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Issue 38, 2012
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Hydrogenation properties of KSi and NaSi Zintl phases

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The recently reported KSi–KSiH3 system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (Ea) of 56.0 ± 5.7 kJ mol−1 and 121 ± 17 kJ mol−1 for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K8Si46, instead of forming the KSiH3 hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na8Si46, indicating a very poorly reversible reaction.

Graphical abstract: Hydrogenation properties of KSi and NaSi Zintl phases

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Publication details

The article was received on 16 May 2012, accepted on 07 Aug 2012 and first published on 07 Aug 2012

Article type: Paper
DOI: 10.1039/C2CP41589E
Citation: Phys. Chem. Chem. Phys., 2012,14, 13319-13324
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    Hydrogenation properties of KSi and NaSi Zintl phases

    W. S. Tang, J. Chotard, P. Raybaud and R. Janot, Phys. Chem. Chem. Phys., 2012, 14, 13319
    DOI: 10.1039/C2CP41589E

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