From M(BH4)3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors

Autor: Yaroslav Filinchuk, Radovan Černý, Torben R. Jensen, Morten B. Ley, Mathias Jørgensen
Rok vydání: 2016
Předmět:
Zdroj: Ley, M B, Jørgensen, M, Černý, R, Filinchuk, Y & Jensen, T R 2016, ' From M(BH 4 ) 3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors ', Inorganic Chemistry, vol. 55, no. 19, pp. 9748-9756 . https://doi.org/10.1021/acs.inorgchem.6b01526
Inorganic Chemistry, Vol. 55, No 19 (2016) pp. 9748-9756
Inorganic Chemistry
ISSN: 1520-510X
0020-1669
Popis: Rare 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 (Fm3c) 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.
Databáze: OpenAIRE