Trace benzene capture by decoration of structural defects in metal-organic framework materials

Yu Han; Wenyuan Huang; Meng He; Bing An; Yinlin Chen; Xue Han; Lan An; Meredydd Kippax-Jones; Jiangnan Li; Yuhang Yang; Mark D Frogley; Cheng Li; Danielle Crawshaw; Pascal Manuel; Svemir Rudić; Yongqiang Cheng; Ian Silverwood; Luke L Daemen; Anibal J Ramirez-Cuesta; Sarah J Day; Stephen P Thompson; Ben F Spencer; Marek Nikiel; Daniel Lee; Martin Schröder; Sihai Yang

doi:10.1038/s41563-024-02029-1

Trace benzene capture by decoration of structural defects in metal-organic framework materials

Nat Mater. 2024 Nov;23(11):1531-1538. doi: 10.1038/s41563-024-02029-1. Epub 2024 Oct 29.

Authors

Yu Han¹, Wenyuan Huang², Meng He¹, Bing An¹, Yinlin Chen¹, Xue Han³, Lan An⁴, Meredydd Kippax-Jones^{1

5}, Jiangnan Li², Yuhang Yang⁴, Mark D Frogley⁵, Cheng Li⁶, Danielle Crawshaw¹, Pascal Manuel⁷, Svemir Rudić⁷, Yongqiang Cheng⁶, Ian Silverwood⁷, Luke L Daemen⁶, Anibal J Ramirez-Cuesta⁶, Sarah J Day⁵, Stephen P Thompson⁵, Ben F Spencer^{8

9}, Marek Nikiel^{8

9

10}, Daniel Lee⁴, Martin Schröder¹¹, Sihai Yang^{12

13}

Affiliations

¹ Department of Chemistry, University of Manchester, Manchester, UK.
² College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, China.
³ College of Chemistry, Beijing Normal University, Beijing, China.
⁴ Department of Chemical Engineering, University of Manchester, Manchester, UK.
⁵ Diamond Light Source, Harwell Science and Innovation Campus, Didcot, UK.
⁶ Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, USA.
⁷ ISIS Neutron and Muon Source, STFC Rutherford Appleton Laboratory, Chilton, UK.
⁸ Photon Science Institute, University of Manchester, Manchester, UK.
⁹ Department of Materials, University of Manchester, Manchester, UK.
¹⁰ National Graphene Institute, University of Manchester, Manchester, UK.
¹¹ Department of Chemistry, University of Manchester, Manchester, UK. [email protected].
¹² Department of Chemistry, University of Manchester, Manchester, UK. [email protected].
¹³ College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, China. [email protected].

Abstract

Capture of trace benzene is an important and challenging task. Metal-organic framework materials are promising sorbents for a variety of gases, but their limited capacity towards benzene at low concentration remains unresolved. Here we report the adsorption of trace benzene by decorating a structural defect in MIL-125-defect with single-atom metal centres to afford MIL-125-X (X = Mn, Fe, Co, Ni, Cu, Zn; MIL-125, Ti₈O₈(OH)₄(BDC)₆ where H₂BDC is 1,4-benzenedicarboxylic acid). At 298 K, MIL-125-Zn exhibits a benzene uptake of 7.63 mmol g^-1 at 1.2 mbar and 5.33 mmol g^-1 at 0.12 mbar, and breakthrough experiments confirm the removal of trace benzene (from 5 to <0.5 ppm) from air (up to 111,000 min g^-1 of metal-organic framework), even after exposure to moisture. The binding of benzene to the defect and open Zn(II) sites at low pressure has been visualized by diffraction, scattering and spectroscopy. This work highlights the importance of fine-tuning pore chemistry for designing adsorbents for the removal of air pollutants.

Abstract

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