Citation: YANG Zhan-dong, MA En-juan, ZHANG Qian, LUAN Chun-hui, HUANG Wei. Catalytic performance of CuCoCe supported on nitrogen-doped carbon nanotubes for the synthesis of higher alcohols from syngas[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(7): 804-812. shu

Catalytic performance of CuCoCe supported on nitrogen-doped carbon nanotubes for the synthesis of higher alcohols from syngas

1.
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2.
Key Laboratory of Coal Science and Technology of Education Ministry and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China
3.
Coal Conversion Technology&Engineering Co., Ltd., TYUT, Taiyuan 030024, China

Corresponding author: HUANG Wei, huangwei@tyut.edu.cn
Received Date: 3 April 2020
Revised Date: 15 May 2020

Figures(5)

A series of nitrogen-doped carbon nanotubes (xN-CNTs) were obtained by treating the mixture of melamine and carbon nanotubes at high temperature; the CuCoCe catalysts supported on xN-CNTs were then prepared by impregnation method and used in the synthesis of higher alcohols from syngas. The CuCoCe/xN-CNTs catalysts were characterized by XRD, N₂ sorption, H₂-TPR, NH₃-TPD and XPS and the effect of nitrogen content in xN-CNTs on the catalytic performance of CuCoCe/xN-CNTs in the higher alcohols synthesis was investigated. The results show that the content of nitrogen in xN-CNTs has a significant influence on the existence and dispersion of Cu on the CuCoCe/xN-CNTs catalysts; the presence of nitrogen can reduce the number of reducible Co species and lower the acid strength and amount on the catalyst surface, which helps to suppress the long-chain hydrocarbons formation and improve total alcohol selectivity. It is proposed that the morphological distribution and doping amount of nitrogen on the carbon tubes may play a crucial role in enhancing the catalytic performance of CuCoCe/xN-CNTs in the higher alcohols synthesis.
- nitrogen doping,
- carbon nanotubes,
- syngas,
- higher alcohols,
- CuCoCe
1. [1]
  GUPTA M, SMITH M, SPIVEY J. Heterogeneous catalytic conversion of dry syngas to ethanol and higher alcohols on Cu-based catalysts[J]. ACS Catal, 2011,1(6):641-656. doi: 10.1021/cs2001048
2. [2]
  SUBRAMANI V, GANGWAL S K. A review of recent literature to search for an efficient catalytic process for the conversion of syngas to ethanol[J]. Energy Fuels, 2008,22(2):117-136.
3. [3]
  LUK H T, MONDELLI C, FERRÉ D C, STEWART J A, PÉREZ-RAMÍREZ J. Status and prospects in higher alcohols synthesis from syngas[J]. Chem Soc Rev, 2017,46(5):1358-1426. doi: 10.1039/C6CS00324A
4. [4]
  AO M, PHAM G H, SUNARSO J, TADE M, LIU S. Active centers of catalysts for higher alcohol synthesis from syngas:A review[J]. ACS Catal, 2018,8(8):7025-7050. doi: 10.1021/acscatal.8b01391
5. [5]
  XIAO K, BAO Z H, QI X Z, WANG X X. Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J]. Chin J Catal, 2013,34(1):116-129.
6. [6]
  XU, E-B-M-DOESBURG. Synthesis of higher alcohols from syngas-recently patented catalysts and tentative ideas on the mechanism[J]. Catal Today, 1987,2(1):125-170. doi: 10.1016/0920-5861(87)80002-0
7. [7]
  SHI L, WEI C, DENG S. Catalytic properties of Cu-Co catalysts supported on HNO₃-pretreated CNTs for higher-alcohol synthesis[J]. J Nat Gas Chem, 2011,1:53-57.
8. [8]
  FANG Y, LIU Y, DENG W. Cu-Co bi-metal catalyst prepared by perovskite CuO/LaCoO₃ used for higher alcohol synthesis from syngas[J]. J Energy Chem, 2014,4:527-534.
9. [9]
  ANTON J, NEBEL J, GÖBEL C, GABRYSCH J, SONG H, FROESE C, RULAND H, MUHLER M, KALVZA S. CO hydrogenation to higher alcohols over Cu-Co-based catalysts derived from hydrotalcite-type precursors[J]. Top Catal, 2016,59(15/16):1361-1370.
10. [10]
  HUANG C, ZHANG M, ZHU C. Fabrication of highly stable SiO₂ encapsulated multiple CuFe nanoparticles for higher alcohols synthesis via CO hydrogenation[J]. Catal Lett, 2018,148(4):1080-1092. doi: 10.1007/s10562-018-2329-0
11. [11]
  LIN M, FANG K, LI D. CO hydrogenation to mixed alcohols over co-precipitated Cu-Fe catalysts[J]. Catal Commun, 2008,9(9):1869-1873. doi: 10.1016/j.catcom.2008.03.004
12. [12]
  BAO Z, XIAO K, QI X. Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C₂₊OH[J]. J Energy Chem, 2013,22(1):107-113.
13. [13]
  CHEN T, SU J, ZHANG Z. Structure evolution of Co-CoO_x interface for higher alcohol synthesis from syngas over Co/CeO₂ catalysts[J]. ACS Catal, 2018,8(9):8606-8617. doi: 10.1021/acscatal.8b00453
14. [14]
  PEI Y, DING Y, ZHU H. Study on the effect of alkali promoters on the formation of cobalt carbide (Co₂C) and on the performance of Co₂C via CO hydrogenation reaction[J]. React Kinet Mech Catal, 2014,111(2):505-520. doi: 10.1007/s11144-013-0663-1
15. [15]
  ZHAO Z, LU W, YANG R. Insight into the formation of Co@Co₂C catalysts for direct synthesis of higher alcohols and olefins from syngas[J]. ACS Catal, 2017,8(1):228-241.
16. [16]
  PAN X L, BAO X H. The effects of confinement inside carbon nanotubes on catalysis[J]. Accounts Chem Res, 2011,44(8):553-562. doi: 10.1021/ar100160t
17. [17]
  PAN X L, BAO X H. Reactions over catalysts confined in carbon nanotubes[J]. Chem Commun, 2008,47:6271-6281.
18. [18]
  LEE W J, MAITI U N, LEE J M, LIM J, HAN T H, KIM S O. Nitrogen-doped carbon nanotubes and graphene composite structures for energy and catalytic applications[J]. Chem Commun, 2014,5(52):6683-6818.
19. [19]
  SOARES OS G P, ROCHA R P, GONÇALVES A G, FIGUEIREDO J L. Easy method to prepare N-doped carbon nanotubes by ball milling[J]. Carbon, 2015,91:114-121. doi: 10.1016/j.carbon.2015.04.050
20. [20]
  CHEN S, QI P, CHEN J. Platinum nanoparticles supported on N-doped carbon nanotubes for the selective oxidation of glycerol to glyceric acid in a base-free aqueous solution[J]. Rsc Adv, 2015,5:31566-31574. doi: 10.1039/C5RA02112J
21. [21]
  HE L, WENIGER F, NEUMANN H. Synthesis, characterization, and application of metal nanoparticles supported on nitrogen-doped carbon:Catalysis beyond elec[J]. Angew Chem Int Ed, 2016,55:12582-12594. doi: 10.1002/anie.201603198
22. [22]
  LU J Z, YANG L J, XU B L, W Q, ZHANG D, YUAN S J, ZHAI Y, WANG X Z, FAN Y N, HU Z. Promotion effects of nitrogen doping into carbon nanotubes on supported iron Fischer-Tropsch catalysts for lower olefins[J]. ACS Catal, 2013,4(2):613-621.
23. [23]
  FU T J, LI Z H. Highly dispersed cobalt on N-doped carbon nanotubes with improved Fischer-Tropsch synthesis activity[J]. Catal Commun, 2014,47:54-57. doi: 10.1016/j.catcom.2014.01.008
24. [24]
  SHI X P, YU H B, GAO S, LI X Y, FANG H H, LI R J, LI Y Y. Synergistic effect of nitrogen-doped carbon-nanotube-supported Cu-Fe catalyst for the synthesis of higher alcohols from syngas[J]. Fuel, 2017,210:241-248. doi: 10.1016/j.fuel.2017.08.064
25. [25]
  LI Zhi-wen, CHEN Cong-biao, WANG Jun-gang, LIN Ming-gui, HOU Bo, JIA Li-tao, LI De-bao. Nitrogen-doped mesoporous carbon supported FeCu bimetallic catalyst and its CO hydrogenation performance[J]. J Fuel Chem Technol, 2019,47(6):709-717. doi: 10.3969/j.issn.0253-2409.2019.06.008
26. [26]
  XIAO K, QI X Z, BAO Z H, WANG X X, ZHONG L S, FANG K G, LIN M G, SUN Y H. CuFe, CuCo and CuNi nanoparticles as catalysts for higher alcohol synthesis from syngas:A comparative study[J]. Catal Sci Technol, 2013,3(6):1162-1591.
27. [27]
  HAN Tao, HUANG Wei, WANG Xiao-dong, TANG Yu, LIU Shuang-qiang, YOU Xiang-xuan. Study of Ce-Cu-Co/CNTs Catalysts for the synthesis of higher alcohols and ethanol from syngas[J]. Acta Phys-Chim Sin, 2014,30(11):2127-2133. doi: 10.3866/PKU.WHXB201409121
28. [28]
  HANG Zu-sheng, TAN Ling-hua, JU Fa-yin, ZHOU Bin, YING San-jiu. Non-isothermal kinetic studies on the thermal decomposition of melamine by thermogravimetric analysis[J]. J Analyt Sci, 2011,27(3):279-283.
29. [29]
  KUNDU S, WANG Y, XIA W. Thermal stability and reducibility of oxygen-containing functional groups on multiwalled carbon nanotube surfaces:A quantitative high-resolution XPS and TPD/TPR study[J]. J Phys Chem C, 2008,112(43):16869-16878. doi: 10.1021/jp804413a
30. [30]
  TARAWNEH K M, AI-AQTASH N. Boron-and nitrogen-doped carbon nanotubes with surface defects:An Ab initio study(Article)[J]. J Comput Theor Nanos, 2013,6:1446-1452.
31. [31]
  AI P P, TAN M H, YAMANE N, LIU G G, FAN R G, YANG G H, YONEYAMA Y. Synergistic effect of boron-doped carbon nanotubes supported Cu catalyst for selective hydrogenation of dimethyl oxalate to ethanol[J]. Chem-Eur J, 2017,23(34):8252-8261. doi: 10.1002/chem.201700821
32. [32]
  POLSTER C S, NAIR H, BAERTSCH C D. Study of active sites and mechanism responsible for highly selective CO oxidation in H₂, rich atmospheres on a mixed Cu and Ce oxide catalyst[J]. J Catal, 2009,266(2):308-319.
33. [33]
  KIM J Y, RODRIGUEZ J A, HANSON J C, FRENKEL A I, LEE P L. Reduction of CuO and Cu₂O with H₂:H Embedding and kinetic effects in the formation of suboxides[J]. J Am Chem Soc, 2003,125(35):10684-10692. doi: 10.1021/ja0301673
34. [34]
  WANG P, ZHANG J F, BAI Y X, XIAO H, TIAN S P, XIE H J, YANG G H, TSUBAKI N, HAN Y Z, TAN Y S. Ternary copper-cobalt-cerium catalyst for the production of ethanol and higher alcohols through CO hydrogenation[J]. Appl Catal A:Gen, 2016,514:14-23. doi: 10.1016/j.apcata.2016.01.007
35. [35]
  ZHANG Yu, WANG Kang-jun, ZHANG Ya-jing, DU Jie, LI De-bao, REN Bao-jin, WU Jing. Synthesis of dimethyl ether from CO₂ hydrogenation over La_1-yZryCu_0.7Zn_0.3O_x/HZSM-5 catalysts[J]. J Mol Catal, 2015,6:525-533.
36. [36]
  LI B, SUN X, SU D. Calibration of the basic strength of the nitrogen groups on the nanostructured carbon materials[J]. Phys Chem Chem Phys, 2015,17(10):6691-6694. doi: 10.1039/C4CP05765A
37. [37]
  FENG W, WANG Q W, JIANG B, JI P J. Carbon nanotubes coated on silica gels as a support of Cu-Co catalyst for the synthesis of higher alcohols from syngas[J]. Ind Eng Chem Res, 2011,50(19):11067-11072. doi: 10.1021/ie2014907
38. [38]
  FIERRO G, JACONO M L, INVERSI M, DRAGONE R, PORTA P. TPR and XPS study of cobalt-copper mixed oxide catalysts:Evidence of a strong Co-Cu interaction[J]. Top Catal, 2000,10(1):39-48.
39. [39]
  LU R L, MAO D S, YU J. Enhanced activity of Cu-Fe/SiO₂ catalyst for CO hydrogenation to higher alcohols by pretreating the support with ammonia[J]. J Ind Eng Chem, 2015,25:338-343. doi: 10.1016/j.jiec.2014.11.013
40. [40]
  GUO Qiang-sheng, MAO Dong-sen, YU Jun, HAN Lu-peng. Effects of different supports on the catalytic performance of supported Cu-Fe catalyst for CO hydrogenation[J]. J Fuel Chem Technol, 2012,40(9):1103-1109. doi: 10.3969/j.issn.0253-2409.2012.09.013
41. [41]
  LI X L, ZHANG J F, ZHANG M, ZHANG W, ZHANG M. The support effects on the direct conversion of syngas to higher alcohol synthesis over copper-based catalysts[J]. Catalysts, 2019,9(2)199. doi: 10.3390/catal9020199
42. [42]
  HERACLEOUS E, LIAKAKOU E T, LAPPAS A A, LEMONIDOU A A. Investigation of K-promoted Cu-Zn-Al, Cu-X-Al and Cu-Zn-X (X=Cr, Mn) catalysts for carbon monoxide hydrogenation to higher alcohols[J]. Appl Catal A:Gen, 2013,455:145-154. doi: 10.1016/j.apcata.2013.02.001
43. [43]
  SUN Yu-han, CHEN Jian-gang, WANG Jun-gang, JIA Li-tao, HOU Bo, LI De-bao, ZHANG Juan. The development of cobalt-based catalysts for Fischer-Tropsch synthesis[J]. Chin J Catal, 2010,31(8):919-927.
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