The previously observed intermediate from thermal decomposition of Ca(BH4)(2) has been identified as a calcium borohydride borate with composition Ca-3((BD4)-B-11)3((BO3)-B-11), synthesized from a double-isotope substituted sample Ca((BD4)-B-11)(2). The crystal structure was determined on the basis of Synchrotron Radiation Powder X-ray Diffraction, supported by infrared spectroscopy measurements. The stability of the structure at ambient conditions is confirmed by Density Functional Theory calculations. Ca-3((BH4)-B-11)(3)((BO3)-B-11) is the first example of a product from a borohydride oxidation containing both B-H(D) and B-O bonds and represents a novel category of compounds, being completely different from the hydroxoborate products upon borohydride hydrolysis. The result represents hence an important contribution to fundamental boron chemistry.
Riktor M. D., Sørby M. H., Chłopek K., Fichtner M., Buchter F., Züttel A., Hauback B. C., In situ synchrotron diffraction studies of phase transitions and thermal decomposition of Mg(BH4)2 and Ca(BH4)2, 10.1039/b712750b
Aoki M., Miwa K., Noritake T., Ohba N., Matsumoto M., Li H.-W., Nakamori Y., Towata S., Orimo S., Structural and dehydriding properties of Ca(BH4)2, 10.1007/s00339-008-4548-5
Kim Yoonyoung, Reed Daniel, Lee Young-Su, Lee Ji Youn, Shim Jae-Hyeok, Book David, Cho Young Whan, Identification of the Dehydrogenated Product of Ca(BH4)2, 10.1021/jp8094038
FILINCHUK Y, RONNEBRO E, CHANDRA D, Crystal structures and phase transformations in Ca(BH4)2, 10.1016/j.actamat.2008.10.034
Buchter F., Łodziana Z., Remhof A., Friedrichs O., Borgschulte A., Mauron Ph., Züttel A., Sheptyakov D., Palatinus L., Chłopek K., Fichtner M., Barkhordarian G., Bormann R., Hauback B. C., Structure of the Orthorhombic γ-Phase and Phase Transitions of Ca(BD4)2, 10.1021/jp810521p
Buchter F., Łodziana Z., Remhof A., Friedrichs O., Borgschulte A., Mauron Ph., Züttel A., Sheptyakov D., Barkhordarian G., Bormann R., Chłopek K., Fichtner M., Sørby M., Riktor M., Hauback B., Orimo S., Structure of Ca(BD4)2β-Phase from Combined Neutron and Synchrotron X-ray Powder Diffraction Data and Density Functional Calculations, 10.1021/jp800435z
Riktor M. D., Sørby M. H., Chłopek K., Fichtner M., Hauback B. C., The identification of a hitherto unknown intermediate phase CaB2Hx from decomposition of Ca(BH4)2, 10.1039/b818127f
Hammersley A. P., Svensson S. O., Hanfland M., Fitch A. N., Hausermann D., Two-dimensional detector software: From real detector to idealised image or two-theta scan, 10.1080/08957959608201408
Ehm, Adv. X-Ray Anal., 45, 31 (2002)
Boultif A., Louër D., Indexing of powder diffraction patterns for low-symmetry lattices by the successive dichotomy method, 10.1107/s0021889891006441
Favre-Nicolin Vincent, Černý Radovan, FOX, `free objects for crystallography': a modular approach toab initiostructure determination from powder diffraction, 10.1107/s0021889802015236
Favre-Nicolin Vincent, Černý Radovan, A better FOX: using flexible modelling and maximum likelihood to improve direct-space ab initio structure determination from powder diffraction, 10.1524/zkri.219.12.847.55869
Perdew John P., Burke Kieron, Wang Yue, Generalized gradient approximation for the exchange-correlation hole of a many-electron system, 10.1103/physrevb.54.16533
Perdew John P., Burke Kieron, Ernzerhof Matthias, Generalized Gradient Approximation Made Simple, 10.1103/physrevlett.77.3865
Clark Stewart J., Segall Matthew D., Pickard Chris J., Hasnip Phil J., Probert Matt I. J., Refson Keith, Payne Mike C., First principles methods using CASTEP, 10.1524/zkri.220.5.567.65075
Refson Keith, Tulip Paul R., Clark Stewart J., Variational density-functional perturbation theory for dielectrics and lattice dynamics, 10.1103/physrevb.73.155114
Fichtner M., Chlopek K., Longhini M., Hagemann H., Vibrational Spectra of Ca(BH4)2, 10.1021/jp801482b
Blanchard D., Riktor M. D., Maronsson J. B., Jacobsen H. S., Kehres J., Sveinbjörnsson D., Bardají E. Gil, Léon A., Juranyi F., Wuttke J., Hauback B. C., Fichtner M., Vegge T., Hydrogen Rotational and Translational Diffusion in Calcium Borohydride from Quasielastic Neutron Scattering and DFT Calculations, 10.1021/jp107281v
Wee Jung-Ho, Lee Kwan-Young, Kim Sung Hyun, Sodium borohydride as the hydrogen supplier for proton exchange membrane fuel cell systems, 10.1016/j.fuproc.2006.05.001
Demirci U.B., Akdim O., Miele P., Aluminum chloride for accelerating hydrogen generation from sodium borohydride, 10.1016/j.jpowsour.2009.03.015
Hong Jian, Fang Bin, Wang Chunsheng, Currie Kenneth, Intrinsic borohydride fuel cell/battery hybrid power sources, 10.1016/j.jpowsour.2006.05.018
Bibliographic reference
Riktor, M. D. ; Filinchuk, Yaroslav ; Vajeeston, P. ; Bardaji, E. G. ; Fichtner, M. ; et. al. The crystal structure of the first borohydride borate, Ca3(BD4)(3)(BO3). In: Journal of Materials Chemistry, Vol. 21, no. 20, p. 7188-7193 (2011)