Analysis of Intermediates and Products from the Dehydrogenation of Mg(BH4)2
Abstract
The thermodynamic properties of key compounds, Mg(B3H8)2, MgB2H6, MgB10H10, Mg(B11H14)2, Mg3(B3H6)2, and MgB12H12, proposed to be formed in the release of hydrogen from magnesium borohydride Mg(BH4)2 and uptake of hydrogen by MgB2, have been investigated using solid–state density functional theory (DFT) calculations. Further, more accurate treatment of cell–size effects to the entropies were also investigated, in order to improve the accuracy of the thermodynamic properties of complex borohydrides. We find that the zero–point energy corrections can lower the electronic energies of reaction by 20–30 kJ/(mol H2) for these intermediates, while adding the thermal and entropy contributions results in the total decrease up to ~50 kJ/(mol H2). Although our treatment lowers the calculated formation energy of Mg(B3H8)2, it is still too high to explain the experimental observation of B3H8–. We discuss possible reasons for this disparity and propose that the formation of B3H8– and H– in a disordered amorphous phase has a large energy difference compared to the phase–separated Mg(B3H8)2 and MgH2 considered in calculations. Comparison of the experimental and NMR chemical shifts calculated within a DFT approach for known species Mg(BH4)2, Mg(B3H8)2, Mg(B11H14)2, MgB10H10 and MgB12H12 provides validation for predicting the chemical shifts of the other compounds which are yetmore »
- Authors:
-
[1];
[1];
[1];
[1];
[1]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Minnesota State Univ., Moorhead, MN (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1846392
- Report Number(s):
- PNNL-SA-168448
Journal ID: ISSN 1089-5639
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 3; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical reactions; Boron; Anions; Chemical calculations; Organic reactions
Citation Formats
Nayyar, Iffat H., Ginovska, Bojana, Bowden, Mark E., Edvenson, Gary M., Tran, Ba L., and Autrey, S. Thomas. Analysis of Intermediates and Products from the Dehydrogenation of Mg(BH4)2. United States: N. p., 2022.
Web. doi:10.1021/acs.jpca.1c09690.
Nayyar, Iffat H., Ginovska, Bojana, Bowden, Mark E., Edvenson, Gary M., Tran, Ba L., & Autrey, S. Thomas. Analysis of Intermediates and Products from the Dehydrogenation of Mg(BH4)2. United States. https://doi.org/10.1021/acs.jpca.1c09690
Nayyar, Iffat H., Ginovska, Bojana, Bowden, Mark E., Edvenson, Gary M., Tran, Ba L., and Autrey, S. Thomas. Fri .
"Analysis of Intermediates and Products from the Dehydrogenation of Mg(BH4)2". United States. https://doi.org/10.1021/acs.jpca.1c09690. https://www.osti.gov/servlets/purl/1846392.
@article{osti_1846392,
title = {Analysis of Intermediates and Products from the Dehydrogenation of Mg(BH4)2},
author = {Nayyar, Iffat H. and Ginovska, Bojana and Bowden, Mark E. and Edvenson, Gary M. and Tran, Ba L. and Autrey, S. Thomas},
abstractNote = {The thermodynamic properties of key compounds, Mg(B3H8)2, MgB2H6, MgB10H10, Mg(B11H14)2, Mg3(B3H6)2, and MgB12H12, proposed to be formed in the release of hydrogen from magnesium borohydride Mg(BH4)2 and uptake of hydrogen by MgB2, have been investigated using solid–state density functional theory (DFT) calculations. Further, more accurate treatment of cell–size effects to the entropies were also investigated, in order to improve the accuracy of the thermodynamic properties of complex borohydrides. We find that the zero–point energy corrections can lower the electronic energies of reaction by 20–30 kJ/(mol H2) for these intermediates, while adding the thermal and entropy contributions results in the total decrease up to ~50 kJ/(mol H2). Although our treatment lowers the calculated formation energy of Mg(B3H8)2, it is still too high to explain the experimental observation of B3H8–. We discuss possible reasons for this disparity and propose that the formation of B3H8– and H– in a disordered amorphous phase has a large energy difference compared to the phase–separated Mg(B3H8)2 and MgH2 considered in calculations. Comparison of the experimental and NMR chemical shifts calculated within a DFT approach for known species Mg(BH4)2, Mg(B3H8)2, Mg(B11H14)2, MgB10H10 and MgB12H12 provides validation for predicting the chemical shifts of the other compounds which are yet to be confirmed experimentally. These include MgB2H6 and the proposed tri–anion species Mg3(B3H6)2 that both have favorable thermodynamics for reversible hydrogen storage in Mg(BH4)2 without the formation of MgH2 as a co–product which could phase–separate and inhibit rehydrogenation.},
doi = {10.1021/acs.jpca.1c09690},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 3,
volume = 126,
place = {United States},
year = {Fri Jan 14 00:00:00 EST 2022},
month = {Fri Jan 14 00:00:00 EST 2022}
}
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Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Structure of unsolvated magnesium borohydride Mg(BH 4 ) 2
journal, July 2007
- Her, Jae-Hyuk; Stephens, Peter W.; Gao, Yan
- Acta Crystallographica Section B Structural Science, Vol. 63, Issue 4
Interplay between the Reorientational Dynamics of the B 3 H 8 – Anion and the Structure in KB 3 H 8
journal, February 2021
- Andersson, M. S.; Grinderslev, J. B.; Chen, X. -M.
- The Journal of Physical Chemistry C, Vol. 125, Issue 7
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Ab initio characterization of the flexural anion found in the reversible dehydrogenation
journal, July 2011
- Olson, Jared K.; Boldyrev, Alexander I.
- Computational and Theoretical Chemistry, Vol. 967, Issue 1
NWChem: Past, present, and future
journal, May 2020
- Aprà, E.; Bylaska, E. J.; de Jong, W. A.
- The Journal of Chemical Physics, Vol. 152, Issue 18
Formation of [BH3]2- and [B2H6]2- From the Homogeneous Reduction of B2H6
journal, December 1994
- Godfroid, Robert A.; Hill, Tara G.; Onak, Thomas P.
- Journal of the American Chemical Society, Vol. 116, Issue 26
First-Principles Study of Experimental and Hypothetical Mg(BH 4 ) 2 Crystal Structures
journal, February 2008
- Dai, Bing; Sholl, David S.; Johnson, J. Karl
- The Journal of Physical Chemistry C, Vol. 112, Issue 11
Dehydriding and rehydriding processes of well-crystallized Mg(BH4)2 accompanying with formation of intermediate compounds
journal, April 2008
- Li, H.
- Acta Materialia, Vol. 56, Issue 6
Effects of Glymes on the Distribution of Mg(B10H10) and Mg(B12H12) from the Thermolysis of Mg(BH4)2
journal, May 2021
- Tran, Ba L.; Allen, Tamara N.; Bowden, Mark E.
- Inorganics, Vol. 9, Issue 6
NMR study of proton and boron dynamics in KB 3 H 8
journal, May 1980
- Reynhardt, E. C.; Lourens, J. A. J.
- Journal of Physics C: Solid State Physics, Vol. 13, Issue 14
High yield preparation of the tetradecahydroundecaborate(1-) anion, [B11H14]-, from pentaborane(9)
journal, October 1987
- Hosmane, Narayan S.; Wermer, Joseph R.; Hong, Zhu
- Inorganic Chemistry, Vol. 26, Issue 21
The role of energy storage in deep decarbonization of electricity production
journal, July 2019
- Arbabzadeh, Maryam; Sioshansi, Ramteen; Johnson, Jeremiah X.
- Nature Communications, Vol. 10, Issue 1
Controllable decomposition of Ca(BH 4 ) 2 for reversible hydrogen storage
journal, January 2017
- Yan, Y.; Rentsch, D.; Remhof, A.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 11
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Theoretical Prediction of Metastable Intermediates in the Decomposition of Mg(BH 4 ) 2
journal, May 2012
- Zhang, Yongsheng; Majzoub, Eric; Ozoliņš, Vidvuds
- The Journal of Physical Chemistry C, Vol. 116, Issue 19
Structure and hindered motion of B3H8 anions in solids: An NMR study
journal, May 1975
- Paine, R. T.; Fukushima, Eiichi; Roeder, S. B. W.
- Chemical Physics Letters, Vol. 32, Issue 3
Prototype electrostatic ground state approach to predicting crystal structures of ionic compounds: Application to hydrogen storage materials
journal, March 2008
- Majzoub, E. H.; Ozoliņš, V.
- Physical Review B, Vol. 77, Issue 10
Selective Reversible Hydrogenation of Mg(B 3 H 8 ) 2 /MgH 2 to Mg(BH 4 ) 2 : Pathway to Reversible Borane-Based Hydrogen Storage?
journal, March 2015
- Chong, Marina; Matsuo, Motoaki; Orimo, Shin-ichi
- Inorganic Chemistry, Vol. 54, Issue 8
Porous and Dense Magnesium Borohydride Frameworks: Synthesis, Stability, and Reversible Absorption of Guest Species
journal, September 2011
- Filinchuk, Yaroslav; Richter, Bo; Jensen, Torben R.
- Angewandte Chemie International Edition, Vol. 50, Issue 47
NMR Confirmation for Formation of [B 12 H 12 ] 2- Complexes during Hydrogen Desorption from Metal Borohydrides
journal, March 2008
- Hwang, Son-Jong; Bowman, Robert C.; Reiter, Joseph W.
- The Journal of Physical Chemistry C, Vol. 112, Issue 9
In-Situ X-ray Diffraction Study of γ-Mg(BH 4 ) 2 Decomposition
journal, July 2012
- Paskevicius, Mark; Pitt, Mark P.; Webb, Colin J.
- The Journal of Physical Chemistry C, Vol. 116, Issue 29
van der Waals interactions in the ground state of Mg(BH ) from density functional theory
journal, June 2011
- Bil, A.; Kolb, B.; Atkinson, R.
- Physical Review B, Vol. 83, Issue 22
A new phase in the decomposition of Mg(BH4)2: first-principles simulated annealing
journal, January 2009
- van Setten, M. J.; Lohstroh, W.; Fichtner, M.
- Journal of Materials Chemistry, Vol. 19, Issue 38
Supercritical N 2 Processing as a Route to the Clean Dehydrogenation of Porous Mg(BH 4 ) 2
journal, May 2014
- Stadie, Nicholas P.; Callini, Elsa; Richter, Bo
- Journal of the American Chemical Society, Vol. 136, Issue 23
Lewis Base Complexes of Magnesium Borohydride: Enhanced Kinetics and Product Selectivity upon Hydrogen Release
journal, December 2017
- Chong, Marina; Autrey, Tom; Jensen, Craig
- Inorganics, Vol. 5, Issue 4
Hydrogen at Scale (H 2 @Scale): Key to a Clean, Economic, and Sustainable Energy System
journal, January 2018
- Pivovar, Bryan; Rustagi, Neha; Satyapal, Sunita
- The Electrochemical Society Interface, Vol. 27, Issue 1
Reduction of borane THF by alkali metal (potassium, rubidium, cesium) and ytterbium mercury amalgams to form salts of octahydrotriborate(1-); a simple procedure for the synthesis of tetraborane(10)
journal, July 1991
- Hill, Tara G.; Godfroid, Robert A.; White, James P.
- Inorganic Chemistry, Vol. 30, Issue 14
The question of fluxional behavior in octahydrotriborate(1-) and pentaborane(11)
journal, March 1978
- Pepperberg, I. M.; Dixon, D. A.; Lipscomb, W. N.
- Inorganic Chemistry, Vol. 17, Issue 3
Morphology‐Dependent Stability of Complex Metal Hydrides and Their Intermediates Using First‐Principles Calculations
journal, March 2019
- Kang, ShinYoung; Heo, Tae Wook; Allendorf, Mark D.
- ChemPhysChem, Vol. 20, Issue 10
Hydrogen technologies for energy storage: A perspective
journal, July 2020
- Stetson, Ned; Wieliczko, Marika
- MRS Energy & Sustainability, Vol. 7, Issue 1
First-Principles Prediction of a Ground State Crystal Structure of Magnesium Borohydride
journal, March 2008
- Ozolins, V.; Majzoub, E. H.; Wolverton, C.
- Physical Review Letters, Vol. 100, Issue 13
Reversibility and Improved Hydrogen Release of Magnesium Borohydride
journal, February 2010
- Newhouse, Rebecca J.; Stavila, Vitalie; Hwang, Son-Jong
- The Journal of Physical Chemistry C, Vol. 114, Issue 11
Experimental investigation of Mg(B 3 H 8 ) 2 dimensionality, materials for energy storage applications
journal, January 2020
- Moury, Romain; Gigante, Angelina; Remhof, Arndt
- Dalton Transactions, Vol. 49, Issue 35
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 78, Issue 7
Thermal Conversion of Unsolvated Mg(B 3 H 8 ) 2 to BH 4 – in the Presence of MgH 2
journal, April 2021
- Gigante, Angelina; Leick, Noemi; Lipton, Andrew S.
- ACS Applied Energy Materials, Vol. 4, Issue 4
Using first principles calculations to identify new destabilized metal hydride reactions for reversible hydrogen storage
journal, January 2007
- Alapati, Sudhakar V.; Karl Johnson, J.; Sholl, David S.
- Physical Chemistry Chemical Physics, Vol. 9, Issue 12
Insight into Mg(BH 4 ) 2 with Synchrotron X-ray Diffraction: Structure Revision, Crystal Chemistry, and Anomalous Thermal Expansion
journal, March 2009
- Filinchuk, Yaroslav; Černý, Radovan; Hagemann, Hans
- Chemistry of Materials, Vol. 21, Issue 5
Reversible dehydrogenation of magnesium borohydride to magnesium triborane in the solid state under moderate conditions
journal, January 2011
- Chong, Marina; Karkamkar, Abhi; Autrey, Tom
- Chem. Commun., Vol. 47, Issue 4
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
Large-scale screening of metal hydrides for hydrogen storage from first-principles calculations based on equilibrium reaction thermodynamics
journal, January 2011
- Kim, Ki Chul; Kulkarni, Anant D.; Johnson, J. Karl
- Physical Chemistry Chemical Physics, Vol. 13, Issue 15
A novel strategy for reversible hydrogen storage in Ca(BH 4 ) 2
journal, January 2015
- Yan, Yigang; Remhof, Arndt; Rentsch, Daniel
- Chemical Communications, Vol. 51, Issue 55
Thermodynamic modelling of Mg(BH4)2
journal, October 2015
- Pinatel, E. R.; Albanese, E.; Civalleri, B.
- Journal of Alloys and Compounds, Vol. 645
First-Principles Prediction of Thermodynamically Reversible Hydrogen Storage Reactions in the Li-Mg-Ca-B-H System
journal, January 2009
- Ozolins, V.; Majzoub, E. H.; Wolverton, C.
- Journal of the American Chemical Society, Vol. 131, Issue 1
Decomposition and formation of magnesium borohydride
journal, July 2016
- Saldan, Ivan
- International Journal of Hydrogen Energy, Vol. 41, Issue 26
Magnesium borohydride as a hydrogen storage material: Properties and dehydrogenation pathway of unsolvated Mg(BH4)2
journal, January 2009
- Soloveichik, G.; Gao, Y.; Rijssenbeek, J.
- International Journal of Hydrogen Energy, Vol. 34, Issue 2, p. 916-928
Decomposition pathway of Mg(BH4)2 under pressure: Metastable phases and thermodynamic parameters
journal, February 2011
- Yang, Junzhi; Zhang, Xuanzhou; Zheng, Jie
- Scripta Materialia, Vol. 64, Issue 3
Potassium octahydridotriborate: diverse polymorphism in a potential hydrogen storage material and potassium ion conductor
journal, January 2019
- Grinderslev, Jakob B.; Møller, Kasper T.; Yan, Yigang
- Dalton Transactions, Vol. 48, Issue 24
The structure, thermal properties and phase transformations of the cubic polymorph of magnesium tetrahydroborate
journal, January 2012
- David, W. I. F.; Callear, S. K.; Jones, M. O.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 33
Examining the robustness of first-principles calculations for metal hydride reaction thermodynamics by detection of metastable reaction pathways
journal, January 2011
- Kim, Ki Chul; Kulkarni, Anant D.; Johnson, J. Karl
- Physical Chemistry Chemical Physics, Vol. 13, Issue 48
Formation Process of [B12H12]2− from [BH4]− during the Dehydrogenation Reaction of Mg(BH4)2
journal, January 2011
- Yan, Yigang; Li, Hai-Wen; Maekawa, Hideki
- MATERIALS TRANSACTIONS, Vol. 52, Issue 7
Direct hydrogenation of magnesium boride to magnesium borohydride: demonstration of >11 weight percent reversible hydrogenstorage
journal, January 2010
- Severa, Godwin; Rönnebro, Ewa; Jensen, Craig M.
- Chem. Commun., Vol. 46, Issue 3