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Title: Enhanced O 2 selectivity versus N 2 by partial metal substitution in Cu-BTC

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 O 2/N 2 selectivities determined experimentally at 77 K and the difference in O 2 and N 2 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 N 2 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 Montemore » Carlo simulations.« less
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Report Number(s):
SAND-2014-20037J
Journal ID: ISSN 0897-4756; 547384
Grant/Contract Number:
AC04-94AL85000
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)
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1184988