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Atomic-scale imaging of carbon nanofibre growth

Abstract

The synthesis of carbon nanotubes with predefined structure and functionality plays a central role in the field of nanotechnology1,2, whereas the inhibition of carbon growth is needed to prevent a breakdown of industrial catalysts for hydrogen and synthesis gas production3. The growth of carbon nanotubes and nanofibres has therefore been widely studied4,5,6,7,8,9,10. Recent advances in in situ techniques now open up the possibility of studying gas–solid interactions at the atomic level11,12. Here we present time-resolved, high-resolution in situ transmission electron microscope observations of the formation of carbon nanofibres from methane decomposition over supported nickel nanocrystals. Carbon nanofibres are observed to develop through a reaction-induced reshaping of the nickel nanocrystals. Specifically, the nucleation and growth of graphene layers are found to be assisted by a dynamic formation and restructuring of mono-atomic step edges at the nickel surface. Density-functional theory calculations indicate that the observations are consistent with a growth mechanism involving surface diffusion of carbon and nickel atoms. The finding that metallic step edges act as spatiotemporal dynamic growth sites may be important for understanding other types of catalytic reactions and nanomaterial syntheses.

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Figure 1: Electron micrographs of the Ni catalyst and carbon nanofibres.
Figure 2: Image sequence of a growing carbon nanofibre extracted from movie N1.
Figure 3: Illustration of the surface processes on the Ni(111) surface modelled in the DFT calculations.

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Acknowledgements

We gratefully acknowledge the participation of the CTCI Foundation, Taiwan, in the establishment of the TEM facility at Haldor Topsøe A/S. S.H. acknowledges support from the Danish Research Council, STVF. F.A.P. and J.K.N. acknowledge computational resources from the Danish Center for Scientific Computing. C.L.-C. acknowledges support from Facultad de Ciencias, Universidad de Cádiz, Puerto Real, Spain, for a sabbatical visit to Haldor Topsøe A/S.

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Correspondence to Stig Helveg.

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Haldor Topsøe A/S is a private research-based company delivering catalysts and process technology to the fertilizer, chemical and petrochemical industries, and the energy sector.

Supplementary information

41586_2004_BFnature02278_MOESM1_ESM.mp4

Supplementary Movie 1: An in situ TEM movie showing the formation of a tubular carbon nanofiber by catalytic decomposition of CH4 over a Ni nanocrystal. The image size is 21.3x21.3nm2. (MP4 383 kb)

41586_2004_BFnature02278_MOESM2_ESM.mp4

Supplementary Movie 2: An in situ TEM movie showing the formation of a whisker-type carbon nanofiber. The film reveals the growth of graphene layers from step edge formation and restructuring at the C-Ni interface. The image size is 21.3x21.3nm2. (MP4 298 kb)

Supplementary Movie Legends (DOC 19 kb)

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Helveg, S., López-Cartes, C., Sehested, J. et al. Atomic-scale imaging of carbon nanofibre growth. Nature 427, 426–429 (2004). https://doi.org/10.1038/nature02278

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