TY - JOUR
T1 - Structural Diversity of Zirconium Metal-Organic Frameworks and Effect on Adsorption of Toxic Chemicals
AU - Chen, Yongwei
AU - Zhang, Xuan
AU - Mian, Mohammad Rasel
AU - Son, Florencia A.
AU - Zhang, Kun
AU - Cao, Ran
AU - Chen, Zhijie
AU - Lee, Seung Joon
AU - Idrees, Karam B.
AU - Goetjen, Timothy A.
AU - Lyu, Jiafei
AU - Li, Peng
AU - Xia, Qibin
AU - Li, Zhong
AU - Hupp, Joseph T.
AU - Islamoglu, Timur
AU - Napolitano, Amedeo
AU - Peterson, Gregory W.
AU - Farha, Omar K.
N1 - Funding Information:
The authors gratefully acknowledge support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). F.A.S. is supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate (NDSEG) Fellowship Program. Y.C. gratefully acknowledges support from the China Scholarship Council (CSC) during his visit to Northwestern University (201806150078). The authors employed the X-ray diffractometers and NMR in the IMSERC facility at Northwestern University, which receives support from the NSF (CHE-1048773 and DMR-0521267). This work made use of SEM measurement in the Keck-II Facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205).
PY - 2020
Y1 - 2020
N2 - While linkers with various conformations pose challenges in the design and prediction of metal-organic framework (MOF) structures, they ultimately provide great opportunities for the discovery of novel structures thereby enriching structural diversity. Tetratopic carboxylate linkers, for example, have been widely used in the formation of Zr-based MOFs due to the ability to target diverse topologies, providing a promising platform to explore their mechanisms of formation. However, it remains a challenge to control the resulting structures when considering the complex assembly of linkers with unpredicted conformations and diverse Zr6 node connectivities. Herein, we systematically explore how solvents and modulators employed during synthesis influence the resulting topologies of Zr-MOFs, choosing H4TCPB-Br2 (1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene) as a representative tetratopic carboxylate linker. By modulating the reaction conditions, the conformations of the linker and the connectivities of the Zr6 node can be simultaneously tuned, resulting in four types of structures: a new topology (NU-500), she (NU-600), scu (NU-906), and csq (NU-1008). Importantly, we have synthesized the first 5-connected Zr6 node to date with the (4,4,4,5)-connected framework, NU-500. We subsequently performed detailed structural analyses to uncover the relationship between the structures and topologies of these MOFs and demonstrated the crucial role that the flexible linker played to access varied structures by different degrees of linker deformation. Due to a variety of pore structures ranging from micropores to hierarchical micropores and mesopores, the resulting MOFs show drastically different behaviors for the adsorption of n-hexane and dynamic adsorption of 2-chloroethyl ethyl sulfide (CEES) under dry and humid conditions.
AB - While linkers with various conformations pose challenges in the design and prediction of metal-organic framework (MOF) structures, they ultimately provide great opportunities for the discovery of novel structures thereby enriching structural diversity. Tetratopic carboxylate linkers, for example, have been widely used in the formation of Zr-based MOFs due to the ability to target diverse topologies, providing a promising platform to explore their mechanisms of formation. However, it remains a challenge to control the resulting structures when considering the complex assembly of linkers with unpredicted conformations and diverse Zr6 node connectivities. Herein, we systematically explore how solvents and modulators employed during synthesis influence the resulting topologies of Zr-MOFs, choosing H4TCPB-Br2 (1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene) as a representative tetratopic carboxylate linker. By modulating the reaction conditions, the conformations of the linker and the connectivities of the Zr6 node can be simultaneously tuned, resulting in four types of structures: a new topology (NU-500), she (NU-600), scu (NU-906), and csq (NU-1008). Importantly, we have synthesized the first 5-connected Zr6 node to date with the (4,4,4,5)-connected framework, NU-500. We subsequently performed detailed structural analyses to uncover the relationship between the structures and topologies of these MOFs and demonstrated the crucial role that the flexible linker played to access varied structures by different degrees of linker deformation. Due to a variety of pore structures ranging from micropores to hierarchical micropores and mesopores, the resulting MOFs show drastically different behaviors for the adsorption of n-hexane and dynamic adsorption of 2-chloroethyl ethyl sulfide (CEES) under dry and humid conditions.
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U2 - 10.1021/jacs.0c10400
DO - 10.1021/jacs.0c10400
M3 - Article
C2 - 33290083
AN - SCOPUS:85097763732
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
ER -