TY - JOUR
T1 - Noninvasive Substitution of K+ Sites in Cyclodextrin Metal-Organic Frameworks by Li+ Ions
AU - Patel, Hasmukh A.
AU - Islamoglu, Timur
AU - Liu, Zhichang
AU - Nalluri, Siva Krishna Mohan
AU - Samanta, Avik
AU - Anamimoghadam, Ommid
AU - Malliakas, Christos D.
AU - Farha, Omar K.
AU - Stoddart, J. Fraser
N1 - Funding Information:
This research has been supported by the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). O.K.F. acknowledges support from the U.S. Department of Energy, the Office of Science through grant DE-FG02-08ER15967. The authors thank both KACST and NU for their continued support of this research. The X-ray crystallographic investigations made use of the IMSERC facility at NU, which receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN).
PY - 2017/8/16
Y1 - 2017/8/16
N2 - 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. 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.
AB - 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. 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.
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U2 - 10.1021/jacs.7b06287
DO - 10.1021/jacs.7b06287
M3 - Article
C2 - 28772069
AN - SCOPUS:85027414657
VL - 139
SP - 11020
EP - 11023
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 32
ER -