Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates
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Accepted Version
Date
2012-05-15
Authors
Díaz, Carlos
Valenzuela, María Luisa
Lavayen, Vladimir
O'Dwyer, Colm
Journal Title
Journal ISSN
Volume Title
Publisher
American Chemical Society
Published Version
Abstract
We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn2P2O7 can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host–guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials
Description
Keywords
Metal pyrophosphates , Raman spectroscopy , Infrared spectroscopy , Graphitic carbon
Citation
Diaz, C., Valenzuela, M. L., Lavayen, V. and O'Dwyer, C. (2012) 'Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates', Inorganic Chemistry, 51(11), pp 6228–6236. http://dx.doi.org/10.1021/ic300767h
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Copyright
© 2012 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ic300767h