Enhanced Benzene Adsorption in Chloro-Functionalized 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-Functionalized 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 functionalization 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 functionalized 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 modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, 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
State	Accepted/In press - 2024

Funding

We thank EPSRC (EP/I011870, EP/V056409), the University of Manchester, the National Science Foundation of China, and BNLMS for funding. This project has received funding from the European Research Council (ERC) under the European Union\u2019s Horizon 2020 research and innovation programme (grant agreement No. 742401, NANOCHEM and PoC665632). We are grateful to the STFC/ISIS Facility, Diamond Light Source, European Synchrotron Radiation Facility (ESRF), and Oak Ridge National Laboratory (ORNL) for access to beamlines TOSCA, I11/B22 (CY33115; SM30398), ID22 and VISION, respectively. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by ORNL, as well as the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under contract no. DE-AC02-05CH11231 using NERSC award ERCAP0024340. Additional computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. Y. H., M. H., and W. H. are supported by the China Scholarship Council (CSC).

Funders	Funder number
Compute and Data Environment for Science
Oak Ridge National Laboratory
China Scholarship Council
Laboratory Directed Research and Development
Beijing National Laboratory for Molecular Sciences
Office of Science
European Research Council
University of Manchester
National Natural Science Foundation of China
Lawrence Berkeley National Laboratory	DE-AC02-05CH11231, ERCAP0024340
Engineering and Physical Sciences Research Council	EP/V056409, EP/I011870
Horizon 2020 Framework Programme	PoC665632, 742401

Access to Document

10.1021/jacs.4c07207

Cite this

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. (Accepted/In press). Enhanced Benzene Adsorption in Chloro-Functionalized Metal-Organic Frameworks. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.4c07207

@article{84f1fa8931884a98a67b563fea5641f7,

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

abstract = "The functionalization 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 functionalized 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 modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, 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",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

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-Functionalized Metal-Organic Frameworks', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.4c07207

TY - JOUR

T1 - Enhanced Benzene Adsorption in Chloro-Functionalized 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

Y1 - 2024

N2 - The functionalization 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 functionalized 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 modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, 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 functionalization 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 functionalized 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 modeling, reveal the mechanism of binding of benzene in these materials. Overall, the excellent adsorption performance is promoted by an unprecedented cooperation between chloro-groups, the optimized pore size, aromatic functionality, 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.

UR - http://www.scopus.com/inward/record.url?scp=85206270942&partnerID=8YFLogxK

U2 - 10.1021/jacs.4c07207

DO - 10.1021/jacs.4c07207

M3 - Article

C2 - 39365881

AN - SCOPUS:85206270942

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Enhanced Benzene Adsorption in Chloro-Functionalized Metal-Organic Frameworks

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this