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Melting of Magnesium Borohydride under High Hydrogen Pressure: Thermodynamic Stability and Effects of Nanoconfinement

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    Melting of Magnesium Borohydride under High Hydrogen Pressure: Thermodynamic Stability and Effects of Nanoconfinement
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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 13, 5604–5615
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    https://doi.org/10.1021/acs.chemmater.0c01050
    Published June 4, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The thermodynamic stability and melting point of magnesium borohydride were probed under hydrogen pressures up to 1000 bar (100 MPa) and temperatures up to 400 °C. At 400 °C, Mg(BH4)2 was found to be chemically stable between 700 and 1000 bar H2, whereas under 350 bar H2 or lower pressures, the bulk material partially decomposed into MgH2 and MgB12H12. The melting point of solvent-free Mg(BH4)2 was estimated to be 367–375 °C, which was above previously reported values by 40–90 °C. Our results indicated that a high hydrogen backpressure is needed to prevent the decomposition of Mg(BH4)2 before measuring the melting point and that molten Mg(BH4)2 can exist as a stable liquid phase between 367 and 400 °C under hydrogen overpressures of 700 bar or above. The occurrence of a pure molten Mg(BH4)2 phase enabled efficient melt-infiltration of Mg(BH4)2 into the pores of porous templated carbons (CMK-3 and CMK-8) and graphene aerogels. Both transmission electron microscopy and small-angle X-ray scattering confirmed efficient incorporation of the borohydride into the carbon pores. The Mg(BH4)2@carbon samples exhibited comparable hydrogen capacities to bulk Mg(BH4)2 upon desorption up to 390 °C based on the mass of the active component; the onset of hydrogen release was reduced by 15–25 °C compared to the bulk. Importantly, melt-infiltration under hydrogen pressure was shown to be an efficient way to introduce metal borohydrides into the pores of carbon-based materials, helping to prevent particle agglomeration and formation of stable closo-polyborate byproducts.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c01050.

    • Photographs of the high-pressure hydrogen system and heat-treated Mg(BH4)2; nitrogen adsorption isotherms and results of porous carbon hosts; TEM images and EELS and EDS maps of melt-infiltrated composites; SAXS patterns of carbon hosts and composites; desorption traces of composites; and XRD patterns and IR spectra of hosts, composites, and bulk Mg(BH4)2 before and after desorption (PDF)

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    Cited By

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    This article is cited by 23 publications.

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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 13, 5604–5615
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.0c01050
    Published June 4, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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