Core/shell-Structured ZSM-5@Mesoporous Silica Composites for Shape-Selective Alkylation of Toluene with Methanol

doi:10.6023/A12110980

Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (03): 371-380.DOI: 10.6023/A12110980 Previous Articles Next Articles

Article

ZSM-5@Mesoporous Silica核壳复合结构分子筛的制备及其甲苯甲醇烷基化择形催化性能的研究

纪永军, 张斌, 张坤, 徐乐, 彭洪根, 吴鹏

上海市绿色化学与化工过程绿色化重点实验室华东师范大学化学系上海 200062

投稿日期:2012-11-29 发布日期:2013-02-01
通讯作者: 张坤,吴鹏 E-mail:kzhang@chem.ecnu.edu.cn;pwu@chem.ecnu.edu.cn
基金资助:
项目受国家自然科学基金(Nos.20925310,21003050,U1162102)、科技部(No.2012BAE05B02)和上海市重点学科(No.B409)资助.

Core/shell-Structured ZSM-5@Mesoporous Silica Composites for Shape-Selective Alkylation of Toluene with Methanol

Ji Yongjun, Zhang Bin, Zhang Kun, Xu Le, Peng Honggeng, Wu Peng

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal University, Shanghai 200062

Received:2012-11-29 Published:2013-02-01
Supported by:
Project supported by the the National Natural Science Foundation of China (Nos. 20925310, 21003050, U1162102), the Science and Technology Commission (No. 2012BAE05B02), and the Shanghai Leading Academic Discipline Project (No. B409).

A shape-selective core/shell-structured ZSM-5@mesosilica composite catalyst has been synthesized by a facile surfactant-directed sol-gel coating strategy in basic medium using cetyltrimethylammonium bromide as a template. Typically, ZSM-5 with Si/Al ratio of 80 was hydrothermally synthesized using sodium aluminate, tetraethylorthosilicate, and tetrapropylammonium hydroxide (25% aqueous solution). Then it was functionalized with positively charged polymer of polydiallyldimethylammonium chloride (PDDA). Finally, the PDDA-modified ZSM-5 powder was dispersed into a gel of mesoporous silica, and reacted at 303 K for 6 h, thus the ZSM-5@mesosilica composite catalysts were obtained. The characterizations with scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HR-TEM) evidence that mesoporous silica with disordered pores can be evenly coated on the external-surface of ZSM-5 crystals with defined shell thickness. N₂ adsorption isotherms implies the connectivity between the nanopores of mesoporous silica and subnano pores of ZSM-5 zeolite. Additionally, the adsorption-desorption measurement using pyridine or ammonia as probing molecules further demonstrates that, the acid sites within ZSM-5 nanochannels are still accessible and the numbers and intensity of which are nearly unvaried. In the probe reaction of the alkylation of toluene and methanol on a fixed-bed reactor, the ZSM-5@mesosilica composite exhibits higher para-xylene selectivity in comparison to pristine ZSM-5. The unique catalytic behaviors of ZSM-5@mesosilica are ascribed to an effective removal of non-shape-selective acid sites located on the external surface of ZSM-5 by coating nonacidic mesoporous silica shell. In addition, the relationship between acidity and catalytic performance is discussed in detail, particularly in correlation to the enhancement of the para-selectivity by covering the external Br?nsted acid sites with the generated layer of mesoporous silica. The present synthetic strategy was also applicable to preparation of other materials having micro-mesoporous core-shell composite with different topology and catalytic application.

Key words: core/shell-structured zeolite, ZSM-5, mesoporous silica, para-xylene, shape-selective alkylation

Cite this article

Ji Yongjun, Zhang Bin, Zhang Kun, Xu Le, Peng Honggeng, Wu Peng. Core/shell-Structured ZSM-5@Mesoporous Silica Composites for Shape-Selective Alkylation of Toluene with Methanol[J]. Acta Chimica Sinica, 2013, 71(03): 371-380.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Chen, N. Y.; Kaeding, W. W.; Dwyer, F. G. J. Am. Chem. Soc. 1979, 101, 6783.

[2] Kaeding, W. W.; Chu, C.; Young, L. B.; Weinstein, B.; Butter, S. A. J. Catal. 1981, 67, 159.

[3] Uguina, M. A.; Sotelo, J. L.; Serrano, D. P. Appl. Catal. A 1991, 76, 183.

[4] Mirth, G.; ?ejka, J.; Lercher, J. A. J. Catal. 1993, 139, 24.

[5] Mirth, G.; Lercher, J. A. J. Catal. 1994, 147, 199.

[6] ?ejka, J.; ?ilková, N.; Wichterlova, B.; Elder-Mirth, G.; Lercher, J. A. Zeolites 1996, 17, 265.

[7] Mantha, R.; Bhatia, S.; Rao, M. S. Ind. Eng. Chem. Res. 1991, 30, 281.

[8] Yashima, T.; Ahmad, H.; Yamazaki, K.; Katsuta, M.; Hara, N. J. Catal. 1970, 16, 273.

[9] Yashima, T.; Sato, K.; Hayasaka, T.; Hara, N. J. Catal. 1972, 26, 303.

[10] Palomares, A. E.; Elder-Mirth, G.; Lercher, J. A. J. Catal. 1997, 442.

[11] Dumitriu, E.; Hulea, V.; Kaliaguine, S.; Huang, M. M. Appl. Catal. A 1996, 135, 57.

[12] Ratnasarmy, P.; Bhat, R. N.; Pokhriyal, S. K. J. Catal. 1989, 119, 65.

[13] Das, J.; Bhat, Y. S.; Halgeri, A. B. Catal. Lett. 1994, 23, 161.

[14] Zheng, S.; Heydenrych, H. R.; Jentys, A.; Lercher, J. A. J. Phys. Chem. B 2002, 106, 9552.

[15] ?ejka, J.; Krej?í, A.; ?ilková, N.; Kotrla, J.; Ernst, S.; Weber, A. Microporous Mesoporous Mater. 2002, 53, 121.

[16] Bauer, F.; Chen, W. H.; Zhao, Q.; Freyer, A.; Liu, S. B. Microporous Mesoporous Mater. 2001, 47, 67.

[17] Bauer, F.; Chen, W. H.; Bilz, E.; Freyer, A.; Sauerland, V.; Liu, S. B. J. Catal. 2007, 251, 258.

[18] Kim, J. H.; Ishida, A.; Okajima, M.; Niwa, M. J. Catal. 1996, 161, 387.

[19] Halgeri, A. B.; Das, J. Catal. Today 2002, 73, 65.

[20] Zheng, S.; Tanaka, H.; Jentys, A.; Lercher, J. A. J. Phys. Chem. B 2004, 108, 1337.

[21] Laforge, S.; Martin, D.; Paillaud, J. L.; Gusinet, M. J. Catal. 2003, 220, 92.

[22] Prokesova, P.; ?ilková, N.; Mintova, S.; Bein, T.; ?ejka, J. Appl. Catal. A 2005, 281, 85.

[23] Prokesova, P.; Mintova, S.; ?ejka, J.; Bein, T. Mater. Sci. Eng. C 2003, 23, 1001.

[24] Zhou, F.; Li, X.; Wang, A. J.; Wang, L. Y.; Yang, X. D.; Hu, Y. K. Catal. Today 2010, 150, 218.

[25] Xu, H. Y.; Guan, J. Q.; Wu, S. J.; Kan, Q. B. J. Colloid Interface Sci. 2009, 329, 346.

[26] Prokesova, P.; Mintova, S.; ?ejka, J.; Bein, T. Microporous Mesoporous Mater. 2003, 64, 165.

[27] Qian, X. F.; Du, J. M.; Li, B.; Si, M.; Yang, Y. S.; Hu, Y. Y.; Niu, G. X.; Zhang, Y. H.; Xu, H. L.; Tu, B.; Tang, Y.; Zhao, D. Y. Chem. Sci. 2011, 2, 2006.

[28] Qian, X. F.; Li, B.; Hu, Y. Y.; Niu, G. X.; Zhang, Y. H.; Che, R.; Tang, Y.; Su, D. S.; Asiri, A.; Zhao, D. Y. Chem. Eur. J. 2012, 18, 931.

[29] Xu, L.; Ren, Y. J.; Wu, H. H.; Liu, Y. M.; Wang, Z. D.; Zhang, Y. T.; Xu, J. J.; Peng, H. G.; Wu, P. J. Mater. Chem. 2011, 21, 10852.

[30] Rollmann, L. D.; Princeton, N. J. US 4088605, 1978 [Chem. Abstr. 1979, 89, 61925].

[31] Nishiyama, N.; Miyamoto, M.; Kamei, T.; Egashira, Y.; Ueyama, K. Stud. Surf. Sci. Catal. 2006, 162, 275.

[32] Van Vu, D.; Miyamoto, M.; Nishiyama, N.; Egashira, Y.; Ueyama, K. J. Catal. 2006, 243, 389.

[33] Miyamoto, M.; Kamei, T.; Nishiyama, N.; Egashira, Y.; Ueyama, K. Adv. Mater. 2005, 17, 1985.

[34] Bouizi, Y.; Rouleau, L.; Valtchev, V. P. Chem. Mater. 2006, 18, 4959.

[35] Li, Q. H.; Wang, Z.; Hedlund, J.; Creaser, D.; Zhang, H.; Zou, X. D.; Bons, A. J. Microporous Mesoporous Mater. 2005, 78, 1.

[36] Ji, Y. J.; Zhang, B.; Xu, L.; Wu, H. H.; Peng, H. G.; Chen, L.; Liu, Y. M.; Wu, P. J. Catal. 2011, 283, 168.

[37] Xue, B.; Xu, J.; Xu, C. F.; Wu, R. Z.; Li, Y. X.; Zhang, K. Catal. Commun. 2010, 12, 95.

[38] Chatterjee, M.; Iwasaki, T.; Onodera, Y.; Nagase, T.; Hayashi, H.; Ebina, T. Chem. Mater. 2000, 12, 1654.

[39] Bagshaw, S. A.; Prouzet, E.; Pinnavaia, T. J. Science 1995, 267, 865.

[40] Möller, K.; Kobler, J.; Bein, T. Adv. Funct. Mater. 2007, 17, 605.

[41] Zhang, K.; Zhang, Y.; Hou, Q. W.; Yuan, E. H.; Jiang, J. G.; Albela, B.; He, M. Y.; Bonneviot, L. Microporous Mesoporous Mater. 2011, 143, 401.

[42] Zhang, K.; Chen, H. L.; Albela, B.; Jiang, J. G.; Wang, Y. M.; He, M. Y.; Bonneviot, L. Eur. J. Inorg. Chem. 2011, (1), 59.

[43] Kokotailo, G. T.; Lawton, S. L.; Olson, D. H. Nature 1978, 272, 437.

[44] Gregg, S. J.; Sing, K. S. W. Adsorption, Surface Area and Porosity, 2nd ed., Academic Press, London, 1982.

[45] Shang, Y. C.; Yang, P. P.; Jia, M. J.; Zhang, W. X.; Wu, T. H. Catal. Commun. 2008, 9, 907.

[46] Xue, B.; Li, Y. X.; Deng, L. J. Catal. Commun. 2009, 10, 1609.

[47] Datka, J.; Gil, B.; Zlamaniec, J.; Batamack, P.; Fraissard, J.; Massiani, P. Polish. J. Chem. 1999, 73, 535.

[48] Zhu, Z. R.; Chen, Q. L.; Xie, Z. K.; Yang, W. M.; Li, C. Microporous Mesoporous Mater. 2006, 88, 16.

[49] Mavrodinova, V.; Popova, M. Catal. Commun. 2005, 6, 247.

ZSM-5@Mesoporous Silica核壳复合结构分子筛的制备及其甲苯甲醇烷基化择形催化性能的研究

Core/shell-Structured ZSM-5@Mesoporous Silica Composites for Shape-Selective Alkylation of Toluene with Methanol

PDF

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Dong Sun, Bo Sun, Yan Pei, Shirun Yan, Kangnian Fan, Minghua Qiao, Xiaoxin Zhang, Baoning Zong. Effect of Shell Thickness on Skeletal Fe@HZSM-5 Core-Shell Catalysts for Fischer-Tropsch Synthesis [J]. Acta Chimica Sinica, 2021, 79(6): 771-777.
[2]	Yang Xiaodong, Wang Xinmiao, Gao Shanbin, Wang Anjie. Hydrodesulfurization Performances of Pd Catalysts Supported on ZSM-5/MCM-41 Composite Zeolite [J]. Acta Chim. Sinica, 2017, 75(5): 479-484.
[3]	Wang Xin, Tan Lili, Yang Yingwei. Controlled Drug Release Systems Based on Mesoporous Silica Capped by Gold Nanoparticles [J]. Acta Chim. Sinica, 2016, 74(4): 303-311.
[4]	Liu Delong, Lu Danfeng, Zhao Qiao, Chen Chen, Qi Zhimei. Large-area High-performance SERS Substrates Prepared with a Combination of Mesoporous Silica Film and AuAg Alloy film [J]. Acta Chim. Sinica, 2015, 73(1): 41-46.
[5]	Lin Jiehua, Zhang Huihui, Shao Meijia. A Label-free Immunosensor based on Ionic Liquids Modified Mesoporous Silica for Simultaneous Determination of Two Tumor Markers [J]. Acta Chimica Sinica, 2014, 72(2): 241-245.
[6]	Jiang Chunjie, Sun Shengnan, Wang Xuyang, Wang Xiangsheng, Guo Hongchen, Guo Xinwen, Chen Lidong. Synthesis of Dimethyl Ether from Methanol over Heteropoly Acid/Nanocrystalline HZSM-5 Complex Solid Acidic Catalyst [J]. Acta Chimica Sinica, 2013, 71(05): 810-814.
[7]	Cao Yanfeng, Wang Jinguo, Qiao Jieqiong, Wan Huixin, Li Hexing, Zhu Jian. Adsorption-Photocatalytic Synergistic Removal of Toluene Vapor in Air on ZSM-5-TiO₂ Composites [J]. Acta Chimica Sinica, 2013, 71(04): 567-572.
[8]	Zhang Jianbo, Yang Yuxiang, Tian Meijuan, Deng Changjian, Cao Lei, Yuan Hongming. Synthesis of Worm-like Mesoporous Silica and Enzymatic Activity of the Immobilized Laccase [J]. Acta Chimica Sinica, 2013, 71(04): 602-612.
[9]	YU Chao, QIN Feng, XIONG De-Sheng, HOU Lei, SHEN Wei, XU Hua-Long. Coking and Modification of MgO on Ga₂O₃/HZSM-5 for Dehydrogenation of Ethane to Ethylene [J]. Acta Chimica Sinica, 2011, 69(20): 2413-2419.
[10]	LI Meng, YU Jian-Chang. Synthesis and Phase Transition of Ordered Mesoporous Carbon [J]. Acta Chimica Sinica, 2011, 69(02): 226-230.
[11]	TANG Qian-Qian, YUAN Li, YANG Dong, HU Jian-Hua. Preparation and Characterization of Disulfide Bond Functionalized Mesoporous Silica Microspheres [J]. Acta Chimica Sinica, 2010, 68(18): 1925-1929.
[12]	YIN An-Yuan, GUO Xiao-Yang, DAI Wei-Lin-*, FAN Kang-Nian. Textural Structure Effect of SiO₂ on the Catalytic Performance for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol over Different Cu-based Catalysts [J]. Acta Chimica Sinica, 2010, 68(13): 1285-1290.
[13]	Hu Jian-Hua. Preparation of Multi-responsive Mesoporous Silica Microspheres and Its Application in Controlled Drug Release [J]. Acta Chimica Sinica, 2009, 67(8): 843-849.
[14]	. Adsorption Behavior of NPE on Ordered Mesoporous Carbons [J]. Acta Chimica Sinica, 2009, 67(2): 1771-1778.
[15]	. Effect of Plasmas on C2H4 in the Combined System of Dielectric Barrier Discharge Plasmas and CuZSM-5 [J]. Acta Chimica Sinica, 2009, 67(15): 1779-1783.