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Title: Effect of metal in M 3(btc) 2 and M 2(dobdc) MOFs for O 2/N 2 separations: A combined density functional theory and experimental study

Abstract

Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M 2(dobdc) and M 3(btc) 2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trend in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is lessmore » important than the metal identity.« less

Authors:
 [1];  [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1184990
Report Number(s):
SAND-2014-20069J
Journal ID: ISSN 1932-7447; 547409
Grant/Contract Number:
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal-organic framework; density functional theory; adsorption; isotherm; oxygen; nitrogen

Citation Formats

Parkes, Marie V., Sava Gallis, Dorina F., Greathouse, Jeffery A., and Nenoff, Tina M. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study. United States: N. p., 2015. Web. doi:10.1021/jp511789g.
Parkes, Marie V., Sava Gallis, Dorina F., Greathouse, Jeffery A., & Nenoff, Tina M. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study. United States. doi:10.1021/jp511789g.
Parkes, Marie V., Sava Gallis, Dorina F., Greathouse, Jeffery A., and Nenoff, Tina M. Mon . "Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study". United States. doi:10.1021/jp511789g. https://www.osti.gov/servlets/purl/1184990.
@article{osti_1184990,
title = {Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study},
author = {Parkes, Marie V. and Sava Gallis, Dorina F. and Greathouse, Jeffery A. and Nenoff, Tina M.},
abstractNote = {Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trend in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.},
doi = {10.1021/jp511789g},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 119,
place = {United States},
year = {Mon Mar 02 00:00:00 EST 2015},
month = {Mon Mar 02 00:00:00 EST 2015}
}

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