Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition

© 2017 The Royal Society of Chemistry. A new synthesis method of samarium borohydride, Sm(BH4)2, using tetrahydrofuran borane, THF-BH3, and samarium hydride, SmH2, has been demonstrated and verified. The synthesised Sm(BH4)2was mechanochemically treated with MBH4, M = K, Rb, Cs. Initially, the forma...

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Main Authors: Moller, Kasper, Jørgensen, M., Fogh, A., Jensen, Torben
Format: Journal Article
Published: R S C Publications 2017
Online Access:http://hdl.handle.net/20.500.11937/71435
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author Moller, Kasper
Jørgensen, M.
Fogh, A.
Jensen, Torben
author_facet Moller, Kasper
Jørgensen, M.
Fogh, A.
Jensen, Torben
author_sort Moller, Kasper
building Curtin Institutional Repository
collection Online Access
description © 2017 The Royal Society of Chemistry. A new synthesis method of samarium borohydride, Sm(BH4)2, using tetrahydrofuran borane, THF-BH3, and samarium hydride, SmH2, has been demonstrated and verified. The synthesised Sm(BH4)2was mechanochemically treated with MBH4, M = K, Rb, Cs. Initially, the formation of KSm(BH4)3is observed while subsequent heat treatment is necessary to form MSm(BH4)3, M = Rb, Cs. The new compounds crystallise in orthorhombic unit cells adopting perovskite-type 3D frameworks containing distorted [Sm(BH4)6] octahedra. In situ X-ray diffraction studies reveal two second-order polymorphic transitions of a-CsSm(BH4)3via a tetragonal intermediate, a'-CsSm(BH4)3, into a cubic high-temperature polymorph, ß-CsSm(BH4)3, resembling an ideal perovskite structure. The new compounds, MSm(BH4)3, are thermally stable up to T ~ 280 °C after which they decompose into mainly MBH4, SmH2and possibly SmB6and SmB12H12. Finally, after three cycles of hydrogen release and uptake, the storage capacity was 1.0 wt% for KSm(BH4)3and 0.84 wt% for RbSm(BH4)3and CsSm(BH4)3.
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spelling curtin-20.500.11937-714352018-12-13T09:32:59Z Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition Moller, Kasper Jørgensen, M. Fogh, A. Jensen, Torben © 2017 The Royal Society of Chemistry. A new synthesis method of samarium borohydride, Sm(BH4)2, using tetrahydrofuran borane, THF-BH3, and samarium hydride, SmH2, has been demonstrated and verified. The synthesised Sm(BH4)2was mechanochemically treated with MBH4, M = K, Rb, Cs. Initially, the formation of KSm(BH4)3is observed while subsequent heat treatment is necessary to form MSm(BH4)3, M = Rb, Cs. The new compounds crystallise in orthorhombic unit cells adopting perovskite-type 3D frameworks containing distorted [Sm(BH4)6] octahedra. In situ X-ray diffraction studies reveal two second-order polymorphic transitions of a-CsSm(BH4)3via a tetragonal intermediate, a'-CsSm(BH4)3, into a cubic high-temperature polymorph, ß-CsSm(BH4)3, resembling an ideal perovskite structure. The new compounds, MSm(BH4)3, are thermally stable up to T ~ 280 °C after which they decompose into mainly MBH4, SmH2and possibly SmB6and SmB12H12. Finally, after three cycles of hydrogen release and uptake, the storage capacity was 1.0 wt% for KSm(BH4)3and 0.84 wt% for RbSm(BH4)3and CsSm(BH4)3. 2017 Journal Article http://hdl.handle.net/20.500.11937/71435 10.1039/c7dt02405c R S C Publications restricted
spellingShingle Moller, Kasper
Jørgensen, M.
Fogh, A.
Jensen, Torben
Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition
title Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition
title_full Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition
title_fullStr Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition
title_full_unstemmed Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition
title_short Perovskite alkali metal samarium borohydrides: Crystal structures and thermal decomposition
title_sort perovskite alkali metal samarium borohydrides: crystal structures and thermal decomposition
url http://hdl.handle.net/20.500.11937/71435