Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC
Abstract
Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O2/N2 selectivities determined experimentally at 77 K and the difference in O2 and N2 binding energies calculated from DFT modeling data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N2 and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Argonne National Lab. (ANL), Argonne, IL (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:
- 1184988
- Report Number(s):
- SAND-2014-20037J
Journal ID: ISSN 0897-4756; 547384
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 27; Journal Issue: 6; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sava Gallis, Dorina F., Parkes, Marie V., Greathouse, Jeffery A., Zhang, Xiaoyi, and Nenoff, Tina M. Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC. United States: N. p., 2015.
Web. doi:10.1021/cm5042293.
Sava Gallis, Dorina F., Parkes, Marie V., Greathouse, Jeffery A., Zhang, Xiaoyi, & Nenoff, Tina M. Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC. United States. https://doi.org/10.1021/cm5042293
Sava Gallis, Dorina F., Parkes, Marie V., Greathouse, Jeffery A., Zhang, Xiaoyi, and Nenoff, Tina M. Thu .
"Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC". United States. https://doi.org/10.1021/cm5042293. https://www.osti.gov/servlets/purl/1184988.
@article{osti_1184988,
title = {Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC},
author = {Sava Gallis, Dorina F. and Parkes, Marie V. and Greathouse, Jeffery A. and Zhang, Xiaoyi and Nenoff, Tina M.},
abstractNote = {Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O2/N2 selectivities determined experimentally at 77 K and the difference in O2 and N2 binding energies calculated from DFT modeling data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N2 and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.},
doi = {10.1021/cm5042293},
journal = {Chemistry of Materials},
number = 6,
volume = 27,
place = {United States},
year = {Thu Mar 05 00:00:00 EST 2015},
month = {Thu Mar 05 00:00:00 EST 2015}
}
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