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Synthesis of high quality nitrogen-doped single-wall carbon nanotubes

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Abstract

Nitrogen-doped single-wall carbon nanotubes (SWCNTs) with diameters in the range of 1.1–1.6 nm were synthesized on a large scale by floating catalyst chemical vapor deposition. Ferrocene, methane and melamine were respectively used as the catalyst precursor, carbon source and nitrogen source. The content of nitrogen introduced into the SWCNT lattice was characterized to be ~0.4 at.%. This resulted in a decreased mean diameter, narrower tube diameter distribution, and increased surface area of the SWCNTs. The temperatures at which the rate of weight loss reaches the maximum value for N-SWCNTs are ~785°C, similar to that of pure SWCNTs, indicative of their high-quality and good crystallinity. These N-SWCNTs exhibited a metallic behavior and desirable electrochemical oxygen reduction reaction activity.

中文摘要

本文以二茂铁为催化剂、三聚氰胺为氮源、甲烷为碳源, 采用浮动催化剂化学气相沉积法制备了氮掺杂单壁碳纳米管. 通 过控制三聚氰胺的挥发量, 实现了氮原子在单壁碳纳米管石墨网格中的微量掺杂, 获得了高质量的氮掺杂单壁碳纳米管, 其抗氧化温 度高达795°C. 这种微量氮掺杂使得单壁碳纳米管的直径变小、直径分布范围变窄, 并表现出金属性行为及提高的氧还原性能.

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References

  1. Dresselhaus MS, Dresselhaus G, Eklund P. Science of Fullerenes and Carbon Nanotubes. Waltham: Academic Press, 1996

    Google Scholar 

  2. Saito R, Dresselhaus G, Dresselhaus MS. Physical Properties of Carbon Nanotubes. London: Imperial college press, 1998

    Book  Google Scholar 

  3. Avouris P, Chen ZH, Perebeinos V. Carbon-based electronics. Nat Nanotechnol, 2007; 2: 605–615

    Article  Google Scholar 

  4. Itkis ME, Yu A, Haddon RC. Single-walled carbon nanotube thin film emitter-detector integrated optoelectronic device. Nano Lett, 2008; 8: 2224–2228

    Article  Google Scholar 

  5. Ding L, Wang S, Zhang ZY, et al. Y-contacted high-performance n-type single-walled carbon nanotube field-effect transistors: scaling and comparison with Sc-contacted devices. Nano Lett, 2009; 9: 4209–4214

    Article  Google Scholar 

  6. Gabor NM, Zhong ZH, Bosnick K, et al. Extremely efficient multiple electron-hole pair generation in carbon nanotube photodiodes. Science, 2009; 325: 1367–1371

    Article  Google Scholar 

  7. Mueller T, Kinoshita M, Steiner M, et al. Efficient narrow-band light emission from a single carbon nanotube p–n diode. Nat Nanotechnol, 2010; 5: 27–31

    Article  Google Scholar 

  8. Tahvili MS, Jahanmiri S, Sheikhi MH. High-frequency transmission through metallic single-walled carbon nanotube interconnects. Int J Numer Modell Electron, 2009; 22: 369–378

    Article  Google Scholar 

  9. Chai Y, Xiao Z, Chan PCH. Horizontally aligned carbon nanotube bundles for interconnect application: diameter-dependent contact resistance and mean free path. Nanotechnology, 2010, 21: 235705

    Article  Google Scholar 

  10. Li H, Xu CA, Banerjee K. Carbon nanomaterials: the ideal interconnect technology for next-generation ICs. IEEE Des Test Comput, 2010; 27: 20–31

    Google Scholar 

  11. Yu B, Liu C, Hou PX, et al. Bulk synthesis of large diameter semiconducting single-walled carbon nanotubes by oxygen-assisted floating catalyst chemical vapor deposition. J Am Chem Soc, 2011; 133: 5232–5235

    Article  Google Scholar 

  12. Ding L, Tselev A, Wang JY, et al. Selective growth of well-aligned semiconducting single-walled carbon nanotubes. Nano Lett, 2009; 9: 800–805

    Article  Google Scholar 

  13. Hong G, Zhang B, Peng BH, et al. Direct growth of semiconducting single-walled carbon nanotube array. J Am Chem Soc, 2009, 131: 14642–14643

    Article  Google Scholar 

  14. Harutyunyan AR, Chen GG, Paronyan TM, et al. Preferential growth of single-walled carbon nanotubes with metallic conductivity. Science, 2009; 326: 116–120

    Article  Google Scholar 

  15. Hou PX, Li WS, Zhao SY, et al. Preparation of metallic single-wall carbon nanotubes by selective etching. Acs Nano, 2014, 8: 7156–7162

    Article  Google Scholar 

  16. Wang Y, Liu YQ, Li XL, et al. Direct enrichment of metallic single- walled carbon nanotubes induced by the different molecular composition of monohydroxy alcohol homologues. Small, 2007; 3: 1486–1490

    Article  Google Scholar 

  17. Sundaram RM,Koziol KKK, Windle AH. Continuous direct spinning of fibers of single-walled carbon nanotubes with metallic chirality. Adv Mater, 2011; 23: 5064–5068

    Article  Google Scholar 

  18. Voggu R, Ghosh S, Govindaraj A, et al. New strategies for the enrichment of metallic single-walled carbon nanotubes. J Nanosci Nanotechnol, 2010; 10: 4102–4108

    Article  Google Scholar 

  19. Hwang SK, Lee JM, Kim S, et al. Flexible multilevel resistive memory with controlled charge trap band N-doped carbon nanotubes. Nano Lett, 2012; 12: 2217–2221

    Article  Google Scholar 

  20. Hashim DP, Narayanan NT, Romo-Herrera JM, et al. Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions. Sci Rep, 2012, 2: 363

    Article  Google Scholar 

  21. Sumpter BG, Meunier V, Romo-Herrera JM, et al. Nitrogen-mediated carbon nanotube growth: diameter reduction, metallicity, bundle dispersability, and bamboo-like structure formation. Acs Nano, 2007; 1: 369–375

    Article  Google Scholar 

  22. Gong KP, Du F, Xia ZH, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 2009; 323: 760–764

    Article  Google Scholar 

  23. Maciel IO, Campos-Delgado J, Cruz-Silva E, et al. Synthesis, electronic structure, and Raman scattering of phosphorus-doped single- wall carbon nanotubes. Nano Lett, 2009; 9: 2267–2272

    Article  Google Scholar 

  24. Campos-Delgado J, Maciel IO, Cullen DA, et al. Chemical vapor deposition synthesis of N-, P-, and Si-doped single-walled carbon nanotubes. ACS Nano, 2010; 4: 1696–1702

    Article  Google Scholar 

  25. Fagan SB, Mota R, Silva AJR, et al. Substitutional Si doping in deformed carbon nanotubes. Nano Lett, 2004; 4: 975–977

    Article  Google Scholar 

  26. Cruz-Silva E, López-Urías F, Muñoz-Sandoval E, et al. Electronic transport and mechanical properties of phosphorus- and phosphorus- nitrogen-doped carbon nanotubes. ACS Nano, 2009; 3: 1913–1921

    Article  Google Scholar 

  27. Pattinson SW, Ranganathan V, Murakami HK, et al. Nitrogen-induced catalyst restructuring for epitaxial growth of multiwalled carbon nanotubes. Acs Nano, 2012; 6: 7723–7730

    Article  Google Scholar 

  28. Barzegar HR, Gracia-Espino E, Sharifi T, et al. Nitrogen doping mechanism in small diameter single-walled carbon nanotubes: impact on electronic properties and growth selectivity. J Phys Chem C, 2013, 117: 25805–25816

    Article  Google Scholar 

  29. Koó s AA, Dowling M, Jurkschat K, et al. Effect of the experimental parameters on the structure of nitrogen-doped carbon nanotubes produced by aerosol chemical vapour deposition. Carbon, 2009; 47: 30–37

    Article  Google Scholar 

  30. Pattinson SW, Diaz RE, Stelmashenko NA, et al. In situ observation of the effect of nitrogen on carbon nanotube synthesis. Chem Mater, 2013; 25: 2921–2923

    Article  Google Scholar 

  31. Liu J, Rinzler AG, Dai HJ, et al. Fullerene pipes. Science, 1998; 280: 1253–1256

    Article  Google Scholar 

  32. Maiti UN, Lee WJ, Lee JM, et al. 25th anniversary article: chemically modified/doped carbon nanotubes & graphene for optimized nanostructures & nanodevices. Adv Mater, 2014; 26: 40–67

    Article  Google Scholar 

  33. Pint CL, Sun ZZ, Moghazy S, et al. Supergrowth of nitrogen-doped single-walled carbon nanotube arrays: active species, dopant characterization, and doped/undoped heterojunctions. Acs Nano, 2011; 5: 6925–6934

    Article  Google Scholar 

  34. Yu B, Hou PX, Li F, et al. Selective removal of metallic single-walled carbon nanotubes by combined in situ and post-synthesis oxidation. Carbon, 2010; 48: 2941–2947

    Article  Google Scholar 

  35. Hir aoka T, Izadi-Najafabadi A, Yamada T, et al. Compact and light supercapacitor electrodes from a surface-only solid by opened carbon nanotubes with 2200 m2 g-1 surface area. Adv Funct Mater, 2010. 20: 422–428

    Article  Google Scholar 

  36. Villalpando-Paez F, Zamudio A, Elias AL, et al. Synthesis and characterization of long strands of nitrogen-doped single-walled carbon nanotubes. Chem Phys Lett, 2006; 424: 345–352

    Article  Google Scholar 

  37. Zhu J, Wang Y, Li WJ, et al. A density functional study of nitrogen adsorption in single-wall carbon nanotubes. Nanotechnology, 2007, 1: 095707

    Article  Google Scholar 

  38. Zhang XR, Wang WC, Chen JF, Shen ZG. Characterization of a sample of single-walled carbon nanotube array by nitrogen adsorp tion isotherm and density functional theory. Langmuir, 2003; 19: 6088–6096

    Article  Google Scholar 

  39. Beguin F, Frackowiek E (eds.), Carbons for Electrochemical Energy Storage and Conversion Systems. Boca Raton: CRC Press, 2010

    Google Scholar 

  40. Zhou W, Ooi YH, Russo R, et al. Structural characterization and diameter-dependent oxidative stability of single wall carbon nanotubes synthesized by the catalytic decomposition of CO. Chem Phys Lett, 2001; 350: 6–14

    Article  Google Scholar 

  41. Liu Y, Jin Z, Wang JY, et al. Nitrogen-doped single-walled carbon nanotubes grown on substrates: evidence for framework doping and their enhanced properties. Adv Funct Mater, 2011; 21: 986–992

    Article  Google Scholar 

  42. Maciel IO, Anderson N, Pimenta MA, et al. Electron and phonon renormalization near charged defects in carbon nanotubes. Nat Mater, 2008; 7: 878–883

    Article  Google Scholar 

  43. Maciel IO, Pimenta MA, Terrones M, et al. The two peaks G’ band in carbon nanotubes. Phys Status Solidi B, 2008; 245: 2197–2200

    Article  Google Scholar 

  44. Hou PX, Orikasa H, Yamazaki T, et al. Synthesis of nitrogen-containing microporous carbon with a highly ordered structure and effect of nitrogen doping on H2O adsorption. Chem Mater, 2005; 17: 5187–5193

    Article  Google Scholar 

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Authors and Affiliations

  1. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China

    Peng-Xiang Hou, Man Song, Jin-Cheng Li, Chang Liu, Shi-Sheng Li & Hui-Ming Cheng

Authors
  1. Peng-Xiang Hou
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  2. Man Song
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  3. Jin-Cheng Li
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  4. Chang Liu
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  5. Shi-Sheng Li
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  6. Hui-Ming Cheng
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Corresponding author

Correspondence to Chang Liu.

Additional information

These authors contributed equally to this work.

Peng-Xiang Hou is a professor in materials science and engineering at the Institute of Metal Research, Chinese Academy of Sciences (CAS). She received her BSc and PhD degrees, both in materials science from the Institute of Metal Research in 1999 and 2003, respectively. Her research focuses on the controlled synthesis, properties and applications of single-wall carbon nanotubes.

Chang Liu is a professor at the Institute of Metal Research, CAS. He received his PhD degree in materials science in 2000 at the Institute of Metal Research, CAS. He is a group leader of “the synthesis, property and application of carbon nanotubes”.

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Hou, PX., Song, M., Li, JC. et al. Synthesis of high quality nitrogen-doped single-wall carbon nanotubes. Sci. China Mater. 58, 603–610 (2015). https://doi.org/10.1007/s40843-015-0074-x

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