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Nanoseashells and Nanooctahedra of MoS2: Routes to Inorganic Fullerenes

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Physikalische Chemie, Technische Universität Dresden, D-01062 Dresden, Germany
Institute of Solid State Chemistry UB RAS, GSP-145, 620990 Ekaterinburg, Russia
§ Institute of Solid State Research and Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Department of Physics, University of Warwick, Coventry, Warwickshire CV4 7AL, U.K.
*Corresponding author. E-mail: [email protected]
⊥These authors contributed equally to this work.
Cite this: Chem. Mater. 2009, 21, 23, 5627–5636
Publication Date (Web):October 27, 2009
https://doi.org/10.1021/cm9021326
Copyright © 2009 American Chemical Society

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    Abstract

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    Nanooctahedra of MoS2 are considered to be the true inorganic fullerenes, exhibiting different properties from the bulk and also other closed-cage morphologies of the same material. These structures are produced in high energy systems where the synthesis is performed far from equilibrium conditions, and the reaction mechanism involved remains unknown. Here, the discovery of two imperfect structures of nanooctahedra−the distorted octahedra and seashell structures with meander-like cross sections−is reported and studied in detail using transmission electron microscopy and quantum-mechanical methods. These nanoparticles can serve to understand the synthesis route by establishing the basic principles of their morphology and stability. The fundamental properties of the inorganic lattice are the basis for matching the projections observed in microscopy images with a suggested atomistic model. Quantum-mechanical calculations are used to estimate their stability and electronic properties. It was concluded that the production of nanooctahedra involves a high temperature stage, where lattice defects enable the formation of a closed structure without a templating particle. Thereafter at lower temperatures, the mixture of products is carried forward and the annealing contributes to the enrichment of the product with more symmetric structures.

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    Figure S1 shows a gallery of different morphologies of distorted MoS2 nanooctahedra, Figure S2 displays graphs of the energies of distorted MoS2 nanooctahedra as a function of their morphology and size, and Figure S3 shows energies per atom of distorted MoS2 nanooctahedra (PDF). This material is available free of charge via the Internet at http://pubs.acs.org.

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