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

J Am Chem Soc. 2024 Oct 4;146(41):28080-28087. doi: 10.1021/jacs.4c07207. Online ahead of print.

Authors

Yu Han¹, David Brooks¹, Meng He¹, Yinlin Chen¹, Wenyuan Huang², Boya Tang¹, Bing An¹, Xue Han³, Meredydd Kippax-Jones^{1

4}, Mark D Frogley⁴, Sarah J Day⁴, Stephen P Thompson⁴, Svemir Rudić⁵, Yongqiang Cheng⁶, Luke L Daemen⁶, Anibal J Ramirez-Cuesta⁶, Catherine Dejoie⁷, Martin Schröder¹, Sihai Yang^{1

2}

Affiliations

¹ Department of Chemistry, University of Manchester, Manchester M13 9PL, U.K.
² College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, China.
³ College of Chemistry, Beijing Normal University, Beijing 100875, China.
⁴ Diamond Light Source, Harwell Science Campus, Oxfordshire OX11 0DE, U.K.
⁵ ISIS Facility, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Chilton OX11 0QX, U.K.
⁶ Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.
⁷ The European Synchrotron Radiation Facility, Beamline ID22, 71 Avenue des Martyrs, CS40220, Grenoble Cedex 9 38043, France.

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.