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Interplay Between Size and Crystal Structure of Molybdenum Dioxide Nanoparticles—Synthesis, Growth Mechanism, and Electrochemical Performance
Author(s) -
Koziej Dorota,
Rossell Marta D.,
Ludi Bettina,
Hintennach Andreas,
Novák Petr,
Grunwaldt JanDierk,
Niederberger Markus
Publication year - 2011
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.201001606
Subject(s) - materials science , nanorod , nucleation , crystallization , monoclinic crystal system , dissolution , chemical engineering , crystallography , nanoparticle , crystal (programming language) , crystal structure , nanotechnology , chemistry , organic chemistry , programming language , computer science , engineering
A detailed study is presented on the formation of MoO 2 nanoparticles from the dissolution of the precursor to the final rodlike product, with a focus on the exploration of the inorganic reaction occurring ahead of the nucleation step, and interplay between size and crystal structure of MoO 2 . In situ X‐ray absorption spectroscopy experiments show that the crystallization and the growth process of MoO 2 nanorods is initiated by rapid reduction of the MoO 2 Cl 2 precursor in benzyl alcohol and acetophenone. This reaction triggers the nucleation of 2 nm MoO 2 particles with spherical shape and hexagonal crystal structure. The transformation from spheres into rods emerges as a complex process driven by oriented attachment. High‐resolution transmission electron microscopy and X‐ray diffraction results provide evidence that the 2 nm particles first aggregate into 5–20 nm‐large oriented assemblies. The increase in particle size induces the phase transition from hexagonal to the less symmetrical monoclinic crystal structure, and finally the transformation into rods. Is it shown that electrodes for lithium‐ion batteries based on MoO 2 nanorods have a long‐term cycling life. The specific discharge capacity even after 200 cycles at a discharge rate of 1 C is about 300 Ah kg −1 .