Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks

Yu Han; David Brooks; Meng He; Yinlin Chen; Wenyuan Huang; Boya Tang; Bing An; Xue Han; Meredydd Kippax-Jones; Mark D. Frogley; Sarah J.  Day; Stephen P Thompson; Svemir Rudić; Yongqiang Cheng; Luke L Daemen; Anibal J Ramirez-Cuesta; Catherine  Dejoie; Martin Schröder; Sihai Yang

doi:10.1021/jacs.4c07207

Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks

Yu Han, David Brooks, Meng He, Yinlin Chen, Wenyuan Huang, Boya Tang, Bing An, Xue Han, Meredydd Kippax-Jones, Mark D. Frogley, Sarah J. Day, Stephen P Thompson, Svemir Rudić, Yongqiang Cheng, Luke L Daemen, Anibal J Ramirez-Cuesta, Catherine Dejoie, Martin Schröder, Sihai Yang

Research output: Contribution to journal › Article › peer-review

Abstract

The functionalisation of metal-organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalised with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g-1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy and inelastic neutron scattering, coupled with density functional theory modelling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between the chloro-groups, optimised pore size, extensive aromatic moieties, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by –CH···Cl and Cl∙∙∙π interactions in porous materials.

Original language	English
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.4c07207
Publication status	Published - 4 Oct 2024

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Han, Y., Brooks, D., He, M., Chen, Y., Huang, W., Tang, B., An, B., Han, X., Kippax-Jones, M., Frogley, M. D., Day, S. J., Thompson, S. P., Rudić, S., Cheng, Y., Daemen, L. L., Ramirez-Cuesta, A. J., Dejoie, C., Schröder, M., & Yang, S. (2024). Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.4c07207

@article{1899dd8776a74b45b9e200122403fe1c,

title = "Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks",

abstract = "The functionalisation of metal-organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalised with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g-1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy and inelastic neutron scattering, coupled with density functional theory modelling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between the chloro-groups, optimised pore size, extensive aromatic moieties, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by –CH···Cl and Cl∙∙∙π interactions in porous materials.",

author = "Yu Han and David Brooks and Meng He and Yinlin Chen and Wenyuan Huang and Boya Tang and Bing An and Xue Han and Meredydd Kippax-Jones and Frogley, {Mark D.} and Day, {Sarah J.} and Thompson, {Stephen P} and Svemir Rudi{\'c} and Yongqiang Cheng and Daemen, {Luke L} and Ramirez-Cuesta, {Anibal J} and Catherine Dejoie and Martin Schr{\"o}der and Sihai Yang",

year = "2024",

month = oct,

day = "4",

doi = "10.1021/jacs.4c07207",

language = "English",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

}

Han, Y, Brooks, D, He, M, Chen, Y, Huang, W, Tang, B, An, B, Han, X, Kippax-Jones, M, Frogley, MD, Day, SJ, Thompson, SP, Rudić, S, Cheng, Y, Daemen, LL, Ramirez-Cuesta, AJ, Dejoie, C, Schröder, M & Yang, S 2024, 'Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.4c07207

TY - JOUR

T1 - Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks

AU - Han, Yu

AU - Brooks, David

AU - He, Meng

AU - Chen, Yinlin

AU - Huang, Wenyuan

AU - Tang, Boya

AU - An, Bing

AU - Han, Xue

AU - Kippax-Jones, Meredydd

AU - Frogley, Mark D.

AU - Day, Sarah J.

AU - Thompson, Stephen P

AU - Rudić, Svemir

AU - Cheng, Yongqiang

AU - Daemen, Luke L

AU - Ramirez-Cuesta, Anibal J

AU - Dejoie, Catherine

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2024/10/4

Y1 - 2024/10/4

N2 - The functionalisation of metal-organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalised with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g-1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy and inelastic neutron scattering, coupled with density functional theory modelling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between the chloro-groups, optimised pore size, extensive aromatic moieties, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by –CH···Cl and Cl∙∙∙π interactions in porous materials.

AB - The functionalisation of metal-organic frameworks (MOFs) to enhance the adsorption of benzene at trace levels remains a significant challenge. Here, we report the exceptional adsorption of trace benzene in a series of zirconium-based MOFs functionalised with chloro groups. Notably, MFM-68-Cl2, constructed from an anthracene linker incorporating chloro groups, exhibits a remarkable benzene uptake of 4.62 mmol g-1 at 298 K and 0.12 mbar, superior to benchmark materials. In situ synchrotron X-ray diffraction, Fourier transform infrared microspectroscopy and inelastic neutron scattering, coupled with density functional theory modelling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between the chloro-groups, optimised pore size, extensive aromatic moieties, and the flexibility of the linkers in response to benzene uptake in MFM-68-Cl2. This study represents the first example of enhanced adsorption of trace benzene promoted by –CH···Cl and Cl∙∙∙π interactions in porous materials.

U2 - 10.1021/jacs.4c07207

DO - 10.1021/jacs.4c07207

M3 - Article

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Enhanced Benzene Adsorption in Chloro-Functionalised Metal-Organic Frameworks

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