skip to main content
OSTI.GOV 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, H 2 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 H 2 agree best with our experimental data except in the case of MOF-5, in which H 2 adsorption is best replicated with a five-site potential. However,more » for the purpose of ranking materials, these two choices for H 2 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:
Journal Article: 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. doi: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. doi:10.1021/acs.jpcc.8b04021.
@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},
issn = {1932-7447},
number = 33,
volume = 122,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 26, 2019
Publisher's Version of Record

Save / Share: