Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca)

Bjarne R.S. Hansen, Nikolay Tumanov, Antonio Santoru, Claudio Pistidda, Jozef Bednarcik, Thomas Klassen, Martin Dornheim, Yaroslav Filinchuk, Torben R. Jensen

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

A series of ammine metal-dodecahydro-closo-dodecaboranes, MxB12H12·nNH3 (M = Li, Na, Ca) were synthesized and their structural and thermal properties studied with in situ time-resolved synchrotron radiation powder X-ray diffraction, thermal analysis, Fourier transformed infrared spectroscopy, and temperature-programmed photographic analysis. The synthesized compounds, Li2B12H12·7NH3, Na2B12H12·4NH3 and CaB12H12·6NH3, contain high amounts of NH3, 43.3, 26.6 and 35.9 wt% NH3, respectively, which can be released and absorbed reversibly at moderate conditions without decomposition, thereby making the closo-boranes favorable 'host' materials for ammonia or indirect hydrogen storage in the solid state. In this work, fifteen new ammine metal dodecahydro-closo-dodecaborane compounds are observed by powder X-ray diffraction, of which six are structurally characterized, Li2B12H12·4NH3, Li2B12H12·2NH3, Na2B12H12·4NH3, Na2B12H12·2NH3, CaB12H12·4NH3 and CaB12H12·3NH3. Li2B12H12·4NH3 and Na2B12H12·4NH3 are isostructural and monoclinic (P21/n) whereas Na2B12H12·2NH3 and CaB12H12·3NH3 are both trigonal with space groups P3m1 and R3c, respectively. Generally, coordination between the metal and the icosahedral closo-borane anion is diverse and includes point sharing, edge sharing, or face sharing, while coordination of ammonia always occurs via the lone pair on nitrogen to the metal. Furthermore, a liquid intermediate is observed during heating of Li2B12H12·7NH3. This work provides deeper insight into the structural, physical, and chemical properties related to thermal decomposition and possible ammonia and hydrogen storage.

langueAnglais
Pages7770-7781
Nombre de pages12
journalDalton Transactions
Volume46
Numéro24
Les DOIs
étatPublié - 30 mai 2017

Empreinte digitale

Pyrolysis
Metals
Ammonia
Boranes
Hydrogen storage
X ray powder diffraction
Structural properties
Synchrotron radiation
Chemical properties
Thermoanalysis
Anions
Infrared spectroscopy
Nitrogen
Thermodynamic properties
Physical properties
Decomposition
Heating
Liquids
Temperature

Citer ceci

Hansen, B. R. S., Tumanov, N., Santoru, A., Pistidda, C., Bednarcik, J., Klassen, T., ... Jensen, T. R. (2017). Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca). Dalton Transactions, 46(24), 7770-7781. DOI: 10.1039/c7dt01414g
Hansen, Bjarne R.S. ; Tumanov, Nikolay ; Santoru, Antonio ; Pistidda, Claudio ; Bednarcik, Jozef ; Klassen, Thomas ; Dornheim, Martin ; Filinchuk, Yaroslav ; Jensen, Torben R./ Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca). Dans: Dalton Transactions. 2017 ; Vol 46, Numéro 24. p. 7770-7781
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abstract = "A series of ammine metal-dodecahydro-closo-dodecaboranes, MxB12H12·nNH3 (M = Li, Na, Ca) were synthesized and their structural and thermal properties studied with in situ time-resolved synchrotron radiation powder X-ray diffraction, thermal analysis, Fourier transformed infrared spectroscopy, and temperature-programmed photographic analysis. The synthesized compounds, Li2B12H12·7NH3, Na2B12H12·4NH3 and CaB12H12·6NH3, contain high amounts of NH3, 43.3, 26.6 and 35.9 wt{\%} NH3, respectively, which can be released and absorbed reversibly at moderate conditions without decomposition, thereby making the closo-boranes favorable 'host' materials for ammonia or indirect hydrogen storage in the solid state. In this work, fifteen new ammine metal dodecahydro-closo-dodecaborane compounds are observed by powder X-ray diffraction, of which six are structurally characterized, Li2B12H12·4NH3, Li2B12H12·2NH3, Na2B12H12·4NH3, Na2B12H12·2NH3, CaB12H12·4NH3 and CaB12H12·3NH3. Li2B12H12·4NH3 and Na2B12H12·4NH3 are isostructural and monoclinic (P21/n) whereas Na2B12H12·2NH3 and CaB12H12·3NH3 are both trigonal with space groups P3m1 and R3c, respectively. Generally, coordination between the metal and the icosahedral closo-borane anion is diverse and includes point sharing, edge sharing, or face sharing, while coordination of ammonia always occurs via the lone pair on nitrogen to the metal. Furthermore, a liquid intermediate is observed during heating of Li2B12H12·7NH3. This work provides deeper insight into the structural, physical, and chemical properties related to thermal decomposition and possible ammonia and hydrogen storage.",
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Hansen, BRS, Tumanov, N, Santoru, A, Pistidda, C, Bednarcik, J, Klassen, T, Dornheim, M, Filinchuk, Y & Jensen, TR 2017, 'Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca)' Dalton Transactions, VOL. 46, Numéro 24, p. 7770-7781. DOI: 10.1039/c7dt01414g

Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca). / Hansen, Bjarne R.S.; Tumanov, Nikolay; Santoru, Antonio; Pistidda, Claudio; Bednarcik, Jozef; Klassen, Thomas; Dornheim, Martin; Filinchuk, Yaroslav; Jensen, Torben R.

Dans: Dalton Transactions, Vol 46, Numéro 24, 30.05.2017, p. 7770-7781.

Résultats de recherche: Contribution à un journal/une revueArticle

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T1 - Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca)

AU - Hansen,Bjarne R.S.

AU - Tumanov,Nikolay

AU - Santoru,Antonio

AU - Pistidda,Claudio

AU - Bednarcik,Jozef

AU - Klassen,Thomas

AU - Dornheim,Martin

AU - Filinchuk,Yaroslav

AU - Jensen,Torben R.

PY - 2017/5/30

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AB - A series of ammine metal-dodecahydro-closo-dodecaboranes, MxB12H12·nNH3 (M = Li, Na, Ca) were synthesized and their structural and thermal properties studied with in situ time-resolved synchrotron radiation powder X-ray diffraction, thermal analysis, Fourier transformed infrared spectroscopy, and temperature-programmed photographic analysis. The synthesized compounds, Li2B12H12·7NH3, Na2B12H12·4NH3 and CaB12H12·6NH3, contain high amounts of NH3, 43.3, 26.6 and 35.9 wt% NH3, respectively, which can be released and absorbed reversibly at moderate conditions without decomposition, thereby making the closo-boranes favorable 'host' materials for ammonia or indirect hydrogen storage in the solid state. In this work, fifteen new ammine metal dodecahydro-closo-dodecaborane compounds are observed by powder X-ray diffraction, of which six are structurally characterized, Li2B12H12·4NH3, Li2B12H12·2NH3, Na2B12H12·4NH3, Na2B12H12·2NH3, CaB12H12·4NH3 and CaB12H12·3NH3. Li2B12H12·4NH3 and Na2B12H12·4NH3 are isostructural and monoclinic (P21/n) whereas Na2B12H12·2NH3 and CaB12H12·3NH3 are both trigonal with space groups P3m1 and R3c, respectively. Generally, coordination between the metal and the icosahedral closo-borane anion is diverse and includes point sharing, edge sharing, or face sharing, while coordination of ammonia always occurs via the lone pair on nitrogen to the metal. Furthermore, a liquid intermediate is observed during heating of Li2B12H12·7NH3. This work provides deeper insight into the structural, physical, and chemical properties related to thermal decomposition and possible ammonia and hydrogen storage.

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Hansen BRS, Tumanov N, Santoru A, Pistidda C, Bednarcik J, Klassen T et al. Synthesis, structures and thermal decomposition of ammine MxB12H12 complexes (M = Li, Na, Ca). Dalton Transactions. 2017 mai 30;46(24):7770-7781. Disponible �, DOI: 10.1039/c7dt01414g