Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu3(BTC)2

Kim, Ki-Joong; Culp, Jeffrey T.; Sorescu, Dan C.; Ellis, James E.; Cvetic, Patricia C.; Howard, Bret H.; Ohodnicki, Paul R.; Goodman, Angela L.; Steckel, Janice A.; Kwon, Hyuk Taek

doi:10.1021/acs.cgd.0c01118

Title: Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu₃(BTC)₂

Journal Article · Thu Jan 07 00:00:00 EST 2021 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.0c01118· OSTI ID:1843210

^[1]; Culp, Jeffrey T. ^[1]; Sorescu, Dan C. ^[2]; Ellis, James E. ^[2]; Cvetic, Patricia C. ^[1]; Howard, Bret H. ^[2]; Ohodnicki, Paul R. ^[2]; Goodman, Angela L. ^[2]; Steckel, Janice A. ^[2]; Kwon, Hyuk Taek ^[2]

National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA (United States). Leidos Research Support Team
National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)

Confinement of guest molecules in porous materials such as metal organic frameworks (MOFs) promises to deliver emergent properties separate from those of the individual components. Understanding the confinement mechanism is therefore important for the development of new synthesis routes that adjust MOF properties for specific applications. In this work, we developed a new synthetic method to confine guest molecules into MOF pores through a stepwise thermal annealing process, wherein the confinement of 7,7,8,8-tetracyanoquinodimethane (TCNQ) guest molecules into Cu₃(BTC)₂ (BTC = benzene-1,3,5-tricarboxylic acid) MOF host is used as an example of how novel materials can be created with new physical properties. The stepwise thermal annealing process includes 1) an activation process of pristine Cu₃(BTC)₂ MOF to maximizes the TCNQ guest loading in the MOF host by effectively removing the residual solvents and 2) post-annealing of the TCNQ infiltrated MOF to enhances the interaction of the confined guest molecules with the MOF host. Obtained experimental results based on thermogravimetric analysis, N₂ gas adsorption, electron microscopy, X-ray diffraction and infrared absorption, combined with density functional theory calculations provide evidence that the use of a stepwise thermal annealing process yields enhancements in the guest loading, packing and interaction between the TCNQ guest and the MOF host. The new hybrid TCNQ@Cu₃(BTC)₂ system is stable and shows no significant signs of structural degradation even after submersion in water. This is due to the presence of significantly stronger interactions of TCNQ with the frame-work metal ions compared to those of the water molecules competing for the same framework binding sites. It was also found that TCNQ@Cu₃(BTC)₂ system maintains a significant CO₂ and CH₄ adsorption potential compared to the pristine MOF. The synthetic route developed in this work yields novel guest@MOF hybrid systems that will be useful for many MOF-based applications such as gas separations and chemical sensors performed under humid conditions.

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Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: 89243318CFE000003

OSTI ID:: 1843210

Journal Information:: Crystal Growth and Design, Vol. 21, Issue 2; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Metal-Organic Framework
molecular confinement
thermal annealing
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water stability
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Title: Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu3(BTC)2

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