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Title: Noninvasive Substitution of K + Sites in Cyclodextrin Metal–Organic Frameworks by Li + Ions

Co-crystallization of K + and Li + ions with γ-cyclodextrin (γ-CD) has been shown to substitute the K + ion sites partially by Li + ions, while retaining the structural integrity and accessible porosity of CD-MOF-1 (MOF, metal–organic framework). A series of experiments, in which the K +/Li + ratio was varied with respect to that of γ-CD, have been conducted in order to achieve the highest possible proportion of Li + ions in the framework. Here, attempts to obtain a CD-MOF containing only Li+ ions resulted in nonporous materials. The structural occupancy on the part of the Li + ions in the new CD-MOF has been confirmed by single-crystal X-ray analysis by determining the vacancies of K +-ion sites and accounting for the cation/γ-CD ratio in CD-MOF-1. The proportion of Li + ions has also been confirmed by elemental analysis, whereas powder X-ray diffraction has established the stability of the extended framework. This noninvasive synthetic approach to generating mixed-metal CD-MOFs is a promising method for obtaining porous framework unattainable de novo. Furthermore, the CO 2 and H 2 capture capacities of the Li +-ion-substituted CD-MOF have been shown to exceed the highest sorption capacities reported so far for CD-MOFs.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ;  [1] ;  [2] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry, and Integrated Molecular Structure Education and Research Center
Publication Date:
Grant/Contract Number:
FG02-08ER15967
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 32; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Northwestern Univ., Evanston, IL (United States). Integrated Molecular Structure Education and Research Center
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1374234
Alternate Identifier(s):
OSTI ID: 1473896

Patel, Hasmukh A., Islamoglu, Timur, Liu, Zhichang, Nalluri, Siva Krishna Mohan, Samanta, Avik, Anamimoghadam, Ommid, Malliakas, Christos D., Farha, Omar K., and Stoddart, J. Fraser. Noninvasive Substitution of K + Sites in Cyclodextrin Metal–Organic Frameworks by Li + Ions. United States: N. p., Web. doi:10.1021/jacs.7b06287.
Patel, Hasmukh A., Islamoglu, Timur, Liu, Zhichang, Nalluri, Siva Krishna Mohan, Samanta, Avik, Anamimoghadam, Ommid, Malliakas, Christos D., Farha, Omar K., & Stoddart, J. Fraser. Noninvasive Substitution of K + Sites in Cyclodextrin Metal–Organic Frameworks by Li + Ions. United States. doi:10.1021/jacs.7b06287.
Patel, Hasmukh A., Islamoglu, Timur, Liu, Zhichang, Nalluri, Siva Krishna Mohan, Samanta, Avik, Anamimoghadam, Ommid, Malliakas, Christos D., Farha, Omar K., and Stoddart, J. Fraser. 2017. "Noninvasive Substitution of K + Sites in Cyclodextrin Metal–Organic Frameworks by Li + Ions". United States. doi:10.1021/jacs.7b06287.
@article{osti_1374234,
title = {Noninvasive Substitution of K + Sites in Cyclodextrin Metal–Organic Frameworks by Li + Ions},
author = {Patel, Hasmukh A. and Islamoglu, Timur and Liu, Zhichang and Nalluri, Siva Krishna Mohan and Samanta, Avik and Anamimoghadam, Ommid and Malliakas, Christos D. and Farha, Omar K. and Stoddart, J. Fraser},
abstractNote = {Co-crystallization of K+ and Li+ ions with γ-cyclodextrin (γ-CD) has been shown to substitute the K+ ion sites partially by Li+ ions, while retaining the structural integrity and accessible porosity of CD-MOF-1 (MOF, metal–organic framework). A series of experiments, in which the K+/Li+ ratio was varied with respect to that of γ-CD, have been conducted in order to achieve the highest possible proportion of Li+ ions in the framework. Here, attempts to obtain a CD-MOF containing only Li+ ions resulted in nonporous materials. The structural occupancy on the part of the Li+ ions in the new CD-MOF has been confirmed by single-crystal X-ray analysis by determining the vacancies of K+-ion sites and accounting for the cation/γ-CD ratio in CD-MOF-1. The proportion of Li+ ions has also been confirmed by elemental analysis, whereas powder X-ray diffraction has established the stability of the extended framework. This noninvasive synthetic approach to generating mixed-metal CD-MOFs is a promising method for obtaining porous framework unattainable de novo. Furthermore, the CO2 and H2 capture capacities of the Li+-ion-substituted CD-MOF have been shown to exceed the highest sorption capacities reported so far for CD-MOFs.},
doi = {10.1021/jacs.7b06287},
journal = {Journal of the American Chemical Society},
number = 32,
volume = 139,
place = {United States},
year = {2017},
month = {8}
}