Facile synthesis of anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) from M(BH4)2

Liqing He; Hai Wen Li; Nikolay Tumanov; Yaroslav Filinchuk; Etsuo Akiba

doi:10.1039/c5dt02343b

Facile synthesis of anhydrous alkaline earth metal dodecaborates MB₁₂H₁₂ (M = Mg, Ca) from M(BH₄)₂

Liqing He, Hai Wen Li, Nikolay Tumanov, Yaroslav Filinchuk, Etsuo Akiba

Research output: Contribution to journal › Article › peer-review

Abstract

Metal dodecaborates M_2/nB₁₂H₁₂ are among the dehydrogenation intermediates of metal borohydrides M(BH₄)_n with a high hydrogen density of approximately 10 mass%, the latter is a potential hydrogen storage material. There is therefore a great need to synthesize anhydrous M_2/nB₁₂H₁₂ in order to investigate the thermal decomposition of M_2/nB₁₂H₁₂ and to understand its role in the dehydrogenation and rehydrogenation of M(BH₄)_n. In this work, anhydrous alkaline earth metal dodecaborates MB₁₂H₁₂ (M = Mg, Ca) have been successfully synthesized by sintering M(BH₄)₂ (M = Mg, Ca) and B₁₀H₁₄ in a stoichiometric molar ratio of 1 : 1. Thermal decomposition of MB₁₂H₁₂ shows multistep pathways with the formation of H-deficient monomers MB₁₂H_12-x containing icosahedral B₁₂ skeletons and is followed by the formation of (MB_yH_z)_n polymers. Comparison of the thermal decomposition of MB₁₂H₁₂ and M(BH₄)₂ suggests different behaviours of the anhydrous MB₁₂H₁₂ and those formed from the decomposition of M(BH₄)_n.

Original language	English
Pages (from-to)	15882-15887
Number of pages	6
Journal	Dalton Transactions
Volume	44
Issue number	36
DOIs	https://doi.org/10.1039/c5dt02343b
Publication status	Published - 30 Jul 2015
Externally published	Yes

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title = "Facile synthesis of anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) from M(BH4)2",

abstract = "Metal dodecaborates M2/nB12H12 are among the dehydrogenation intermediates of metal borohydrides M(BH4)n with a high hydrogen density of approximately 10 mass%, the latter is a potential hydrogen storage material. There is therefore a great need to synthesize anhydrous M2/nB12H12 in order to investigate the thermal decomposition of M2/nB12H12 and to understand its role in the dehydrogenation and rehydrogenation of M(BH4)n. In this work, anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) have been successfully synthesized by sintering M(BH4)2 (M = Mg, Ca) and B10H14 in a stoichiometric molar ratio of 1 : 1. Thermal decomposition of MB12H12 shows multistep pathways with the formation of H-deficient monomers MB12H12-x containing icosahedral B12 skeletons and is followed by the formation of (MByHz)n polymers. Comparison of the thermal decomposition of MB12H12 and M(BH4)2 suggests different behaviours of the anhydrous MB12H12 and those formed from the decomposition of M(BH4)n.",

author = "Liqing He and Li, {Hai Wen} and Nikolay Tumanov and Yaroslav Filinchuk and Etsuo Akiba",

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T1 - Facile synthesis of anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) from M(BH4)2

AU - He, Liqing

AU - Li, Hai Wen

AU - Tumanov, Nikolay

AU - Filinchuk, Yaroslav

AU - Akiba, Etsuo

PY - 2015/7/30

Y1 - 2015/7/30

N2 - Metal dodecaborates M2/nB12H12 are among the dehydrogenation intermediates of metal borohydrides M(BH4)n with a high hydrogen density of approximately 10 mass%, the latter is a potential hydrogen storage material. There is therefore a great need to synthesize anhydrous M2/nB12H12 in order to investigate the thermal decomposition of M2/nB12H12 and to understand its role in the dehydrogenation and rehydrogenation of M(BH4)n. In this work, anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) have been successfully synthesized by sintering M(BH4)2 (M = Mg, Ca) and B10H14 in a stoichiometric molar ratio of 1 : 1. Thermal decomposition of MB12H12 shows multistep pathways with the formation of H-deficient monomers MB12H12-x containing icosahedral B12 skeletons and is followed by the formation of (MByHz)n polymers. Comparison of the thermal decomposition of MB12H12 and M(BH4)2 suggests different behaviours of the anhydrous MB12H12 and those formed from the decomposition of M(BH4)n.

AB - Metal dodecaborates M2/nB12H12 are among the dehydrogenation intermediates of metal borohydrides M(BH4)n with a high hydrogen density of approximately 10 mass%, the latter is a potential hydrogen storage material. There is therefore a great need to synthesize anhydrous M2/nB12H12 in order to investigate the thermal decomposition of M2/nB12H12 and to understand its role in the dehydrogenation and rehydrogenation of M(BH4)n. In this work, anhydrous alkaline earth metal dodecaborates MB12H12 (M = Mg, Ca) have been successfully synthesized by sintering M(BH4)2 (M = Mg, Ca) and B10H14 in a stoichiometric molar ratio of 1 : 1. Thermal decomposition of MB12H12 shows multistep pathways with the formation of H-deficient monomers MB12H12-x containing icosahedral B12 skeletons and is followed by the formation of (MByHz)n polymers. Comparison of the thermal decomposition of MB12H12 and M(BH4)2 suggests different behaviours of the anhydrous MB12H12 and those formed from the decomposition of M(BH4)n.

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DO - 10.1039/c5dt02343b

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Facile synthesis of anhydrous alkaline earth metal dodecaborates MB₁₂H₁₂ (M = Mg, Ca) from M(BH₄)₂

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