Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental–theoretical study
Abstract
Mg(BH4)2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB2. Although several dehydrogenation pathways have been proposed, the hydrogenation process is less well understood. Here, we present a joint experimental-theoretical study that elucidates the key atomistic mechanisms associated with the initial stages of hydrogen uptake within MgB2. Fourier transform infrared, X-ray absorption, and X-ray emission spectroscopies are integrated with spectroscopic simulations to show that hydrogenation can initially proceed via direct conversion of MgB2 to Mg(BH4)2 complexes. The associated energy landscape is mapped by combining ab initio calculations with barriers extracted from the experimental uptake curves, from which a kinetic model is constructed. The results from the kinetic model suggest that initial hydrogenation takes place via a multi-step process: molecular H2 dissociation, likely at Mg-terminated MgB2 surfaces, is followed by migration of atomic hydrogen to defective boron sites, where the formation of stable B-H bonds ultimately leads to the direct creation of Mg(BH4)2 complexes without persistent BxHy intermediates. Implications for understanding the chemical, structural, and electronic changes upon hydrogenation of MgB2 are discussed.
- Authors:
-
[1];
[1];
[1];
[3];
[2];
- 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:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- 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:
- 1399499
- Alternate Identifier(s):
- OSTI ID: 1404846; OSTI ID: 1475014
- Report Number(s):
- SAND-2017-4011J; LLNL-JRNL-718699
Journal ID: ISSN 1463-9076; PPCPFQ; 652539
- Grant/Contract Number:
- AC04-94AL85000; AC52-07NA27344; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 19; Journal Issue: 34; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 08 HYDROGEN; 36 MATERIALS SCIENCE
Citation Formats
Ray, Keith G., Klebanoff, Leonard E., Lee, Jonathan R. I., Stavila, Vitalie, Heo, Tae Wook, Shea, Patrick, Baker, Alexander A., Kang, Shinyoung, Bagge-Hansen, Michael, Liu, Yi-Sheng, White, James L., and Wood, Brandon C. Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental–theoretical study. United States: N. p., 2017.
Web. doi:10.1039/c7cp03709k.
Ray, Keith G., Klebanoff, Leonard E., Lee, Jonathan R. I., Stavila, Vitalie, Heo, Tae Wook, Shea, Patrick, Baker, Alexander A., Kang, Shinyoung, Bagge-Hansen, Michael, Liu, Yi-Sheng, White, James L., & Wood, Brandon C. Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental–theoretical study. United States. https://doi.org/10.1039/c7cp03709k
Ray, Keith G., Klebanoff, Leonard E., Lee, Jonathan R. I., Stavila, Vitalie, Heo, Tae Wook, Shea, Patrick, Baker, Alexander A., Kang, Shinyoung, Bagge-Hansen, Michael, Liu, Yi-Sheng, White, James L., and Wood, Brandon C. Wed .
"Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental–theoretical study". United States. https://doi.org/10.1039/c7cp03709k. https://www.osti.gov/servlets/purl/1399499.
@article{osti_1399499,
title = {Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental–theoretical study},
author = {Ray, Keith G. and Klebanoff, Leonard E. and Lee, Jonathan R. I. and Stavila, Vitalie and Heo, Tae Wook and Shea, Patrick and Baker, Alexander A. and Kang, Shinyoung and Bagge-Hansen, Michael and Liu, Yi-Sheng and White, James L. and Wood, Brandon C.},
abstractNote = {Mg(BH4)2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB2. Although several dehydrogenation pathways have been proposed, the hydrogenation process is less well understood. Here, we present a joint experimental-theoretical study that elucidates the key atomistic mechanisms associated with the initial stages of hydrogen uptake within MgB2. Fourier transform infrared, X-ray absorption, and X-ray emission spectroscopies are integrated with spectroscopic simulations to show that hydrogenation can initially proceed via direct conversion of MgB2 to Mg(BH4)2 complexes. The associated energy landscape is mapped by combining ab initio calculations with barriers extracted from the experimental uptake curves, from which a kinetic model is constructed. The results from the kinetic model suggest that initial hydrogenation takes place via a multi-step process: molecular H2 dissociation, likely at Mg-terminated MgB2 surfaces, is followed by migration of atomic hydrogen to defective boron sites, where the formation of stable B-H bonds ultimately leads to the direct creation of Mg(BH4)2 complexes without persistent BxHy intermediates. Implications for understanding the chemical, structural, and electronic changes upon hydrogenation of MgB2 are discussed.},
doi = {10.1039/c7cp03709k},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 34,
volume = 19,
place = {United States},
year = {Wed Jul 19 00:00:00 EDT 2017},
month = {Wed Jul 19 00:00:00 EDT 2017}
}
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