Reactions of the inner surface of carbon nanotubes and nanoprotrusion processes imaged at the atomic scale

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Although the outer surface of single-walled carbon nanotubes (atomically thin cylinders of carbon) can be involved in a wide range of chemical reactions, it is generally thought that the interior surface of nanotubes is unreactive. In this study, we show that in the presence of catalytically active atoms of rhenium inserted into nanotubes, the nanotube sidewall can be engaged in chemical reactions from the inside. Aberration-corrected high-resolution transmission electron microscopy operated at 80 keV allows visualization of the formation of nanometre-sized hollow protrusions on the nanotube sidewall at the atomic level in real time at ambient temperature. Our direct observations and theoretical modelling demonstrate that the nanoprotrusions are formed in three stages: (i) metal-assisted deformation and rupture of the nanotube sidewall, (ii) the fast formation of a metastable asymmetric nanoprotrusion with an open edge and (iii) a slow symmetrization process that leads to a stable closed nanoprotrusion.

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Figure 1: Transition metal–fullerene complex within carbon nanotubes.
Figure 2: Three examples of 80 kV AC-HRTEM image sequences that show the different stages of nanoprotrusion formation on SWNT.
Figure 3: Activation of the concave side of SWNT for chemical reactions.


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This work was supported by the German Research Foundation (DFG) and the Federal State of Baden-Württemberg within the Sub-Ångstrøm Low-Voltage Electron Microscopy project, by the Collaborative Research Centre SFB 569 of the DFG, by the UK Engineering and Physical Research Council (Career Acceleration Fellowship to E.B.), by the High Performance Computing (HPC) facility at the University of Nottingham (E.B., N.A.B. and A.S.) and by the Royal Society and the European Science Foundation (A.N.K.).

Author information

T.W.C. conceived the experiments, synthesized the materials and analysed the microscopy data. J.B., J.C.M. and J.L. recorded the AC-HRTEM images and contributed to the initial explanation of the observations. J.B. analysed the images and carried out TEM image simulations. E.B., N.A.B. and A.S. performed the theoretical modelling and explained the details of the reaction mechanisms. U.K. contributed to the development of the experimental methodology and discussion of the results. A.N.K. conceived the initial idea, proposed the general mechanism and wrote the original manuscript. All authors discussed the results and commented on the manuscript.

Correspondence to Elena Bichoutskaia or Ute Kaiser or Andrei N. Khlobystov.

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Chamberlain, T., Meyer, J., Biskupek, J. et al. Reactions of the inner surface of carbon nanotubes and nanoprotrusion processes imaged at the atomic scale. Nature Chem 3, 732–737 (2011) doi:10.1038/nchem.1115

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