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Title: Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework

Authors:
 [1];  [2];  [3];  [2];  [4]; ORCiD logo [2]
  1. Department of Chemistry and Chemical Biology, Rutgers University, Piscataway New Jersey 08854 USA, Fundamental and Computational Science Directorate, Pacific Northwest National Laboratory, Richland Washington 99352 USA
  2. Department of Chemistry and Chemical Biology, Rutgers University, Piscataway New Jersey 08854 USA
  3. Department of Geosciences, Stony Brook University, Stony Brook New York 11794 USA, Physics Department, Yeshiva University, New York NY 10016 USA
  4. Department of Geosciences, Stony Brook University, Stony Brook New York 11794 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400463
Grant/Contract Number:
FG02-08ER46491; BES DE-FG02-09ER46650
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 22; Journal Issue: 33; Related Information: CHORUS Timestamp: 2017-10-20 14:56:50; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Banerjee, Debasis, Wang, Hao, Plonka, Anna M., Emge, Thomas J., Parise, John B., and Li, Jing. Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework. Germany: N. p., 2016. Web. doi:10.1002/chem.201601784.
Banerjee, Debasis, Wang, Hao, Plonka, Anna M., Emge, Thomas J., Parise, John B., & Li, Jing. Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework. Germany. doi:10.1002/chem.201601784.
Banerjee, Debasis, Wang, Hao, Plonka, Anna M., Emge, Thomas J., Parise, John B., and Li, Jing. Thu . "Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework". Germany. doi:10.1002/chem.201601784.
@article{osti_1400463,
title = {Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework},
author = {Banerjee, Debasis and Wang, Hao and Plonka, Anna M. and Emge, Thomas J. and Parise, John B. and Li, Jing},
abstractNote = {},
doi = {10.1002/chem.201601784},
journal = {Chemistry - A European Journal},
number = 33,
volume = 22,
place = {Germany},
year = {Thu Jul 07 00:00:00 EDT 2016},
month = {Thu Jul 07 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/chem.201601784

Citation Metrics:
Cited by: 6works
Citation information provided by
Web of Science

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  • Here, the efficiency of physisorption-based separation of gas-mixtures depends on the selectivity of adsorbent which is directly linked to size, shape, polarizability and other physical properties of adsorbed molecules. Commensurate adsorption is an interesting and important adsorption phenomenon, where the adsorbed amount, location, and orientation of an adsorbate are commensurate with the crystal symmetry of the adsorbent. Understanding this phenomenon is important and beneficial as it can provide vital information about adsorbate–adsorbent interaction and adsorption–desorption mechanism. So far, only sporadic examples of commensurate adsorption have been reported in porous materials such as zeolites and metal organic frameworks (MOFs). In thismore » work we show for the first time direct structural evidence of commensurate-to-incommensurate transition of linear hydrocarbon molecules (C 2–C7) in a microporous MOF, by employing a number of analytical techniques including single crystal X-ray diffraction (SCXRD), in situ powder X-ray diffraction coupled with differential scanning calorimetry (PXRD-DSC), gas adsorption and molecular simulations.« less
  • Cited by 3
  • A three-dimensional triply interpenetrated mixed metal-organic framework, Zn{sub 2}(BBA){sub 2}(CuPyen) {center_dot} G{sub x} (M'MOF-20; BBA = biphenyl-4,4'-dicarboxylate; G = guest solvent molecules), of primitive cubic net was obtained through the solvothermal reaction of Zn(NO{sub 3}){sub 2}, biphenyl-4,4'-dicarboxylic acid, and the salen precursor Cu(PyenH{sub 2})(NO{sub 3}){sub 2} by a metallo-ligand approach. The triple framework interpenetration has stabilized the framework in which the activated M'MOF-20a displays type-I N{sub 2} gas sorption behavior with a Langmuir surface area of 62 m{sup 2} g{sup -1}. The narrow pores of about 3.9 {angstrom} and the open metal sites on the pore surfaces within M'MOF-20a collaborativelymore » induce its highly selective C{sub 2}H{sub 2}/CH{sub 4} and CO{sub 2}/CH{sub 4} gas separation at ambient temperature.« less
  • We found that the cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal–organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid-state adsorbents, but no experimental insights into the nature of the Xe–network interaction are available to date. Here we report a new microporous MOF (designated SBMOF-2) that is selective toward Xe over Kr under ambient conditions, with a Xe/Kr selectivity of about 10 and a Xe capacity of 27.07 wt % at 298 K. Single-crystal diffraction results show that the Xe selectivity may be attributedmore » to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both of which serve as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBMOF-2 was investigated with experimental and computational breakthrough methods. These experiments showed that Kr broke through the column first, followed by Xe, which confirmed that SBMOF-2 has a real practical potential for separating Xe from Kr. Our calculations showed that the capacity and adsorption selectivity of SBMOF-2 are comparable to those of the best-performing unmodified MOFs such as NiMOF-74 or Co formate.« less