Abstract
Mixtures of regularly coiled and straight multi-walled carbon nanotubes (MWNTs) were synthesised on alumina supported Co catalysts prepared by pH controlled, wet impregnation. The synthesis reaction was performed under C2H2:H2:N2 at 750 °C in a fluidised-bed for 30 min. Scanning electron microscopy/energy dispersive X-ray spectroscopy shows good distribution of the active Co particles on the surface of the alumina support. Determined from 10 individual SEM images from the same product batch, the CNTs present are typically from 10 to 40 nm in diameter. Thermogravimetric analysis (TGA) and Raman spectroscopy indicate the total oxidative weight loss is independent of pH during catalyst preparation. This study is the first to report the use of a fluidised-bed for the synthesis of coiled MWNTs, using alumina supported Co catalysts.
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References
Amelinckx S, Zhang XB, Bernaerts D, Zhang XF, Ivanov V, Nagy JB (1994) A formation mechanism for catalytically grown helix-shaped graphite nanotubes. Science 265(5172):635–639. doi:10.1126/science.265.5172.635
Cao PJ, Zhu DL, Liu WJ, Ma XC (2007) The effect of substrate morphology on the diameter distribution of carbon nanotubes grown on silica and ceramic substrates. Mater Lett 61(8–9):1899–1903. doi:10.1016/j.matlet.2006.07.151
Chen Y, Liu C, Du JH, Cheng HM (2005) Preparation of carbon microcoils by catalytic decomposition of acetylene using nickel foam as both catalyst and substrate. Carbon 43(9):1874–1878. doi:10.1016/j.carbon.2005.02.034
Cheung CL, Kurtz A, Park H, Lieber CM (2002) Diameter-controlled synthesis of carbon nanotubes. J Phys Chem B 106(10):2429–2433. doi:10.1021/jp0142278
Dunlap BI (1992) Connecting carbon tubules. Phys Rev B 46(3):1933–1936. doi:10.1103/PhysRevB.46.1933
Dunlap BI (1994a) Constraints on small graphitic helices. Phys Rev B 50(11):8134–8137. doi:10.1103/PhysRevB.50.8134
Dunlap BI (1994b) Relating carbon tubules. Phys Rev B 49(8):5643–5650. doi:10.1103/PhysRevB.49.5643
Fonseca A, Hernadi K, Piedigrosso P, Colomer JF, Mukhopadhyay K, Doome R, Lazarescu S, Biro LP, Lambin P, Thiry PA, Bernaerts D, Nagy JB (1998) Synthesis of single- and multi-wall carbon nanotubes over supported catalysts. Appl Phys A Mater Sci Process 67(1):11–22. doi:10.1007/s003390050732
Geldart D (1973) Types of gas fluidization. Powder Technol 7(5):285–292. doi:10.1016/0032-5910(73)80037-3
Hernadi K, Fonseca A, Nagy JB, Bernaerts D, Lucas AA (1996) Fe-catalyzed carbon nanotube formation. Carbon 34(10):1249–1257. doi:10.1016/0008-6223(96)00074-7
Hernadi K, Thien-Nga L, Forro L (2001) Growth and microstructure of catalytically produced coiled carbon nanotubes. J Phys Chem B 105(50):12464–12468. doi:10.1021/jp011208p
Hou HQ, Jun Z, Weller F, Greiner A (2003) Large-scale synthesis and characterization of helically coiled carbon nanotubes by use of Fe(CO)(5) as floating catalyst precursor. Chem Mater 15(16):3170–3175. doi:10.1021/cm021290g
Ihara S, Itoh S, Kitakami J (1993) Helically coiled cage forms of graphitic carbon. Phys Rev B 48(8):5643–5647. doi:10.1103/PhysRevB.48.5643
Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354(6348):56–58. doi:10.1038/354056a0
Iijima S, Ichihashi T (1993) Single-shell carbon nanotubes of 1-nm diameter. Nature 363(6430):603–605. doi:10.1038/363603a0
Itoh S, Ihara S (1993) Toroidal forms of graphitic carbon. 2. Elongated tori. Phys Rev B 48(11):8323–8328. doi:10.1103/PhysRevB.48.8323
Itoh S, Ihara S, Kitakami J (1993) Toroidal form of carbon C-360. Phys Rev B 47(3):1703–1704. doi:10.1103/PhysRevB.47.1703
Katok KV, Tertykh VA, Brichka SY, Prikhod’ko GP (2006) Pyrolytic synthesis of carbon nanostructures on Ni, Co, Fe/MCM-41 catalysts. Mater Chem Phys 96(2–3):396–401. doi:10.1016/j.matchemphys.2005.07.029
Kibria A, Mo YH, Nahm KS, Kim MJ (2002) Synthesis of narrow-diameter carbon nanotubes from acetylene decomposition over an iron–nickel catalyst supported on alumina. Carbon 40(8):1241–1247. doi:10.1016/S0008-6223(01)00298-6
Ko CJ, Lee CY, Ko FH, Chen HL, Chu TC (2004) Highly efficient microwave-assisted purification of multiwalled carbon nanotubes. Microelectron Eng 73–74:570–577. doi:10.1016/S0167-9317(04)00141-8
Ko FH, Lee CY, Ko CJ, Chu TC (2005) Purification of multi-walled carbon nanotubes through microwave heating of nitric acid in a closed vessel. Carbon 43(4):727–733. doi:10.1016/j.carbon.2004.10.042
Lau KT, Lu M, Hui D (2006) Coiled carbon nanotubes: synthesis and their potential applications in advanced composite structures. Compos Part B Eng 37(6):437–448. doi:10.1016/j.compositesb.2006.02.008
Li J, Papadopoulos C, Xu J (1999) Nanoelectronics—growing Y-junction carbon nanotubes. Nature 402(6759):253–254
Li YM, Kim W, Zhang YG, Rolandi M, Wang DW, Dai HJ (2001) Growth of single-walled carbon nanotubes from discrete catalytic nanoparticles of various sizes. J Phys Chem B 105(46):11424–11431. doi:10.1021/jp012085b
Lu M, Li HL, Lau KT (2004) Formation and growth mechanism of dissimilar coiled carbon nanotubes by reduced-pressure catalytic chemical vapor deposition. J Phys Chem B 108(20):6186–6192. doi:10.1021/jp0360265
Luo T, Liu JW, Chen LY, Zeng SY, Qian YT (2005) Synthesis of helically coiled carbon nanotubes by reducing ethyl ether with metallic zinc. Carbon 43(4):755–759. doi:10.1016/j.carbon.2004.10.048
Mao JM, Xie SS (1999) Carbon nanotube formation on cobalt-implanted germanium substrate. J Mater Sci Lett 18(14):1151–1153. doi:10.1023/A:1006617620649
McKee GSB, Vecchio KS (2006) Thermogravimetric analysis of synthesis variation effects on CVD generated multiwalled carbon nanotubes. J Phys Chem B 110(3):1179–1186. doi:10.1021/jp054265h
Messina G, Modafferi V, Santangelo S, Tripodi P, Donato MG, Lanza M, Galvagno S, Milone C, Piperopoulos E, Pistone A (2008) Large-scale production of high-quality multi-walled carbon nanotubes: role of precursor gas and of Fe-catalyst support. Diam Relat Mater 17(7–10):1482–1488. doi:10.1016/j.diamond.2008.01.060
Motojima S, Kawaguchi M, Nozaki K, Iwanaga H (1991) Preparation of coiled carbon-fibers by catalytic pyrolysis of acetylene, and its morphology and extension characteristics. Carbon 29(3):379–385. doi:10.1016/0008-6223(91)90207-Y
Mukhopadhyay K, Ram K, Rao KUB (2007) Thin film of carbon micro-spring forest. Mater Lett 61(10):2004–2006. doi:10.1016/j.matlet.2006.08.001
Osswald S, Havel M, Gogotsi Y (2007) Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy. J Raman Spectrosc 38(6):728–736. doi:10.1002/jrs.1686
Pan LJ, Hayashida T, Harada A, Nakayama Y (2002) Effects of iron and indium tin oxide on the growth of carbon tubule nanocoils. Physica B 323(1–4):350–351. doi:10.1016/S0921-4526(02)01001-3
Perez-Cabero M, Rodriguez-Ramos I, Guerrero-Ruiz A (2003) Characterization of carbon nanotubes and carbon nanofibers prepared by catalytic decomposition of acetylene in a fluidized bed reactor. J Catal 215(2):305–316. doi:10.1016/S0021-9517(03)00026-5
Piedigrosso P, Konya Z, Colomer JF, Fonseca A, Van Tendeloo G, Nagy JB (2000) Production of differently shaped multi-wall carbon nanotubes using various cobalt supported catalysts. Phys Chem Chem Phys 2(1):163–170. doi:10.1039/a905622j
Ramesh P, Okazaki T, Sugai T, Kimura J, Kishi N, Sato K, Ozeki Y, Shinohara H (2006) Purification and characterization of double-wall carbon nanotubes synthesized by catalytic chemical vapor deposition on mesoporous silica. Chem Phys Lett 418(4–6):408–412. doi:10.1016/j.cplett.2005.11.018
See CH, Harris AT (2007) A review of carbon nanotube synthesis via fluidized-bed chemical vapor deposition. Ind Eng Chem Res 46(4):997–1012. doi:10.1021/ie060955b
See CH, Harris AT (2008) A comparison of carbon nanotube synthesis in fixed and fluidised bed reactors. Chem Eng J 144(2):267–269. doi:10.1016/j.cej.2008.06.002
Sun XL, Li RY, Stansfield B, Dodelet JP, Menard G, Desilets S (2007) Controlled synthesis of pointed carbon nanotubes. Carbon 45(4):732–737. doi:10.1016/j.carbon.2006.11.033
Szabo A, Fonseca A, Nagy JB, Volodin A, Van Haesendonck C, Biro LP, Colomer JF (2005) Synthesis, properties and applications of helical carbon nanotubes. Fuller Nanotub Carbon Nanostruct 13:139–146. doi:10.1081/FST-200039237
Tang NJ, Zhong W, Au CT, Gedanken A, Yang Y, Du YW (2007) Large-scale synthesis, annealing, purification, and magnetic properties of crystalline helical carbon nanotubes with symmetrical structures. Adv Funct Mater 17(9):1542–1550. doi:10.1002/adfm.200600767
Teo KBK, Singh C, Chhowalla M, Milne WI (2003) Catalytic synthesis of carbon nanotubes and nanofibers. In: Nalwa HS (ed) Encyclopaedia of the nanoscience and nanotechnology, vol X. American Scientific Publishers, USA, pp 1–22
Triantafyllidis KS, Karakoulia SA, Gournis D, Delimitis A, Nalbandian L, Maccallini E, Rudolf P (2008) Formation of carbon nanotubes on iron/cobalt oxides supported on zeolite-Y: effect of zeolite textural properties and particle morphology. Microporous Mesoporous Mater 110(1):128–140. doi:10.1016/j.micromeso.2007.10.007
Varadan VK, Hollinger RD, Varadan VV, Xie J, Sharma PK (2000) Development and characterization of micro-coil carbon fibers by a microwave CVD system. Smart Mater Struct 9(4):413–420. doi:10.1088/0964-1726/9/4/304
Volodin A, Buntinx D, Ahlskog M, Fonseca A, Nagy JB, Van Haesendonck C (2004) Coiled carbon nanotubes as self-sensing mechanical resonators. Nano Lett 4(9):1775–1779. doi:10.1021/nl0491576
Volodin AA, Fursikov PV, Kasumov YA, Khodos II, Tarasov BP (2006) Synthesis of carbon nanostructures on the Fe–Mo catalysts supported on modified SiO2. Russ Chem Bull 55(8):1425–1429. doi:10.1007/s11172-006-0433-6
Wen YK, Shen ZM (2001) Synthesis of regular coiled carbon nanotubes by Ni-catalyzed pyrolysis of acetylene and a growth mechanism analysis. Carbon 39(15):2369–2374. doi:10.1016/S0008-6223(01)00149-X
Wong TC (2003) Synthesis of carbon nanotubes using fluidised-bed CCVD. Department of Chemical Engineering, Bachelor University of Sydney, Sydney
Xie JN, Mukhopadyay K, Yadev J, Varadan VK (2003) Catalytic chemical vapor deposition synthesis and electron microscopy observation of coiled carbon nanotubes. Smart Mater Struct 12(5):744–748. doi:10.1088/0964-1726/12/5/010
Xu CB, Zhu J (2004) One-step preparation of highly dispersed metal-supported catalysts by fluidized-bed MOCVD for carbon nanotube synthesis. Nanotechnology 15(11):1671–1681. doi:10.1088/0957-4484/15/11/052
Yang S, Chen X, Kusunoki M, Yamamoto K, Iwanaga H, Motojima S (2005) Microstructure and microscopic deposition mechanism of twist-shaped carbon nanocoils based on the observation of helical nanoparticles on the growth tips. Carbon 43(5):916–922. doi:10.1016/j.carbon.2004.11.040
Zhang Q, Pan W-P, Lee WM (1993) The thermal analysis of bismaleimide/graphite fiber composite by TG/FTIR. Thermochim Acta 226:115–122. doi:10.1016/0040-6031(93)80212-S
Zhang XB, Zhang XF, Bernaerts D, Vantendeloo GT, Amelinckx S, Vanlanduyt J, Ivanov V, Nagy JB, Lambin P, Lucas AA (1994) The texture of catalytically grown coil-shaped carbon nanotubules. Europhys Lett 27(2):141–146. doi:10.1209/0295-5075/27/2/011
Zhong DY, Liu S, Wang EG (2003) Patterned growth of coiled carbon nanotubes by a template-assisted technique. Appl Phys Lett 83(21):4423–4425. doi:10.1063/1.1630164
Acknowledgements
JL is grateful to the School of Chemical and Biomolecular Engineering at the University of Sydney for a Postgraduate Research Scholarship. The authors are grateful to University of Sydney’s Electron Microscopy Unit for assistance with the acquisition of the SEM/EDX and TEM images and Dr. E. Carter for assistance with Raman spectroscopy.
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Liu, J., Harris, A.T. Synthesis of coiled carbon nanotubes on Co/Al2O3 catalysts in a fluidised-bed. J Nanopart Res 12, 645–653 (2010). https://doi.org/10.1007/s11051-009-9634-x
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DOI: https://doi.org/10.1007/s11051-009-9634-x