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    Carbon Atoms in Ethanol Do Not Contribute Equally to Formation of Single-Walled Carbon Nanotubes
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    † State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou 510275, China
    ‡ ‡Department of Mechanical Engineering and §Global Center of Excellence for Mechanical Systems Innovation, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    ⊥ Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
    PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan
    # Department of Physics, Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China
    *Address correspondence to [email protected], [email protected]
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    ACS Nano

    Cite this: ACS Nano 2013, 7, 4, 3095–3103
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    https://doi.org/10.1021/nn305180g
    Published March 4, 2013
    Copyright © 2013 American Chemical Society
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    Abstract

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    We propose a unique experimental technique in which isotopically labeled ethanol, e.g., 12CH3–13CH2–OH, is used to trace the carbon atoms during the formation of single-walled carbon nanotubes (SWNTs) by chemical vapor deposition (CVD). The proportion of 13C is determined from Raman spectra of the obtained SWNTs, yielding the respective contribution of ethanol’s two different carbon atoms to SWNT formation. Surprisingly, the carbon away from the hydroxyl group is preferably incorporated into the SWNT structure, and this preference is significantly affected by growth temperature, presence of secondary catalyst metal species such as Mo, and even by the substrate material. These experiments provide solid evidence confirming that the active carbon source is not limited to products of gas-phase decomposition such as ethylene and acetylene, but ethanol itself is arriving at and reacting with the metal catalyst particles. Furthermore, even the substrate or other catalytically inactive species directly influences the formation of SWNTs, possibly by changing the local environment around the catalyst or even the reaction pathway of SWNT formation. These unexpected effects, which are inaccessible by conventional techniques, paint a clearer picture regarding the decomposition and bond breaking process of the ethanol precursor during the entire CVD process and how this might influence the quality of the obtained SWNTs.

    Copyright © 2013 American Chemical Society

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    Supporting Information

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    Thermal decomposition of ethanol at 750, 800, and 850 °C; full Raman spectra of SWNTs obtained on Co/Si catalyst at 750, 800, and 850 °C with and without Mo addition using 1-13C ethanol as the carbon source; Raman spectra of SWNTs obtained on zeolite supported Fe, Co, Ni catalyst grown at 750 °C using 1-13C ethanol as the carbon source; Schematics of reaction pathway and resulting ratio of no. 1 and no. 2 carbon incorporated in SWNTs; cross-sectional Raman spectra of vertically aligned SWNT array; Raman spectra of a standard 12C SWNT sample measured with different lens and laser power; Raman spectra of a 13C-enriched SWNT sample taken at different sites; Raman spectra of a standard 12C SWNT sample measured with different gratings of the monochromator. This material is available free of charge via the Internet at http://pubs.acs.org.

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    ACS Nano

    Cite this: ACS Nano 2013, 7, 4, 3095–3103
    Click to copy citationCitation copied!
    https://doi.org/10.1021/nn305180g
    Published March 4, 2013
    Copyright © 2013 American Chemical Society
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