Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks

Jiangnan Li; Gemma L. Smith; Yinlin Chen; Yujie Ma; Meredydd Kippax-Jones; Mengtian Fan; Wanpeng Lu; Mark D. Frogley; Gianfelice Cinque; Sarah J. Day; Stephen P. Thompson; Yongqiang Cheng; Luke L. Daemen; Anibal J. Ramirez-Cuesta; Martin Schröder; Sihai Yang

doi:10.1002/anie.202207259

Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks

Jiangnan Li, Gemma L. Smith, Yinlin Chen, Yujie Ma, Meredydd Kippax-Jones, Mengtian Fan, Wanpeng Lu, Mark D. Frogley, Gianfelice Cinque, Sarah J. Day, Stephen P. Thompson, Yongqiang Cheng, Luke L. Daemen, Anibal J. Ramirez-Cuesta, Martin Schröder, Sihai Yang

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

23 Scopus citations

Abstract

We report reversible high capacity adsorption of SO₂ in robust Zr-based metal–organic framework (MOF) materials. Zr-bptc (H₄bptc=biphenyl-3,3′,5,5′-tetracarboxylic acid) shows a high SO₂ uptake of 6.2 mmol g⁻¹ at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO₂ at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed Cu^II or heteroatomic sulphur sites into the pores enhance the capture of SO₂ at low concentrations. The captured SO₂ can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO₂ molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.

Original language	English
Article number	e202207259
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	36
DOIs	https://doi.org/10.1002/anie.202207259
State	Published - Sep 5 2022

Funding

We thank EPSRC (EP/I011870), the Royal Society and The University of Manchester for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement No 742401, NANOCHEM). We are grateful to Diamond Light Source and Oak Ridge National Laboratory (ORNL) for access to Beamlines I11/B22 and VISION, respectively. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. We thank EPSRC (EP/I011870), the Royal Society and The University of Manchester for funding. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement No 742401, ). We are grateful to Diamond Light Source and Oak Ridge National Laboratory (ORNL) for access to Beamlines I11/B22 and VISION, respectively. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The computing resources were made available through the VirtuES and the ICE‐MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. NANOCHEM

Funders	Funder number
Compute and Data Environment for Science
Office of Science
Oak Ridge National Laboratory	I11/B22
Laboratory Directed Research and Development
Engineering and Physical Sciences Research Council	EP/I011870
Royal Society
University of Manchester
European Research Council
Horizon 2020	742401

Keywords

Capture
Conversion
Crystallography
Metal–Organic Frameworks
Sulfur Dioxide

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10.1002/anie.202207259

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Li, J., Smith, G. L., Chen, Y., Ma, Y., Kippax-Jones, M., Fan, M., Lu, W., Frogley, M. D., Cinque, G., Day, S. J., Thompson, S. P., Cheng, Y., Daemen, L. L., Ramirez-Cuesta, A. J., Schröder, M., & Yang, S. (2022). Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks. Angewandte Chemie - International Edition, 61(36), Article e202207259. https://doi.org/10.1002/anie.202207259

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title = "Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks",

abstract = "We report reversible high capacity adsorption of SO2 in robust Zr-based metal–organic framework (MOF) materials. Zr-bptc (H4bptc=biphenyl-3,3′,5,5′-tetracarboxylic acid) shows a high SO2 uptake of 6.2 mmol g−1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed CuII or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.",

keywords = "Capture, Conversion, Crystallography, Metal–Organic Frameworks, Sulfur Dioxide",

author = "Jiangnan Li and Smith, {Gemma L.} and Yinlin Chen and Yujie Ma and Meredydd Kippax-Jones and Mengtian Fan and Wanpeng Lu and Frogley, {Mark D.} and Gianfelice Cinque and Day, {Sarah J.} and Thompson, {Stephen P.} and Yongqiang Cheng and Daemen, {Luke L.} and Ramirez-Cuesta, {Anibal J.} and Martin Schr{\"o}der and Sihai Yang",

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year = "2022",

month = sep,

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doi = "10.1002/anie.202207259",

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Li, J, Smith, GL, Chen, Y, Ma, Y, Kippax-Jones, M, Fan, M, Lu, W, Frogley, MD, Cinque, G, Day, SJ, Thompson, SP, Cheng, Y, Daemen, LL, Ramirez-Cuesta, AJ, Schröder, M & Yang, S 2022, 'Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks', Angewandte Chemie - International Edition, vol. 61, no. 36, e202207259. https://doi.org/10.1002/anie.202207259

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T1 - Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks

AU - Li, Jiangnan

AU - Smith, Gemma L.

AU - Chen, Yinlin

AU - Ma, Yujie

AU - Kippax-Jones, Meredydd

AU - Fan, Mengtian

AU - Lu, Wanpeng

AU - Frogley, Mark D.

AU - Cinque, Gianfelice

AU - Day, Sarah J.

AU - Thompson, Stephen P.

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Ramirez-Cuesta, Anibal J.

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2022/9/5

Y1 - 2022/9/5

N2 - We report reversible high capacity adsorption of SO2 in robust Zr-based metal–organic framework (MOF) materials. Zr-bptc (H4bptc=biphenyl-3,3′,5,5′-tetracarboxylic acid) shows a high SO2 uptake of 6.2 mmol g−1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed CuII or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.

AB - We report reversible high capacity adsorption of SO2 in robust Zr-based metal–organic framework (MOF) materials. Zr-bptc (H4bptc=biphenyl-3,3′,5,5′-tetracarboxylic acid) shows a high SO2 uptake of 6.2 mmol g−1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed CuII or heteroatomic sulphur sites into the pores enhance the capture of SO2 at low concentrations. The captured SO2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO2 molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.

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KW - Conversion

KW - Crystallography

KW - Metal–Organic Frameworks

KW - Sulfur Dioxide

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DO - 10.1002/anie.202207259

M3 - Article

C2 - 35735124

AN - SCOPUS:85134673301

SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 36

M1 - e202207259

ER -

Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks

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