Enhanced O-2 Selectivity versus N-2 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

Title: Enhanced O-2 Selectivity versus N-2 by Partial Metal Substitution in Cu-BTC

Journal Article · Tue Mar 24 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/cm5042293· OSTI ID:1241356

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

Here, we describe the homogeneous substitution of Mn, Fe, and Co at various levels into a prototypical metal organic framework (MOP), 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 (273-298 K) as compared to all other metals studied, indicative of favorable interactions between N-2 and coordinatively unsaturated Fe metal centers. Interestingly, 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1241356

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

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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