Electronic Resource
LiCe(BH 4) 3Cl, a new lithium-ion conductor and hydrogen storage material with isolated tetranuclear anionic clusters
| العنوان: | LiCe(BH 4) 3Cl, a new lithium-ion conductor and hydrogen storage material with isolated tetranuclear anionic clusters |
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| المؤلفون: | UCL - SST/IMCN/MOST - Molecules, Solids and Reactivity, Ley, M.B., Ravnsbæk, D.B., Filinchuk, Yaroslav, Lee, Y.-S., Janot, R., Cho, Y.W., Skibsted, J., Jensen, T.R. |
| المصدر: | Chemistry of Materials, Vol. 24, no.9, p. 1654-1663 (2012) |
| بيانات النشر: | American Chemical Society 2012 |
| نوع الوثيقة: | Electronic Resource |
| مستخلص: | Mechanochemical synthesis using CeCl 3-MBH 4 (M = Li, Na or K) mixtures are investigated and produced a new compound, LiCe(BH 4) 3Cl, which crystallizes in a cubic space group I4̄3m, a = 11.7204(2) Å. The structure contains isolated tetranuclear anionic clusters [Ce 4Cl 4(BH 4) 12] 4- with a distorted cubane Ce 4Cl 4 core, charge-balanced by Li + cations. Each Ce atom coordinates three chloride ions and three borohydride groups via the Ε 3- BH 3 faces, thus completing the coordination environment to an octahedron. Combination of synchrotron radiation powder X-ray diffraction (SR-PXD), powder neutron diffraction and density functional theory (DFT) optimization show that Li cations are disordered, occupying 2/3 of the 12d Wyckoff site. DFT calculation indicates that LiCe(BH 4) 3Cl is stabilized by higher entropy rather than lower enthalpy, in accord with the disorder in Li positions. The structural model also agrees well with the very high lithium ion conductivity measured for LiCe(BH 4) 3Cl of 1 à - 10 -4 Scm -1 at T = 20 °C. In situ SR-PXD reveals that the decomposition products consist of LiCl, CeB 6 and CeH 2. The Sieverts measurements show that 4.7 wt % H 2 is released during heating to 500 °C. After rehydrogenation at 400 °C and p(H 2) = 100 bar for 24 h an amount of 1.8 wt % H 2 is released in the second dehydrogenation. The 11B MAS NMR spectra of the central and satellite transitions for LiCe(B(D/H) 4) 3Cl reveal highly asymmetric manifolds of spinning sidebands from a single 11B site, reflecting dipolar couplings of the 11B nuclear spin with the paramagnetic electron spin of the Ce 3+ ions. © 2012 American Chemical Society. |
| مصطلحات الفهرس: | Borohydride, Cubic space, Decomposition products, Density functional theories (DFT), DFT calculation, Dipolar couplings, Electron spins, Hydrogen storage materials, In-situ, Lithium ion conductors, Lithium-ion conductivity, Hydrogen storage, Lithium-ion conductor, MAS NMR, Mechanochemical synthesis, Nuclear spins, Powder neutron diffraction, Powder X ray diffraction, Rehydrogenation, Reversibility, Satellite transitions, Spinning sidebands, Lithium ion conductor, Structural models, Density functional theory, Lithium compounds, Magnetic moments, Model structures, Nuclear magnetic resonance spectroscopy, Paramagnetism, Positive ions, Spin dynamics, Powder x-ray diffraction, X ray diffraction, Chlorine compounds, Anionic clusters, Borohydrides, Chloride ions, Coordination environment, info:eu-repo/semantics/article |
| URL: | |
| الاتاحة: | Open access content. Open access content info:eu-repo/semantics/restrictedAccess |
| ملاحظة: | English |
| Other Numbers: | UCDLC oai:dial.uclouvain.be:boreal:126361 boreal:126361 info:doi/10.1021/cm300792t urn:ISSN:0897-4756 960544941 |
| المصدر المساهم: | UNIVERSITE CATHOLIQUE DE LOUVAIN From OAIster®, provided by the OCLC Cooperative. |
| رقم الانضمام: | edsoai.ocn960544941 |
| قاعدة البيانات: | OAIster |
| الوصف غير متاح. |