Analysis of Intermediates and Products from the Dehydrogenation of Mg(BH4)2

The thermodynamic properties of key compounds Mg(B3H8)(2), MgB2H6, MgB10H10, Mg(B11H14)(2), Mg-3(B3H6)(2), and MgB12H12, proposed to be formed in the release of hydrogen from magnesium borohydride Mg(BH4)(2) and the uptake of hydrogen by MgB2, have been investigated using solid-state density functional theory (DFT) calculations. More accurate tretment of the cell-size effects with respect to the entropies was also investigated in order to improve the accuracy of the thermodynamic properties of complex borohydrides. We find that the zero-point energy corrections can lower the electronic energies of reaction by 20-30 kJ/(mol H-2) for these intermediates, while adding the thermal and entropy contibutions results in a total decrease of up to similar to 50 kJ/(mol H-2). Although our treatment lowers the calculated formation energy of Mg(B3H8)(2), it is still too high to explain the experimental observation of B3H8-. We discuss possible reasons for this disparity and propose that the formation of B3H8- and H- in a disordered amorphous phase has a large energy difference compared to the phaseseparated Mg(B3H8)(2) and MgH2 considered in calculations. A comparison of the experimental and NMR chemical shifts calculated within a DFT approach for known species Mg(BH4)(2), Mg(B3H8)(2), Mg(B11H14)(2), MgB10H10, and MgB12H12 provides validation for predicting the chemical shifts of the other compounds which are yet to be confirmed experimentally. These include MgB2H6 and the proposed trianion species Mg-3(B3H6)(2) that both have favorable thermodynamics for reversible hydrogen storage in Mg(BH4)(2) without the formation of MgH2 as a coproduct which could phase separate and inhibit rehydrogenation.

Automated summary

The thermodynamic properties of key compounds formed in the release and uptake of hydrogen by magnesium borohydride have been investigated using solid-state density functional theory calculations. The effects of cell-size and zero-point energy corrections on the entropies were analyzed. Experimental validation for the predicted chemical shifts of various compounds was provided. The reversible hydrogen storage characteristics of MgB2H6 and Mg-3(B3H6)(2) were discussed.