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Economical synthesis of vanadia aerogels via epoxide-assisted gelation of VOCl3

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Abstract

Herein is reported the first synthesis of vanadium oxide (vanadia) aerogels via epoxide-assisted gelation. Vanadia aerogels fabricated via epoxide-assisted gelation using VOCl3 and epichlorohydrin mimic those fabricated via the hydrolysis of vanadium oxytripropoxide while reducing cost per mole by a factor of 10, on par with silica gels synthesized from alkyl orthosilicates. Typical vanadia aerogels possess a macroporous nanoworm morphology, a density of 0.103 g/cm3, 96.9 % porosity, a specific surface area of 102 m2/g, and ~18 % reversible hydration capacity by mass. 1H and 13C NMR reveal that epoxide ring-opening does not proceed through epoxide protonation, as is the typical case with other transition metal oxide gels, but rather through Lewis-acid-catalyzed ring-opening. A multi-step gelation mechanism is proposed involving a fast initial VV oxide gelation, driven by H+ and Cl consumption during epoxide ring-opening, followed by partial vanadia dissolution, VV → VIV reduction, and secondary gelation of low-valent VIV/V oxide.

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Acknowledgments

T. M. F. would like to thank Dr. Shruti Mahadik-Khanolkar for her expertise in synthesizing vanadia aerogels, Dr. H. Lu (of The University of Texas-Dallas) for quasi-static compression measurements, and Dr. Chakkaravarthy Chidambareswarapattar for N2 porosimetry measurements. The authors would also like to thank Bayer Corporation, USA, for their generous supply of Desmodur N3200A isocyanate.

Funding

This project was funded by the Army Research Office (W911NF-14-1-0369). The Materials Research Center of Missouri S&T provided partial support with materials characterization. Student support was provided in part by the National Science Foundation through a University of Missouri Neutron Scattering IGERT Traineeship (Grant DGE-1069091).

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Fears, T.M., Sotiriou-Leventis, C., Winiarz, J.G. et al. Economical synthesis of vanadia aerogels via epoxide-assisted gelation of VOCl3 . J Sol-Gel Sci Technol 77, 244–256 (2016). https://doi.org/10.1007/s10971-015-3850-x

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  • DOI: https://doi.org/10.1007/s10971-015-3850-x

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