Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties
International Journal of Computational and Theoretical Chemistry
Volume 3, Issue 6, November 2015, Pages: 58-67
Received: Nov. 9, 2015; Accepted: Nov. 26, 2015; Published: Dec. 18, 2015
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Authors
Melkizedeck Hiiti Tsere, The Nelson Mandela African Institution of Science and Technology (NM – AIST), Arusha, Tanzania; Department of Materials, Energy Science and Engineering, the Nelson Mandela African Institution of Science and Technology (NM – AIST), Arusha, Tanzania
Tatiana P. Pogrebnaya, The Nelson Mandela African Institution of Science and Technology (NM – AIST), Arusha, Tanzania; Department of Materials, Energy Science and Engineering, the Nelson Mandela African Institution of Science and Technology (NM – AIST), Arusha, Tanzania
Alexander M. Pogrebnoi, The Nelson Mandela African Institution of Science and Technology (NM – AIST), Arusha, Tanzania; Department of Materials, Energy Science and Engineering, the Nelson Mandela African Institution of Science and Technology (NM – AIST), Arusha, Tanzania
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Abstract
Gaseous lithium complex hydrides Li2MH5 (M = B, Al) have been studied using DFT/B3P86 and MP2 methods with 6-311++G(d,p) basis set. High content of hydrogen by these materials accord them with good candidacy as a class of hydrogen storage materials. The optimized geometrical parameters, vibrational spectra and thermodynamic properties of the hydrides and the subunits LiH, Li2H+, Li2H2, MH3, MH4, and LiMH4 have been determined. For the LiBH4 the equilibrium configuration was tridentate of C3v symmetry. For LiAlH4 two isomeric forms, bidentate (C2v) and tridentate (C3v), were confirmed to exist, and C2v isomer was shown to dominate in saturated vapor. For complex hydrides Li2MH5, different structural forms were considered but only one asymmetric form (C1) appeared to be equilibrium. Several possible channels of dissociation of Li2MH5 were considered; the enthalpies and Gibbs free energies of the reactions were computed. The enthalpies of formation ∆fH(0) of the complex hydrides in gaseous phase were determined: 60 ± 10 kJmol1 (Li2BH5) and 33 ± 10 kJmol1 (Li2AlH5). Heterophase decomposition of the gaseous Li2MH5 with solid products LiH and B/Al and hydrogen gas release was shown to be spontaneous at ambient temperature. Production of hydrogen gas via gaseous decomposition is highly endothermic and achievable at elevated temperatures. The complexes Li2MH5 are therefore proposed to be useful hydrogen storage materials under appropriate conditions.
Keywords
Complex Hydrides, Hydrogen Storage, Geometrical Structure, Vibrational Spectra, Density Functional Theory, Møller–Plesset Perturbation Theory, Basis Set, Isomers, Thermodynamic Properties
To cite this article
Melkizedeck Hiiti Tsere, Tatiana P. Pogrebnaya, Alexander M. Pogrebnoi, Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties, International Journal of Computational and Theoretical Chemistry. Vol. 3, No. 6, 2015, pp. 58-67. doi: 10.11648/j.ijctc.20150306.13
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Copyright © 2015 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
References
[1]
Delmelle, R., Gehrig, J. C., Borgschulte, A. & Züttel, A. Reactivity enhancement of oxide skins in reversible Ti-doped NaAlH4. AIP Adv. 4, 127130 (2014).
[2]
Yang, J., Sudik, A., Wolverton, C. & Siegel, D. J. High capacity hydrogen storage materials: attributes for automotive applications and techniques for materials discovery. Chem. Soc. Rev. 39, 656–675 (2010).
[3]
Pottmaier, D. & Baricco, M. Materials for hydrogen storage and the Na-Mg-B-H system. AIMS Energy 3, 75–100 (2015).
[4]
Zhang, T., Isobe, S., Wang, Y., Oka, H., Hashimoto, N. & Ohnuki, S. A metal-oxide catalyst enhanced the desorption properties in complex metal hydrides. J. Mater. Chem. A 2, 4361 (2014).
[5]
Sundqvist, B. Pressure-temperature phase relations in complex hydrides. in Solid State Phenomena 150, 175–195 (Trans Tech Publ, 2009).
[6]
Seayad, A. M. & Antonelli, D. M. Recent Advances in Hydrogen Storage in Metal-Containing Inorganic Nanostructures and Related Materials. Adv. Mater. 16, 765–777 (2004).
[7]
Grochala, W. & Edwards, P. P. Thermal Decomposition of the Non-Intersitial Hydrides for the Storage and Production of Hydrogen. Chem. Rev. 104, p1283 – 1315 (2004).
[8]
Dovgaliuk, I., Le Duff, C. S., Robeyns, K., Devillers, M. & Filinchuk, Y. Mild Dehydrogenation of Ammonia Borane Complexed with Aluminum Borohydride. Chem. Mater. 27, 768–777 (2015).
[9]
Jaroń, T., Wegner, W. & Grochala, W. M[Y(BH4)4] and M2Li [Y(BH4)6−xClx] (M = Rb, Cs): new borohydride derivatives of yttrium and their hydrogen storage properties. Dalt. Trans., 42, 6886-6893. (2013).
[10]
Bogdanović, B. & Schwickardi, M. Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials. J. Alloys Compd. 253, 1–9 (1997).
[11]
Goudon, J. P., Bernard, F., Renouard, J. & Yvart, P. Experimental investigation on lithium borohydride hydrolysis. Int. J. Hydrogen Energy 35, 11071–11076 (2010).
[12]
Ley M. B., Jepsen, L. H., Lee, Y. S., Cho, Y. W., Bellosta von Colbe, J. M., Dornheim, M., Rokni, M., Jensen, J. O.,Sloth M., Filinchuk, Y., Jørgensen, J. E., Besenbacher, F. & Jensen, T. R. Complex hydrides for hydrogen storage–new perspectives. Mater. Today 17, 122-128 (2014).
[13]
Stasinevich, D. & Egorenko, G. Thermographic investigation of alkali metal and magnesium tetrahydroborates at pressures up to 10 atm. Russ. J. Inorg. Chem., 13, 341-343 (1968).
[14]
Züttel, A., Wenger, P., Rentsch, S., Sudan, P., Mauron, Ph., and Emmenegger, Ch. Hydrogen storage properties of LiBH4. J. Alloys Compd. 356, 515–520 (2003).
[15]
Orimo, S., Nakamori, Y. & Kitahara, G. Dehydriding and rehydriding reactions of LiBH4. J. Alloys Compd. 404-406, 427-430 (2005).
[16]
Gross, K. J., Thomas, G. J. & Jensen, C. M. Catalyzed alanates for hydrogen storage. J. Alloys Compd. 330-332, 683–690 (2002).
[17]
Schmidt M. W., Baldridge K. K., Boatz J. A., Elbert S. T., Gordon M. S., Jensen J. H., Koseki S., Matsunaga N., Nguyen K. A., Su S., Windus T. L., Dupuis M., Montgomery J. A.“General Atomic and Molecular Electronic Structure System”. J. Comput. Chem. 1993; 14:1347-1363; doi: 10.1002/jcc. 540141112.
[18]
Granovsky, A. A. Firefly version 8.1.0, www http://classic.chem.msu.su/gran/firefly/index.html.
[19]
Chemcraft. Version 1.7 (build 132). G.A. Zhurko, D.A. Zhurko. HTML: www.chemcraftprog.com.
[20]
Tokarev, K. L. "OpenThermo", v.1.0 Beta 1 (C) ed., 2007-2009. http://openthermo.software.informer.com/.
[21]
Gurvich L. V., Yungman V. S., Bergman G. A., Veitz I. V., Gusarov A. V., Iorish V. S., Leonidov V. Y., Medvedev V. A., Belov G. V., Aristova N. M., Gorokhov L. N., Dorofeeva O. V., Ezhov Y. S., Efimov M.E., Krivosheya N. S., Nazarenko I.I, Osina E. L., Ryabova V. G., Tolmach P. I., Chandamirova N. E., Shenyavskaya E.A., “Thermodynamic Properties of individual Substances. Ivtanthermo for Windows Database on Thermodynamic Properties of Individual Substances and Thermodynamic Modeling Software”, Version 3.0 (Glushko Thermocenter of RAS, Moscow, 1992-2000).
[22]
Ruden, T. A., Taylor, P. R. & Helgaker, T. Automated calculation of fundamental frequencies: Application to AlH3 using the coupled-cluster singles-and-doubles with perturbative triples method. J. Chem. Phys. 119, 1951 (2003).
[23]
Chen, Y. L., Huang, C.-H., Hu, W.-P. & Wei-Ping, H. Theoretical Study on the Small Clusters of LiH, NaH, BeH2, and MgH2. J. Phys. Chem. A 109, 9627–9636 (2005).
[24]
Wu, C. & Ihle, H. Thermochemistry of the Dimer Lithium Hydride Molecule Li2H2 (g). ACS Symposium Series, 179, 265–273 (1982).
[25]
Graner, G. & Kuchitsu, K. (1998), Structure of Free Polyatomic Molecules: Basic Data, Berlin; New York: Springer.
[26]
Tague T. T. Jr & Andrews, L. Reactions of pulsed-laser evaporated boron atoms with hydrogen. Infrared spectra of boron hydride intermediate species in solid argon. J. Am. Chem. Soc. 116(11), 4970–4976 (1994).
[27]
Kurth, F. & Eberlein, R. Molecular aluminium trihydride, AlH3: generation in a solid noble gas matrix and characterisation by its infrared spectrum and Ab initio calculations. J. Chem. Soc., Chem. Commun. 16, 1302-1304 (1993).
[28]
Jacox, M. “Vibrational and electronic energy levels of polyatomic transient molecules” Monograph 3, J. Phys. Chem. Ref. Data, 461, (1994).
[29]
Andrews, L. & Wang, X. Infrared spectra of dialanes in solid hydrogen. J. Phys. Chem. A 108 (19), 4202–4210 (2004).
[30]
Gurvich, L. Reference books and data banks on the thermodynamic properties of individual substances. Pure Appl. Chem. 61(6): 027-1031, (1989).
[31]
Nakamoto, K. (1986). Infrared and Raman spectra of inorganic and coordination compounds: Wiley Online Library.
[32]
Spoliti, M., Sanna, N. & Di Martino, V. Ab initio study on the MBF4 and MAlF4 molecules. J. Mol. Struct. Theochem 258, 83–107 (1992).
[33]
Wang, X., Andrews, L., Tam, S., DeRose, M. E., & Fajardo, M. E. Infrared spectra of aluminum hydrides in solid hydrogen: Al2H4 and Al2H6. Chem. Soc., 125(30), 9218-9228, (2003).
[34]
Linstrom, P. & Mallard, W. NIST chemistry webbook. (2001).
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