Journal
CHEMISTRY OF MATERIALS
Volume 27, Issue 6, Pages 2018-2025Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm5042293
Keywords
-
Funding
- U.S. DOE's NNSA [DE-AC04-94AL85000]
- U.S. DOE [DE-AC02-06CH11357]
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available