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Title: Structural and Reorientational Dynamics of Tetrahydroborate (BH4-) and Tetrahydrofuran (THF) in a Mg(BH4)2 3THF Adduct: Neutron-Scattering Characterization

Abstract

Metal borohydrides are considered promising materials for hydrogen storage applications due to their high volumetric and gravimetric hydrogen density. Recently, different Lewis bases have been complexed with Mg(BH4)2 in efforts to improve hydrogenation/dehydrogenation properties. Notably, Mg(BH4)2 xTHF adducts involving tetrahydrofuran (THF; C4H8O) have proven to be especially interesting. This work focuses on exploring the physicochemical properties of the THF-rich Mg(BH4)2 3THF adduct using neutron-scattering methods and molecular DFT calculations. Structural analysis, based on neutron diffraction measurements of Mg(11BH4)2 3TDF (D-deuterium), has confirmed a lowering of the symmetry upon cooling, from monoclinic C2/c to P[1 with combining macron] via a triclinic distortion. Vibrational properties are strongly influenced by the THF environment, showing a splitting in spectral features as a result of changes in the bond lengths, force constants, and lowering of the overall symmetry. Interestingly, the orientational mobilities of the BH4- anions obtained from quasielastic neutron scattering (QENS) are not particularly sensitive to the presence of THF and compare well with the mobilities of BH4- anions in unsolvated Mg(BH4)2. The QENS data point to uniaxial 180 degree jump reorientations of the BH4- anions around a preferred C2 anion symmetry axis. The THF rings are also found to be orientationally mobile, undergoingmore » 180 degree reorientational jumps around their C2 molecular symmetry axis with jump frequencies about an order of magnitude lower than those for the BH4- anions. In contrast, no dynamical behavior of the THF rings is observed with QENS for a more THF-deficient 2Mg(BH4)2 THF adduct. This lack of comparable THF mobility may reflect a stronger Mg2+-THF bonding interaction for lower THF/Mg(BH4)2 stoichiometric ratios, which is consistent with DFT calculations showing a decrease in the binding energy with each additional THF ring in the adduct. Based on the combined experimental and computational results, we propose that combining THF and Mg(BH4)2 is beneficial to (i) preventing weakly bound THF from coming free from the Mg2+ cation and reducing the concentration of any unwanted impurity in the hydrogen and (ii) disrupting the stability of the crystalline phase, leading to a lower melting point and enhanced kinetics for any potential hydrogen storage applications.« less

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [3];  [2];  [2];  [1];  [2];  [4];  [3]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. Pacific Northwest National Laboratory
  3. National Institute of Standards and Technology
  4. University of Hawaii, Manoa
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1581496
Report Number(s):
NREL/JA-5900-75712
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Volume: 22; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; hydrogen storage; adducts; neutron scattering

Citation Formats

Dimitrievska, Mirjana, Chong, Marina, Bowden, Mark E., Wu, Hui, Zhou, Wei, Nayyar, Iffat, Ginovska, Bojana, Gennett, Thomas, Autrey, Tom, Jensen, Craig M., and Udovic, Terrence J. Structural and Reorientational Dynamics of Tetrahydroborate (BH4-) and Tetrahydrofuran (THF) in a Mg(BH4)2 3THF Adduct: Neutron-Scattering Characterization. United States: N. p., 2019. Web. doi:https://dx.doi.org/10.1039/C9CP03311D.
Dimitrievska, Mirjana, Chong, Marina, Bowden, Mark E., Wu, Hui, Zhou, Wei, Nayyar, Iffat, Ginovska, Bojana, Gennett, Thomas, Autrey, Tom, Jensen, Craig M., & Udovic, Terrence J. Structural and Reorientational Dynamics of Tetrahydroborate (BH4-) and Tetrahydrofuran (THF) in a Mg(BH4)2 3THF Adduct: Neutron-Scattering Characterization. United States. doi:https://dx.doi.org/10.1039/C9CP03311D.
Dimitrievska, Mirjana, Chong, Marina, Bowden, Mark E., Wu, Hui, Zhou, Wei, Nayyar, Iffat, Ginovska, Bojana, Gennett, Thomas, Autrey, Tom, Jensen, Craig M., and Udovic, Terrence J. Wed . "Structural and Reorientational Dynamics of Tetrahydroborate (BH4-) and Tetrahydrofuran (THF) in a Mg(BH4)2 3THF Adduct: Neutron-Scattering Characterization". United States. doi:https://dx.doi.org/10.1039/C9CP03311D.
@article{osti_1581496,
title = {Structural and Reorientational Dynamics of Tetrahydroborate (BH4-) and Tetrahydrofuran (THF) in a Mg(BH4)2 3THF Adduct: Neutron-Scattering Characterization},
author = {Dimitrievska, Mirjana and Chong, Marina and Bowden, Mark E. and Wu, Hui and Zhou, Wei and Nayyar, Iffat and Ginovska, Bojana and Gennett, Thomas and Autrey, Tom and Jensen, Craig M. and Udovic, Terrence J.},
abstractNote = {Metal borohydrides are considered promising materials for hydrogen storage applications due to their high volumetric and gravimetric hydrogen density. Recently, different Lewis bases have been complexed with Mg(BH4)2 in efforts to improve hydrogenation/dehydrogenation properties. Notably, Mg(BH4)2 xTHF adducts involving tetrahydrofuran (THF; C4H8O) have proven to be especially interesting. This work focuses on exploring the physicochemical properties of the THF-rich Mg(BH4)2 3THF adduct using neutron-scattering methods and molecular DFT calculations. Structural analysis, based on neutron diffraction measurements of Mg(11BH4)2 3TDF (D-deuterium), has confirmed a lowering of the symmetry upon cooling, from monoclinic C2/c to P[1 with combining macron] via a triclinic distortion. Vibrational properties are strongly influenced by the THF environment, showing a splitting in spectral features as a result of changes in the bond lengths, force constants, and lowering of the overall symmetry. Interestingly, the orientational mobilities of the BH4- anions obtained from quasielastic neutron scattering (QENS) are not particularly sensitive to the presence of THF and compare well with the mobilities of BH4- anions in unsolvated Mg(BH4)2. The QENS data point to uniaxial 180 degree jump reorientations of the BH4- anions around a preferred C2 anion symmetry axis. The THF rings are also found to be orientationally mobile, undergoing 180 degree reorientational jumps around their C2 molecular symmetry axis with jump frequencies about an order of magnitude lower than those for the BH4- anions. In contrast, no dynamical behavior of the THF rings is observed with QENS for a more THF-deficient 2Mg(BH4)2 THF adduct. This lack of comparable THF mobility may reflect a stronger Mg2+-THF bonding interaction for lower THF/Mg(BH4)2 stoichiometric ratios, which is consistent with DFT calculations showing a decrease in the binding energy with each additional THF ring in the adduct. Based on the combined experimental and computational results, we propose that combining THF and Mg(BH4)2 is beneficial to (i) preventing weakly bound THF from coming free from the Mg2+ cation and reducing the concentration of any unwanted impurity in the hydrogen and (ii) disrupting the stability of the crystalline phase, leading to a lower melting point and enhanced kinetics for any potential hydrogen storage applications.},
doi = {https://dx.doi.org/10.1039/C9CP03311D},
journal = {Physical Chemistry Chemical Physics},
number = 1,
volume = 22,
place = {United States},
year = {2019},
month = {11}
}

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