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

Abstract

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 themore » 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.« less

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [1];  [2];  [2];  [2];  [2];  [2]
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  1. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA (United States). Leidos Research Support Team
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
Publication Date:
Research Org.:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1843210
Grant/Contract Number:  
89243318CFE000003
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 21; Journal Issue: 2; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal-Organic Framework; molecular confinement; thermal annealing; density functional theory; water stability; gas adsorption isotherms

Citation Formats

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., and Kwon, Hyuk Taek. Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu3(BTC)2. United States: N. p., 2021. Web. doi:10.1021/acs.cgd.0c01118.
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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. Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu3(BTC)2. United States. https://doi.org/10.1021/acs.cgd.0c01118
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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., and Kwon, Hyuk Taek. Thu . "Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu3(BTC)2". United States. https://doi.org/10.1021/acs.cgd.0c01118. https://www.osti.gov/servlets/purl/1843210.
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@article{osti_1843210,
title = {Enhanced Guest@MOF Interaction via Stepwise Thermal Annealing: TCNQ@Cu3(BTC)2},
author = {Kim, Ki-Joong and Culp, Jeffrey T. and Sorescu, Dan C. and Ellis, James E. and Cvetic, Patricia C. and Howard, Bret H. and Ohodnicki, Paul R. and Goodman, Angela L. and Steckel, Janice A. and Kwon, Hyuk Taek},
abstractNote = {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.},
doi = {10.1021/acs.cgd.0c01118},
journal = {Crystal Growth and Design},
number = 2,
volume = 21,
place = {United States},
year = {Thu Jan 07 00:00:00 EST 2021},
month = {Thu Jan 07 00:00:00 EST 2021}
}
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https://doi.org/10.1021/acs.cgd.0c01118
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