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

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. DayStephen P. Thompson, Ben F. Spencer, Marek Nikiel, Daniel Lee, Martin Schröder, Sihai Yang

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

1 Scopus citations

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.

Original language	English
Pages (from-to)	1531-1538
Number of pages	8
Journal	Nature Materials
Volume	23
Issue number	11
DOIs	https://doi.org/10.1038/s41563-024-02029-1
State	Published - Nov 2024

Funding

We thank the Engineering and Physical Sciences Research Council (EPSRC; EP/I011870, EP/V056409), the University of Manchester, National Science Foundation of China and Peking University 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). We are grateful to the STFC/ISIS Facility for access to beamlines WISH and TOSCA. We acknowledge the Diamond Light Source for access to beamlines I11 and B22. A portion of this research used resources at the Spallation Neutron Source, a US Department of Energy (DOE) Office of Science User Facility operated by the Oak Ridge National Laboratory (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 programme and Compute and Data Environment for Science (CADES) at ORNL. Y.H., M.H., W.H. and Y.Y. thank the China Scholarship Council (CSC) for funding.

Funders	Funder number
Compute and Data Environment for Science
Science and Technology Facilities Council
Oak Ridge National Laboratory
ISIS
U.S. Department of Energy
China Scholarship Council
Laboratory Directed Research and Development
Peking University
Office of Science
European Research Council
University of Manchester
National Natural Science Foundation of China
Lawrence Berkeley National Laboratory	DE-AC02-05CH11231, ERCAP0024340
Lawrence Berkeley National Laboratory
Engineering and Physical Sciences Research Council	EP/V056409, EP/I011870
Engineering and Physical Sciences Research Council
Horizon 2020 Framework Programme	742401
Horizon 2020 Framework Programme

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Han, Y., Huang, W., He, M., An, B., Chen, Y., Han, X., An, L., Kippax-Jones, M., Li, J., Yang, Y., Frogley, M. D., Li, C., Crawshaw, D., Manuel, P., Rudić, S., Cheng, Y., Silverwood, I., Daemen, L. L., Ramirez-Cuesta, A. J., ... Yang, S. (2024). Trace benzene capture by decoration of structural defects in metal–organic framework materials. Nature Materials, 23(11), 1531-1538. https://doi.org/10.1038/s41563-024-02029-1

@article{0c39413ef58049c0925dbdd9651cb6be,

title = "Trace benzene capture by decoration of structural defects in metal–organic framework materials",

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.",

author = "Yu Han and Wenyuan Huang and Meng He and Bing An and Yinlin Chen and Xue Han and Lan An and Meredydd Kippax-Jones and Jiangnan Li and Yuhang Yang and Frogley, {Mark D.} and Cheng Li and Danielle Crawshaw and Pascal Manuel and Svemir Rudi{\'c} and Yongqiang Cheng and Ian Silverwood and Daemen, {Luke L.} and Ramirez-Cuesta, {Anibal J.} and Day, {Sarah J.} and Thompson, {Stephen P.} and Spencer, {Ben F.} and Marek Nikiel and Daniel Lee and Martin Schr{\"o}der and Sihai Yang",

note = "Publisher Copyright: {\textcopyright} The Author(s) 2024.",

year = "2024",

month = nov,

doi = "10.1038/s41563-024-02029-1",

language = "English",

volume = "23",

pages = "1531--1538",

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Han, Y, Huang, W, He, M, An, B, Chen, Y, Han, X, An, L, Kippax-Jones, M, Li, J, Yang, Y, Frogley, MD, Li, C, Crawshaw, D, Manuel, P, Rudić, S, Cheng, Y, Silverwood, I, Daemen, LL, Ramirez-Cuesta, AJ, Day, SJ, Thompson, SP, Spencer, BF, Nikiel, M, Lee, D, Schröder, M & Yang, S 2024, 'Trace benzene capture by decoration of structural defects in metal–organic framework materials', Nature Materials, vol. 23, no. 11, pp. 1531-1538. https://doi.org/10.1038/s41563-024-02029-1

TY - JOUR

T1 - Trace benzene capture by decoration of structural defects in metal–organic framework materials

AU - Han, Yu

AU - Huang, Wenyuan

AU - He, Meng

AU - An, Bing

AU - Chen, Yinlin

AU - Han, Xue

AU - An, Lan

AU - Kippax-Jones, Meredydd

AU - Li, Jiangnan

AU - Yang, Yuhang

AU - Frogley, Mark D.

AU - Li, Cheng

AU - Crawshaw, Danielle

AU - Manuel, Pascal

AU - Rudić, Svemir

AU - Cheng, Yongqiang

AU - Silverwood, Ian

AU - Daemen, Luke L.

AU - Ramirez-Cuesta, Anibal J.

AU - Day, Sarah J.

AU - Thompson, Stephen P.

AU - Spencer, Ben F.

AU - Nikiel, Marek

AU - Lee, Daniel

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2024/11

Y1 - 2024/11

N2 - 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.

AB - 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.

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U2 - 10.1038/s41563-024-02029-1

DO - 10.1038/s41563-024-02029-1

M3 - Article

AN - SCOPUS:85207866773

SN - 1476-1122

VL - 23

SP - 1531

EP - 1538

JO - Nature Materials

JF - Nature Materials

IS - 11

ER -

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

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