liu, Z.; Asahina, S.; Kazumori, H.; O''Keeffe, M.; Terasaki, O.; Stoddart, J. F.; Yaghi, O. M. Science, 2012, 336, 1018
(56)Gaab, M.;Trukhan, N.;Maurer, S.;Gummaraju, R.;Mülle, U. Microporous Mesoporous Mater., 2012, 157, 131-136
(57)Alvarez, E,; Guillou, N.; Martineau, C.;Bueken,B.;Voorde, B. V.; Guillouzer, C. L.;Fabry, P.;Nouar, F.;Taulelle, F.;Vos, D.;Chang,J.-S.;Cho, K. H.;Ramsahye, N.;Devic, T.;Daturi, M.;Maurin, G.;Serre, C. Angew. Chem. 2015, 127, 3735 –3739
(58)https://www.intechopen.com/books/metal-organic-frameworks/introductory-chapter-metal-organic-frameworks-mofs-
(59)World Nuclear Association Home Page. http://www.world-nuclear.org/ (accessed Jul 1, 2017)
(60)Weber, W. J.; Roberts, F. P. Nucl. Technol. 1983, 60, 178.
(61)Yu, J.; Xie, L. H.; Li, J. R.; Ma, Y.; Seminario, J. M.; Balbuena, P. B. Chem. Rev. 2017, 117, 9674.
(62)Decoste, J. B.; Peterson, G. W. Chem. Rev. 2014, 114, 5695.
(63)Cadiau, A.; Belmabkhout, Y.; Adil, K.; Bhatt, P. M.; Pillai, R. S.; Shkurenko, A.; Martineau, C.; Maurin, G.; Eddaoudi, M. Science 2017, 735, 731.
(64)Li, P.; Vermeulen, N. A.; Gong, X.; Malliakas, C. D.; Stoddart, J. F.; Hupp, J. T.; Farha, O. K. Angew. Chem., Int. Ed. 2016, 55, 1.
(65)Valizadeh, B.; Nguyen, T. N.;Smit, B.; Stylianou, K.C.Adv. Funct. Mater. 2018, 28, 1801596