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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 萬本儒(Ben-Zu Wan) | |
dc.contributor.author | Yi-Hsiu Chen | en |
dc.contributor.author | 陳怡秀 | zh_TW |
dc.date.accessioned | 2021-06-15T03:03:34Z | - |
dc.date.available | 2012-08-03 | |
dc.date.copyright | 2009-08-03 | |
dc.date.issued | 2009 | |
dc.date.submitted | 2009-07-30 | |
dc.identifier.citation | [1] W. W. Crew and R. J. Madix, 'CO adsorption and oxidation on oxygen precovered Cu(110) at 150 K: Reactivity of two types of adsorbed atomic oxygen determined by scanning tunneling microscopy,' Surface Science, vol. 356, pp. 1-18, Jun 10 1996.
[2] W. W. Crew and R. J. Madix, 'A scanning tunneling microscopy study of the oxidation of CO on Cu(110) at 400 K: Site specificity and reaction kinetics,' Surface Science, vol. 349, pp. 275-293, Apr 10 1996. [3] W. Liu and M. Flytzani-Stephanopoulos, 'Transition metal-promoted oxidation catalysis by fluorite oxides: A study of CO oxidation over Cu-CeO2,' Chemical Engineering Journal, vol. 64, pp. 283-294, Nov 1996. [4] F. J. R. vanNeer, B. vanderLinden, and A. Bliek, 'Forced concentration oscillations of CO and O-2 in CO oxidation over Cu/Al2O3,' Catalysis Today, vol. 38, pp. 115-128, Oct 5 1997. [5] J. Lauterbach, G. Bonilla, and T. D. Pletcher, 'Non-linear phenomena during CO oxidation in the mbar pressure range: a comparison between Pt/SiO2 and Pt(100),' Chemical Engineering Science, vol. 54, pp. 4501-4512, Oct 1999. [6] P. A. Carlsson, L. Osterlund, P. Thormahlen, A. Palmqvist, E. Fridell, J. Jansson, and M. Skoglundh, 'A transient in situ FTIR and XANES study of CO oxidation over Pt/Al2O3 catalysts,' Journal of Catalysis, vol. 226, pp. 422-434, Sep 10 2004. [7] R. H. Nibbelke, A. J. L. Nievergeld, J. H. B. J. Hoebink, and G. B. Marin, 'Development of a transient kinetic model for the CO oxidation by O-2 over a Pt/Rh/CeO2/gamma-Al2O3 three-way catalyst,' Applied Catalysis B-Environmental, vol. 19, pp. 245-259, Dec 7 1998. [8] Y. M. Kang and B. Z. Wan, 'Preparation of Gold in Y-Type Zeolite for Carbon-Monoxide Oxidation,' Applied Catalysis a-General, vol. 128, pp. 53-60, Jul 20 1995. [9] Y. M. Kang and B. Z. Wan, 'Pretreatment Effect of Gold Iron Zeolite-Y on Carbon-Monoxide Oxidation,' Catalysis Today, vol. 26, pp. 59-69, Aug 30 1995. [10] Y. M. Kang and B. Z. Wan, 'Gold and iron supported on Y-type zeolite for carbon monoxide oxidation,' Catalysis Today, vol. 35, pp. 379-392, Apr 11 1997. [11] J. N. Lin, J. H. Chen, C. Y. Hsiao, Y. M. Kang, and B. Z. Wan, 'Gold supported on surface acidity modified Y-type and iron/Y-type zeolite for CO oxidation,' Applied Catalysis B-Environmental, vol. 36, pp. 19-29, Feb 8 2002. [12] J. N. Lin and B. Z. Wan, 'Effects of preparation conditions on gold/Y-type zeolite for CO oxidation,' Applied Catalysis B-Environmental, vol. 41, pp. 83-95, Mar 10 2003. [13] J. H. Chen, J. N. Lin, Y. M. Kang, W. Y. Yu, C. N. Kuo, and B. Z. Wan, 'Preparation of nano-gold in zeolites for CO oxidation: Effects of structures and number of ion exchange sites of zeolites,' Applied Catalysis a-General, vol. 291, pp. 162-169, Sep 12 2005. [14] 陳任和, '國立台灣大學化學工程研究所碩士論文,' 1995. [15] 劉詩婷, '國立台灣大學化學工程研究所碩士論文,' 2008. [16] M. Haruta, T. Kobayashi, H. Sano, and N. Yamada, 'Novel Gold Catalysts for the Oxidation of Carbon-Monoxide at a Temperature Far Below 0-Degrees-C,' Chemistry Letters, pp. 405-408, 1987. [17] 林俊男, '國立台灣大學化學工程研究所博士論文,' 2002. [18] F. Moreau and G. C. Bond, 'CO oxidation activity of gold catalysts supported on various oxides and their improvement by inclusion of an iron component,' Catalysis Today, vol. 114, pp. 362-368, May 30 2006. [19] T. Hayashi, K. Tanaka, and M. Haruta, 'Selective vapor-phase epoxidation of propylene over Au/TiO2 catalysts in the presence of oxygen and hydrogen,' Journal of Catalysis, vol. 178, pp. 566-575, Sep 10 1998. [20] M. D. Hughes, Y. J. Xu, P. Jenkins, P. McMorn, P. Landon, D. I. Enache, A. F. Carley, G. A. Attard, G. J. Hutchings, F. King, E. H. Stitt, P. Johnston, K. Griffin, and C. J. Kiely, 'Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions,' Nature, vol. 437, pp. 1132-1135, Oct 20 2005. [21] S. Biella, L. Prati, and M. Rossi, 'Selective oxidation of D-glucose on gold catalyst,' Journal of Catalysis, vol. 206, pp. 242-247, Mar 10 2002. [22] C. Milone, C. Crisafulli, R. Ingoglia, L. Schipilliti, and S. Galvagno, 'A comparative study on the selective hydrogenation of alpha,beta unsaturated aldehyde and ketone to unsaturated alcohols on Au supported catalysts,' Catalysis Today, vol. 122, pp. 341-351, Apr 30 2007. [23] G. C. Bond and D. T. Thompson, 'Catalysis by gold,' Catalysis Reviews-Science and Engineering, vol. 41, pp. 319-388, 1999. [24] Q. Xu, K. C. C. Kharas, and A. K. Datye, 'The preparation of highly dispersed Au/Al2O3 by aqueous impregnation,' Catalysis Letters, vol. 85, pp. 229-235, Feb 2003. [25] M. Haruta, 'Size- and support-dependency in the catalysis of gold,' Catalysis Today, vol. 36, pp. 153-166, Apr 25 1997. [26] F. Moreau, G. C. Bond, and A. O. Taylor, 'Gold on titania catalysts for the oxidation of carbon monoxide: control of pH during preparation with various gold contents,' Journal of Catalysis, vol. 231, pp. 105-114, Apr 1 2005. [27] D. Guillemot, V. Y. Borovkov, V. B. Kazansky, M. PolissetThfoin, and J. Fraissard, 'Surface characterization of Au/HY by Xe-129 NMR and diffuse reflectance IR spectroscopy of adsorbed CO. Formation of electron-deficient gold particles inside HY cavities,' Journal of the Chemical Society-Faraday Transactions, vol. 93, pp. 3587-3591, Oct 7 1997. [28] E. Smolentseva, N. Bogdanchikova, A. Simakov, A. Pestryakov, M. Avalos, M. H. Farias, A. Tompos, and V. Gurin, 'Catalytic activity of gold nanoparticles incorporated into modified zeolites,' Journal of Nanoscience and Nanotechnology, vol. 7, pp. 1882-1886, Jun 2007. [29] A. Simakov, I. Tuzovskaya, N. Bogdanchikova, A. Pestryakov, M. Avalos, M. H. Farias, and E. Smolentseva, 'Influence of sodium on activation of gold species in Y-zeolites,' Catalysis Communications, vol. 9, pp. 1277-1281, Mar 31 2008. [30] T. M. Salama, R. Ohnishi, and M. Ichikawa, 'Studies of the selective reduction of nitric oxide by carbon monoxide in the presence and absence of hydrogen over Au/NaY catalysts,' Journal of the Chemical Society-Faraday Transactions, vol. 92, pp. 301-306, Jan 21 1996. [31] S. L. Qiu, R. Ohnishi, and M. Ichikawa, 'Formation and Interaction of Carbonyls and Nitrosyls on Gold(I) in Zsm-5 Zeolite Catalytically Active in No Reduction with Co,' Journal of Physical Chemistry, vol. 98, pp. 2719-2721, Mar 17 1994. [32] E. Smolentseva, A. Pestryakov, N. Bogdanchikova, A. Simakov, M. Avalos, M. Farias, J. Diaz, V. Gurin, and A. Tompos, 'Influence of Fe introduction method on gold state in NaY zeolite,' International Journal of Modern Physics B, vol. 19, pp. 2496-2501, Jul 10 2005. [33] J. C. Fierro-Gonzalez, Y. L. Hao, and B. C. Gates, 'Gold nanoclusters entrapped in the alpha-cages of Y zeolites: Structural characterization by X-ray absorption spectroscopy,' Journal of Physical Chemistry C, vol. 111, pp. 6645-6651, May 10 2007. [34] K. Torigoe and K. Esumi, 'Preparation of Colloidal Gold by Photoreduction of Aucl4--Cationic Surfactant Complexes,' Langmuir, vol. 8, pp. 59-63, Jan 1992. [35] J. Rocha, S. W. Carr, and J. Klinowski, 'Al-27 Quadrupole Nutation and H-1-Al-27 Cross-Polarization Solid-State Nmr-Studies of Ultrastable Zeolite-Y with Fast Magic-Angle Spinning,' Chemical Physics Letters, vol. 187, pp. 401-408, Dec 13 1991. [36] 楊振昌, '看不見的殺手──淺談一氧化碳,' 2007. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/44535 | - |
dc.description.abstract | 本研究以氯化金酸為前軀物,Y型沸石為擔體,在溶液中將金載負於擔體上製備Au/Y觸媒,在0℃溫度下催化一氧化碳氧化反應,鑑定工具為AA、TPR、HRTEM、SEM、solid-state NMR、XRD和TGA。研究主要分為三部分。首先,嘗試就以下製程變因:(1) 修飾擔體溶液的pH值,(2) 擔體乾燥方式,了解製程變化對觸媒活性的影響,並探討金載負於擔體的機制。第二,為了解觸媒催化反應過程中,累積的熱量(一氧化碳氧化反應為放熱反應)對觸媒活性造成的影響,設計以下兩種變因:(1) 透過觸媒製備中的擔體用量控制Au/Y的金載負量,以及(2)反應中用以幫助熱傳的石英砂用量,探討熱傳效應在觸媒催化反應中所扮演的角色。第三,在相同程序下所製備的Au/Y中,會有明顯的金載負量差異,研究結果顯示製備觸媒的pH值微量變化會對金載負量有顯著的影響,因此本研究結論出一製備程序,透過有效地控制製程中金溶液pH值,解決相同製程下金載負量差異的問題。
以下是部份的研究成果:(1) 相較於室溫和60℃乾燥的沸石,金於未經乾燥之沸石載負量最低, (2) 修飾沸石的溶液pH值越低,則金的載負量越高, (3) 由XRD和SEM的鑑定結果指出,沸石的修飾過程對晶體結構會產生破壞,然而,金在沒有經過任何修飾過的沸石上載負量卻是最低的, (4) 比較室溫乾燥和60℃乾燥沸石的solid-state NMR鑑定結果,發現室溫乾燥的沸石含有較多的OH基,而金於室溫乾燥下沸石的載負量大於60℃乾燥下的沸石。 本研究針對金載負於Y型沸石的機制,提出以下可能的情況:(1) 當乾燥的Y型沸石放入金溶液時,沸石吸收溶液的程序使金化合物初步的沈積於沸石孔洞內,(2) H+催化脫水反應形成更多金化合物的鍵結,(3) 沸石結構損壞有助於金化合物擴散及吸附於孔洞內部,(4) 沸石內部OH基與金化合物脫水形成鍵結。 針對石英砂用量對觸媒活性影響,結果顯示,石英砂的添加有助於觸媒活性穩定度的提升,這是因為石英砂可以幫助熱傳以及減少觸媒內部熱的累積。此外,比較金載負量差異對觸媒活性的影響,高載負量的Au/Y雖然有較高的催化活性,但活性穩定性明顯較差。綜合以上結果,由於沸石的孔洞結構,熱傳導能力不佳,一氧化碳氧化反應所釋放的熱能會累積於觸媒內部,熱能不但有助於提升初始反應時金的還原速率(活化金的催化能力),同時也會提升觸媒內部的溫度而加快氧化反應速率。然而過多的熱量累積也會造成金顆粒的聚集,導致Au/Y觸媒活性的衰退,此一現象在金載負量較高的Au/Y觸媒活性表現中尤其明顯。 | zh_TW |
dc.description.provenance | Made available in DSpace on 2021-06-15T03:03:34Z (GMT). No. of bitstreams: 1 ntu-98-R96524045-1.pdf: 3404284 bytes, checksum: 3e23ef8ec474b5946f6405dc6f289887 (MD5) Previous issue date: 2009 | en |
dc.description.tableofcontents | 摘要……………………………… I
Abstract………………………… III 目錄…………………… V 圖索引………………… VIII 表索引……………….. XI 第一章 緒論…………. 1 1-1 研究動機 1 1-2 研究背景 3 1-3 研究方向 4 第二章 文獻回顧 6 2-1 金觸媒的發展 6 2-2 沸石Y的介紹 7 2-3 金觸媒製備方式 10 2-3-1 含浸法 (Impregnation, IMP or Incipient wetness, IW) 10 2-3-2 共沈澱法 (Co-Precipitation) 11 2-3-3 沈澱沈積法 (Deposition Preciptation, DP) 12 2-3-4 離子交換法 (Ion Exchange, IE) 13 2-4 AuY觸媒的發展 14 第三章 實驗與鑑定方法 17 3-1 實驗藥品和器材 17 3-1-1 實驗藥品來源 17 3-1-2 反應氣體來源 18 3-1-3 實驗使用器材 18 3-2 Au/Y 觸媒製備 19 3-2-1 擔體Y表面處理程序 19 3-2-2 Au/Y 觸媒製備程序 20 3-3 觸媒鑑定 22 3-3-1 原子吸收光譜儀 (AA) 22 3-3-2 高解析穿透式電子顯微鏡 (HRTEM) 22 3-3-3 X射線繞射光譜儀 (XRD) 23 3-3-4 熱重分析 (TGA) 23 3-3-5 掃描式電子顯微鏡 (SEM) 24 3-3-6 固態核磁共振 (solid-state NMR) 24 3-3-7 程溫規劃還原 (TPR) 25 3-4 觸媒活性測試 27 第四章 研究結果 29 4-1 修飾擔體之pH值的影響 29 4-1-1 Au/Y的製備與元素分析 (AA) 29 4-1-2 活性測試 30 4-1-3 程溫規劃還原 (TPR) 31 4-1-4 紫外光/可見光光譜 (UV/vis) 31 4-1-5 X-射線繞射光譜 (XRD) 33 4-1-6 穿透式電子顯微鏡 (HRTEM) 33 4-1-6-1 鑑定結果 33 4-1-6-2 反應前後顆粒大小統計 (particle size distribution) 36 4-1-7 掃描式電子顯微鏡 (SEM) 37 4-2 擔體乾燥之影響 39 4-2-1 觸媒的製備與元素分析 (AA) 39 4-2-2 活性測試 40 4-2-3 高磁場核磁共振儀 (solid-state NMR) 40 4-2-4 X-射線繞射光譜 (XRD) 45 4-2-5 熱重分析 (TGA) 46 4-3 擔體添加量對製備Au/Y之影響 47 4-3-1 觸媒的製備與元素分析 (AA) 47 4-3-2 活性測試 47 4-3-3 程溫規劃還原 (TPR) 48 4-3-4 穿透式電子顯微鏡 (HRTEM) 49 4-3-4-1 鑑定結果 49 4-3-4-2 反應前後顆粒大小統計 (particle size distribution) 51 4-4 反應過程添加石英砂之影響 52 4-4-1 觸媒的製備與元素分析 (AA) 52 4-4-2 活性測試 53 4-4-3 穿透式電子顯微鏡 (HRTEM) 54 4-4-3-1 鑑定結果 54 4-4-3-2 反應前後顆粒大小統計 (particle size distribution) 56 第五章 研究討論 57 5-1 Au載負機制 57 5-1-1 金溶液灌入乾燥擔體帶入Au沈積於沸石孔洞內 57 5-1-2 H+催化金錯合物脫水形成鍵結 58 5-1-3 沸石結構損壞有助於金載負於孔洞內部 61 5-1-4 沸石內部OH基與金錯合物脫水形成鍵結 64 5-1-5 結論 66 5-2 Au/Y觸媒催化一氧化碳氧化反應 66 5-2-1 活性位置 66 5-2-2 熱傳效應 67 5-2-3 顆粒位置影響催化穩定性 73 5-2-4 加入石英砂加速熱傳 77 5-2-5 結論 79 5-3 金載負量再現性探討 80 5-3-1 金載負量再現性問題 80 5-3-2 Au/Y製備流程 81 5-3-3 分析討論 82 5-3-4 製程改善 84 5-3-5 結果討論 86 5-3-6 結論 88 第六章 結論…… 89 第七章 參考文獻 91 | |
dc.language.iso | zh-TW | |
dc.title | Au/Y製備及催化一氧化碳氧化反應之熱傳效應探討 | zh_TW |
dc.title | Study on Au/Y Preparation and Heat Transfer Effects on CO Oxidation | en |
dc.type | Thesis | |
dc.date.schoolyear | 97-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 林俊男(Jiunn-Nan Lin),郭錦龍(Chin-Lung Kuo) | |
dc.subject.keyword | Au/Y觸媒,Y型沸石,一氧化碳氧化反應,熱傳效應, | zh_TW |
dc.subject.keyword | Au/Y catalyst,Y-type zeolite,CO oxidation,heat transfer effect, | en |
dc.relation.page | 94 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2009-07-30 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 化學工程學研究所 | zh_TW |
顯示於系所單位: | 化學工程學系 |
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