Co或Ni促进的Cu/SiO2-Al2O3催化剂上丙三醇和苯胺气相合成3-甲基吲哚

doi:10.3866/PKU.WHXB201309091

摘要/Abstract

摘要：

对丙三醇和苯胺在Co或Ni促进的Cu/SiO₂-Al₂O₃催化剂上气相合成3-甲基吲哚进行了研究.采用N₂吸附、氢气程序升温还原(H₂-TPR)、电感耦合等离子体(ICP)发射光谱、X射线衍射(XRD)、透射电子显微镜(TEM)、氨程序升温脱附(NH₃-TPD)及热重(TG)分析等技术对催化剂进行了表征.结果表明,向Cu/SiO₂-Al₂O₃催化剂加入钴或镍助剂改善了催化剂的催化性能,钴比镍更加有效.在催化剂Cu-Co/SiO₂-Al₂O₃和Cu-Ni/SiO₂-Al₂O₃上,反应第3h,3-甲基吲哚收率分别达到47%和45%,而且催化剂经过6次再生收率仍能达到44%和42%.各种表征表明,向Cu/SiO₂-Al₂O₃催化剂加入钴或镍助剂能增强铜和载体之间的相互作用,其结果不仅促进了铜粒子在载体表面的分散度,而且有效减少了反应过程中铜组分的流失.另外,加入钴或镍助剂还能减少催化剂的中强酸中心数,从而提高3-甲基吲哚的选择性,并且抑制积炭的形成.此外,钴助剂还能增加催化剂的弱酸中心数,促进3-甲基吲哚的生成.提出了金属铜与弱酸中心共同促进3-甲基吲哚合成的催化反应机理.

关键词: Cu/SiO₂-Al₂O₃, 钴, 镍, 3-甲基吲哚, 丙三醇, 苯胺

Abstract:

This paper investigated the vapor-phase synthesis of 3-methylindole from glycerol and aniline over the catalyst of Cu/SiO₂-Al₂O₃ modified by Co or Ni. The catalysts were characterized by N₂ adsorption, H₂ temperature-programmed reduction (H₂-TPR), inductively coupled plasma (ICP) emission spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed desorption of ammonia (NH₃-TPD), and thermogravimetric (TG) analysis. The results indicated that adding Co or Ni to Cu/SiO₂-Al₂O₃ improved the performance of the catalyst and Co exhibited higher efficiency than Ni. The yields of 3-methylindole over Cu-Co/SiO₂-Al₂O₃ and Cu-Ni/SiO₂-Al₂O₃ reached 47% and 45%, respectively at the third hour of reaction and the yields remained 44% and 42% after the catalysts were regenerated six times. The characterizations revealed that the addition of Co or Ni to Cu/SiO₂-Al₂O₃ improved the interaction between copper and the support, which promoted the dispersion of Cu particles on the surface of the support, and also prevented the loss of the copper component during the reaction. Furthermore, Co or Ni promoter decreased the amount of the middle-strong acid sites on the catalyst surface, which gave rise to a high selectivity for 3-methylindole, and inhibited the formation of the coke. In addition, Co promoter increased the amount of the weak acid sites on the catalyst, which was favorable for the production of 3-methylindole. Acatalytic mechanism in which copper and weak acid sites acted together to promote the formation of 3-methylindole was proposed.

Key words: Cu/SiO₂-Al₂O₃, Cobalt, Nickel, 3-Methylindole, Glycerol, Aniline

MSC2000:

O643

包卓然, 崔艳喜, 孙鹏, 孙琪, 石雷. Co或Ni促进的Cu/SiO₂-Al₂O₃催化剂上丙三醇和苯胺气相合成3-甲基吲哚[J]. 物理化学学报, 2013, 29(11): 2444-2450.

BAO Zhuo-Ran, CUI Yan-Xi, SUN Peng, SUN Qi, SHI Lei. Vapor-Phase Synthesis of 3-Methylindole from Glycerol and Aniline over Cu/SiO₂-Al₂O₃ Catalyst Modified by Co or Ni[J]. Acta Phys. -Chim. Sin., 2013, 29(11): 2444-2450.

参考文献

(1) Kamijo, S.; Yamamoto, Y. J. Org. Chem. 2003, 68 (12), 4764.doi: 10.1021/jo034254p
(2) Hulcoop, D. G.; Lautens, M. Org. Lett. 2007, 9 (9), 1761. doi: 10.1021/ol070475w
(3) Xie, C. S.; Zhang, Y. H.; Huang, Z. D.; Xu, P. X. J. Org. Chem.2007, 72 (14), 5431. doi: 10.1021/jo070625g
(4) Howe-Grant, M. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.; JohnWiley & Sons: New York, 1989; pp213-215.
(5) Howe-Grant, M. Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; JohnWiley & Sons: New York, 1995; pp161-162.
(6) Yin, B.; Gu, J. D. Hum. Ecol. Risk Assess. 2006, 12 (2), 248.doi: 10.1080/10807030500531539
(7) Doran, E.; Whittington, F.W.;Wood, J. D.; McGivan, J. D.Chem. Biol. Interact. 2002, 140 (1), 81. doi: 10.1016/S0009-2797(02)00015-7
(8) Chen, G.; Cue, R. A.; Lundstrom, K.;Wood, J. G.; Doran, O.Drug Metab. Dispos. 2008, 36 (1), 56.
(9) Weems, J. M.; Yost, G. S. Chem. Res. Toxicol. 2010, 23 (3),696. doi: 10.1021/tx9004506
(10) Deslandes, B.; Gariépy, C.; Houde, A. Livest. Prod. Sci. 2001,71 (9), 193.
(11) Bandini, M.; Eichholzer, A. Angew. Chem. Int. Edit. 2009, 48 (51), 9608. doi: 10.1002/anie.200901843
(12) Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106 (7),2875. doi: 10.1021/cr0505270
(13) Simoneau, C. A.; Strohl, A. M.; Ganem, B. Tetrahedron Lett.2007, 48 (10), 1809. doi: 10.1016/j.tetlet.2007.01.031
(14) Robinson, B. Chem. Rev. 1963, 63 (4), 373. doi: 10.1021/cr60224a003
(15) Magnus, P.; Mitchell, L. S. Tetrahedron Lett. 1998, 39 (26),4595. doi: 10.1016/S0040-4039(98)00847-8
(16) Cho, C. S.; Kim, J. H.; Kim, T. J.; Shim, S. C. Tetrahedron2001, 57 (16), 3321. doi: 10.1016/S0040-4020(01)00202-2
(17) Gopal, D. V.; Srinivas, B.; Durgakumari, V.; Subrahmanyam, M.Appl. Catal. A 2002, 224 (1-2), 121. doi: 10.1016/S0926-860X(01)00787-6
(18) Siwach, P.; Singh, S.; Gupta, R. K. Catal. Commun. 2009, 10 (12), 1577. doi: 10.1016/j.catcom.2009.04.019
(19) Campanati, M.; Franceschini, S.; Piccolo, O.; Vaccari, A.J. Catal. 2005, 232 (1), 1. doi: 10.1016/j.jcat.2005.02.014
(20) Zheng, J. C.; Liu, J.; Tan,W.; Shi, L.; Sun, Q. Chin. J. Catal.2008, 29 (12), 1199. [郑佳聪, 刘静, 谭伟, 石雷, 孙琪. 催化学报, 2008, 29 (12), 1199.] doi: 10.1016/S1872-2067(09)60025-5
(21) Hu, Y.; Lü,W. H.; Liu, D. Y.; Liu, J.; Shi, L.; Sun, Q. J. Nat. Gas Chem. 2009, 18 (4), 445. doi: 10.1016/S1003-9953(08)60139-5
(22) Lü,W. H.; Liu, X. H.; Liu, D. Y.; Shi, L.; Sun, Q. Chin. J. Catal.2009, 30 (12), 1287. [吕文辉, 刘兴海, 刘冬妍, 石雷, 孙琪. 催化学报, 2009, 30 (12), 1287.] doi: 10.1016/S1872-2067(08)60145-X
(23) Zhou, C. H.; Beltramini, J. N.; Fan, Y. X.; Lu, G. Q. Chem. Soc. Rev. 2008, 37 (3), 527. doi: 10.1039/b707343g
(24) Balaraju, M.; Rekha, V.; Prasad, P. S. S.; Prasad, R. B. N.;Lingaiah, N. Catal. Lett. 2008, 126 (1-2), 119. doi: 10.1007/s10562-008-9590-6
(25) Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F.Green Chem. 2008, 10 (1), 13. doi: 10.1039/b710561d
(26) Guo, X. H.; Li, Y.; Song,W.; Shen,W. J. Catal. Lett. 2011, 141 (10), 1458. doi: 10.1007/s10562-011-0642-y
(27) Skaf, D.W.; Natrin, N. G.; Brodwater, K. C.; Bongo, C. R.Catal. Lett. 2012, 142 (10), 1175. doi: 10.1007/s10562-012-0886-1
(28) Sun,W.; Liu, D. Y.; Zhu, H. Y.; Shi, L.; Sun, Q. Catal. Commun.2010, 12 (2), 147. doi: 10.1016/j.catcom.2010.08.011
(29) Wang, Z. Y.; Li, X. H.; Zhang, Y.; Sun, Q.; Shi, L. Chin. J. Catal. 2012, 33 (7), 1139. [王兆宇, 李晓辉, 张跃, 孙琪,石雷. 催化学报, 2012, 33 (7), 1139.]
(30) Zhang, Y.; Sun,W.; Shi, L.; Sun, Q. Chin. J. Catal. 2012, 33 (6),1055. [张跃, 孙薇, 石雷, 孙琪. 催化学报, 2012, 33 (6), 1055.]
(31) Li, X. S.; Hou, Z. S.;Wei, Z. B.; Xin, Q. Acta Phys. -Chim. Sin.1991, 7 (6), 673. [李新生, 侯震山, 魏昭彬, 辛勤. 物理化学学报, 1991, 7 (6), 673.]
(32) Zhan, Y. Y.; Cai, G. H.; Zheng, Y.; Shen, Y. N.; Zheng, Y.;Wei,K. M. Acta Phys. -Chim. Sin. 2008, 24 (1), 171. [詹瑛瑛, 蔡国辉, 郑勇, 沈小女, 郑瑛, 魏可镁. 物理化学学报, 2008, 24 (1), 171.] doi: 10.3866/PKU.WHXB20080131
(33) Wen, C.; Cui, Y. Y.; Yin, A. Y.; Fan, K. N.; Dai,W. L.ChemCatChem 2013, 5 (1), 138. doi: 10.1002/cctc.201200444
(34) Wu, M.; Chou, L. J.; Song, H. L. Catal. Lett. 2012, 142 (5),627. doi: 10.1007/s10562-012-0792-6
(35) Ji, D. H.; Zhu,W. C.;Wang, Z. L.;Wang, G. J. Catal. Commun.2007, 8 (12), 1891. doi: 10.1016/j.catcom.2007.03.001
(36) Tian, P.; Liu, Z. M.;Wu, Z. B.; Xu, L.; He, Y. L. Catal. Today2004, 93 -95, 735.
(37) Mane, R. B.; Rode, C. V. Green Chem. 2012, 14 (10), 2780. doi: 10.1039/c2gc35661a
(38) Zhao, J.; Yu,W. Q.; Chen, C.; Miao, H.; Ma, H.; Xu, J. Catal. Lett. 2010, 134 (1-2), 184. doi: 10.1007/s10562-009-0208-4
(39) Dasari, M. A.; Kiatsimkul, P. P.; Sutterlin,W. R.; Suppes, G. J.Appl. Catal. A 2005, 281 (1-2), 225. doi: 10.1016/j.apcata.2004.11.033
(40) Huang, Z.W.; Cui, F.; Kang, H. X.; Chen, J.; Zhang, X. Z.; Xia,C. G. Chem. Mater. 2008, 20 (15), 5090. doi: 10.1021/cm8006233

[1]	张继宏, 钟地长, 鲁统部. 钴(Ⅱ)基分子配合物用于光催化二氧化碳还原[J]. 物理化学学报, 2021, 37(5): 2008068 -0 .
[2]	谢安, 潘中华, 骆耿耿. 一类受生物启发的双膦双硒镍配合物的合成及其电催化产氢性能[J]. 物理化学学报, 2021, 37(3): 1910058 -0 .
[3]	王玖,吴南石,刘涛,曹少文,余家国. 用于超级电容器的锰钴氧化物/碳纤维材料[J]. 物理化学学报, 2020, 36(7): 1907072 -0 .
[4]	潘志明,刘明辉,牛萍萍,郭芳松,付贤智,王心晨. Ni₂P纳米片用于光催化二氧化碳还原[J]. 物理化学学报, 2020, 36(1): 1906014 -0 .
[5]	王露, 孙威, 刘超. 同核铁系双金属络合物及其在均相催化体系中的应用[J]. 物理化学学报, 2019, 35(7): 697 -708 .
[6]	赵喆, 卢岳, 张振华, 隋曼龄. 原位透射电子显微镜观察电荷驱动的氧化物纳米颗粒水中自组装[J]. 物理化学学报, 2019, 35(5): 539 -545 .
[7]	张书山,周剑章,吴德印,田中群. Ag纳米粒子修饰光纤探针在等离激元催化反应中的应用[J]. 物理化学学报, 2019, 35(3): 307 -316 .
[8]	申海波,江浩,刘易斯,郝佳瑜,李文章,李洁. 氮、硫共掺杂的碳负载的钴@碳化钴:一种高效的非贵金属氧还原电催化剂[J]. 物理化学学报, 2017, 33(9): 1811 -1821 .
[9]	钱慧慧,韩潇,肇研,苏玉芹. 柔性Pd@PANI/rGO纸阳极在甲醇燃料电池中的应用[J]. 物理化学学报, 2017, 33(9): 1822 -1827 .
[10]	廖珮懿,张辰,张丽君,杨彦章,钟良枢,郭晓亚,王慧,孙予罕. Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响[J]. 物理化学学报, 2017, 33(8): 1672 -1680 .
[11]	连超,张垲,王远. 氧化铁负载铂纳米簇催化卤代硝基苯本体氢化性质研究[J]. 物理化学学报, 2017, 33(5): 984 -992 .
[12]	甄绪,郭雪静. 三维介孔钴酸锌立方体的制备及其优异的储锂性能[J]. 物理化学学报, 2017, 33(4): 845 -852 .
[13]	黄明辉,金碧瑶,赵莲花,孙世刚. PtNiSnO₂/C的制备、表征及其电催化氧化乙醇活性[J]. 物理化学学报, 2017, 33(3): 563 -572 .
[14]	曾向东,赵晓昱,韦会鸽,王彦飞,唐娜,沙作良. 聚苯胺-还原氧化石墨烯复合材料的比电容及超级电容性能[J]. 物理化学学报, 2017, 33(10): 2035 -2041 .
[15]	翁小龙,王艳,贾春阳,万中全,陈喜明,姚小军. 新型四硫富瓦烯-三苯胺类光敏染料理论研究[J]. 物理化学学报, 2016, 32(8): 1990 -1998 .

Co或Ni促进的Cu/SiO₂-Al₂O₃催化剂上丙三醇和苯胺气相合成3-甲基吲哚

Vapor-Phase Synthesis of 3-Methylindole from Glycerol and Aniline over Cu/SiO₂-Al₂O₃ Catalyst Modified by Co or Ni

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 0