Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental–theoretical study

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.

doi:10.1039/c7cp03709k

Title: Elucidating the mechanism of MgB₂ initial hydrogenation via a combined experimental–theoretical study

Journal Article · Wed Jul 19 00:00:00 EDT 2017 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c7cp03709k· OSTI ID:1399499

^[1]; Klebanoff, Leonard E. ^[2];

^[1]; Stavila, Vitalie ^[2]; Heo, Tae Wook ^[1]; Shea, Patrick ^[1];

^[1]; Kang, Shinyoung ^[1]; Bagge-Hansen, Michael ^[1];

^[3];

^[2]; Wood, Brandon 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)

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.

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Research Organization:: 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 Organization:: 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)

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

OSTI ID:: 1399499

Alternate ID(s):: OSTI ID: 1404846; OSTI ID: 1475014

Report Number(s):: SAND-2017-4011J; LLNL-JRNL-718699; PPCPFQ; 652539

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 19, Issue 34; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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References (36)

Reversibility and Improved Hydrogen Release of Magnesium Borohydride Newhouse, Rebecca J.; Stavila, Vitalie; Hwang, Son-Jong The Journal of Physical Chemistry C, Vol. 114, Issue 11 https://doi.org/10.1021/jp9116744	journal	February 2010
Vibrational Property Study of SrGa ₂ H ₂ and BaGa ₂ H ₂ by Inelastic Neutron Scattering and First Principles Calculations Lee, Myeong H.; Evans, Michael J.; Daemen, Luke L. Inorganic Chemistry, Vol. 47, Issue 5 https://doi.org/10.1021/ic7019318	journal	March 2008
Thermodynamic stability of transition metals on the Mg-terminated ${MgB}_{2}$ (0001) surface and their effects on hydrogen dissociation and diffusion Wang, Yongli; Michel, Kyle; Zhang, Yongsheng Physical Review B, Vol. 91, Issue 15 https://doi.org/10.1103/PhysRevB.91.155431	journal	April 2015
Recent Progress in Metal Borohydrides for Hydrogen Storage Li, Hai-Wen; Yan, Yigang; Orimo, Shin-ichi Energies, Vol. 4, Issue 1 https://doi.org/10.3390/en4010185	journal	January 2011
Synthesis and properties of magnesium tetrahydroborate, Mg(BH4)2 Chłopek, Krzysztof; Frommen, Christoph; Léon, Aline Journal of Materials Chemistry, Vol. 17, Issue 33 https://doi.org/10.1039/b702723k	journal	January 2007
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Nanostructure-induced hydrogenation of layered compound MgB2 Li, Hai-Wen; Matsunaga, Tomoya; Yan, Yigang Journal of Alloys and Compounds, Vol. 505, Issue 2 https://doi.org/10.1016/j.jallcom.2010.06.101	journal	September 2010
Correlation between thermodynamical stabilities of metal borohydrides and cation electronegativites: First-principles calculations and experiments Nakamori, Yuko; Miwa, Kazutoshi; Ninomiya, Akihito Physical Review B, Vol. 74, Issue 4 https://doi.org/10.1103/PhysRevB.74.045126	journal	July 2006
Review of the superconducting properties of MgB ₂ Buzea, Cristina; Yamashita, Tsutomu Superconductor Science and Technology, Vol. 14, Issue 11 https://doi.org/10.1088/0953-2048/14/11/201	journal	November 2001
Reversible dehydrogenation of magnesium borohydride to magnesium triborane in the solid state under moderate conditions Chong, Marina; Karkamkar, Abhi; Autrey, Tom Chem. Commun., Vol. 47, Issue 4 https://doi.org/10.1039/C0CC03461D	journal	January 2011
Formation of an intermediate compound with a B ₁₂ H ₁₂ cluster: experimental and theoretical studies on magnesium borohydride Mg(BH ₄ ) ₂ Li, H-W; Miwa, K.; Ohba, N. Nanotechnology, Vol. 20, Issue 20 https://doi.org/10.1088/0957-4484/20/20/204013	journal	April 2009
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Valence band structure and decay process in the inner-shell excitation of boron oxide Muramatsu, Yasuji; Takenaka, Hisataka; Oyama, Takashi X-Ray Spectrometry, Vol. 28, Issue 6 https://doi.org/10.1002/(SICI)1097-4539(199911/12)28:6<503::AID-XRS385>3.0.CO;2-F	journal	November 1999
First-Principles Prediction of Thermodynamically Reversible Hydrogen Storage Reactions in the Li-Mg-Ca-B-H System Ozolins, V.; Majzoub, E. H.; Wolverton, C. Journal of the American Chemical Society, Vol. 131, Issue 1 https://doi.org/10.1021/ja8066429	journal	January 2009
Theoretical Prediction of Metastable Intermediates in the Decomposition of Mg(BH ₄ ) ₂ Zhang, Yongsheng; Majzoub, Eric; Ozoliņš, Vidvuds The Journal of Physical Chemistry C, Vol. 116, Issue 19 https://doi.org/10.1021/jp302303z	journal	May 2012
Synthesis of amorphous Mg(BH4)2 from MgB2 and H2 at room temperature Pistidda, Claudio; Garroni, Sebastiano; Dolci, Francesco Journal of Alloys and Compounds, Vol. 508, Issue 1 https://doi.org/10.1016/j.jallcom.2010.07.226	journal	October 2010
Vibrational Properties of Polyanionic Hydrides SrAl ₂ H ₂ and SrAlSiH: New Insights into Al−H Bonding Interactions Lee, Myeong H.; Sankey, Otto F.; Björling, Thomas Inorganic Chemistry, Vol. 46, Issue 17 https://doi.org/10.1021/ic700722b	journal	August 2007
Metal hydride material requirements for automotive hydrogen storage systems Pasini, José Miguel; Corgnale, Claudio; van Hassel, Bart A. International Journal of Hydrogen Energy, Vol. 38, Issue 23 https://doi.org/10.1016/j.ijhydene.2012.08.112	journal	August 2013
Magnesium borohydride as a hydrogen storage material: Properties and dehydrogenation pathway of unsolvated Mg(BH₄)₂ Soloveichik, G.; Gao, Y.; Rijssenbeek, J. International Journal of Hydrogen Energy, Vol. 34, Issue 2, p. 916-928 https://doi.org/10.1016/j.ijhydene.2008.11.016	journal	January 2009
Soft-x-ray spectroscopy measurements of the $p$ -like density of states of B in ${MgB}_{2}$ and evidence for surface boron oxides on exposed surfaces Callcott, T. A.; Lin, L.; Woods, G. T. Physical Review B, Vol. 64, Issue 13 https://doi.org/10.1103/PhysRevB.64.132504	journal	August 2001
Electronic structure of ${MgB}_{2} :$ X-ray emission and absorption studies Kurmaev, E. Z.; Lyakhovskaya, I. I.; Kortus, J. Physical Review B, Vol. 65, Issue 13 https://doi.org/10.1103/PhysRevB.65.134509	journal	March 2002
Kinetics studies of the reversible partial decomposition reaction in Mg(BH4)2 Zavorotynska, Olena; Deledda, Stefano; Hauback, Bjørn C. International Journal of Hydrogen Energy, Vol. 41, Issue 23 https://doi.org/10.1016/j.ijhydene.2016.02.153	journal	June 2016
Undulator‐radiation‐excited x‐ray fluorescence analysis system for light elements Muramatsu, Yasuji; Oshima, Masaharu; Shoji, Takashi Review of Scientific Instruments, Vol. 63, Issue 12 https://doi.org/10.1063/1.1143388	journal	December 1992
Decomposition pathway of Mg(BH4)2 under pressure: Metastable phases and thermodynamic parameters Yang, Junzhi; Zhang, Xuanzhou; Zheng, Jie Scripta Materialia, Vol. 64, Issue 3 https://doi.org/10.1016/j.scriptamat.2010.10.019	journal	February 2011
Selective Reversible Hydrogenation of Mg(B ₃ H ₈ ) ₂ /MgH ₂ to Mg(BH ₄ ) ₂ : Pathway to Reversible Borane-Based Hydrogen Storage? Chong, Marina; Matsuo, Motoaki; Orimo, Shin-ichi Inorganic Chemistry, Vol. 54, Issue 8 https://doi.org/10.1021/acs.inorgchem.5b00373	journal	March 2015
Facile High-Yield Synthesis of Pure, Crystalline Mg(BH ₄ ) ₂ Zanella, Pierino; Crociani, Laura; Masciocchi, Norberto Inorganic Chemistry, Vol. 46, Issue 22 https://doi.org/10.1021/ic701436c	journal	October 2007
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Comparison shopping for a gradient-corrected density functional Perdew, John P.; Burke, Kieron International Journal of Quantum Chemistry, Vol. 57, Issue 3 https://doi.org/10.1002/(SICI)1097-461X(1996)57:3<309::AID-QUA4>3.0.CO;2-1	journal	February 1996
Unraveling the Symmetry of the Hole States near the Fermi Level in the ${MgB}_{2}$ Superconductor Zhu, Y.; Moodenbaugh, A. R.; Schneider, G. Physical Review Letters, Vol. 88, Issue 24 https://doi.org/10.1103/PhysRevLett.88.247002	journal	May 2002
Hydrogen diffusion in bulk MgB2 Wang, Yongli; Michel, Kyle; Wolverton, C. Scripta Materialia, Vol. 117 https://doi.org/10.1016/j.scriptamat.2016.02.020	journal	May 2016
High-resolution X-ray emission and absorption study of the B 2 p valence band electronic structure of MgB ₂ McGuinness, C.; Smith, K. E.; Butorin, S. M. Europhysics Letters (EPL), Vol. 56, Issue 1 https://doi.org/10.1209/epl/i2001-00495-1	journal	October 2001
The origin of the anomalous superconducting properties of MgB2 Choi, Hyoung Joon; Roundy, David; Sun, Hong Nature, Vol. 418, Issue 6899 https://doi.org/10.1038/nature00898	journal	August 2002
5 Years of hydrogen storage research in the U.S. DOE Metal Hydride Center of Excellence (MHCoE) Klebanoff, L. E.; Keller, J. O. International Journal of Hydrogen Energy, Vol. 38, Issue 11 https://doi.org/10.1016/j.ijhydene.2013.01.051	journal	April 2013
Some properties of magnesium borohydride Konoplev, V. N.; Bakulina, V. M. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 20, Issue 1 https://doi.org/10.1007/BF00849335	journal	January 1971
Direct hydrogenation of magnesium boride to magnesium borohydride: demonstration of >11 weight percent reversible hydrogenstorage Severa, Godwin; Rönnebro, Ewa; Jensen, Craig M. Chem. Commun., Vol. 46, Issue 3 https://doi.org/10.1039/B921205A	journal	January 2010

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In‐Situ/Operando X‐ray Characterization of Metal Hydrides Liu, Yi‐Sheng; Jeong, Sohee; White, James L. ChemPhysChem, Vol. 20, Issue 10 https://doi.org/10.1002/cphc.201801185	journal	March 2019
Kinetic Enhancement of Direct Hydrogenation of MgB ₂ to Mg(BH ₄ ) ₂ upon Mechanical Milling with THF, MgH ₂ , and/or Mg Sugai, Cody; Kim, Stephen; Severa, Godwin ChemPhysChem, Vol. 20, Issue 10 https://doi.org/10.1002/cphc.201801187	journal	March 2019

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