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Title: Tuning Binding Tendencies of Small Molecules in Metal–Organic Frameworks with Open Metal Sites by Metal Substitution and Linker Functionalization

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [2];  [2]; ORCiD logo [2]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering; Nanoporous Materials Genome Center
  2. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
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Metal-organic frameworks (MOFs) with open metal sites (OMS) are known to be selective for ethylene relative to ethane. In practical applications of this separation, the presence of other small molecules such as H2O, CO, and C2H2 may affect the suitability of sorbents. We used density functional theory (DFT) calculations to compute the binding energies of H2O, CO, C2H2, C2H4, and C2H6 in M-BTC (BTC = 1,3,5-benzenetricarboxylic acid) with 12 different metals forming OMS (M = Mg, Ti, V, Cr, Mo, Mn, Fe, Ru, Co, Ni, Cu, and Zn). To probe the generality of these results for MOFs containing other ligands, we performed similar calculations for metal-substituted MOFs based on four more materials with dimeric Cu sites. Here, our results provide useful insights into the variations in binding energies that are achievable by metal substitution in this broad class of MOFs, as well as pointing towards feasible adsorption-based separation strategies for complex molecular mixtures. Zn OMS MOFs were predicted to have the highest C2H4/C2H6 selectivity, but the strong binding energy of solvents and other small molecules in these materials may create practical challenges. Finally, we used DFT calculations to examine whether functionalizing linkers in these materials with electron withdrawing (-fluorine) and donating (-methyl) groups offer a useful way to tune molecular binding energies on OMS in these materials.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Georgia Inst. of Technology, Atlanta, GA (United States); Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Organization:
Dow Chemical Company; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0008688; SC0012577
OSTI ID:
1491719
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 48 Vol. 122; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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