TY - JOUR
T1 - Transient Catenation in a Zirconium-Based Metal-Organic Framework and Its Effect on Mechanical Stability and Sorption Properties
AU - Robison, Lee
AU - Gong, Xinyi
AU - Evans, Austin M.
AU - Son, Florencia A.
AU - Wang, Xingjie
AU - Redfern, Louis R.
AU - Wasson, Megan C.
AU - Syed, Zoha H.
AU - Chen, Zhijie
AU - Idrees, Karam B.
AU - Islamoglu, Timur
AU - Delferro, Massimiliano
AU - Dichtel, William R.
AU - Coudert, François Xavier
AU - Gianneschi, Nathan C.
AU - Farha, Omar K.
N1 - Funding Information:
O.K.F. gratefully acknowledges the financial support from the Air Force Research Laboratory (FA8650-15-2-5518) for the MOF materials synthesis. O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007) for the physical stability and sorption measurements. O.K.F. and N.C.G. gratefully acknowledge support from National Science Foundation’s MRSEC program (grant number NSF DMR-1720139). N.C.G. acknowledges the Army Research Office for support of the development of TEM for MOFs (W911NF-15-1-0189). M.D. acknowledges the financial support from the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, Catalysis Science Program under contract DE-AC-02-06CH11357 (Argonne National Laboratory). F.-X.C. is supported by the Agence Nationale de la Recherche (project MATAREB, ANR-18-CE29-0009-01), and access to HPC platforms was provided by a GENCI grant (A0090807069). X.G. gratefully acknowledges the support of the Northwestern University Ryan Fellowship granted by the International Institute of Nanotechnology and The Graduate School at Northwestern University. M.C.W. and Z.H.S. are supported by the NSF Graduate Research Fellowship under grant DGE-1842165. A.M.E. is supported by the NSF Graduate Research Fellowship under grant DGE-1324585. F.A.S. is supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate (NDSEG) Fellowship Program. The authors thank Dr. Yuyang Wu and Dr. Yongbo Zhang for assistance in acquiring and interpreting the solid state NMR data reported herein. Use was made of the IMSERC X-ray facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). Use was made of NMR-Hg400-solids at Northwestern University, which has received support from National Science Foundation (CHE-9871268) and International Institute for Nanotechnology (IIN). This work made use of the IMSERC NMR facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), Int. Institute of Nanotechnology, and Northwestern University.This work made use of the SPID facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, though the IIN. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the IIN, the Keck Foundation, and the State of Illinois through the IIN. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357.
Publisher Copyright:
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PY - 2021/1/27
Y1 - 2021/1/27
N2 - Interpenetration of two or more sublattices is common among many metal-organic frameworks (MOFs). Herein, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.
AB - Interpenetration of two or more sublattices is common among many metal-organic frameworks (MOFs). Herein, we study the evolution of one zirconium cluster-based, 3,8-connected MOF from its non-interpenetrated (NU-1200) to interpenetrated (STA-26) isomer. We observe this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy. The approach detailed here will serve as a template for other researchers to monitor the interpenetration of their MOF samples at the bulk and single-particle limits. We investigate the mechanical stability of both lattices experimentally by pressurized in situ X-ray diffraction and nanoindentation as well as computationally with density functional theory calculations. Both lines of study reveal that STA-26 is considerably more mechanically stable than NU-1200. We conclude this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent sulfur mustard gas.
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U2 - 10.1021/jacs.0c11266
DO - 10.1021/jacs.0c11266
M3 - Article
C2 - 33433209
AN - SCOPUS:85099917768
SN - 0002-7863
VL - 143
SP - 1503
EP - 1512
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -