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We report direct hydrogenation of MgB2 in a planetary ball mill. Magnesium borohydride, Mg(BH4)2, and various polyhedral borane anion salts have been synthesized at pressures between 50 and 350 bar H2 without the need for subsequent isothermal hydrogenation at elevated temperature and pressure. The obtained products release 4 wt% H2 below 390 °C, and a major portion of Mg(BH4)2 transforms back to MgB2 at around 300 °C, demonstrating the possibility of reversible hydrogen storage in an Mg(BH4)2–MgB2 system.
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