Assessing the reactivity of TiCl3 and TiF3 with hydrogen

Kang, S.; Klebanoff, L. E.; Baker, A. A.; Cowgill, D. F.; Stavila, V.; Lee, J. R. I.; Nielsen, M. H.; Ray, K. G.; Liu, Y. -S.; Wood, B. C.

doi:10.1016/j.ijhydene.2018.05.128

Title: Assessing the reactivity of TiCl₃ and TiF₃ with hydrogen

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Abstract

TiCl₃ and TiF₃ additives are known to facilitate hydrogenation and dehydrogenation in a variety of hydrogen storage materials, yet the associated mechanism remains under debate. In this paper, experimental and computational studies are reported for the reactivity with hydrogen gas of bulk and ball-milled TiCl₃ and TiF₃ at the temperatures and pressures for which these additives are observed to accelerate reactions when added to hydrogen storage materials. TiCl₃, in either the α or δ polymorphic forms and of varying crystallite size ranging from ~5 to 95 nm, shows no detectable reaction with prolonged exposure to hydrogen gas at elevated pressures (~120 bar) and temperatures (up to 200 °C). Similarly, TiF₃ with varying crystallite size from ~4 to 25 nm exhibits no detectable reaction with hydrogen gas. Post-exposure vibrational and electronic structure investigations using Fourier transform infrared spectroscopy and x-ray absorption spectroscopy confirm this analysis. Moreover, there is no significant promotion of H₂ dissociation at either interior or exterior surfaces, as demonstrated by H₂/D₂ exchange studies on pure TiF₃. The computed energy landscape confirms that dissociative adsorption of H₂ on TiF₃ surfaces is thermodynamically inhibited. However, Ti-based additives could potentially promote H₂ dissociation at interfaces where structural and compositional varieties aremore »« less

Authors:

Kang, S. ^[1]; Klebanoff, L. E. ^[2]; Baker, A. A. ^[1]; Cowgill, D. F. ^[2]; Stavila, V. ^[2]; Lee, J. R. I. ^[1]; Nielsen, M. H. ^[1]; Ray, K. G. ^[1]; Liu, Y. -S. ^[3]; Wood, B. C. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Tue Jul 03 00:00:00 EDT 2018

Research Org.:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1488803

Alternate Identifier(s):: OSTI ID: 1467026; OSTI ID: 1495304

Report Number(s):: LLNL-JRNL-748061; SAND2018-2700J
Journal ID: ISSN 0360-3199; 932975

Grant/Contract Number:: AC04-94AL85000; AC52-07NA27344; NA0003525; AC02-05CH11231; AC02–05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: International Journal of Hydrogen Energy

Additional Journal Information:: Journal Volume: 43; Journal Issue: 31; Journal ID: ISSN 0360-3199

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 08 HYDROGEN; titanium fluoride; titanium chloride; hydrogen storage; additives; hydrogen reactivity

Citation Formats


                    Kang, S., Klebanoff, L. E., Baker, A. A., Cowgill, D. F., Stavila, V., Lee, J. R. I., Nielsen, M. H., Ray, K. G., Liu, Y. -S., and Wood, B. C. Assessing the reactivity of TiCl3 and TiF3 with hydrogen.  United States: N. p., 2018. 
Web.  doi:10.1016/j.ijhydene.2018.05.128.

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                    Kang, S., Klebanoff, L. E., Baker, A. A., Cowgill, D. F., Stavila, V., Lee, J. R. I., Nielsen, M. H., Ray, K. G., Liu, Y. -S., & Wood, B. C. Assessing the reactivity of TiCl3 and TiF3 with hydrogen.  United States.  https://doi.org/10.1016/j.ijhydene.2018.05.128

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                    Kang, S., Klebanoff, L. E., Baker, A. A., Cowgill, D. F., Stavila, V., Lee, J. R. I., Nielsen, M. H., Ray, K. G., Liu, Y. -S., and Wood, B. C. Tue .  
"Assessing the reactivity of TiCl3 and TiF3 with hydrogen".  United States.  https://doi.org/10.1016/j.ijhydene.2018.05.128.  https://www.osti.gov/servlets/purl/1488803.

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@article{osti_1488803,

  title        = {Assessing the reactivity of TiCl3 and TiF3 with hydrogen},

  author       = {Kang, S. and Klebanoff, L. E. and Baker, A. A. and Cowgill, D. F. and Stavila, V. and Lee, J. R. I. and Nielsen, M. H. and Ray, K. G. and Liu, Y. -S. and Wood, B. C.},

  abstractNote = {TiCl3 and TiF3 additives are known to facilitate hydrogenation and dehydrogenation in a variety of hydrogen storage materials, yet the associated mechanism remains under debate. In this paper, experimental and computational studies are reported for the reactivity with hydrogen gas of bulk and ball-milled TiCl3 and TiF3 at the temperatures and pressures for which these additives are observed to accelerate reactions when added to hydrogen storage materials. TiCl3, in either the α or δ polymorphic forms and of varying crystallite size ranging from ~5 to 95 nm, shows no detectable reaction with prolonged exposure to hydrogen gas at elevated pressures (~120 bar) and temperatures (up to 200 °C). Similarly, TiF3 with varying crystallite size from ~4 to 25 nm exhibits no detectable reaction with hydrogen gas. Post-exposure vibrational and electronic structure investigations using Fourier transform infrared spectroscopy and x-ray absorption spectroscopy confirm this analysis. Moreover, there is no significant promotion of H2 dissociation at either interior or exterior surfaces, as demonstrated by H2/D2 exchange studies on pure TiF3. The computed energy landscape confirms that dissociative adsorption of H2 on TiF3 surfaces is thermodynamically inhibited. However, Ti-based additives could potentially promote H2 dissociation at interfaces where structural and compositional varieties are expected, or else by way of subsequent chemical transformations. Finally, at interfaces, metallic states could be formed intrinsically or extrinsically, possibly enabling hydrogen-coupled electronic transfer by donating electrons.},

  doi          = {10.1016/j.ijhydene.2018.05.128},

  journal      = {International Journal of Hydrogen Energy},

  number       = 31,

  volume       = 43,

  place        = {United States},

  year         = {Tue Jul 03 00:00:00 EDT 2018},

  month        = {Tue Jul 03 00:00:00 EDT 2018}

}

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Title: Assessing the reactivity of TiCl3 and TiF3 with hydrogen

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Title: Assessing the reactivity of TiCl₃ and TiF₃ with hydrogen