Citation: 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 Physico-Chimica Sinica, ;2013, 29(11): 2444-2450. doi: 10.3866/PKU.WHXB201309091 shu

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

1.
Institute of Chemistry for Functionalized Materials, Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China

Received Date: 14 June 2013
Available Online: 9 September 2013
Fund Project: 国家自然科学基金(21173110)资助项目 (21173110)

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.
- Cu/SiO₂-Al₂O₃,
- Cobalt,
- Nickel,
- 3-Methylindole,
- Glycerol,
- Aniline
1. [1]
  
  (1) Kamijo, S.; Yamamoto, Y. J. Org. Chem. 2003, 68 (12), 4764.doi: 10.1021/jo034254p
2. [2]
  (2) Hulcoop, D. G.; Lautens, M. Org. Lett. 2007, 9 (9), 1761. doi: 10.1021/ol070475w
3. [3]
  (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. [4]
  (4) Howe-Grant, M. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.; JohnWiley & Sons: New York, 1989; pp213-215.
5. [5]
  (5) Howe-Grant, M. Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; JohnWiley & Sons: New York, 1995; pp161-162.
6. [6]
  (6) Yin, B.; Gu, J. D. Hum. Ecol. Risk Assess. 2006, 12 (2), 248.doi: 10.1080/10807030500531539
7. [7]
  (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. [8]
  (8) Chen, G.; Cue, R. A.; Lundstrom, K.;Wood, J. G.; Doran, O.Drug Metab. Dispos. 2008, 36 (1), 56.
9. [9]
  (9) Weems, J. M.; Yost, G. S. Chem. Res. Toxicol. 2010, 23 (3),696. doi: 10.1021/tx9004506
10. [10]
  (10) Deslandes, B.; Gariépy, C.; Houde, A. Livest. Prod. Sci. 2001,71 (9), 193.
11. [11]
  (11) Bandini, M.; Eichholzer, A. Angew. Chem. Int. Edit. 2009, 48 (51), 9608. doi: 10.1002/anie.200901843
12. [12]
  (12) Humphrey, G. R.; Kuethe, J. T. Chem. Rev. 2006, 106 (7),2875. doi: 10.1021/cr0505270
13. [13]
  (13) Simoneau, C. A.; Strohl, A. M.; Ganem, B. Tetrahedron Lett.2007, 48 (10), 1809. doi: 10.1016/j.tetlet.2007.01.031
14. [14]
  (14) Robinson, B. Chem. Rev. 1963, 63 (4), 373. doi: 10.1021/cr60224a003
15. [15]
  (15) Magnus, P.; Mitchell, L. S. Tetrahedron Lett. 1998, 39 (26),4595. doi: 10.1016/S0040-4039(98)00847-8
16. [16]
  (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. [17]
  (17) pal, 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. [18]
  (18) Siwach, P.; Singh, S.; Gupta, R. K. Catal. Commun. 2009, 10 (12), 1577. doi: 10.1016/j.catcom.2009.04.019
19. [19]
  (19) Campanati, M.; Franceschini, S.; Piccolo, O.; Vaccari, A.J. Catal. 2005, 232 (1), 1. doi: 10.1016/j.jcat.2005.02.014
20. [20]
  (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. [21]
  (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. [22]
  (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. [23]
  (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. [24]
  (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. [25]
  (25) Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F.Green Chem. 2008, 10 (1), 13. doi: 10.1039/b710561d
26. [26]
  (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. [27]
  (27) Skaf, D.W.; Natrin, N. G.; Brodwater, K. C.; Bon , C. R.Catal. Lett. 2012, 142 (10), 1175. doi: 10.1007/s10562-012-0886-1
28. [28]
  (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. [29]
  (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. [30]
  (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. [31]
  (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. [32]
  (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. [33]
  (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. [34]
  (34) Wu, M.; Chou, L. J.; Song, H. L. Catal. Lett. 2012, 142 (5),627. doi: 10.1007/s10562-012-0792-6
35. [35]
  (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. [36]
  (36) Tian, P.; Liu, Z. M.;Wu, Z. B.; Xu, L.; He, Y. L. Catal. Today2004, 93 -95, 735.
37. [37]
  (37) Mane, R. B.; Rode, C. V. Green Chem. 2012, 14 (10), 2780. doi: 10.1039/c2gc35661a
38. [38]
  (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. [39]
  (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. [40]
  (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. [1]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
2. [2]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Corrosion inhibition of nickel-cobalt-phosphide in water by coating TiO₂ layer. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 365-384. doi: 10.11862/CJIC.20240063
3. [3]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
4. [4]
  Yifeng TAN , Ping CAO , Kai MA , Jingtong LI , Yuheng WANG . Synthesis of pentaerythritol tetra(2-ethylthylhexoate) catalyzed by h-MoO₃/SiO₂. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2155-2162. doi: 10.11862/CJIC.20240147
5. [5]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
6. [6]
  Zhicheng JU , Wenxuan FU , Baoyan WANG , Ao LUO , Jiangmin JIANG , Yueli SHI , Yongli CUI . MOF-derived nickel-cobalt bimetallic sulfide microspheres coated by carbon: Preparation and long cycling performance for sodium storage. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 661-674. doi: 10.11862/CJIC.20240363
7. [7]
  Hao GUO , Tong WEI , Qingqing SHEN , Anqi HONG , Zeting DENG , Zheng FANG , Jichao SHI , Renhong LI . Electrocatalytic decoupling of urea solution for hydrogen production by nickel foam-supported Co₉S₈/Ni₃S₂ heterojunction. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2141-2154. doi: 10.11862/CJIC.20240085
8. [8]
  Xinhao Yan , Guoliang Hu , Ruixi Chen , Hongyu Liu , Qizhi Yao , Jiao Li , Lingling Li . Polyethylene Glycol-Ammonium Sulfate-Nitroso R Salt System for the Separation of Cobalt (II). University Chemistry, 2024, 39(6): 287-294. doi: 10.3866/PKU.DXHX202310073
9. [9]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
10. [10]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480
11. [11]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
12. [12]
  Kaihui Huang , Boning Feng , Xinghua Wen , Lei Hao , Difa Xu , Guijie Liang , Rongchen Shen , Xin Li . Effective photocatalytic hydrogen evolution by Ti3C2-modified CdS synergized with N-doped C-coated Cu2O in S-scheme heterojunctions. Chinese Journal of Structural Chemistry, 2023, 42(12): 100204-100204. doi: 10.1016/j.cjsc.2023.100204
13. [13]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
14. [14]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
15. [15]
  Yuexiang Liu , Xiangqiao Yang , Tong Lin , Guantian Yang , Xiaoyong Xu , Bubing Zeng , Zhong Li , Weiping Zhu , Xuhong Qian . Efficient continuous synthesis of 2-[3-(trifluoromethyl)phenyl]malonic acid, a key intermediate of Triflumezopyrim, coupling with esterification-condensation-hydrolysis. Chinese Chemical Letters, 2025, 36(1): 109747-. doi: 10.1016/j.cclet.2024.109747
16. [16]
  Juan Guo , Mingyuan Fang , Qingsong Liu , Xiao Ren , Yongqiang Qiao , Mingju Chao , Erjun Liang , Qilong Gao . Zero thermal expansion in Cs₂W₃O₁₀. Chinese Chemical Letters, 2024, 35(7): 108957-. doi: 10.1016/j.cclet.2023.108957
17. [17]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
18. [18]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
19. [19]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
20. [20]
  Yuan ZHU , Xiaoda ZHANG , Shasha WANG , Peng WEI , Tao YI . Conditionally restricted fluorescent probe for Fe³⁺ and Cu²⁺ based on the naphthalimide structure. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 183-192. doi: 10.11862/CJIC.20240232

Get Citation

PDF

XML

Metrics

PDF Downloads(654)
Abstract views(1015)
HTML views(3)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

Metrics

通讯作者: 陈斌, bchen63@163.com

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