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From M(BH4)3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors
journal contribution
posted on 2016-09-13, 13:03 authored by Morten Brix Ley, Mathias Jørgensen, Radovan Černý, Yaroslav Filinchuk, Torben R. JensenRare earth metal borohydrides show
a number of interesting properties, e.g., Li ion conductivity and
luminescence, and the series of materials is well explored. However,
previous attempts to obtain M(BH4)3 (M = La,
Ce) by reacting MCl3 and LiBH4 yielded LiM(BH4)3Cl. Here, a synthetic approach
is presented, which allows the isolation of M(BH4)3 (M = La, Ce) via formation of intermediate complexes with
dimethyl sulfide. The cubic c-Ce(BH4)3 (Fm3̅c) is isostructural
to high-temperature polymorphs of A(BH4)3 (A
= Y, Sm, Er, Yb) borohydrides. The larger size of the Ce3+ ion makes the empty void in the open ReO3-type framework
structure potentially accessible to small guest molecules like H2. Another new rhombohedral polymorph, r-M(BH4)3 (M = La, Ce), is a closed form of the framework,
prone to stacking faults. The new compounds M(BH4)3 (M = La, Ce) can be combined with LiCl in an addition reaction
to form LiM(BH4)3Cl also known as Li4[M4(BH4)12Cl4]; the latter
contains the unique tetranuclear cluster [M4(BH4)12Cl4]4– and shows high
Li-ion conductivity. This reaction pathway opens a way to synthesize
a series of A4[M4(BH4)12X4] (M = La, Ce) compounds with different anions (X) and
metal ions (A) and potentially high ion conductivity.