DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Critical Factors in Computational Characterization of Hydrogen Storage in Metal–Organic Frameworks

Abstract

Inconsistencies in high-pressure H2 adsorption data and a lack of comparative experiment–theory studies have made the evaluation of both new and existing metal–organic frameworks (MOFs) challenging in the context of hydrogen storage applications. In this work, we performed grand canonical Monte Carlo (GCMC) simulations in nearly 500 experimentally refined MOF structures to examine the variance in simulation results because of the equation of state, H2 potential, and the effect of density functional theory structural optimization. We find that hydrogen capacity at 77 K and 100 bar, as well as hydrogen 100-to-5 bar deliverable capacity, is correlated more strongly with the MOF pore volume than with the MOF surface area (the latter correlation is known as the Chahine’s rule). The tested methodologies provide consistent rankings of materials. In addition, four prototypical MOFs (MOF-74, CuBTC, ZIF-8, and MOF-5) with a range of surface areas, pore structures, and surface chemistries, representative of promising adsorbents for hydrogen storage, are evaluated in detail with both GCMC simulations and experimental measurements. Simulations with a three-site classical potential for H2 agree best with our experimental data except in the case of MOF-5, in which H2 adsorption is best replicated with a five-site potential. However, for the purposemore » of ranking materials, these two choices for H2 potential make little difference. Here more significantly, 100 bar loading estimates based on more accurate equations of state for the vapor–liquid equilibrium yield the best comparisons with the experiment.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1507406
Report Number(s):
SAND-2019-3246J
Journal ID: ISSN 1932-7447; 673700
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 33; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Camp, Jeffrey, Stavila, Vitalie, Allendorf, Mark D., Prendergast, David, and Haranczyk, Maciej. Critical Factors in Computational Characterization of Hydrogen Storage in Metal–Organic Frameworks. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b04021.
Camp, Jeffrey, Stavila, Vitalie, Allendorf, Mark D., Prendergast, David, & Haranczyk, Maciej. Critical Factors in Computational Characterization of Hydrogen Storage in Metal–Organic Frameworks. United States. https://doi.org/10.1021/acs.jpcc.8b04021
Camp, Jeffrey, Stavila, Vitalie, Allendorf, Mark D., Prendergast, David, and Haranczyk, Maciej. Thu . "Critical Factors in Computational Characterization of Hydrogen Storage in Metal–Organic Frameworks". United States. https://doi.org/10.1021/acs.jpcc.8b04021. https://www.osti.gov/servlets/purl/1507406.
@article{osti_1507406,
title = {Critical Factors in Computational Characterization of Hydrogen Storage in Metal–Organic Frameworks},
author = {Camp, Jeffrey and Stavila, Vitalie and Allendorf, Mark D. and Prendergast, David and Haranczyk, Maciej},
abstractNote = {Inconsistencies in high-pressure H2 adsorption data and a lack of comparative experiment–theory studies have made the evaluation of both new and existing metal–organic frameworks (MOFs) challenging in the context of hydrogen storage applications. In this work, we performed grand canonical Monte Carlo (GCMC) simulations in nearly 500 experimentally refined MOF structures to examine the variance in simulation results because of the equation of state, H2 potential, and the effect of density functional theory structural optimization. We find that hydrogen capacity at 77 K and 100 bar, as well as hydrogen 100-to-5 bar deliverable capacity, is correlated more strongly with the MOF pore volume than with the MOF surface area (the latter correlation is known as the Chahine’s rule). The tested methodologies provide consistent rankings of materials. In addition, four prototypical MOFs (MOF-74, CuBTC, ZIF-8, and MOF-5) with a range of surface areas, pore structures, and surface chemistries, representative of promising adsorbents for hydrogen storage, are evaluated in detail with both GCMC simulations and experimental measurements. Simulations with a three-site classical potential for H2 agree best with our experimental data except in the case of MOF-5, in which H2 adsorption is best replicated with a five-site potential. However, for the purpose of ranking materials, these two choices for H2 potential make little difference. Here more significantly, 100 bar loading estimates based on more accurate equations of state for the vapor–liquid equilibrium yield the best comparisons with the experiment.},
doi = {10.1021/acs.jpcc.8b04021},
journal = {Journal of Physical Chemistry. C},
number = 33,
volume = 122,
place = {United States},
year = {2018},
month = {7}
}

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

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Density, void fraction, and surface areas of MCIFs

Save / Share:

Works referenced in this record:

High-Throughput Screening of Metal–Organic Frameworks for Hydrogen Storage at Cryogenic Temperature
journal, November 2016

  • Bobbitt, N. Scott; Chen, Jiayi; Snurr, Randall Q.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 48
  • DOI: 10.1021/acs.jpcc.6b08729

An international multi-laboratory investigation of carbon-based hydrogen sorbent materials
journal, January 2016

  • Hurst, Katherine E.; Parilla, Philip A.; O’Neill, Kevin J.
  • Applied Physics A, Vol. 122, Issue 1
  • DOI: 10.1007/s00339-015-9537-x

Hydrogen Storage in Metal-Organic Frameworks: A Review
journal, May 2014


Hydrogen Storage in Metal–Organic Frameworks
journal, September 2011

  • Suh, Myunghyun Paik; Park, Hye Jeong; Prasad, Thazhe Kootteri
  • Chemical Reviews, Vol. 112, Issue 2, p. 782-835
  • DOI: 10.1021/cr200274s

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Hydrogen adsorption in different carbon nanostructures
journal, August 2005


Theoretical Limits of Hydrogen Storage in Metal–Organic Frameworks: Opportunities and Trade-Offs
journal, August 2013

  • Goldsmith, Jacob; Wong-Foy, Antek G.; Cafarella, Michael J.
  • Chemistry of Materials, Vol. 25, Issue 16
  • DOI: 10.1021/cm401978e

An Ab Initio Force Field for Predicting Hydrogen Storage in IRMOF Materials
journal, November 2009

  • Fu, Jia; Sun, Huai
  • The Journal of Physical Chemistry C, Vol. 113, Issue 52
  • DOI: 10.1021/jp907921q

Accurate Prediction of Hydrogen Adsorption in Metal−Organic Frameworks with Unsaturated Metal Sites via a Combined Density-Functional Theory and Molecular Mechanics Approach
journal, October 2010

  • Fischer, Michael; Kuchta, Bogdan; Firlej, Lucyna
  • The Journal of Physical Chemistry C, Vol. 114, Issue 44
  • DOI: 10.1021/jp1058963

Computational approaches to study adsorption in MOFs with unsaturated metal sites
journal, February 2014


UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations
journal, December 1992

  • Rappe, A. K.; Casewit, C. J.; Colwell, K. S.
  • Journal of the American Chemical Society, Vol. 114, Issue 25, p. 10024-10035
  • DOI: 10.1021/ja00051a040

Hydrogen Storage in Mesoporous Coordination Frameworks: Experiment and Molecular Simulation
journal, July 2009

  • Xiang, Zhonghua; Lan, Jianhui; Cao, Dapeng
  • The Journal of Physical Chemistry C, Vol. 113, Issue 34
  • DOI: 10.1021/jp906387m

Path integral simulations of mixed para ‐D 2 and ortho ‐D 2 clusters: The orientational effects
journal, May 1994

  • Buch, V.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466854

Monte Carlo simulations of hydrogen storage in carbon nanotubes
journal, September 2002

  • Levesque, D.; Gicquel, A.; Darkrim, F. Lamari
  • Journal of Physics: Condensed Matter, Vol. 14, Issue 40
  • DOI: 10.1088/0953-8984/14/40/318

An Accurate and Transferable Intermolecular Diatomic Hydrogen Potential for Condensed Phase Simulation
journal, July 2008

  • Belof, Jonathan L.; Stern, Abraham C.; Space, Brian
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 8
  • DOI: 10.1021/ct800155q

Atomic-scale modeling of hydrogen storage in the UiO-66 and UiO-67 metal-organic frameworks
journal, April 2016


The Cambridge Structural Database: a quarter of a million crystal structures and rising
journal, May 2002


Computation-Ready, Experimental Metal–Organic Frameworks: A Tool To Enable High-Throughput Screening of Nanoporous Crystals
journal, October 2014

  • Chung, Yongchul G.; Camp, Jeffrey; Haranczyk, Maciej
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm502594j

Large-Scale Refinement of Metal−Organic Framework Structures Using Density Functional Theory
journal, November 2016


Chemically Meaningful Atomic Charges That Reproduce the Electrostatic Potential in Periodic and Nonperiodic Materials
journal, July 2010

  • Manz, Thomas A.; Sholl, David S.
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 8
  • DOI: 10.1021/ct100125x

Base-Induced Formation of Two Magnesium Metal-Organic Framework Compounds with a Bifunctional Tetratopic Ligand
journal, August 2008

  • Dietzel, Pascal D. C.; Blom, Richard; Fjellvåg, Helmer
  • European Journal of Inorganic Chemistry, Vol. 2008, Issue 23
  • DOI: 10.1002/ejic.200701284

Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015

  • Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
  • Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
  • DOI: 10.1021/cm502760q

Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials
journal, February 2012


High accuracy geometric analysis of crystalline porous materials
journal, January 2013

  • Pinheiro, Marielle; Martin, Richard L.; Rycroft, Chris H.
  • CrystEngComm, Vol. 15, Issue 37
  • DOI: 10.1039/c3ce41057a

Accurate Characterization of the Pore Volume in Microporous Crystalline Materials
journal, July 2017


RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials
journal, February 2015


Review and Analysis of Molecular Simulations of Methane, Hydrogen, and Acetylene Storage in Metal–Organic Frameworks
journal, September 2011

  • Getman, Rachel B.; Bae, Youn-Sang; Wilmer, Christopher E.
  • Chemical Reviews, Vol. 112, Issue 2, p. 703-723
  • DOI: 10.1021/cr200217c

A Comprehensive Set of High-Quality Point Charges for Simulations of Metal–Organic Frameworks
journal, January 2016


A New Two-Constant Equation of State
journal, February 1976

  • Peng, Ding-Yu; Robinson, Donald B.
  • Industrial & Engineering Chemistry Fundamentals, Vol. 15, Issue 1
  • DOI: 10.1021/i160057a011

Determination of compressibility factor and fugacity coefficient of hydrogen in studies of adsorptive storage
journal, June 2001


Some Topics in the Theory of Fluids
journal, December 1963

  • Widom, B.
  • The Journal of Chemical Physics, Vol. 39, Issue 11
  • DOI: 10.1063/1.1734110

Best Practices for the Synthesis, Activation, and Characterization of Metal–Organic Frameworks
journal, September 2016


Transition State Theory Methods To Measure Diffusion in Flexible Nanoporous Materials: Application to a Porous Organic Cage Crystal
journal, January 2016

  • Camp, Jeffrey S.; Sholl, David S.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 2
  • DOI: 10.1021/acs.jpcc.5b11111

Development of a Cambridge Structural Database Subset: A Collection of Metal–Organic Frameworks for Past, Present, and Future
journal, March 2017


Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002

  • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
  • Science, Vol. 295, Issue 5554, p. 469-472
  • DOI: 10.1126/science.1067208

Effect of Synthesis Conditions on Formation Pathways of Metal Organic Framework (MOF-5) Crystals
journal, November 2013

  • McKinstry, Colin; Cussen, Edmund J.; Fletcher, Ashleigh J.
  • Crystal Growth & Design, Vol. 13, Issue 12
  • DOI: 10.1021/cg4014619

Techno-economic Analysis of Metal–Organic Frameworks for Hydrogen and Natural Gas Storage
journal, January 2017


Experimental and Theoretical Studies of Gas Adsorption in Cu 3 (BTC) 2 :  An Effective Activation Procedure
journal, July 2007

  • Liu, Jinchen; Culp, Jeffrey T.; Natesakhawat, Sittichai
  • The Journal of Physical Chemistry C, Vol. 111, Issue 26
  • DOI: 10.1021/jp071449i

Materials Genome in Action: Identifying the Performance Limits of Physical Hydrogen Storage
journal, March 2017


Ab Initio Derived Force Fields for Predicting CO 2 Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)
journal, June 2015

  • Haldoupis, Emmanuel; Borycz, Joshua; Shi, Huiliang
  • The Journal of Physical Chemistry C, Vol. 119, Issue 28
  • DOI: 10.1021/acs.jpcc.5b03700

Temperature-dependent supramolecular stereoisomerism in porous copper coordination networks based on a designed carboxylate ligand
journal, January 2005

  • Sun, Daofeng; Ke, Yanxiong; Mattox, Tracy M.
  • Chemical Communications, Issue 43
  • DOI: 10.1039/b505664k

Evaluating topologically diverse metal–organic frameworks for cryo-adsorbed hydrogen storage
journal, January 2016

  • Gómez-Gualdrón, Diego A.; Colón, Yamil J.; Zhang, Xu
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/c6ee02104b

The materials genome in action: identifying the performance limits for methane storage
journal, January 2015

  • Simon, Cory M.; Kim, Jihan; Gomez-Gualdron, Diego A.
  • Energy & Environmental Science, Vol. 8, Issue 4
  • DOI: 10.1039/c4ee03515a

The BACK equation of state for hydrogen and related compounds
journal, February 2006


Requirements for advanced mobile storage systems
journal, September 1998


On the Mechanism of Hydrogen Storage in a Metal−Organic Framework Material
journal, November 2007

  • Belof, Jonathan L.; Stern, Abraham C.; Eddaoudi, Mohamed
  • Journal of the American Chemical Society, Vol. 129, Issue 49
  • DOI: 10.1021/ja0737164

Net, excess and absolute adsorption and adsorption of helium
journal, February 2016


Adsorption Sites of Hydrogen in Zeolitic Imidazolate Frameworks
journal, August 2009

  • Zhou, Min; Wang, Qi; Zhang, Li
  • The Journal of Physical Chemistry B, Vol. 113, Issue 32
  • DOI: 10.1021/jp904170s

Novel experimental methods for assessment of hydrogen storage capacity and modelling of sorption in Cu-BTC
journal, October 2010


Adsorption of hydrogen in covalent organic frameworks: Comparison of simulations and experiments
journal, September 2010


Molecular simulation of hydrogen adsorption in single-walled carbon nanotubes and idealized carbon slit pores
journal, January 1999

  • Wang, Qinyu; Johnson, J. Karl
  • The Journal of Chemical Physics, Vol. 110, Issue 1
  • DOI: 10.1063/1.478114

A Predictive Model of Hydrogen Sorption for Metal−Organic Materials
journal, May 2009

  • Belof, Jonathan L.; Stern, Abraham C.; Space, Brian
  • The Journal of Physical Chemistry C, Vol. 113, Issue 21
  • DOI: 10.1021/jp901988e

Balancing gravimetric and volumetric hydrogen density in MOFs
journal, January 2017

  • Ahmed, Alauddin; Liu, Yiyang; Purewal, Justin
  • Energy & Environmental Science, Vol. 10, Issue 11
  • DOI: 10.1039/c7ee02477k

Volumetric Hydrogen Storage Capacity in Metal-Organic Frameworks
journal, December 2017

  • Balderas-Xicohténcatl, R.; Schlichtenmayer, Maurice; Hirscher, Michael
  • Energy Technology, Vol. 6, Issue 3
  • DOI: 10.1002/ente.201700636

Adsorption and Diffusion of Light Gases in ZIF-68 and ZIF-70: A Simulation Study
journal, September 2009

  • Rankin, Rees B.; Liu, Jinchen; Kulkarni, Anant D.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 39
  • DOI: 10.1021/jp903735m

Structures and H2 Adsorption Properties of Porous Scandium Metal-Organic Frameworks
journal, October 2010

  • Ibarra, Ilich A.; Lin, Xiang; Yang, Sihai
  • Chemistry - A European Journal, Vol. 16, Issue 46
  • DOI: 10.1002/chem.201000926

Outlook and challenges for hydrogen storage in nanoporous materials
journal, February 2016


Impact of Preparation and Handling on the Hydrogen Storage Properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5)
journal, November 2007

  • Kaye, Steven S.; Dailly, Anne; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 129, Issue 46, p. 14176-14177
  • DOI: 10.1021/ja076877g

Independent verification of the saturation hydrogen uptake in MOF-177 and establishment of a benchmark for hydrogen adsorption in metal–organic frameworks
journal, January 2007

  • Furukawa, Hiroyasu; Miller, Michael A.; Yaghi, Omar M.
  • Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3197-3204
  • DOI: 10.1039/b703608f

Benchmark Study of Hydrogen Storage in Metal–Organic Frameworks under Temperature and Pressure Swing Conditions
journal, February 2018


Thermophysical properties of MOF-5 powders
journal, February 2014


Hydrogen and Methane Adsorption in Metal−Organic Frameworks:  A High-Pressure Volumetric Study
journal, November 2007

  • Zhou, Wei; Wu, Hui; Hartman, Michael R.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 44
  • DOI: 10.1021/jp074889i

Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal–Organic Frameworks
journal, December 2015

  • Gómez-Gualdrón, Diego A.; Moghadam, Peyman Z.; Hupp, Joseph T.
  • Journal of the American Chemical Society, Vol. 138, Issue 1
  • DOI: 10.1021/jacs.5b10266

Trinuclear Cage-Like Zn II Macrocyclic Complexes: Enantiomeric Recognition and Gas Adsorption Properties
journal, December 2015

  • Janczak, Jan; Prochowicz, Daniel; Lewiński, Janusz
  • Chemistry - A European Journal, Vol. 22, Issue 2
  • DOI: 10.1002/chem.201503479

Works referencing / citing this record:

Design Rules for Metal‐Organic Framework Stability in High‐Pressure Hydrogen Environments
journal, March 2019


Molecular modelling and machine learning for high-throughput screening of metal-organic frameworks for hydrogen storage
journal, April 2019