Boosting Adsorption and Selectivity of Acetylene by Nitro Functionalisation in Copper(II)‐Based Metal–Organic Frameworks
Purification and storage of acetylene (C<sub>2</sub>H<sub>2</sub>) are important to many industrial processes. The exploitation of metal-organic framework (MOF) materials to address the balance between selectivity for C<sub>2</sub>H<sub>2</sub> vs carbon dioxide (CO<sub>2</sub>) against maximising uptake of C<sub>2</sub>H<sub>2</sub> has attracted much interest. Herein, we report that the synergy between unsaturated Cu(II) sites and functional groups, fluoro (-F), methyl (-CH<sub>3</sub>), nitro (-NO<sub>2</sub>) in a series of isostructural MOF materials MFM-190(R) that show exceptional adsorption and selectivity of C<sub>2</sub>H<sub>2</sub>. At 298 K, MFM-190(NO<sub>2</sub>) exhibits an C<sub>2</sub>H<sub>2</sub> uptake of 216 cm<sup>3</sup> g<sup>-1</sup> (320 cm<sup>3</sup> g<sup>-1</sup> at 273 K) at 1.0 bar and a high selectivity for C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> (up to ~150 for v/v = 2/1) relevant to that in the industrial cracking stream. Dynamic breakthrough studies validate and confirm the excellent separation of C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> by MFM-190(NO<sub>2</sub>) under ambient conditions. In situ neutron powder diffraction reveals the cooperative binding, packing and selectivity of C<sub>2</sub>H<sub>2</sub> by unsaturated Cu(II) sites and free -NO<sub>2</sub> groups.
Authors
- Sihai Yang⧫ (ORCID: https://orcid.org/0000-0002-1111-9272)
- Lixia Guo (ORCID: https://orcid.org/0000-0003-1735-3841)
- Martin Schröder (ORCID: https://orcid.org/0000-0001-6992-0700)
- Pascal Manuel (ORCID: https://orcid.org/0000-0002-8845-6576)
- Jiangnan Li (ORCID: https://orcid.org/0000-0001-7042-6478)
- Yinlin Chen (ORCID: https://orcid.org/0000-0001-7878-2063)
- Weiyao Li (ORCID: https://orcid.org/0000-0002-2802-6208)
- Xue Han (ORCID: https://orcid.org/0000-0002-0390-422X)
Institutions
- Rutherford Appleton Laboratory (GB)
- Science and Technology Facilities Council (GB)
- Peking University (CN)
- Beijing Normal University (CN)
- University of Manchester (GB)
- Beijing National Laboratory for Molecular Sciences (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2024-12-04
- DOI
- https://doi.org/10.1002/anie.202417183
- Citations
- 19
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 3.01
Funders
- National Science Foundation
- European Commission
- National Natural Science Foundation of China
- Engineering and Physical Sciences Research Council
- Science and Technology Facilities Council
- Beijing National Laboratory for Molecular Sciences