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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭淑芬 | |
dc.contributor.author | Chih-Cheng Chang | en |
dc.contributor.author | 張志成 | zh_TW |
dc.date.accessioned | 2021-06-16T09:27:01Z | - |
dc.date.available | 2022-06-12 | |
dc.date.copyright | 2017-06-12 | |
dc.date.issued | 2017 | |
dc.date.submitted | 2017-05-23 | |
dc.identifier.citation | 1. J. B. Higgins, Catalysis Today, 1994, 19, 7-26.
2. A. K. Cheetham and P. M. Forster, in The Chemistry of Nanomaterials, Wiley-VCH Verlag GmbH & Co. KGaA, 2005, DOI: 10.1002/352760247X.ch18, pp. 589-619. 3. W. J. Roth and D. L. Dorset, Microporous and Mesoporous Materials, 2011, 142, 32-36. 4. M. E. Leonowicz, J. A. Lawton, S. L. Lawton and M. K. Rubin, Science, 1994, 264, 1910-1913. 5. A. Corma, C. Corell and J. Pérez-Pariente, Zeolites, 1995, 15, 2-8. 6. K. Okumura, M. Hashimoto, T. Mimura and M. Niwa, Journal of Catalysis, 2002, 206, 23-28. 7. C. Delitala, M. D. Alba, A. I. Becerro, D. Delpiano, D. Meloni, E. Musu and I. Ferino, Microporous and Mesoporous Materials, 2009, 118, 1-10. 8. R. Millini, G. Perego, W. O. Parker, G. Bellussi and L. Carluccio, Microporous Materials, 1995, 4, 221-230. 9. G. J. Kennedy, S. L. Lawton and M. K. Rubin, Journal of the American Chemical Society, 1994, 116, 11000-11003. 10. W. Kolodziejski, C. Zicovich-Wilson, C. Corell, J. Perez-Pariente and A. Corma, The Journal of Physical Chemistry, 1995, 99, 7002-7008. 11. G. J. Kennedy, S. L. Lawton, A. S. Fung, M. K. Rubin and S. Steuernagel, Catalysis Today, 1999, 49, 385-399. 12. W. J. Roth, C. T. Kresge, J. C. Vartuli, M. E. Leonowicz, A. S. Fung and S. B. McCullen, MCm-36: The first pillared molecular sieve with zeolite properties, 1995. 13. S. Maheshwari, E. Jordan, S. Kumar, F. S. Bates, R. L. Penn, D. F. Shantz and M. Tsapatsis, Journal of the American Chemical Society, 2008, 130, 1507-1516. 14. P. Chlubná, W. J. Roth, A. Zukal, M. Kubů and J. Pavlatová, Catalysis Today, 2012, 179, 35-42. 15. W. J. Roth, Pol. J. Chem., 2006, 80, 703-708. 16. A. Corma, V. Fornés, J. M. Guil, S. Pergher, T. L. M. Maesen and J. G. Buglass, Microporous and Mesoporous Materials, 2000, 38, 301-309. 17. W. J. Roth and J. Cejka, Catalysis Science & Technology, 2011, 1, 43-53. 18. W. J. Roth, in Stud. Surf. Sci. Catal., eds. H. v. B. A. C. Jiří Čejka and S. Ferdi, Elsevier, 2007, vol. Volume 168, pp. 221-239. 19. A. R. Rennie, E. M. Lee, E. A. Simister and R. K. Thomas, Langmuir, 1990, 6, 1031-1034. 20. W. Fan, P. Wu, S. Namba and T. Tatsumi, Journal of Catalysis, 2006, 243, 183-191. 21. J. Ruan, P. Wu, B. Slater and O. Terasaki, Angewandte Chemie International Edition, 2005, 44, 6719-6723. 22. U. Diaz and A. Corma, Dalton Transactions, 2014, 43, 10292-10316. 23. S. Inagaki, H. Imai, S. Tsujiuchi, H. Yakushiji, T. Yokoi and T. Tatsumi, Microporous and Mesoporous Materials, 2011, 142, 354-362. 24. T. Yokoi, S. Mizuno, H. Imai and T. Tatsumi, Dalton Transactions, 2014, 43, 10584-10592. 25. D. M. Antonelli and J. Y. Ying, Angew. Chem., 1995, 107, 2202-2206. 26. D. M. Antonelli, Microporous and Mesoporous Materials, 1999, 30, 315-319. 27. V. F. Stone and R. J. Davis, Chemistry of Materials, 1998, 10, 1468-1474. 28. U. Ciesla, S. Schacht, G. D. Stucky, K. K. Unger and F. Schüth, Angewandte Chemie International Edition in English, 1996, 35, 541-543. 29. D. M. Antonelli and J. Y. Ying, Angewandte Chemie International Edition in English, 1996, 35, 426-430. 30. D. M. Antonelli and J. Y. Ying, Chemistry of Materials, 1996, 8, 874-881. 31. M. Taramasso, G. Perego and B. Notari, Journal, 1983. 32. T. Blasco, A. Corma, M. T. Navarro and J. P. Pariente, Journal of Catalysis, 1995, 156, 65-74. 33. P. Wu, T. Tatsumi, T. Komatsu and T. Yashima, Chemistry of Materials, 2002, 14, 1657-1664. 34. M. S. Morey, S. O'Brien, S. Schwarz and G. D. Stucky, Chemistry of Materials, 2000, 12, 898-911. 35. T. Blasco, M. A. Camblor, A. Corma, P. Esteve, J. M. Guil, A. Martínez, J. A. Perdigón-Melón and S. Valencia, The Journal of Physical Chemistry B, 1998, 102, 75-88. 36. A. Corma, M. A. Camblor, P. Esteve, A. Martinez and J. Perezpariente, Journal of Catalysis, 1994, 145, 151-158. 37. P. Wu, T. Tatsumi, T. Komatsu and T. Yashima, Journal of Catalysis, 2001, 202, 245-255. 38. P. Wu and T. Tatsumi, Chemical Communications, 2002, DOI: 10.1039/b201170k, 1026-1027. 39. P. Wu and T. Tatsumi, Journal of Catalysis, 2003, 214, 317-326. 40. P. Wu and T. Tatsumi, Journal of Physical Chemistry B, 2002, 106, 748-753. 41. W. B. Fan, P. Wu, S. Namba and T. Tatsumi, Journal of Catalysis, 2006, 243, 183-191. 42. J. M. Thomas and R. Raja, Journal of Organometallic Chemistry, 2004, 689, 4110-4124. 43. P. Wu and T. Tatsumi, The Journal of Physical Chemistry B, 2002, 106, 748-753. 44. T. Maschmeyer, F. Rey, G. Sankar and J. M. Thomas, Nature, 1995, 378, 159-162. 45. A. Corma, U. Diaz, V. Fornes, J. L. Jorda, M. Domine and F. Rey, Chemical Communications, 1999, DOI: 10.1039/A900763F, 779-780. 46. J. A. Melero, J. Iglesias, J. M. Arsuaga, J. Sainz-Pardo, P. de Frutos and S. Blazquez, Journal of Materials Chemistry, 2007, 17, 377-385. 47. F. Bérubé, A. Khadhraoui, M. T. Janicke, F. Kleitz and S. Kaliaguine, Industrial & Engineering Chemistry Research, 2010, 49, 6977-6985. 48. R. Ballesteros, Y. Pérez, M. Fajardo, I. Sierra and I. del Hierro, Microporous and Mesoporous Materials, 2008, 116, 452-460. 49. M.-J. Kim, S.-H. Chang, J.-S. Choi and W.-S. Ahn, Reaction Kinetics and Catalysis Letters, 2004, 82, 27-32. 50. D. R. C. Huybrechts, I. Vaesen, H. X. Li and P. A. Jacobs, Catalysis Letters, 1991, 8, 237-244. 51. M. G. Clerici and P. Ingallina, Journal of Catalysis, 1993, 140, 71-83. 52. Z. Liu, G. M. Crumbaugh and R. J. Davis, Journal of Catalysis, 1996, 159, 83-89. 53. D. R. C. Huybrechts, L. Debruycker and P. A. Jacobs, Nature, 1990, 345, 240-242. 54. D. R. C. Huybrechts, I. Vaesen, H. X. Li and P. A. Jacobs, Catalysis Letters, 1991, 8, 237-244. 55. K. Genov, Oxidation of organic compounds on TS-1 and Ti-Beta zeolites synthesized according to the wetness impregnation method, 2004. 56. E. T. C. Vogt, G. T. Whiting, A. Dutta Chowdhury and B. M. Weckhuysen, in Advances in Catalysis, ed. C. J. Friederike, Academic Press, 2015, vol. Volume 58, pp. 143-314. 57. G. Strukul and A. Scarso, in Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis, Elsevier, Amsterdam, 2008, DOI: https://doi.org/10.1016/B978-0-444-53188-9.00002-X, pp. 103-117. 58. M. E. Leonowicz, J. A. Lawton, S. L. Lawton and M. K. Rubin, Science, 1994, 264, 1910-1913. 59. A. Corma, U. Diaz, V. Fornes, J. M. Guil, J. Martinez-Triguero and E. J. Creyghton, Journal of Catalysis, 2000, 191, 218-224. 60. P. Chlubna, W. J. Roth, A. Zukal, M. Kubu and J. Pavlatova, Catalysis Today, 2012, 179, 35-42. 61. P. Frontera, F. Testa, R. Aiello, S. Candamano and J. B. Nagy, Microporous and Mesoporous Materials, 2007, 106, 107-114. 62. X. X. Zhu, S. L. Liu, Y. Q. Song and L. Y. Xu, Applied Catalysis a-General, 2005, 288, 134-142. 63. R. Millini, G. Perego, W. O. Parker, G. Bellussi and L. Carluccio, Microporous Materials, 1995, 4, 221-230. 64. L. Liu, M. Cheng, D. Ma, G. Hu, X. Pan and X. Bao, Microporous and Mesoporous Materials, 2006, 94, 304-312. 65. L. Wang, Y. Wang, Y. Liu, L. Chen, S. Cheng, G. Gao, M. He and P. Wu, Microporous and Mesoporous Materials, 2008, 113, 435-444. 66. P. Matias, J. M. Lopes, P. Ayrault, S. Laforge, P. Magnoux, M. Guisnet and F. R. Ribeiro, Applied Catalysis a-General, 2009, 365, 207-213. 67. S.-Y. Kim, H.-J. Ban and W.-S. Ahn, Catalysis Letters, 2007, 113, 160-164. 68. X. Shen, W. Fan, Y. He, P. Wu, J. Wang and T. Tatsumi, Applied Catalysis a-General, 2011, 401, 37-45. 69. N. Yap, R. P. Andres and W. N. Delgass, Journal of Catalysis, 2004, 226, 156-170. 70. L. D. Gelb and K. E. Gubbins, Langmuir, 1998, 14, 2097-2111. 71. S. Brunauer, P. H. Emmett and E. Teller, Journal of the American Chemical Society, 1938, 60, 309-319. 72. W. E. Vargas and G. A. Niklasson, Appl. Opt., 1997, 36, 5580-5586. 73. J. Klaas, G. SchulzEkloff and N. I. Jaeger, Journal of Physical Chemistry B, 1997, 101, 1305-1311. 74. J. A. Rengifo-Herrera, E. Mielczarski, J. Mielczarski, N. C. Castillo, J. Kiwi and C. Pulgarin, Applied Catalysis B-Environmental, 2008, 84, 448-456. 75. L. Yang and B. Kruse, J. Opt. Soc. Am. A, 2004, 21, 1933-1941. 76. J. F. Ruan, P. Wu, B. Slater and O. Terasaki, Angewandte Chemie-International Edition, 2005, 44, 6719-6723. 77. S. Song, P. Wang, Y. He, J. Li, M. Dong, J. Wang, T. Tatsumi and W. Fan, Microporous and Mesoporous Materials, 2012, 159, 74-80. 78. J. C. Torres and D. Cardoso, Microporous and Mesoporous Materials, 2008, 113, 204-211. 79. S. Gupta, C. P. Vinod and D. Jagadeesan, Rsc Advances, 2015, 5, 92371-92377. 80. Y. Kunitake, T. Takata, Y. Yamasaki, N. Yamanaka, N. Tsunoji, Y. Takamitsu, M. Sadakane and T. Sano, Microporous and Mesoporous Materials, 2015, 215, 58-66. 81. V.-H. Nguyen, S. D. Lin and J. C.-S. Wu, Journal of Catalysis, 2015, 331, 217-227. 82. X. Wang, M. Sun, B. Meng, N. Yang and X. Tan, Materials Letters, 2016, 171, 59-62. 83. Y. Zheng, Y. Zhang, Z. Wang, Y. Liu, M. He and P. Wu, Industrial & Engineering Chemistry Research, 2011, 50, 9587-9593. 84. Y. Zuo, X. Wang and X. Guo, Industrial & Engineering Chemistry Research, 2011, 50, 8485-8491. 85. X. Deng, Y. Wang, L. Shen, H. Wu, Y. Liu and M. He, Industrial & Engineering Chemistry Research, 2013, 52, 1190-1196. 86. S.-Y. Chen, T. Mochizuki, Y. Abe, M. Toba and Y. Yoshimura, Applied Catalysis B-Environmental, 2014, 148, 344-356. 87. S.-Y. Chen, C.-Y. Tang, J.-F. Lee, L.-Y. Jang, T. Tatsumi and S. Cheng, Journal of Materials Chemistry, 2011, 21, 2255-2265. 88. V. Schwartz, D. R. Mullins, W. Yan, H. Zhu, S. Dai and S. H. Overbury, The Journal of Physical Chemistry C, 2007, 111, 17322-17332. 89. Y. Wu, X. Ren and J. Wang, Materials Chemistry and Physics, 2009, 113, 773-779. 90. M. A. Camblor, C. Corell, A. Corma, M.-J. Díaz-Cabañas, S. Nicolopoulos, J. M. González-Calbet and M. Vallet-Regí, Chemistry of Materials, 1996, 8, 2415-2417. 91. G. Engelhardt and R. Radeglia, Chemical Physics Letters, 1984, 108, 271-274. 92. S. Unverricht, M. Hunger, S. Ernst, H. G. Karge and J. Weitkamp, ZEOLITE MCM-22 - SYNTHESIS, DEALUMINATION AND STRUCTURAL CHARACTERIZATION, 1994. 93. C. Delitala, M. D. Alba, A. I. Becerro, D. Delpiano, D. Meloni, E. Musu and I. Ferino, Microporous and Mesoporous Materials, 2009, 118, 1-10. 94. Y. Wang, D. Zhou, G. Yang, X. Liu, D. Ma, D. Liang and X. Bao, Chemical Physics Letters, 2004, 388, 363-366. 95. X. Ouyang, Y.-J. Wanglee, S.-J. Hwang, D. Xie, T. Rea, S. I. Zones and A. Katz, Dalton Transactions, 2014, 43, 10417-10429. 96. B. Elyassi, X. Zhang and M. Tsapatsis, Microporous and Mesoporous Materials, 2014, 193, 134-144. 97. M. Hunger, S. Ernst and J. Weitkamp, Zeolites, 1995, 15, 188-192. 98. D. Ma, Y. Y. Shu, X. W. Han, X. M. Liu, Y. D. Xu and X. H. Bao, Journal of Physical Chemistry B, 2001, 105, 1786-1793. 99. S. Maheshwari, C. Martinez, M. T. Portilla, F. J. Llopis, A. Corma and M. Tsapatsis, Journal of Catalysis, 2010, 272, 298-308. 100. Y. Q. Wu, Z. Lu, L. Emdadi, S. C. Oh, J. Wang, Y. Lei, H. Y. Chen, D. T. Tran, I. C. Lee and D. X. Liu, Journal of Catalysis, 2016, 337, 177-187. 101. F. Berube, B. Nohair, F. Kleitz and S. Kaliaguine, Chemistry of Materials, 2010, 22, 1988-2000. 102. F. Jin, S. Y. Chen, L. Y. Jang, J. F. Lee and S. F. Cheng, Journal of Catalysis, 2014, 319, 247-257. 103. V. H. Nguyen, S. D. Lin and J. C. S. Wu, Journal of Catalysis, 2015, 331, 217-227. 104. D. Cabaret, Y. Joly, H. Renevier and C. R. Natoli, Journal of Synchrotron Radiation, 1999, 6, 258-260. 105. C.-H. Huang, D. Gu, D. Zhao and R.-A. Doong, Chemistry of Materials, 2010, 22, 1760-1767. 106. S. Y. Chen, C. Y. Tang, J. F. Lee, L. Y. Jang, T. Tatsumi and S. Cheng, Journal of Materials Chemistry, 2011, 21, 2255-2265. 107. H.-J. Chen, L. Wang and W.-Y. Chiu, Materials Chemistry and Physics, 2007, 101, 12-19. 108. L. Korosi, S. Papp, I. Bertoti and I. Dekany, Chemistry of Materials, 2007, 19, 4811-4819. 109. Z. Y. Wang, F. X. Zhang, Y. L. Yang, B. Xue, J. Cui and N. J. Guan, Chemistry of Materials, 2007, 19, 3286-3293. 110. D. Skoda, A. Styskalik, Z. Moravec, P. Bezdicka, C. E. Barnes and J. Pinkas, Journal of Sol-Gel Science and Technology, 2015, 74, 810-822. 111. U. Neuenschwander and I. Hermans, The Journal of Organic Chemistry, 2011, 76, 10236-10240. 112. P. R. Khoury, J. D. Goddard and W. Tam, Tetrahedron, 2004, 60, 8103-8112. 113. B. K. Morse, Journal of the American Chemical Society, 1957, 79, 3375-3380. 114. H. Liu, L. Gu, P. Zhu, Z. Liu and B. Zhou, Procedia Engineering, 2012, 45, 574-579. 115. Y. W. Wang, Y. S. Duh and C. M. Shu, Process Safety Progress, 2007, 26, 299-303. 116. X. S. Zhao, G. Q. Lu, A. K. Whittaker, G. J. Millar and H. Y. Zhu, The Journal of Physical Chemistry B, 1997, 101, 6525-6531. 117. S. Pazokifard, S. M. Mirabedini, M. Esfandeh, M. Mohseni and Z. Ranjbar, Surface and Interface Analysis, 2012, 44, 41-47. 118. J. M. Kim, S. M. Chang, S. M. Kong, K.-S. Kim, J. Kim and W.-S. Kim, Ceramics International, 2009, 35, 1015-1019. 119. C. Anand, P. Srinivasu, G. P. Mane, S. N. Talapaneni, D. S. Dhawale, M. A. Wahab, S. V. Priya, S. Varghese, Y. Sugi and A. Vinu, Microporous and Mesoporous Materials, 2012, 160, 159-166. 120. S. M. Solberg, D. Kumar and C. C. Landry, The Journal of Physical Chemistry B, 2005, 109, 24331-24337. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/59535 | - |
dc.description.abstract | 本文以嫁接方式製備含鈦於MWW層狀結構之孔洞材料,包括MCM-22與ERB-1兩種同樣具MWW結構之微孔沸石以及利用氧化矽支撐ERB-1而得同時具微孔與介孔之MCM-36二氧化矽,並針對使用不同鈦前驅物作為嫁接試劑及不同溶劑的影響進行探討。利用XRD、N2 adsorption-desorption isotherms證實嫁接法製備之Ti-MCM-22的MWW層狀結構完整。ICP-MS檢測Ti-MCM-22的鈦量,於合成溶液矽鈦比等同條件下,鈦含量隨著選用體積較小的鈦前驅物可以引入更多Ti(IV) 於MCM-22上,不同鈦前驅物所製備而得的Ti-MCM-22含鈦量的關係為Ti(O-Et)4 > Ti(O-Pr)4 > Ti(O-Bu)4。UV–Vis 與XANES光譜證實有四配位與六配位鈦存在於Ti-MCM-22,其中六配位鈦的訊號隨著合成時的鈦源使用量減少而降低。選用嫁接溶劑對於Ti(O-Et)4製備Ti-MCM-22,UV–Vis 檢測Ti-MCM-22以2 M HNO3水溶液移除骨架外TiO2,1-butanol相較於ethanol更能夠維持鈦活性。29Si NMR光譜揭露Ti-MCM-22樣品中大部分的Ti(IV)可能處在supercage底部。應用Ti-MCM-22催化環己烯與環辛烯的環氧化反應,以t-butylhydrogen peroxide作為氧化劑,發現選用Ti(O-Et)4 作為嫁接劑所製備的Ti-MCM-22具有最佳催化結果,優於Ti-YNU-1或以Ti(O-Pr)4及Ti(O-Bu)4作為嫁接劑所製備的Ti-MCM-22觸媒。
以ERB-1為起始物合成具有微孔與介孔之MCM-36。再利用嫁接法製備Ti-MCM-36觸媒。探討使用Ti(O-Et)4、Ti(O-Pr)4及Ti(O-Bu)4三種鈦嫁接試劑及不同溶劑(1-butanol、ethanol及toluene)的影響。利用XRD、N2 adsorption-desorption isotherms佐證Ti-MCM-36的MWW結構完整。ICP-MS檢測Ti-MCM-36之鈦含量隨著鈦嫁接試劑的體積減小而增加,得到Ti-MCM-36樣品之Si/Ti比值有 Ti(OEt)4 < Ti(OiPr)4 < Ti(OBu)4 的趨勢。由UV–vis 與XANES光譜可觀察Ti(IV)的配位環境,發現以ethanol及toluene為溶劑所進行的嫁接反應所得Ti-MCM-36會有較多TiO2 團簇甚至顆粒生成。在環己烯、環辛烯與雙環戊二烯的環氧化反應裡,使用Ti(O-Et)4為嫁接劑所製備之Ti-MCM-36觸媒顯示良好的催化表現,優於Ti-YNU-1與Ti(O-Pr)4及Ti(O-Bu)4作為嫁接劑製備的Ti-MCM-36觸媒。當TBHP/DCPD=3.5,雙環戊二烯獲得接近100%轉化率及95% diepoxide選擇率 | zh_TW |
dc.description.abstract | Ti(IV) incorporated layered stacking MWW zeolites with containing similar porous structure of ERB-1 and MCM-22 precursors (Ti-MCM-22 and Ti-ERB-1) and ERB-1 precursor as starting material subsequently further prepared micro-/mesoporous silica MCM-36 by silicates pillars (Ti-MCM-36) through a simple grafting method using different titanium alkoxides, including Ti(OEt)4, Ti(OiPr)4 and Ti(OBu)4 onto the post-treated calcined MWW. The X-ray diffraction patterns and N2 sorption isotherms confirmed the retention of basal MWW layer structure in Ti-MCM-22. The Si/Ti molar ratios analyzed by ICP-MS increased with the size of titanium alkoxides and varied in the order of Ti(OEt)4 < Ti(OiPr)4 < Ti(OBu)4 based on the same amounts of titanium alkoxides used in the grafting solutions. The UV-Vis and X-ray absorption spectra revealed that both tetrahedrally and octahedrally coordinated Ti(IV) species were present on Ti-MCM-22 prepared by grafting. However, the amount of octahedral Ti(IV) decreased with the decrease in Ti content. After acidizing with 2 M HNO3 concentration on Ti-MCM-22 due to the purpose of removed extra-framework TiO2 species, UV-Vis observation presents that 1-butanol has a well-retained Ti-anchored activity rather than ethanol as grafting solvent. Solid state 29Si NMR spectra indicated that most Ti(IV) were incorporated near the T-sites on the open bottom of the supercage, which were easily accessed by grafting agent. When applied in epoxidation of cycloalkenes, Ti-MCM-22 prepared by grafting with Ti(OEt)4 demonstrated better catalytic activities than Ti-YNU-1 or those grafting with Ti(OiPr)4 and Ti(OBu)4. The best catalytic performances were obtained over Ti-MCM-22 with Si/Ti molar ratio of ca. 100 prepared by grafting with Ti(OEt)4. The conversions were very high and epoxide selectivities were close to 100% in cyclohexene and cyclooctane oxidation using t-butylhydrogen peroxide as the oxidant.
ERB-1 precursor as initial material follows the step-by-step experimental procedure to derive micro-/mesoporous silica MCM-36. Ti(IV)-incorporated MCM-36 (Ti-MCM-36) was prepared by a simple grafting method using different titanium alkoxides, including Ti(OEt)4, Ti(OiPr)4 and Ti(OBu)4 in various solvents, including ethanol, 1-butanol, and toluene. The X-ray diffraction patterns and N2 sorption isotherms confirmed the retention of the basal MWW layer structure in Ti-MCM-36. The Si/Ti molar ratios analyzed by ICP-MS increased with the size of titanium alkoxides and varied in the order of Ti(OEt)4 < Ti(OiPr)4 < Ti(OBu)4 based on the same amounts of titanium alkoxides used in the grafting solutions, while the solvent had little influence on the Ti loading. UV–vis and XANES spectra showed that titanium species were mainly tetrahedral coordinated Ti(IV) and small amount of titania clusters when grafting in ethanol and 1-butanol, while large bulky titania crystallites were formed in toluene. Ti-MCM-36 prepared by grafting with Ti(OEt)4 in 1-butanol demonstrated better catalytic activities in epoxidation of olefins, including cyclohexene, cyclooctene and dicyclopentadiene (DCPD) than Ti-YNU-1 or those grafted with Ti(OiPr)4 and Ti(OBu)4. In DCPD oxidation using t-butylhydrogen peroxide (TBHP) as the oxidant, about 100% DCPD conversionand 95% diepoxide selectivity could be achieved using TBHP/DCPD molar ratio of 3.5. | en |
dc.description.provenance | Made available in DSpace on 2021-06-16T09:27:01Z (GMT). No. of bitstreams: 1 ntu-106-D00223101-1.pdf: 4409632 bytes, checksum: 9d6c3b9e7bb15ae12a15af872ab319af (MD5) Previous issue date: 2017 | en |
dc.description.tableofcontents | Category
謝誌 I 摘要 II Abstract III Category V Figure VIII Table XIV Scheme XIV Chapter 1 Introduction 1 1.1 Zeolites 1 1.2 MWW family zeolites 6 1.2.1 MCM-22 zeolites 8 1.2.2 MCM-36 11 1.2.3 ITQ-2 13 1.2.4 MCM-36 14 1.2.5 YNU-1 (Ti-YNU-1) 17 1.2.6 IEZ-MWW 19 1.3 The heteroatom incorporation 20 1.3.1 The hydrothermal synthesis of titanosilcates 22 1.3.2 Post synthesis method of titanosilcates 24 1.4 The epoxidation of alkenes 29 1.5 Motivation 34 Chapter 2 Experimental 35 2.1 Reagents 35 2.2 Preparation of Ti-MCM-22, Ti-ERB-1 and Ti-MCM-36 catalysts 37 Ti-MCM-22 catalyst 37 2.3Characterization 40 2.4Catalyticreactions 47 Chapter 3 Effect of grafting agent on the structure Ti-MWW catalysts 49 3.1. Influence of Ti-precursors for grafting of Ti(IV) on MCM-22 49 3.2 Influence of Si/Ti ratio on grafted MCM-22 58 3.3. Solid-state NMR spectroscopy 65 3.4 Influence of Ti-precursor on grafting Ti(IV) onto MCM-36 71 3.5. Influence of solvent for grafting Ti(IV) on MCM-36 81 3.6. Summaries 83 Chapter 4 Catalytic performance on the structure Ti-MWW catalysts 85 4.1. Catalytic properties of Ti-MCM-22 prepared from different precursors 85 4.2. Catalytic properties of Ti-MCM-22 with different Si/Ti ratios. 90 4.3. Recycling of Ti-MCM-22 catalysts 90 4.4. Catalytic properties of Ti-MCM-36 grafted using different precursors 91 4.5. Catalytic properties of Ti-MCM-36 grafted in different solvents 97 4.6. Catalytic epoxidation of DCPD over Ti-MCM-36 prepared from different precursors 98 4.7. Recycling of Ti-MCM-36 catalysts 102 4.8 Catalytic properties of Ti-MCM-22 and Ti-ERB-1 104 4.9. Summaries 106 Chapter 5 Conclusions 108 References 109 | |
dc.language.iso | en | |
dc.title | 嫁接法製備含鈦 MWW 沸石的研究、材料鑑定及催化
活性之探討 | zh_TW |
dc.title | Preparation of Ti-incorporated MWW zeolites by grafting method, material characterization and catalytic performance studies | en |
dc.type | Thesis | |
dc.date.schoolyear | 105-2 | |
dc.description.degree | 博士 | |
dc.contributor.oralexamcommittee | 蔡蘊明,鍾博文,楊家銘,陳浩銘,邱靜雯 | |
dc.subject.keyword | MCM-36,嫁接,介孔,還氧化, | zh_TW |
dc.subject.keyword | MCM-36,grafting,mesoporous,epoxidation, | en |
dc.relation.page | 115 | |
dc.identifier.doi | 10.6342/NTU201700834 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2017-05-24 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
顯示於系所單位: | 化學系 |
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