Article

Analysis of the reactivity and selectivity of fullerene dimerization reactions at the atomic level.

Nanotube Research Centre, National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565 Japan.
Nature Chemistry (Impact Factor: 21.76). 02/2010; 2(2):117-24. DOI: 10.1038/nchem.482
Source: PubMed

ABSTRACT High-resolution transmission electron microscopy has proved useful for its ability to provide time-resolved images of small molecules and their movements. One of the next challenges in this area is to visualize chemical reactions by monitoring time-dependent changes in the atomic positions of reacting molecules. Such images may provide information that is not available with other experimental methods. Here we report a study on bimolecular reactions of fullerene and metallofullerene molecules inside carbon nanotubes as a function of electron dose. Images of how the fullerenes move during the dimerization process reveal the specific orientations in which two molecules interact, as well as how bond reorganization occurs after their initial contact. Studies on the concentration, specimen temperature, effect of catalyst and accelerating voltage indicate that the reactions can be imaged under a variety of conditions.

0 Bookmarks
 · 
107 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: Recent advances in molecule-by-molecule transmission electron microscopy (TEM) have provided time-series structural information of individual molecules supported by nano-carbon materials, enabling researchers to trace their motions and reactions. In this paper, the chemical reactions of fullerenes and metallofullerene derivatives, focusing on their deformation process, are reviewed and discussed based on the single-molecule-resolved TEM analysis.
    Dalton Transactions 03/2014; · 4.10 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: In this article we probe the nature of electronic interactions between the components of hybrid C60-carbon nanotube structures. Utilizing an aromatic mediator we selectively attach C60 molecules to carbon nanotube field-effect transistor devices. Structural characterization via atomic force and transmission electron microscopy confirm the selectivity of this attachment. Charge transfer from the carbon nanotube to the C60 molecules is evidenced by a blue shift of the Raman G(+) peak position and increased threshold voltage of the transistor transfer characteristics. We estimate this charge transfer to increase the device density of holes per unit length by up to 0.85 nm(-1) and demonstrate further optically enhanced charge transfer which increases the hole density by an additional 0.16 nm(-1).
    Nanoscale 11/2013; · 6.73 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Three different types of carbon nanoreactors, double-walled nanotubes (DWNT), multi-walled nanotubes (MWNT) and graphitised carbon nanofibers (GNF) have been appraised for the first time as containers for the reactions of phenylacetylene hydrosilylation catalysed by a confined molecular catalyst [Rh4(CO)12]. Interactions of [Rh4(CO)12] with carbon nanoreactors determining the ratio of β-addition products are unchanged for all nanoreactors and are virtually unaffected by the confinement of [Rh4(CO)12] inside carbon nanostructures. Conversely, the relative concentrations of reactants affecting the ratio of addition and dehydrogenative silylation products is very sensitive to nanoscale confinement, with all nanoreactors demonstrating significant effects on the distribution of reaction products as compared to control experiments with the catalyst in bulk solution or adsorbed on the outer surface of nanoreactors. Surprisingly, the widest nanoreactors (GNF) change the reaction pathway most significantly, which is attributed to the graphitic step-edges inside GNF providing effective anchoring points for the catalyst and creating local environments with greatly altered concentrations of reactants as compared to bulk solution. Possessing diameters significantly wider than molecules, GNF impose no restrictions on the transfer of reactants while providing the strongest confinement effects for the reaction. Furthermore, GNF facilitate the effective recyclability of the catalyst and thus represents a superior nanoreactor system to carbon nanotubes.
    Small 05/2014; · 7.82 Impact Factor

Full-text

Download
1 Download
Available from