Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC

Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; Zhang, Xiaoyi; Nenoff, Tina M.

doi:10.1021/cm5042293

Enhanced O₂ selectivity versus N₂ by partial metal substitution in Cu-BTC

Journal Article · Thu Mar 05 00:00:00 EST 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/cm5042293· OSTI ID:1184988

Sava Gallis, Dorina F. ^[1]; Parkes, Marie V. ^[1]; Greathouse, Jeffery A. ^[1]; Zhang, Xiaoyi ^[2]; Nenoff, Tina M. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1184988

Alternate ID(s):: OSTI ID: 1241356

Report Number(s):: SAND--2014-20037J; 547384

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 6 Vol. 27; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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