Journal of Materials Science

, Volume 54, Issue 2, pp 1291–1303 | Cite as

One-step synthesis of hierarchical metal oxide nanosheet/carbon nanotube composites by chemical vapor deposition

  • Fan Wu
  • Chen Wang
  • Hai-Yan Hu
  • Ming Pan
  • Hua-Fei Li
  • Ning Xie
  • Zheling Zeng
  • Shuguang Deng
  • Marvin H. Wu
  • K. VinodgopalEmail author
  • Gui-Ping DaiEmail author


We report here the one-step water-assisted CVD growth of metal oxide nanosheets/carbon nanotubes (CNTs) composites. The cross-linked composites were characterized by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The results showed that helical CNTs were obtained when the CVD growth process was prolonged to 1 h, and the typical fish-bone-type CNTs can be observed by HRTEM. Moreover, a related growth mechanism is proposed to explain the growth of such novel nanocomposites.



G-PD acknowledges the National Natural Science Foundation of China (Grants 51462022 and 51762032) and the Natural Science Foundation Major Project of Jiangxi Province of China (Grant 20152ACB20012) for financial support of this research. CW acknowledges the Graduate Innovation Foundation of Jiangxi Province (Grant YC2018-S015). KV and MHW acknowledge the support of NSF CREST Award HRD-0833184 and the NSF PREM Award DMR 1523617. The assistance of Dr. AS Kumbhar (SEM and HRTEM measurements), CHANL at UNC Chapel Hill, is also greatly appreciated.


  1. 1.
    Che G, Lakshmi BB, Fisher ER, Martin CR (1998) Carbon nanotubule membranes for electrochemical energy storage and production. Nature 393:346–349CrossRefGoogle Scholar
  2. 2.
    Girishkumar G, Hall TD, Vinodgopal K, Kamat PV (2006) Single wall carbon nanotube supports for portable direct methanol fuel cells. J Phys Chem B 110:107–114CrossRefGoogle Scholar
  3. 3.
    Chen K, Bell AT, Iglesia E (2002) The relationship between the electronic and redox properties of dispersed metal oxides and their turnover rates in oxidative dehydrogenation reactions. J Catal 209:35–42CrossRefGoogle Scholar
  4. 4.
    Sysoev VV, Button BK, Wepsiec K, Dmitriev S, Kolmakov A (2006) Toward the nanoscopic “electronic nose”: hydrogen vs carbon monoxide discrimination with an array of individual metal oxide nano-and mesowire sensors. Nano Lett 6:1584–1588CrossRefGoogle Scholar
  5. 5.
    Wang YG, Li HQ, Xia YY (2006) Ordered whiskerlike polyaniline grown on the surface of mesoporous carbon and its electrochemical capacitance performance. Adv Mater 18:2619–2623CrossRefGoogle Scholar
  6. 6.
    Ding S, Chen JS, Lou XW (2011) One-dimensional hierarchical structures composed of novel metal oxide nanosheets on a carbon nanotube backbone and their lithium-storage properties. Adv Funct Mater 21:4120–4125CrossRefGoogle Scholar
  7. 7.
    Du N, Zhang H, Chen B, Ma X, Huang X, Tu J, Yang D (2009) Synthesis of polycrystalline SnO2 nanotubes on carbon nanotube template for anode material of lithium-ion battery. Mater Res Bull 44:211–215CrossRefGoogle Scholar
  8. 8.
    Noerochim L, Wang JZ, Chou SL, Li HJ, Liu HK (2010) SnO2-coated multiwall carbon nanotube composite anode materials for rechargeable lithium-ion batteries. Electrochim Acta 56:314–320CrossRefGoogle Scholar
  9. 9.
    Du G, Zhong C, Zhang P, Guo Z, Chen Z, Liu H (2010) Tin dioxide/carbon nanotube composites with high uniform SnO2 loading as anode materials for lithium ion batteries. Electrochim Acta 55:2582–2586CrossRefGoogle Scholar
  10. 10.
    Zhu CL, Zhang ML, Qiao YJ, Gao P, Chen YJ (2010) High capacity and good cycling stability of multi-walled carbon nanotube/SnO2 core–shell structures as anode materials of lithium-ion batteries. Mater Res Bull 45:437–441CrossRefGoogle Scholar
  11. 11.
    Dai K, Peng T, Ke D, Wei B (2009) Photocatalytic hydrogen generation using a nanocomposite of multi-walled carbon nanotubes and TiO2 nanoparticles under visible light irradiation. Nanotechnology 20:125603CrossRefGoogle Scholar
  12. 12.
    Fan W, Gao L, Sun J (2006) Anatase TiO2-coated multi-wall carbon nanotubes with the vapor phase method. J Am Ceram Soc 89:731–733CrossRefGoogle Scholar
  13. 13.
    Liu B, Zeng HC (2008) Carbon nanotubes supported mesoporous mesocrystals of anatase TiO2. Chem Mater 20:2711–2718CrossRefGoogle Scholar
  14. 14.
    Wang Y, Lee JY, Zeng HC (2005) Polycrystalline SnO2 nanotubes prepared via infiltration casting of nanocrystallites and their electrochemical application. Chem Mater 17:3899–3903CrossRefGoogle Scholar
  15. 15.
    Du N, Zhang H, Chen BD, Ma XY, Liu ZH, Wu JB, Yang DR (2007) Porous indium oxide nanotubes: layer-by-layer assembly on carbon-nanotube templates and application for room-temperature NH3 gas sensors. Adv Mater 19:1641–1645CrossRefGoogle Scholar
  16. 16.
    Sun Z, Yuan H, Liu Z, Han B, Zhang X (2005) A highly efficient chemical sensor material for H2S: α-Fe2O3 nanotubes fabricated using carbon nanotube templates. Adv Mater 17:2993–2997CrossRefGoogle Scholar
  17. 17.
    Satishkumar BC, Govindaraj A, Vogl EM, Basumallick L, Rao CNR (1997) Oxide nanotubes prepared using carbon nanotubes as templates. J Mater Res 12:604–606CrossRefGoogle Scholar
  18. 18.
    Zhang H, Cao G, Wang Z, Yang Y, Shi Z, Gu Z (2008) Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage. Nano Lett 8:2664–2668CrossRefGoogle Scholar
  19. 19.
    Wu F, Wang C, Wu MH, Vinodgopal K, Dai GP (2018) Large area synthesis of vertical aligned metal oxide nanosheets by thermal oxidation of stainless steel mesh and foil. Materials 11:884CrossRefGoogle Scholar
  20. 20.
    Kumar M, Ando Y (2010) Chemical vapor deposition of carbon nanotubes: a review on growth mechanism and mass production. J Nanosci Nanotechnol 10:3739–3758CrossRefGoogle Scholar
  21. 21.
    Liu F, Zhang X, Cheng J, Tu J, Kong F, Huang W, Chen C (2003) Preparation of short carbon nanotubes by mechanical ball milling and their hydrogen adsorption behavior. Carbon 41:2527–2532CrossRefGoogle Scholar
  22. 22.
    Thostenson ET, Ren Z, Chou TW (2001) Advances in the science and technology of carbon nanotubes and their composites: a review. Compos Sci Technol 61:1899–1912CrossRefGoogle Scholar
  23. 23.
    Bradford PD, Wang X, Zhao H, Maria JP, Jia Q, Zhu YT (2010) A novel approach to fabricate high volume fraction nanocomposites with long aligned carbon nanotubes. Compos Sci Technol 70:1980–1985CrossRefGoogle Scholar
  24. 24.
    Lim H, Jung H, Park C, Joo S (2002) A new process for removal of catalyst in carbon nanotube grown by hot-filament chemical vapor deposition. Jpn J Appl Phys 41:4686CrossRefGoogle Scholar
  25. 25.
    Stypula B, Stoch J (1994) The characterization of passive films on chromium electrodes by XPS. Corros Sci 36:2159–2167CrossRefGoogle Scholar
  26. 26.
    Gaspar AB, Perez CAC, Dieguez LC (2005) Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS. Appl Surf Sci 252:939–949CrossRefGoogle Scholar
  27. 27.
    Huang X, Zhao G, Wang P, Zheng H, Dong W, Wang G (2018) Ce1-xCrxO2−δ nanocrystals as efficient catalysts for the selective oxidation of cyclohexane to KA oil at low temperature under ambient pressure. ChemCatChem 10:1406–1413CrossRefGoogle Scholar
  28. 28.
    Deng S, Wang S, Wang L, Liu J, Wang Y (2017) Influence of chloride on passive film chemistry of 304 stainless steel in sulphuric acid solution by glow discharge optical emission spectrometry analysis. Int J Electrochem Sc 12:1106–1117CrossRefGoogle Scholar
  29. 29.
    Peng H, Mo Z, Liao S, Liang H, Yang L, Luo F, Zhang B (2013) High performance Fe-and N-doped carbon catalyst with graphene structure for oxygen reduction. Sci Rep 3:1765CrossRefGoogle Scholar
  30. 30.
    Yazdanbakhsh A, Hashempour Y, Ghaderpouri M (2018) Performance of granular activated carbon/nanoscale zero-valent iron for removal of humic substances from aqueous solution based on experimental design and response surface modeling. Glob Nest J 20:57–68Google Scholar
  31. 31.
    Wang HB, Wang H, Wang XN, Zhang J, Wu S, Duan JX, Jiang Y (2011) Organic co-decomposition method for the synthesis of Mn and Co doped ZnO submicrometer crystals: photoluminescence and magnetic properties. Phys Status Solidi A 208:2393–2398CrossRefGoogle Scholar
  32. 32.
    Zeng F, Pan Y, Yang Y, Li Q, Li G, Hou Z, Gu G (2016) Facile construction of Mn3O4–MnO2 hetero-nanorods/graphene nanocomposite for highly sensitive electrochemical detection of hydrogen peroxide. Electrochim Acta 196:587–596CrossRefGoogle Scholar
  33. 33.
    Dondi M, Lyubenova TS, Carda JB, Ocana M (2009) M-doped Al2TiO5 (M = Cr, Mn, Co) solid solutions and their use as ceramic pigments. J Am Ceram Soc 92:1972–1980CrossRefGoogle Scholar
  34. 34.
    Pimenta MA, Dresselhaus G, Dresselhaus MS, Cancado LG, Jorio A, Saito R (2007) Studying disorder in graphite-based systems by Raman spectroscopy. Phys Chem Chem Phys 9:1276–1290CrossRefGoogle Scholar
  35. 35.
    Dai GP, Wu MH, Taylor DK, Brennaman MK, Vinodgopal K (2012) Hybrid 3D graphene and aligned carbon nanofiber array architectures. RSC Adv 2:8965–8968CrossRefGoogle Scholar
  36. 36.
    Meng F, Wang Y, Wang Q, Xu X, Jiang M, Zhou X, Zhou Z (2018) High-purity helical carbon nanotubes by trace-water-assisted chemical vapor deposition: large-scale synthesis and growth mechanism. Nano Res 11:3327–3339CrossRefGoogle Scholar
  37. 37.
    Xie K, Yang F, Ebbinghaus P, Erbe A, Muhler M, Xia W (2015) A reevaluation of the correlation between the synthesis parameters and structure and properties of nitrogen-doped carbon nanotubes. J Energy Chem 24:407–415CrossRefGoogle Scholar
  38. 38.
    Zuo J, Xu C, Hou B, Wang C, Xie Y, Qian Y (1996) Raman spectra of nanophase Cr2O3. J Raman Spectrosc 27:921–923CrossRefGoogle Scholar
  39. 39.
    Oh SJ, Cook DC, Townsend HE (1998) Characterization of iron oxides commonly formed as corrosion products on steel. Hyperfine Interact 112:59–66CrossRefGoogle Scholar
  40. 40.
    Zhang P, Zhan Y, Cai B, Hao C, Wang J, Liu C, Chen Q (2010) Shape-controlled synthesis of Mn3O4 nanocrystals and their catalysis of the degradation of methylene blue. Nano Res 3:235–243CrossRefGoogle Scholar
  41. 41.
    Schwinger W, Haring J, Jantscher A, Haubner R, Gerger I, Bodnarchuk M, Schöftner R (2008) Preparation of catalytic nano-particles and growth of aligned CNTs with HF-CVD. J Phys Conf Ser 100:052092CrossRefGoogle Scholar
  42. 42.
    Sawant SY, Somani RS, Bajaj HC (2010) A solvothermal-reduction method for the production of horn shaped multi-wall carbon nanotubes. Carbon 48:668–672CrossRefGoogle Scholar
  43. 43.
    Gao R, Wang ZL, Fan S (2000) Kinetically controlled growth of helical and zigzag shapes of carbon nanotubes. J Phys Chem B 104:1227–1234CrossRefGoogle Scholar
  44. 44.
    Fonseca A, Hernadi K, Nagy JB, Lambin P, Lucas AA (1995) Model structure of perfectly graphitizable coiled carbon nanotubes. Carbon 33:1759–1775CrossRefGoogle Scholar
  45. 45.
    Wang ZL, Kang ZC (1996) Pairing of pentagonal and heptagonal carbon rings in the growth of nanosize carbon spheres synthesized by a mixed-valent oxide-catalytic carbonization process. J Phys Chem 100:17725–17731CrossRefGoogle Scholar
  46. 46.
    Ihara S, Itoh S (1995) Helically coiled and toroidal cage forms of graphitic carbon. Carbon 33:931–939CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Resources Environmental and Chemical EngineeringNanchang UniversityNanchangChina
  2. 2.Institute for Advanced StudyNanchang UniversityNanchangChina
  3. 3.Key Laboratory of Poyang Lake Environment and Resource Utilization, Nanchang UniversityMinistry of EducationNanchangChina
  4. 4.School for Engineering of Matter, Transport and EnergyArizona State UniversityTempeUSA
  5. 5.Department of PhysicsNorth Carolina Central UniversityDurhamUSA
  6. 6.Department of Chemistry and BiochemistryNorth Carolina Central UniversityDurhamUSA

Personalised recommendations