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Title: Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation

Computational high-throughput screening was carried out to assess a large number of experimentally reported metal–organic frameworks (MOFs) and zeolites for their utility in hexane isomer separation. Through the paper, we identified many MOFs and zeolites with high selectivity (S L+M > 10) for the group of n-hexane, 2-methylpentane, and 3-methylpentane (linear and monobranched isomers) versus 2,2-dimethylbutane and 2,3-dimethylbutane (dibranched isomers). This group of selective sorbents includes VICDOC (Fe 2(BDP) 3), a MOF with triangular pores that is known to exhibit high isomer selectivity and capacity. For three of these structures, the adsorption isotherms for a 10-component mixture of hexane and heptane isomers were calculated. Subsequent simulations of column breakthrough curves showed that the DEYVUA MOF exhibits a longer process cycle time than VICDOC MOF or MRE zeolite, which are previously reported, high-performing materials, illustrating the importance of capacity in designing MOFs for practical applications. Among the identified candidates, we synthesized and characterized a MOF in a new copper form with high predicted adsorbent capacity (q L+M > 1.2 mol/L) and moderately high selectivity (S L+M ≈ 10). In conclusion, we examined the role of pore shape in hexane isomer separations, especially of triangular-shaped pores. We show through the potential energymore » surface and three-dimensional siting analyses that linear alkanes do not populate the corners of narrow triangular channels and that structures with nontriangular pores can efficiently separate hexane isomers. Detailed thermodynamic analysis illustrates how differences in the free energy of adsorption contribute to shape-selective separation in nanoporous materials.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ;  [3] ;  [4] ;  [5] ;  [4] ; ORCiD logo [5] ;  [6] ; ORCiD logo [7] ; ORCiD logo [8] ; ORCiD logo [9] ; ORCiD logo [10] ; ORCiD logo [4]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering; Pusan National Univ., Busan (Korea, Republic of). School of Chemical and Biomolecular Engineering
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering
  5. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  6. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering; Vrije Univ. Brussel, Elsene (Belgium). Dept. of Chemical Engineering
  7. Cornell Univ., Ithaca, NY (United States). Robert Frederick Smith School of Chemical and Biomolecular Engineering
  8. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  9. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
  10. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science. Dept. of Chemistry and Chemical Theory Center
Publication Date:
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; FG02-12ER16362; FG02-08ER15967; NRF-2016R1D1A1B03934484
Type:
Published Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 15; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
Univ. of Minnesota, Minneapolis, MN (United States); Northwestern Univ., Evanston, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Pusan National Univ., Busan (Korea, Republic of)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Research Foundation of Korea (NRF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1371787
Alternate Identifier(s):
OSTI ID: 1417602