功能化介孔材料及其清洁有机反应中的应用
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摘要
随着社会的发展,环境污染越来越受到人们的关注,而合成和设计高效、绿色的催化剂是解决污染最有效的途径之一,这是由于90%以上的化学化工反应都是通过催化剂来实现的。均相催化剂虽然有其独特的优势,但也不可避免地造成了环境的污染。而非均相催化剂容易与反应体系分离并且可多次重复使用,在减少污染的同时也降低了成本。有序介孔材料作为一种优异的多孔材料,由于其大的比表面积、有序孔道等性质使其成为理想的非均相催化剂的载体。
本文以绿色化学为背景,设计合成了一系列不同结构和形貌的介孔非均相催化剂,选取不同的碳-碳偶联反应对合成的催化剂进行系统的研究。通过分析活性数据结合材料表征,来探究构效关系。
1在酸性条件下,利用表面活性剂自组装的方法,将Pd(II)有机金属硅源和联苯基桥联硅源共聚,合成了具有类结晶壁的负载型Pd(II)有机金属催化剂,该催化剂可应用于水相Barbier反应,结果表明优于苯基修饰和乙基桥联的Pd(II)有机金属催化剂的催化活性和稳定性,主要归因于类结晶的孔壁结构和强疏水性。
2在碱性条件下,利用CTAB合成二苯基膦功能化的纳米介孔小球,通过后嫁接的方法将有机金属Pd或有机金属Rh固载在载体上,通过对于水相中有机反应的研究发现,纳米介孔小球催化剂比与其类似孔道结构的MCM-41型催化剂有着更好转化率的同时选择性也大大增加,这是因为纳米孔道更有利于反应物的扩散,同时该孔道结构也更倾向于主反应的发生。
3在酸性条件下,利用P123表面活性剂组装共缩聚合成丙基氯功能化的SBA-15材料,然后通过后嫁接将脯氨酸(Proline)铆钉在SBA-15上。该催化剂在分子间共轭加成反应中的活性与均相催化剂相当,并且可以重复使用;同时在不同的反应底物中都有很好的催化活性。
With the development of the society, the environmental pollution has become one of the most concerns. In order to solve the problem, it is critical to find a high efficient green catalyst since more than 90 percent of the chemical reaction was realized through catalysis. Though high efficiency, the homogeneous catalyst inevitably causes great pollution to the environment. While the heterogeneous catalyst is easy to separate from the system and reuse for several times, it can greatly reduce the cost and pollution as well, therefore it is reasonable to immobilize the homogeneous catalyst onto an inert support like mesoporous material because of its high surface area, ordered pore channel.
In the light of green chemistry, a series of mesoporous catalysts were synthesized with different structure and morphology, which were applied in different c-c coupling reactions. By analyzing the result of activity and materials, we are able to investigate the relationship between the efficiency and structure.
1 A new organometallic heterogeneous catalyst with crystal-like wall was synthesized through surfactant induced self assembly under acid condition using Pd(II) organometallic silane and 4,4’-Bis(triethoysiyl)-1,1’-biphenyl as the precursors. When used in the water-medium Barbier reaction, the catalyst exhibited both high activity and strong stability due to the strong hydrophobicity and crystal-like wall structure.
2 Under basic condition, the diphenylphosphine functionalized mesoporous sphere catalyst with short pore channel was obtained using CTAB as the surfactant. Through post-grafting, the Pd(PPh3)2Cl2 or Rh(PPh3)3Cl were successfully immobilized onto the sphere. Under reaction condition, compared with MCM-41 type catalyst which has the same pore structure, the sphere catalyst showed both higher activity and selectivity because of the fast diffusion of the reactants and pore structure.
3 Functionalized SBA-15 was first gained by using P123 as the surfactant under acid condition. After grafting the proline onto the SBA-15, the catalyst highlighted compared activity to the homogeneous catalyst and could be reused for several times without great lose of the activity.
本文以绿色化学为背景,设计合成了一系列不同结构和形貌的介孔非均相催化剂,选取不同的碳-碳偶联反应对合成的催化剂进行系统的研究。通过分析活性数据结合材料表征,来探究构效关系。
1在酸性条件下,利用表面活性剂自组装的方法,将Pd(II)有机金属硅源和联苯基桥联硅源共聚,合成了具有类结晶壁的负载型Pd(II)有机金属催化剂,该催化剂可应用于水相Barbier反应,结果表明优于苯基修饰和乙基桥联的Pd(II)有机金属催化剂的催化活性和稳定性,主要归因于类结晶的孔壁结构和强疏水性。
2在碱性条件下,利用CTAB合成二苯基膦功能化的纳米介孔小球,通过后嫁接的方法将有机金属Pd或有机金属Rh固载在载体上,通过对于水相中有机反应的研究发现,纳米介孔小球催化剂比与其类似孔道结构的MCM-41型催化剂有着更好转化率的同时选择性也大大增加,这是因为纳米孔道更有利于反应物的扩散,同时该孔道结构也更倾向于主反应的发生。
3在酸性条件下,利用P123表面活性剂组装共缩聚合成丙基氯功能化的SBA-15材料,然后通过后嫁接将脯氨酸(Proline)铆钉在SBA-15上。该催化剂在分子间共轭加成反应中的活性与均相催化剂相当,并且可以重复使用;同时在不同的反应底物中都有很好的催化活性。
With the development of the society, the environmental pollution has become one of the most concerns. In order to solve the problem, it is critical to find a high efficient green catalyst since more than 90 percent of the chemical reaction was realized through catalysis. Though high efficiency, the homogeneous catalyst inevitably causes great pollution to the environment. While the heterogeneous catalyst is easy to separate from the system and reuse for several times, it can greatly reduce the cost and pollution as well, therefore it is reasonable to immobilize the homogeneous catalyst onto an inert support like mesoporous material because of its high surface area, ordered pore channel.
In the light of green chemistry, a series of mesoporous catalysts were synthesized with different structure and morphology, which were applied in different c-c coupling reactions. By analyzing the result of activity and materials, we are able to investigate the relationship between the efficiency and structure.
1 A new organometallic heterogeneous catalyst with crystal-like wall was synthesized through surfactant induced self assembly under acid condition using Pd(II) organometallic silane and 4,4’-Bis(triethoysiyl)-1,1’-biphenyl as the precursors. When used in the water-medium Barbier reaction, the catalyst exhibited both high activity and strong stability due to the strong hydrophobicity and crystal-like wall structure.
2 Under basic condition, the diphenylphosphine functionalized mesoporous sphere catalyst with short pore channel was obtained using CTAB as the surfactant. Through post-grafting, the Pd(PPh3)2Cl2 or Rh(PPh3)3Cl were successfully immobilized onto the sphere. Under reaction condition, compared with MCM-41 type catalyst which has the same pore structure, the sphere catalyst showed both higher activity and selectivity because of the fast diffusion of the reactants and pore structure.
3 Functionalized SBA-15 was first gained by using P123 as the surfactant under acid condition. After grafting the proline onto the SBA-15, the catalyst highlighted compared activity to the homogeneous catalyst and could be reused for several times without great lose of the activity.
引文
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[59] P. I. Dalko, L. Moisan, Angew. Chem. Int. Ed. 2004, 43, 5138.
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[61] B. List, J. Am. Chem. Soc. 2000, 122, 9336.
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[63] A. Corma, H. Garcia, Adv. Synth. Catal. 2006, 348,1391.
[64] A. Corma, Chem. Rev. 1997, 97, 2373.
[65] J. L. Huang, F. X. Zhu, W. H. He, F. Zhang, W. Wang, H. X. Li, J. Am. Chem. Soc. 2010, 132, 1492.
[66] Z. An, W. H. Zhang, H. M. Shi, Journal of Catalysis 2006, 241, 319.
[67] G. H. Liu, Y. Gao, X. Q. Lu, M. M. Liu, F. Zhang, H. X. Li, Chem. Commun. 2008, 3184.
[68] X. H. Sun, S. Sengupta, J. L. Petersen, H. Wang, J. P. Lewis, X. D. Shi, Org. Lett., 2007, 9, 4495.
[2] M. Poliakoff, J. M. Fitzpatrick, T. R. Farren, P. T. Anastas, Science, 2002, 297, 807.
[3] M. Poliakoff, P. Licence, Nature, 2007, 450, 810.
[4]麻生明,1999年科学发展报告,科学出版社,1999.
[5] I. T. Horvth, P. T. Anastas, Chem. Rev., 2007, 107, 2169.
[6]闵恩泽,陈家镛等,中国科学院院刊,1998, 6, 413.
[7]彭立颖,贾金虎,环境保护, 2008, 390, 2.
[8] R. L. Lankey, P. T. Anastas, Ind.. Eng. Chem. Res., 2002, 41, 4498.
[9]唐致远,张娜,卢星河,中国稀土学报, 2005, 23, 5.
[10] C. J. Li, Chem. Rev. 2005, 105, 3095.
[11] P. T. Anastas, L. B. Bartlett, M. M. Krichhoff, T. C. Williamson, Catal. Today, 2000, 55, 11.
[12] F. Alardin, P. Ruiz, B. Delmonb, M. Devillers, Applied Catalysis A: General, 2001, 215, 125.
[13]陆熙炎,化学进展, 1998, 2, 10.
[14]袁友珠,张宇,厦门大学学报:自然科学版,1996, 35, 220.
[15]马正飞,石磊,天然气化工:C1化学与化工, 2002, 27, 4.
[16]毛东森,卢立义,石油化工, 1995, 11, 15.
[17]孙斌,朱丽,石油炼制与化工,2004, 27, 3.
[18] P. Hudnall, in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 1991
[19] R. A. Love, T. F. Koetzle, G. J. B. Williams, L. C. Andrews, R. Bau., Inorg. Chem., 1975, 14, 2653.
[20] C. D. Michael, J. T. Regan, J. Am. Chem. Soc., 2009, 131, 14579.
[21] D. H. Kodama, M. Tanaka, J. Chem. Eng., 1999, 44, 1252.
[22] S. G. Nelson, B. K. Kim, T. J. Peelen., J. Am. Chem. Soc., 2000, 122, 9318.
[23] Z. G. Hajos, D. R. Parrish, DE 2102623, 1971.
[24] A. Dondoni, A. Massi, Angew. Chem. Int. Ed., 2008, 47, 4638.
[25] P. I. Dalko, L. Moisan, Angew. Chem. Int. Ed., 2004, 43, 5138.
[26] A. Córdova, W. Notz, C. F. Barbas III, Chem. Comm., 2002, 3024.
[27] Y. Hayashi, W. Tsuboi, I. Ashimine, T. Urushima, M. Shoji, K. Sakai, Angew. Chem. Int. Ed, 2003, 42, 3677.
[28] A. B?gevig, K. Juhl, N. Kumaragurubaran, W. Zhuang, K. A. J?rgensen, Angew. Chem. Int. Ed., 2002, 41, 1790.
[29] J. Wang, H. Li, H. X. Xie, L. S. Zu, X. Shen, W. Wang, Angew. Chem. Int. Ed., 2007, 46, 1.
[30] S. Mizuta, M. Sadamori, T. Fujimoto, I. Yamamoto, Angew. Chem. Int. Ed., 2003, 42, 3383.
[31] M. Heitbaum, F. Glorius, I. Escher, Angew. Chem. Int. Ed., 2006, 45, 4732.
[32] H. X. Ln, i, H. Yi F. Zhang, H. Li, Y. N. Huo, Y. F. Lu, Environ. Sci. Technol., 2009, 43, 188.
[33] C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Nature, 1992, 359, 710.
[34] S. Han, W. Hou, X. Yan, Z. Li, P. Zhang, D. Li, Langmuir, 2003, 19, 4269.
[35] Y. Wan, D. Y. Zhao, Chem. Rev., 2007, 107, 2821.
[36] A.-H. Lu, F. Schüth, Adv. Mater., 2006, 18, 1793.
[37] M. O’keeffe, M. A. Peskov, S. J. Ramsden, O. M. Yaghi, Acc.Chem.Res., 2008, 41, 1782.
[38] D. Y. Zhao, J. L. Feng, Q. S. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science, 1998, 279, 548.
[39] Y. Liu, W. Z. Zhang, T. J. Pinnavaia, Angew. Chem. Int. Ed., 2001, 40, 1255.
[40] C. Aprile, A. Abad, H. García, A. Corma, J. Mater. Chem., 2005, 15, 4408.
[41] Y. Hayashi, Angew. Chem. Int. Ed.., 2006, 45, 8103.
[42] C. J. Li, Chem. Rev., 1993, 93, 2023.
[43] H. X. Li, F. Zhang, Y. Wan, Y. F. Lu, J. Phys.Chem. B, 2006, 110, 22942.
[44] H. X. Li, F. Zhang, H. Yin, Y. Wan, Y. F. Lu, Green Chem., 2007, 9, 500.
[45] H. X. Li, M. W. Xiong, F. Zhang, J. L. Huang, W. Chai, J. Phys. Chem. C, 2003, 107, 12650.
[46] S. Inagaki, S. Y. Guan, T. Ohsuna, O. Terasaki, Nature, 2002, 416, 304.
[47] M. Cornelius, F. Hoffmann, M. Froba, Chem. Mater., 2005, 17, 6674.
[48] A. Sayari, W. H. Wang, J. Am. Chem. Soc., 2005, 127, 12194.
[49] F. Zhang, G. H. Liu, H. X. Li, Y. F. Lu, Adv.Funct.Mater., 2008, 18, 1.
[50] Y. Yang, A. Sayari, Chem. Mater., 2007, 19, 4117.
[51] D. Margolese, J. A. Melero, S. C. Christiansen, B. F. Chmelka, G. D. Stucky, Chem. Mater., 2000, 12, 2448.
[52] O. Krcher, R. A. Kppel, M. Frba, A. Baiker, J. Catal., 1998, 178, 284.
[53] D. Y. Zhao, Q. Huo, J. Feng, B. F. Chmelka, G.. D. Stucky, J. Am. Chem. Soc., 1998, 120, 6024.
[54] A. S. M. Chong, X. S. Zhao, J. Phys. Chem. B, 2003, 107, 12650.
[55] M. P. Kapoor, Q. H. Yang, S. Inagaki, J. Am. Chem. Soc., 2002, 124, 15176.
[56] H. X. Li, W. Chai, F. Zhang, J. Chen, Green Chem., 2007, 9, 1223.
[57] J. L. Gu, W. Fan, A. Shimojima, T. Okubo, Small, 2007, 3, 1740.
[58] X. S. Yang, F. X. Zhu, J. L. Huang, F. Zhang, H. X. Li, Chem. Mater., 2009, 21, 4925.
[59] P. I. Dalko, L. Moisan, Angew. Chem. Int. Ed. 2004, 43, 5138.
[60] B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc. 2000, 122, 2395.
[61] B. List, J. Am. Chem. Soc. 2000, 122, 9336.
[62] X. H. Sun, S. Sengupta, J. L. Petersen, H, Wang, J. P. Lewis, X. S. Dong, Org, Lett. 2007, 9, 4495.
[63] A. Corma, H. Garcia, Adv. Synth. Catal. 2006, 348,1391.
[64] A. Corma, Chem. Rev. 1997, 97, 2373.
[65] J. L. Huang, F. X. Zhu, W. H. He, F. Zhang, W. Wang, H. X. Li, J. Am. Chem. Soc. 2010, 132, 1492.
[66] Z. An, W. H. Zhang, H. M. Shi, Journal of Catalysis 2006, 241, 319.
[67] G. H. Liu, Y. Gao, X. Q. Lu, M. M. Liu, F. Zhang, H. X. Li, Chem. Commun. 2008, 3184.
[68] X. H. Sun, S. Sengupta, J. L. Petersen, H. Wang, J. P. Lewis, X. D. Shi, Org. Lett., 2007, 9, 4495.