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      Chiral-Selective Growth of Single-Walled Carbon Nanotubes on Lattice-Mismatched Epitaxial Cobalt Nanoparticles

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          Abstract

          Controlling chirality in growth of single-walled carbon nanotubes (SWNTs) is important for exploiting their practical applications. For long it has been conceptually conceived that the structural control of SWNTs is potentially achievable by fabricating nanoparticle catalysts with proper structures on crystalline substrates via epitaxial growth techniques. Here, we have accomplished epitaxial formation of monometallic Co nanoparticles with well-defined crystal structure, and its use as a catalyst in the selective growth of SWNTs. Dynamics of Co nanoparticles formation and SWNT growth inside an atomic-resolution environmental transmission electron microscope at a low CO pressure was recorded. We achieved highly preferential growth of semiconducting SWNTs (~90%) with an exceptionally large population of (6, 5) tubes (53%) in an ambient CO atmosphere. Particularly, we also demonstrated high enrichment in (7, 6) and (9, 4) at a low growth temperature. These findings open new perspectives both for structural control of SWNTs and for elucidating the growth mechanisms.

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          Most cited references27

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          Band gap fluorescence from individual single-walled carbon nanotubes.

          Fluorescence has been observed directly across the band gap of semiconducting carbon nanotubes. We obtained individual nanotubes, each encased in a cylindrical micelle, by ultrasonically agitating an aqueous dispersion of raw single-walled carbon nanotubes in sodium dodecyl sulfate and then centrifuging to remove tube bundles, ropes, and residual catalyst. Aggregation of nanotubes into bundles otherwise quenches the fluorescence through interactions with metallic tubes and substantially broadens the absorption spectra. At pH less than 5, the absorption and emission spectra of individual nanotubes show evidence of band gap-selective protonation of the side walls of the tube. This protonation is readily reversed by treatment with base or ultraviolet light.
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            DNA-assisted dispersion and separation of carbon nanotubes.

            Carbon nanotubes are man-made one-dimensional carbon crystals with different diameters and chiralities. Owing to their superb mechanical and electrical properties, many potential applications have been proposed for them. However, polydispersity and poor solubility in both aqueous and non-aqueous solution impose a considerable challenge for their separation and assembly, which is required for many applications. Here we report our finding of DNA-assisted dispersion and separation of carbon nanotubes. Bundled single-walled carbon nanotubes are effectively dispersed in water by their sonication in the presence of single-stranded DNA (ssDNA). Optical absorption and fluorescence spectroscopy and atomic force microscopy measurements provide evidence for individually dispersed carbon nanotubes. Molecular modelling suggests that ssDNA can bind to carbon nanotubes through pi-stacking, resulting in helical wrapping to the surface. The binding free energy of ssDNA to carbon nanotubes rivals that of two nanotubes for each other. We also demonstrate that DNA-coated carbon nanotubes can be separated into fractions with different electronic structures by ion-exchange chromatography. This finding links one of the central molecules in biology to a technologically very important nanomaterial, and opens the door to carbon-nanotube-based applications in biotechnology.
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              Sorting carbon nanotubes by electronic structure using density differentiation.

              The heterogeneity of as-synthesized single-walled carbon nanotubes (SWNTs) precludes their widespread application in electronics, optics and sensing. We report on the sorting of carbon nanotubes by diameter, bandgap and electronic type using structure-discriminating surfactants to engineer subtle differences in their buoyant densities. Using the scalable technique of density-gradient ultracentrifugation, we have isolated narrow distributions of SWNTs in which >97% are within a 0.02-nm-diameter range. Furthermore, using competing mixtures of surfactants, we have produced bulk quantities of SWNTs of predominantly a single electronic type. These materials were used to fabricate thin-film electrical devices of networked SWNTs characterized by either metallic or semiconducting behaviour.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                15 March 2013
                2013
                : 3
                : 1460
                Affiliations
                [1 ]Department of Biotechnology and Chemical Technology, School of Chemical Technology, Aalto University , P.O. Box 16100, FI-00076 Aalto, Finland
                [2 ]NanoMaterials Group, Department of Applied Physics and Center for New Materials, School of Science, Aalto University , P.O. Box 15100, FI-00076 Aalto, Finland
                [3 ]Shenyang National Laboratory for Materials Science, Institute of Metal Research , Chinese Academy of Sciences, Shenyang 110016, P. R. China
                [4 ]A.M. Prokhorov General Physics Institute RAS , 38 Vavilov Street, 119991 Moscow, Russia
                [5 ]Center for Electron Nanoscopy, Technical University of Denmark , DK-2800 Kongens Lyngby, Denmark
                Author notes
                Article
                srep01460
                10.1038/srep01460
                3597999
                23492872
                7cb3d086-eeed-471d-806b-7388871ecec1
                Copyright © 2013, Macmillan Publishers Limited. All rights reserved

                This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-nd/3.0/

                History
                : 09 November 2012
                : 25 February 2013
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