In Situ Hydrogenation and Crystal Chemistry Studies of Co2Si Type Compounds MgPd2 and Pd2Zn

The hydrogenation properties of the intermetallic compounds MgPd2 and Pd2Zn, crystallizing in the Co2Si type, were studied by in situ thermal analysis (DSC) under hydrogen pressure. Pd2Zn does not show any reaction with hydrogen while MgPd2 reversibly forms the hydride MgPd2H. Neutron diffraction on the deuterides reveals the compositions MgPd2D0.861(6) (ambient) and MgPd2D0.97(1) [308(2) K, 2.56(5) MPa deuterium] with hydrogen (deuterium) occupying distorted [MgPd5] octahedral voids. Quantum mechanical calculations support the structure models and show the hydrogenation to be exergonic for MgPd2 and endergonic for Pd2Zn. MgPd2H releases hydrogen under normal conditions or vacuum. Heating under hydrogen pressure leads first reversibly to MgPd2H≈0.2 and subsequently irreversibly to MgPd3H≈1 and MgH2. MgPd2, Pd2Zn, and MgPd2H were classified in a structure map. Trends of axial ratio changes upon hydrogenation of TiNiSi type and ZrBeSi type compounds are discussed.

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