Citation: HAO Wenwen, ZHAO Dan, LI Yanchun, CHU Wenling, LÜ Chengwei, SHI Lei. One-Pot Efficient Synthesis of 3-Methylindole from Biomass-Derived Glycerol with Aniline by Highly Dispersible Nanosilver Catalyst[J]. Chinese Journal of Applied Chemistry, ;2019, 36(4): 465-473. doi: 10.11944/j.issn.1000-0518.2019.04.180265 shu

One-Pot Efficient Synthesis of 3-Methylindole from Biomass-Derived Glycerol with Aniline by Highly Dispersible Nanosilver Catalyst

HAO Wenwen ^a ,
ZHAO Dan ^a ,
LI Yanchun ^b ,
CHU Wenling ^c ,
LÜ Chengwei ^a ,
SHI Lei ^a,,

a.
College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, Liaoning 116029, China
b.
Institute of Theoretical Chemistry, Jilin University, Changchun 130021, China
c.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China

Corresponding author: SHI Lei, shilei515dl@126.com
Received Date: 15 August 2018
Revised Date: 11 September 2018
Accepted Date: 23 October 2018

Fund Project: the National Natural Science Foundation of China 21604031Supported by the National Natural Science Foundation of China(No.21576128, No.21604031, No.21403100)the National Natural Science Foundation of China 21576128the National Natural Science Foundation of China 21403100

Figures(9)

A highly dispersible nanosilver catalyst of ZnO modified Ag/SiO₂ was successfully applied to the one-pot efficient synthesis of 3-methylindole from aniline and biomass-derived glycerol for the first time. The catalyst exhibited an excellent catalytic performance. The investigations of Ag-based catalysts via X-ray diffraction(XRD), transmission electron microscopy(TEM), temperature programmed reduction of H₂(H₂-TPR), temperature programmed desorption(TPD) of NH₃ or CO₂, thermogravimetric(TG) analysis and inductively coupled plasma(ICP) emission spectroscopy indicate that ZnO can enhance the interaction between silver and the support and make Ag particles be firmly anchored on the support of SiO₂-ZnO. As a result, not only the dispersion of silver is increased obviously, but also the aggregation or sintering of silver nanoparticles is inhibited effectively. In addition, ZnO can also increase the acid and base sites of the Ag-based catalyst significantly, which is very beneficial to the hydrogenolysis of glycerol to 1, 2-propanediol and promoted the synthesis of 3-methylindole greatly. The yield of 3-methylindole is up to 64% at the reaction time of 16 h and is only decreased by 4% after Ag/SiO₂-ZnO is reused four times. Furthermore, the synthesis mechanism of 3-methylindole from glycerol and aniline over Ag/SiO₂-ZnO catalyst was proposed, in which 1, 2-propanediol is the intermediate to produce 3-methylindole.
- ZnO,
- Ag/SiO₂,
- 3-methylindole,
- biomass-derived glycerol,
- catalytic performance
1. [1]
  Zhang M Z, Chen Q, Yang G F. A Review on Recent Developments of Indole-Containing Antiviral Agents[J]. Eur J Med Chem, 2015,89:421-441. doi: 10.1016/j.ejmech.2014.10.065
2. [2]
  Cho I, Jeon N J, Kwon O K. Indolo[3, 2-B] Indole-Based Crystalline Hole-Transporting Material for Highly Efficient Perovskite Solar Cells[J]. Chem Sci, 2017,8(1):734-741.
3. [3]
  Liu D Y, Huo X M, Liu J. The Role of La₂O₃ and CeO₂ Promoters in the Ag/SiO₂-ZnO Catalyst for the Vapor Phase Synthesis of Indole[J]. React Kinet Mech Catal, 2010,99(2):335-343.
4. [4]
  Siwach P, Singh S, Gupta R K. Vapor Phase Alkylation of Indole with Methanol and Dimethylcarbonate over Ni-Mn Based Ferrospinels[J]. Catal Commun, 2009,10(12):1577-1581. doi: 10.1016/j.catcom.2009.04.019
5. [5]
  Zhou Z, Li Y, Gong L. Enantioselective 2-Alkylation of 3-Substituted Indoles with Dual Chiral Lewis Acid/Hydrogen-Bond-Mediated Catalyst[J]. Org Lett, 2017,19(1):222-225. doi: 10.1021/acs.orglett.6b03500
6. [6]
  Deslandes B, Gariépy C, Houde A. Review of Microbiological and Biochemical Effects of Skatole on Animal Production[J]. Livest Prod Sci, 2001,71(2/3):193-200.
7. [7]
  Hughes D T, Pelletier J, Luetje C W. Odorant Receptor from the Southern House Mosquito Narrowly Tuned to the Oviposition Attractant Skatole[J]. J Chem Ecol, 2010,36(8):797-800. doi: 10.1007/s10886-010-9828-9
8. [8]
  Simoneau C A, Strohl A M, Ganem B. One-Pot Synthesis of Polysubstituted Indoles from Aliphatic Nitro Compounds under Mild Conditions[J]. Tetrahedron Lett, 2007,48(10):1809-1811. doi: 10.1016/j.tetlet.2007.01.031
9. [9]
  Robinson B. The Fischer Indole Synthesis[J]. Chem Rev, 1963,63(4):373-401. doi: 10.1021/cr60224a003
10. [10]
  Magnus P, Mitchell I S. Synthesis of 3-Methylindoles from N-Aryl-N-(3-Triisopropyl Silylpropargyl) Sulfonamides[J]. Tetrahedron Lett, 1998,39(26):4595-4598. doi: 10.1016/S0040-4039(98)00847-8
11. [11]
  Yu J, Xu J, Yu Z. A Continuous-Flow Fischer Indole Synthesis of 3-Methylindole in an Ionic Liquid[J]. J Flow Chem, 2017,7(2):33-36. doi: 10.1556/1846.2017.00004
12. [12]
  Ritter S K. Biomass or Bust[J]. Chem Eng News, 2004,82(22):31-32. doi: 10.1021/cen-v082n022.p031
13. [13]
  Sabri Faezeh, Idem R, Ibrahim H. Metal Oxide-Based Catalysts for the Autothermal Reforming of Glycerol[J]. Ind Eng Chem Res, 2018,57(7):2486-2497. doi: 10.1021/acs.iecr.7b04582
14. [14]
  ZHAO Jing, YU Weiqiang, LI Decai. Catalytic Dehydration-Hydrogenation of Glycerol to 1, 2-Propylene Glycol at Ambient Hydrogen Pressure[J]. Chinese J Catal, 2010,31(2):74-78.
15. [15]
  Sun W, Liu D Y, Zhu H Y. A New Efficient Approach to 3-Methylindole:Vapor-Phase Synthesis from Aniline and Glycerol over Cu-Based Catalyst[J]. Catal Commun, 2010,12(2):147-150.
16. [16]
  Cui Y X, Zhou X S, Sun Q. Vapor-Phase Synthesis of 3-Methylindole from Glycerol and Aniline over Zeolites-Supported Cu-Based Catalysts[J]. J Mol Catal A:Chem, 2013,378:238-245. doi: 10.1016/j.molcata.2013.06.015
17. [17]
  BAO Zhuoran, CUI Yanxi, SUN Peng. 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. doi: 10.3866/PKU.WHXB201309091
18. [18]
  BAO Zhuoran, HUO Xiaomin, SUN Lidong. Efficient Vapor-Phase Synthesis of 3-Methylindole over Fe Promoted Cu/SiO₂-Al₂O₃ Catalyst[J]. Chinese J Appl Chem, 2013,30(10):1156-1162.
19. [19]
  Wen C, Yin A, Dai W L. Recent Advances in Silver-Based Heterogeneous Catalysts for Green Chemistry Processes[J]. Appl Catal B:Environ, 2014,160/161:730-741. doi: 10.1016/j.apcatb.2014.06.016
20. [20]
  AbdelDayem H M, Al-Shihry S S, Hassan S A. Selective Methanol Oxidation to Hydrogen over Ag/ZnO Catalysts Doped with Mono-and Bi-Rare Earth Oxides[J]. Ind Eng Chem Res, 2014,53(51):19884-19894. doi: 10.1021/ie502609z
21. [21]
  Liu S, Wu X, Liu W. Soot Oxidation over CeO₂ and Ag/CeO₂:Factors Determining the Catalyst Activity and Stability During Reaction[J]. J Catal, 2016,337:188-198. doi: 10.1016/j.jcat.2016.01.019
22. [22]
  LV Wenhui, LIU Xinghui, LIU Dongyan. Vapor-Phase Synthesis of 3-Methylindole over Fe-, Co-, or Ni-Promoted Ag/SiO₂ Catalysts[J]. Chinese J Catal, 2009,30(12):1287-1290. doi: 10.3321/j.issn:0253-9837.2009.12.018
23. [23]
  Liu J, Li X, Zhao Q. Mechanistic Investigation of the Enhanced NH₃-SCR on Cobalt-Decorated Ce-Ti Mixed Oxide:In Situ FTIR Analysis for Structure-Activity Correlation[J]. Appl Catal B:Environ, 2017,200:297-308. doi: 10.1016/j.apcatb.2016.07.020
24. [24]
  Kusunoki Y, Miyazawa T, Kunimori K. Highly Active Metal Acid Bifunctional Catalyst System for Hydrogenolysis of Glycerol under Mild Reaction Conditions[J]. Catal Commun, 2005,6(10):645-649. doi: 10.1016/j.catcom.2005.06.006
25. [25]
  Feng J, Wang J, Zhou Y. Effect of Base Additives on the Selective Hydrogenolysis of Glycerol over Ru/TiO₂ Catalyst[J]. Chem Lett, 2007,36(10):1274-1275. doi: 10.1246/cl.2007.1274
1. [1]
  Siyu HOU , Weiyao LI , Jiadong LIU , Fei WANG , Wensi LIU , Jing YANG , Ying ZHANG . Preparation and catalytic performance of magnetic nano iron oxide by oxidation co-precipitation method. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1577-1582. doi: 10.11862/CJIC.20230469
2. [2]
  Bing Shen , Tongwei Yuan , Wenshuang Zhang , Yang Chen , Jiaqiang Xu . Complex shell Fe-ZnO derived from ZIF-8 as high-quality acetone MEMS sensor. Chinese Chemical Letters, 2024, 35(11): 109490-. doi: 10.1016/j.cclet.2024.109490
3. [3]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
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]
  Min WANG , Dehua XIN , Yaning SHI , Wenyao ZHU , Yuanqun ZHANG , Wei ZHANG . Construction and full-spectrum catalytic performance of multilevel Ag/Bi/nitrogen vacancy g-C₃N₄/Ti₃C₂T_x Schottky junction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1123-1134. doi: 10.11862/CJIC.20230477
6. [6]
  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
7. [7]
  Zhiwen HU , Weixia DONG , Qifu BAO , Ping LI . Low-temperature synthesis of tetragonal BaTiO₃ for piezocatalysis. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 857-866. doi: 10.11862/CJIC.20230462
8. [8]
  Zhiwen HU , Ping LI , Yulong YANG , Weixia DONG , Qifu BAO . Morphology effects on the piezocatalytic performance of BaTiO₃. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 339-348. doi: 10.11862/CJIC.20240172
9. [9]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
10. [10]
  Qianqian Liu , Xing Du , Wanfei Li , Wei-Lin Dai , Bo Liu . Synergistic Effects of Internal Electric and Dipole Fields in SnNb₂O₆/Nitrogen-Enriched C₃N₅ S-Scheme Heterojunction for Boosting Photocatalytic Performance. Acta Physico-Chimica Sinica, 2024, 40(10): 2311016-. doi: 10.3866/PKU.WHXB202311016
11. [11]
  Xiuzheng Deng , Yi Ke , Jiawen Ding , Yingtang Zhou , Hui Huang , Qian Liang , Zhenhui Kang . Construction of ZnO@CDs@Co₃O₄ sandwich heterostructure with multi-interfacial electron-transfer toward enhanced photocatalytic CO₂ reduction. Chinese Chemical Letters, 2024, 35(4): 109064-. doi: 10.1016/j.cclet.2023.109064
12. [12]
  Xin Zhou , Zhi Zhang , Yun Yang , Shuijin Yang . A Study on the Enhancement of Photocatalytic Performance in C/Bi/Bi₂MoO₆ Composites by Ferroelectric Polarization: A Recommended Comprehensive Chemical Experiment. University Chemistry, 2024, 39(4): 296-304. doi: 10.3866/PKU.DXHX202310008
13. [13]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
14. [14]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
15. [15]
  Jiaxing Cai , Wendi Xu , Haoqiang Chi , Qian Liu , Wa Gao , Li Shi , Jingxiang Low , Zhigang Zou , Yong Zhou . 具有0D/2D界面的InOOH/ZnIn₂S₄空心球S型异质结用于增强光催化CO₂转化性能. Acta Physico-Chimica Sinica, 2024, 40(11): 2407002-. doi: 10.3866/PKU.WHXB202407002
16. [16]
  Asif Hassan Raza , Shumail Farhan , Zhixian Yu , Yan Wu . 用于高效制氢的双S型ZnS/ZnO/CdS异质结构光催化剂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406020-. doi: 10.3866/PKU.WHXB202406020
17. [17]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
18. [18]
  Guang-Xu Duan , Queting Chen , Rui-Rui Shao , Hui-Huang Sun , Tong Yuan , Dong-Hao Zhang . Encapsulating lipase on the surface of magnetic ZIF-8 nanosphers with mesoporous SiO₂ nano-membrane for enhancing catalytic performance. Chinese Chemical Letters, 2025, 36(2): 109751-. doi: 10.1016/j.cclet.2024.109751
19. [19]
  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
20. [20]
  Dan Li , Hui Xin , Xiaofeng Yi . Comprehensive Experimental Design on Ni-based Catalyst for Biofuel Production. University Chemistry, 2024, 39(8): 204-211. doi: 10.3866/PKU.DXHX202312046

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(1147)
HTML views(59)

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