Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Structural and reorientational dynamics of tetrahydroborate (BH4-) and tetrahydrofuran (THF) in a Mg(BH4)2·3THF adduct: neutron-scattering characterization

Abstract

In this work, 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 Pvia 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° jump reorientations of the BH4- anions around a preferred C2 anion symmetry axis. Furthermore, the THF rings are also found to be orientationally mobile, undergoing 180° reorientationalmore » jumps around their C2 molecular symmetry axis with jump frequencies about an order of magnitude lower than those for the BH4- anions. Contrastingly, 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]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2];  [2];  [4]; ORCiD logo [2];  [5]; ORCiD logo [3]
+ Show Author Affiliations
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  5. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE
OSTI Identifier:
1645013
Alternate Identifier(s):
OSTI ID: 1577906
Report Number(s):
PNNL-SA-141423
Journal ID: ISSN 1463-9076
Grant/Contract Number:  
AC05-76RL01830; AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 1; 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

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., 2020. Web. doi:10.1039/c9cp03311d.
Copy to clipboard
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. https://doi.org/10.1039/c9cp03311d
Copy to clipboard
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. https://doi.org/10.1039/c9cp03311d. https://www.osti.gov/servlets/purl/1645013.
Copy to clipboard
@article{osti_1645013,
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 = {In this work, 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 Pvia 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° jump reorientations of the BH4- anions around a preferred C2 anion symmetry axis. Furthermore, the THF rings are also found to be orientationally mobile, undergoing 180° reorientational jumps around their C2 molecular symmetry axis with jump frequencies about an order of magnitude lower than those for the BH4- anions. Contrastingly, 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 = {10.1039/c9cp03311d},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 1,
volume = 22,
place = {United States},
year = {2020},
month = {1}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/c9cp03311d
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Synthesis, structures and dehydrogenation of magnesium borohydride–ethylenediamine composites
journal, January 2015

The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies
journal, August 2003

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
  • DOI: 10.1021/jp9116744

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Complex Hydrides for Hydrogen Storage
journal, October 2007

  • Orimo, Shin-ichi; Nakamori, Yuko; Eliseo, Jennifer R.
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr0501846

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

Hindered Rotational Energy Barriers of BH 4 – Tetrahedra in β-Mg(BH 4 ) 2 from Quasielastic Neutron Scattering and DFT Calculations
journal, January 2012

  • Blanchard, D.; Maronsson, J. B.; Riktor, M. D.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 2
  • DOI: 10.1021/jp208670v

New fundamental experimental studies on α-Mg(BH4)2 and other borohydrides
journal, September 2011

Geometric structure and vibrational spectrum of tetrahydrofuran
journal, July 1993

  • Cadioli, Beniamino; Gallinella, Enzo; Coulombeau, Christian
  • The Journal of Physical Chemistry, Vol. 97, Issue 30
  • DOI: 10.1021/j100132a010

Synthesis and properties of magnesium tetrahydroborate, Mg(BH4)2
journal, January 2007

  • Chłopek, Krzysztof; Frommen, Christoph; Léon, Aline
  • Journal of Materials Chemistry, Vol. 17, Issue 33
  • DOI: 10.1039/b702723k

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

The design of a bismuth-based auxiliary filter for the removal of spurious background scattering associated with filter-analyzer neutron spectrometers
journal, April 2008

  • Udovic, T. J.; Brown, C. M.; Leão, J. B.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 588, Issue 3
  • DOI: 10.1016/j.nima.2008.02.006

Ammine Magnesium Borohydride Complex as a New Material for Hydrogen Storage: Structure and Properties of Mg(BH 4 ) 2 ·2NH 3
journal, May 2008

  • Soloveichik, Grigorii; Her, Jae-Hyuk; Stephens, Peter W.
  • Inorganic Chemistry, Vol. 47, Issue 10
  • DOI: 10.1021/ic7023633

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
  • DOI: 10.1021/cm803019e

Correlation between thermodynamical stabilities of metal borohydrides and cation electronegativites: First-principles calculations and experiments
journal, July 2006

LiBH 4 −Mg(BH 4 ) 2 : A Physical Mixture of Metal Borohydrides as Hydrogen Storage Material
journal, March 2011

  • Bardají, Elisa Gil; Zhao-Karger, Zhirong; Boucharat, Nancy
  • The Journal of Physical Chemistry C, Vol. 115, Issue 13
  • DOI: 10.1021/jp110518s

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

On the decomposition of the 0.6LiBH4-0.4Mg(BH4)2 eutectic mixture for hydrogen storage
journal, October 2011

  • Nale, Angeloclaudio; Catti, Michele; Bardají, Elisa Gil
  • International Journal of Hydrogen Energy, Vol. 36, Issue 21
  • DOI: 10.1016/j.ijhydene.2011.08.009

The high-flux backscattering spectrometer at the NIST Center for Neutron Research
journal, May 2003

  • Meyer, A.; Dimeo, R. M.; Gehring, P. M.
  • Review of Scientific Instruments, Vol. 74, Issue 5
  • DOI: 10.1063/1.1568557

Effects of ball milling and additives on dehydriding behaviors of well-crystallized Mg(BH4)2
journal, October 2007

Zeolite-Templated Carbon Materials for High-Pressure Hydrogen Storage
journal, June 2012

  • Stadie, Nicholas P.; Vajo, John J.; Cumberland, Robert W.
  • Langmuir, Vol. 28, Issue 26
  • DOI: 10.1021/la302050m

A complete basis set model chemistry. I. The total energies of closed‐shell atoms and hydrides of the first‐row elements
journal, August 1988

  • Petersson, G. A.; Bennett, Andrew; Tensfeldt, Thomas G.
  • The Journal of Chemical Physics, Vol. 89, Issue 4
  • DOI: 10.1063/1.455064

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Bilbao Crystallographic Server. II. Representations of crystallographic point groups and space groups
journal, March 2006

  • Aroyo, Mois I.; Kirov, Asen; Capillas, Cesar
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 62, Issue 2
  • DOI: 10.1107/S0108767305040286

Thermal decomposition of Mg(BH4)2 under He flow and H2 pressure
journal, January 2008

  • Hanada, Nobuko; Chłopek, Krzysztof; Frommen, Christoph
  • Journal of Materials Chemistry, Vol. 18, Issue 22
  • DOI: 10.1039/b801049h

Hydrogen storage properties and mechanisms of Mg(BH4)2⋅2NH3–xMgH2 combination systems
journal, February 2014

A complete basis set model chemistry. II. Open‐shell systems and the total energies of the first‐row atoms
journal, May 1991

  • Petersson, G. A.; Al‐Laham, Mohammad A.
  • The Journal of Chemical Physics, Vol. 94, Issue 9
  • DOI: 10.1063/1.460447

Improvement in dehydrogenation performance of Mg(BH4)2·2NH3 doped with transition metal: First-principles investigation
journal, July 2015

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
  • DOI: 10.1016/j.ijhydene.2008.11.016

X-ray crystallographic investigation of crystals of bis(tetrahydroborato)tris(tetrahydrofuranato)magnesium
journal, January 1983

  • Lobkovskii, E. B.; Titov, L. V.; Psikha, S. B.
  • Journal of Structural Chemistry, Vol. 23, Issue 4
  • DOI: 10.1007/BF00746182

Effect of several metal chlorides on the thermal decomposition behaviour of α-Mg(BH4)2
journal, September 2011

Advanced Materials for Energy Storage
journal, February 2010

Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003

  • Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed
  • Science, Vol. 300, Issue 5622, p. 1127-1129
  • DOI: 10.1126/science.1083440

Facile Synthesis of Lanthanidocenes by the “Borohydride/Alkyl Route” and Their Application in Isoprene Polymerization
journal, April 2010

  • Visseaux, Marc; Terrier, Michael; Mortreux, André
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 18
  • DOI: 10.1002/ejic.201000184

Enhanced Hydrogen Storage Kinetics of LiBH4 in Nanoporous Carbon Scaffolds
journal, March 2008

  • Gross, Adam F.; Vajo, John J.; Van Atta, Sky L.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 14, p. 5651-5657
  • DOI: 10.1021/jp711066t

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Lewis Base Complexes of Magnesium Borohydride: Enhanced Kinetics and Product Selectivity upon Hydrogen Release
journal, December 2017

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations
journal, January 2016

  • Dimitrievska, Mirjana; White, James L.; Zhou, Wei
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 36
  • DOI: 10.1039/C6CP04469G

Nuclear Magnetic Resonance Study of Reorientational Motion in α-Mg(BH 4 ) 2
journal, June 2010

  • Skripov, Alexander V.; Soloninin, Alexei V.; Babanova, Olga A.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 28
  • DOI: 10.1021/jp1037206

A future energy supply based on Liquid Organic Hydrogen Carriers (LOHC)
journal, January 2011

  • Teichmann, Daniel; Arlt, Wolfgang; Wasserscheid, Peter
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c1ee01454d

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
  • DOI: 10.1039/B921205A

Complex Hydrides for Hydrogen Storage
journal, December 2007

  • Orimo, Shin-ichi; Nakamori, Yuko; Eliseo, Jennifer R.
  • ChemInform, Vol. 38, Issue 51
  • DOI: 10.1002/chin.200751221

Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988

  • Robert, Parr,; Chengteh, Lee,; Weitao, Yang,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/zrp0-ry04
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections:

    Other research related to this record: