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Characterization of titanium dopants in sodium alanate by electron paramagnetic resonance spectroscopy

Published online by Cambridge University Press:  01 December 2005

Meredith T. Kuba
Affiliation:
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822
Sandra S. Eaton
Affiliation:
Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80208
Christine Morales
Affiliation:
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822
Craig M. Jensen*
Affiliation:
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822
*
a) Address all correspondence to this author. e-mail: [email protected]
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Abstract

Electron paramagnetic resonance (EPR) spectra were obtained for samples of Ti-doped NaAlH4 subjected to different numbers of cycles of dehydrogenation/re-hydrogenation. Ti is observed to evolve from its initial Ti(III) state through a series of Ti(0) species during the first 5 cycles. Although the conversion of Ti(III) to Ti(0) occurs much more readily for TiCl3-doped samples than those prepared with TiF3, in both cases the evolution of Ti follows the same sequence that involves 3 distinguishable Ti(0) species and ends in the predominance of the same single Ti(0) species. The spectrum of a sample of NaAlH4 containing 2 mol% of cubic Al3Ti is distinctly different than any of those observed for the Ti(0) species that arise during the hydrogen cycling of the hydride. The major changes in the nature of the predominant Ti species have little if any effect on the dehydrogenation kinetics, which strongly suggests that the profoundly enhanced hydrogen cycling kinetics of Ti-doped NaAlH4 are due to a Ti species present in only a relatively minor amount.

Type
Articles—Energy and The Environment Special Section
Copyright
Copyright © Materials Research Society 2005

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References

REFERENCES

1.Bogdanovic, B. and Schwickardi, M.: Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen-storage materials. J. Alloys Compd. 253, 1 (1997).CrossRefGoogle Scholar
2.Jensen, C.M., Zidan, R., Mariels, N., Hee, A. and Hagen, C.: Advanced titanium doping of sodium aluminum hydride: Segue to a practical hydrogen storage material? Int. J. Hydrogen Energy 24, 461 (1999).CrossRefGoogle Scholar
3.Zidan, R., Takara, S., Hee, A. and Jensen, C.: Hydrogen cycling behavior of zirconium and titanium–zirconium-doped sodium aluminum hydride. J. Alloys Compd. 285, 119 (1999).CrossRefGoogle Scholar
4.Jensen, C.M. and Zidan, R.A.: Hydrogen storage materials and method of making by dry homogenation. U.S. Patent No. 6 471 935 (2002).Google Scholar
5.Bogdanovic, B., Brand, R., Marjanovic, A., Schwickardi, M. and Tolle, J.: Metal-doped sodium aluminium hydrides as potential new hydrogen-storage materials. J. Alloys Compd. 302, 36 (2000).CrossRefGoogle Scholar
6.Jensen, C.M. and Gross, K.J.: Development of catalytically enhanced sodium aluminum hydride as a hydrogen-storage material. Appl. Phys. A 72, 213 (2001).CrossRefGoogle Scholar
7.Bogdanovic, B. and Schwickardi, M.: Ti-doped NaAlH4 as a hydrogen-storage material—Preparation by Ti-catalyzed hydrogenation of aluminum powder in conjunction with sodium powder. Appl. Phys. A 72, 221 (2001).Google Scholar
8.Sandrock, G., Gross, K., Thomas, G., Jensen, C., Meeker, D. and Takara, S.: Engineering considerations in the use of catalyzed sodium alanates for hydrogen storage. J. Alloys Compd. 330–332, 696 (2002).CrossRefGoogle Scholar
9.Gross, K.J., Thomas, G.J. and Jensen, C.M.: Catalyzed alanates for hydrogen storage. J. Alloys Compd. 330–332, 683 (2002).CrossRefGoogle Scholar
10.Sandrock, G., Gross, K. and Thomas, G.: Effect of Ti-catalyst content on the reversible hydrogen storage properties of the sodium alanates. J. Alloys Compd. 339, 299 (2002).Google Scholar
11.Fichtner, M., Fuhr, O., Kircher, O. and Rothe, J.: Small Ti clusters for catalysis of hydrogen exchange in NaAlH4. Nanotechnology 14, 778 (2003).Google Scholar
12.Srinivasan, S.S., Brinks, H.W., Hauback, B.C., Sun, D. and Jensen, C.M.: Long term cycling behavior of titanium doped NaAlH4 prepared through solvent mediated milling of NaH and Al with titanium dopant precursors. J. Alloys Compd. 377, 283 (2004).Google Scholar
13.Wang, P. and Jensen, C.M.: Preparation of Ti-doped sodium aluminum hydride from mechanical milling of NaH/Al with off-the-shelf Ti powder. J. Phys. Chem. B 108, 15829 (2004).Google Scholar
14.Wang, P. and Jensen, C.M.: Method for preparing Ti-doped NaAlH4 using Ti powder: Observation of an unusual reversible dehydrogenation behavior. J. Alloys Compd. 379, 99 (2004).CrossRefGoogle Scholar
15.Ichikawa, T., Isobe, S., Hanada, N. and Fujii, H.: Lithium nitride for reversible hydrogen storage. J. Alloys Compd. 365, 271 (2004).Google Scholar
16.Ichikawa, T., Hanada, N., Isobe, S., Leng, H. and Fujii, H.: Mechanism of novel reaction from LiNH2 and LiH to Li2NH and H2 as a promising hydrogen storage system. J. Phys. Chem. B 108, 7887 (2004).CrossRefGoogle Scholar
17.Vajo, J., Skeith, S. and Mertens, F.: Reversible storage of hydrogen in destabilized LiBH4. J. Phys. Chem. B 109, 3719 (2005).CrossRefGoogle ScholarPubMed
18.Bhattacharya, P., Bellon, P., Averback, R.S. and Hales, S.J.: Nanocrystalline TiAl powders synthesized by high-energy ball milling: Effects of milling parameters on yield and contamination. J. Alloys Compd. 368, 187 (2004).CrossRefGoogle Scholar
19.Atwood, J.L., Barker, G.K., Holton, J., Hunter, W.E., Lappert, M.F. and Pearce, R.: Silylmethyl and related complexes. 5 metalhlocene bis(trimethylsilyl) methyls and benzyldryls of early transition metals [M(η5 − C5H5)2R] (M = Ti or V) and [M(η5 − C5H5)2(x)R] (M = Zr or Hf and x = Cl or R) and the crystal and molecular structures of [M(η5 − C5H5)2 (CHPh2)2] (m = Zr or Hf). J. Am. Chem. Soc. 99, 6645 (1977).CrossRefGoogle Scholar
20.Corradi, G., Zaritskii, I.M., Hofstaetter, A., Polgar, K. and Rakitina, L.G.: Ti3+ on Nb site: A paramagnetic Jahn–Teller center in vacuum-reduced LiNbO3:Mg:Ti single crystals. Phys. Rev. B: Cond. Mater. Mater. Phys. 58, 8329 (1998).CrossRefGoogle Scholar
21.DeVore, T.C., Weltner, W. Jr.: Titanium difluoride and titanium trifluoride molecules: Electron spin resonance spectra in rare-gas matrices at 4 K. J. Am. Chem. Soc. 99, 4700 (1977).CrossRefGoogle Scholar
22.Lagula, V.V., Glinchuk, M.D., Kuzian, R.O., Nokhrin, S.N., Bykov, I.P., Jastrabik, L. and Rosa, J.: Electron spin resonance of Ti3+ in KTa0.9Nb0.1O3. Solid State Commun. 122, 277 (2002).CrossRefGoogle Scholar
23.Prakash, A.M., Sung-Suh, H.M., Hyung, M. and Kevan, L.: Electron spin resonance evidence for isomorphous substitution of titanium into titanosilicate TiMCM-41 mesoporous molecular sieve. J. Phys. Chem. B 102, 857 (1988).CrossRefGoogle Scholar
24.Wilson, R.C. and Myers, R.J.: Electron paramagnetic resonance spectrum and spin relaxation for Ti(H2O) in aqueous solution and in frozen glass. J. Chem. Phys. 64, 2208 (1976).Google Scholar
25.Andrei, C.M., Walmsley, J., Brinks, H.W., Homestad, R., Srinivasan, S.S., Jensen, C.M. and Hauback, B.C.: Electron-microscopy studies of NaAlH4 with TiF3 additive: Hydrogen-cycling efffects. Appl. Phys. A 80, 709 (2005).CrossRefGoogle Scholar
26.Brinks, H.W., Jensen, C.M., Srinivasan, S.S., Hauback, B.C., Blanchard, D. and Murphy, K.: Synchotron x-ray and neutron diffraction studies of NaAlH4 containing Ti additives. J. Alloys Compd. 376, 215 (2003).Google Scholar
27.Graetz, J., Reily, J.J., Johnson, J., Ingatov, A.Y. and Tyson, T.A.: X-ray absorption study of Ti-activated sodium aluminum hydride. Appl. Phys. Lett. 85, 500 (2004).CrossRefGoogle Scholar
28.Leon, A., Kircher, O., Rothe, J. and Fichtner, M.: Chemical state and local structure around Ti atoms in NaAlH4 doped with TiCl3 using x-ray absorption spectroscopy. J. Phys. Chem. B 108, 16372 (2004).CrossRefGoogle Scholar
29.Felderhoff, M., Klementiev, K., Grunert, W., Spliethoff, B., Tesche, B., von Colbe, J.M.B., Bogdanovic, B., Hartel, M., Pommerin, A., Schuth, F. and Weidenthaler, C.: Correlative TEM-EDX and XAFS studies of Ti-doped sodium alanate. Phys. Chem. Chem. Phys. 6, 4369 (2004).Google Scholar
30.Anton, D.L.: Hydrogen desorption kinetics in transition metal modified NaAlH4. J. Alloys Compd. 356–357, 400 (2003).CrossRefGoogle Scholar
31.Jensen, C.M., Kuba, M., Sulic, M., Morales, K., Brown, C., Langley, W. and Dalton, T.: Catalytically enhanced hydrogen storage systems, in Proceedings of the 2005 US DOE Hydrogen Annual Program Review, Washington DC, May 2004, available at: www.hydrogen.energy.gov/pdfs/review05/st3_jensen.pdf.Google Scholar