skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

Abstract

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weaving of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structuresmore » and unusual bonding configurations in dense low-Z materials.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Wake Forest Univ., Winston-Salem, NC (United States)
  3. Wake Forest Univ., Winston-Salem, NC (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1361157
Grant/Contract Number:  
DMR-1145968; 391888; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 15; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Lin, Yu, Welchman, Evan, Thonhauser, Timo, and Mao, Wendy L. The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH3BH3)(H2)x(x = 1.5) compound. United States: N. p., 2017. Web. doi:10.1039/c7ta01005b.
Lin, Yu, Welchman, Evan, Thonhauser, Timo, & Mao, Wendy L. The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH3BH3)(H2)x(x = 1.5) compound. United States. doi:10.1039/c7ta01005b.
Lin, Yu, Welchman, Evan, Thonhauser, Timo, and Mao, Wendy L. Wed . "The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH3BH3)(H2)x(x = 1.5) compound". United States. doi:10.1039/c7ta01005b. https://www.osti.gov/servlets/purl/1361157.
@article{osti_1361157,
title = {The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH3BH3)(H2)x(x = 1.5) compound},
author = {Lin, Yu and Welchman, Evan and Thonhauser, Timo and Mao, Wendy L.},
abstractNote = {Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH3BH3)(H2)x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH3BH3) in an environment with an excess of molecular hydrogen (H2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H2 molecules reside in channels created through the weaving of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.},
doi = {10.1039/c7ta01005b},
journal = {Journal of Materials Chemistry. A},
number = 15,
volume = 5,
place = {United States},
year = {2017},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

High-Pressure Compounds in Methane-Hydrogen Mixtures
journal, March 1996


Lowering the hydrogen desorption temperature of NH 3 BH 3 through B-group substitutions
journal, January 2015

  • Welchman, Evan; Thonhauser, Timo
  • Journal of Materials Chemistry A, Vol. 3, Issue 36
  • DOI: 10.1039/C5TA02955D

Dehydrogenation of Ammonia Borane by Metal Nanoparticle Catalysts
journal, September 2016


Ammonia borane modified zirconium borohydride octaammoniate with enhanced dehydrogenation properties
journal, January 2015

  • Huang, Jianmei; Tan, Yingbin; Gu, Qinfen
  • Journal of Materials Chemistry A, Vol. 3, Issue 10
  • DOI: 10.1039/C4TA05328A

Storage of molecular hydrogen in an ammonia borane compound at high pressure
journal, May 2009

  • Lin, Y.; Mao, W. L.; Mao, H. -k.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 20
  • DOI: 10.1073/pnas.0903511106

Quadratic Corrections to Harmonic Vibrational Frequencies Outperform Linear Models
journal, December 2015

  • Sibaev, Marat; Crittenden, Deborah L.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 52
  • DOI: 10.1021/acs.jpca.5b11386

Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks
journal, September 2015


Raman spectroscopy study of ammonia borane at high pressure
journal, December 2008

  • Lin, Yu; Mao, Wendy L.; Drozd, Vadym
  • The Journal of Chemical Physics, Vol. 129, Issue 23
  • DOI: 10.1063/1.3040276

Superionic and Metallic States of Water and Ammonia at Giant Planet Conditions
journal, January 1999


Dihydrogen Bonding in Compressed Ammonia Borane and Its Roles in Structural Stability
journal, December 2014

  • Yao, Yansun; Yong, Xue; Tse, John S.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 51
  • DOI: 10.1021/jp509633h

Regeneration of Ammonia Borane Spent Fuel by Direct Reaction with Hydrazine and Liquid Ammonia
journal, March 2011


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Manganese-Mediated Hydride Delivery to a Borazine by Stepwise Reduction and Protonation
journal, March 2014

  • Carter, Tyler J.; Wang, Justin Y.; Szymczak, Nathaniel K.
  • Organometallics, Vol. 33, Issue 7
  • DOI: 10.1021/om500157m

Spectroscopic studies of the phase transition in ammonia borane: Raman spectroscopy of single crystal NH3BH3 as a function of temperature from 88to330K
journal, January 2008

  • Hess, Nancy J.; Bowden, Mark E.; Parvanov, Vencislav M.
  • The Journal of Chemical Physics, Vol. 128, Issue 3
  • DOI: 10.1063/1.2820768

High-pressure storage of hydrogen fuel: ammonia borane and its related compounds
journal, September 2014


Clathrate hydrates under pressure
journal, October 2007

  • Mao, Wendy L.; Koh, Carolyn A.; Sloan, E. Dendy
  • Physics Today, Vol. 60, Issue 10
  • DOI: 10.1063/1.2800096

Compression of Ar(H2)2 up to 175 GPa: a new path for the dissociation of molecular hydrogen?
journal, February 1994

  • Loubeyre, Paul; Letoullec, René; Pinceaux, Jean-Pierre
  • Physical Review Letters, Vol. 72, Issue 9, p. 1360-1363
  • DOI: 10.1103/PhysRevLett.72.1360

Study of the N−H···H−B Dihydrogen Bond Including the Crystal Structure of BH 3 NH 3 by Neutron Diffraction
journal, July 1999

  • Klooster, Wim T.; Koetzle, Thomas F.; Siegbahn, Per E. M.
  • Journal of the American Chemical Society, Vol. 121, Issue 27
  • DOI: 10.1021/ja9825332

Novel Cooperative Interactions and Structural Ordering in H 2 S H 2
journal, December 2011


Constrained evolutionary algorithm for structure prediction of molecular crystals: methodology and applications
journal, May 2012

  • Zhu, Qiang; Oganov, Artem R.; Glass, Colin W.
  • Acta Crystallographica Section B Structural Science, Vol. 68, Issue 3
  • DOI: 10.1107/S0108768112017466

Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
journal, September 2007


A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006


Reduction of Borazines Mediated by Low-Valent Chromium Species
journal, November 2012

  • Carter, Tyler J.; Kampf, Jeff W.; Szymczak, Nathaniel K.
  • Angewandte Chemie International Edition, Vol. 51, Issue 52
  • DOI: 10.1002/anie.201206668

Phase coexistence and hysteresis effects in the pressure-temperature phase diagram of NH 3 BH 3
journal, July 2011


Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system
journal, August 2015

  • Drozdov, A. P.; Eremets, M. I.; Troyan, I. A.
  • Nature, Vol. 525, Issue 7567
  • DOI: 10.1038/nature14964

Neutron Powder Diffraction and Molecular Simulation Study of the Structural Evolution of Ammonia Borane from 15 to 340 K
journal, May 2009

  • Hess, Nancy J.; Schenter, Gregory K.; Hartman, Michael R.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 19
  • DOI: 10.1021/jp900839c

Uniform versus Nonuniform Scaling of Normal Modes Predicted by Ab Initio Calculations: A Test on 2-(2,6-Dichlorophenyl)-N-(1,3-thiazol-2yl) Acetamide
journal, July 2014

  • Srivastava, Ambrish K.; Pandey, Anoop K.; Pandey, Saurabh
  • International Journal of Spectroscopy, Vol. 2014
  • DOI: 10.1155/2014/649268

How Evolutionary Crystal Structure Prediction Works—and Why
journal, March 2011

  • Oganov, Artem R.; Lyakhov, Andriy O.; Valle, Mario
  • Accounts of Chemical Research, Vol. 44, Issue 3
  • DOI: 10.1021/ar1001318

Homopolar Dihydrogen Bonding in Alkali Metal Amidoboranes: Crystal Engineering of Low-Dimensional Molecular Materials
journal, February 2013

  • Wolstenholme, David J.; Flogeras, Jenna; Che, Franklin N.
  • Journal of the American Chemical Society, Vol. 135, Issue 7
  • DOI: 10.1021/ja311778k

Experimental and Theoretical Studies on a High Pressure Monoclinic Phase of Ammonia Borane
journal, November 2011

  • Lin, Yu; Ma, Hongwei; Matthews, Charles Wesley
  • The Journal of Physical Chemistry C, Vol. 116, Issue 3
  • DOI: 10.1021/jp206726t

Visualizing ensembles in structural biology
journal, June 2016


Molybdenum Catalyzed Ammonia Borane Dehydrogenation: Oxidation State Specific Mechanisms
journal, July 2014

  • Buss, Joshua A.; Edouard, Guy A.; Cheng, Christine
  • Journal of the American Chemical Society, Vol. 136, Issue 32
  • DOI: 10.1021/ja5059923

Positional disorder in ammonia borane at ambient conditions
journal, May 2014


Ammonia-Borane and Related Compounds as Dihydrogen Sources
journal, July 2010

  • Staubitz, Anne; Robertson, Alasdair P. M.; Manners, Ian
  • Chemical Reviews, Vol. 110, Issue 7
  • DOI: 10.1021/cr100088b

Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions
journal, January 1986

  • Mao, H. K.; Xu, J.; Bell, P. M.
  • Journal of Geophysical Research, Vol. 91, Issue B5, p. 4673-4676
  • DOI: 10.1029/JB091iB05p04673

van der Waals forces in density functional theory: a review of the vdW-DF method
journal, May 2015


High-pressure phase and transition phenomena in ammonia borane NH 3 BH 3 from x-ray diffraction, Landau theory, and ab initio calculations
journal, June 2009

  • Filinchuk, Yaroslav; Nevidomskyy, Andriy H.; Chernyshov, Dmitry
  • Physical Review B, Vol. 79, Issue 21
  • DOI: 10.1103/PhysRevB.79.214111

Novel Pressure-Induced Interactions in Silane-Hydrogen
journal, August 2009


Crystal structure prediction using ab initio evolutionary techniques: Principles and applications
journal, June 2006

  • Oganov, Artem R.; Glass, Colin W.
  • The Journal of Chemical Physics, Vol. 124, Issue 24
  • DOI: 10.1063/1.2210932

Catalytic hydrolysis of ammonia borane for chemical hydrogen storage
journal, July 2011


Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408

Thermal decomposition of ammonia borane at high pressures
journal, January 2009

  • Nylén, Johanna; Sato, Toyoto; Soignard, Emmanuel
  • The Journal of Chemical Physics, Vol. 131, Issue 10
  • DOI: 10.1063/1.3230973

Hydrogen Clusters in Clathrate Hydrate
journal, September 2002


High pressure chemistry in the H2-SiH4 system
journal, August 2009

  • Wang, S.; Mao, H. -k.; Chen, X. -J.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 35
  • DOI: 10.1073/pnas.0907729106

Pressure-induced bonding and compound formation in xenon–hydrogen solids
journal, November 2009

  • Somayazulu, Maddury; Dera, Przemyslaw; Goncharov, Alexander F.
  • Nature Chemistry, Vol. 2, Issue 1
  • DOI: 10.1038/nchem.445

Pressure-induced complexation of NH3BH3–H2
journal, December 2009

  • Chellappa, Raja S.; Somayazulu, Maddury; Struzhkin, Viktor V.
  • The Journal of Chemical Physics, Vol. 131, Issue 22
  • DOI: 10.1063/1.3174262