Temperature-dependent rearrangement of gas molecules in ultramicroporous materials for tunable adsorption of CO2 and C2H2

Zhaoqiang Zhang; Yinlin Chen; Kungang Chai; Chengjun Kang; Shing Bo Peh; He Li; Junyu Ren; Xiansong Shi; Xue Han; Catherine Dejoie; Sarah J Day; Sihai Yang; Dan Zhao

doi:10.1038/s41467-023-39319-2

Temperature-dependent rearrangement of gas molecules in ultramicroporous materials for tunable adsorption of CO₂ and C₂H₂

Nat Commun. 2023 Jun 24;14(1):3789. doi: 10.1038/s41467-023-39319-2.

Authors

Zhaoqiang Zhang^#¹, Yinlin Chen^#², Kungang Chai³, Chengjun Kang¹, Shing Bo Peh¹, He Li¹, Junyu Ren¹, Xiansong Shi¹, Xue Han⁴, Catherine Dejoie⁵, Sarah J Day⁶, Sihai Yang^{7

8}, Dan Zhao⁹

Affiliations

¹ Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore, Singapore.
² Department of Chemistry, The University of Manchester, Manchester, M13 9PL, UK.
³ School of Chemistry and Chemical Engineering, Guangxi University, Nanning, 530004, China.
⁴ College of Chemistry, Beijing Normal University, Beijing, 100875, China.
⁵ The European Synchrotron Radiation Facility, 71 Avenue des Martyrs, CS40220 Cedex 9, 38043, Grenoble, France.
⁶ Diamond Light Source, Harwell Science Campus, Oxfordshire, OX11 0DE, UK.
⁷ Department of Chemistry, The University of Manchester, Manchester, M13 9PL, UK. [email protected].
⁸ College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, 100871, China. [email protected].
⁹ Department of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore, Singapore. [email protected].

^# Contributed equally.

Abstract

The interactions between adsorbed gas molecules within porous metal-organic frameworks are crucial to gas selectivity but remain poorly explored. Here, we report the modulation of packing geometries of CO₂ and C₂H₂ clusters within the ultramicroporous CUK-1 material as a function of temperature. In-situ synchrotron X-ray diffraction reveals a unique temperature-dependent reversal of CO₂ and C₂H₂ adsorption affinities on CUK-1, which is validated by gas sorption and dynamic breakthrough experiments, affording high-purity C₂H₂ (99.95%) from the equimolar mixture of C₂H₂/CO₂ via a one-step purification process. At low temperatures (<253 K), CUK-1 preferentially adsorbs CO₂ with both high selectivity (>10) and capacity (170 cm³ g^-1) owing to the formation of CO₂ tetramers that simultaneously maximize the guest-guest and host-guest interactions. At room temperature, conventionally selective adsorption of C₂H₂ is observed. The selectivity reversal, structural robustness, and facile regeneration of CUK-1 suggest its potential for producing high-purity C₂H₂ by temperature-swing sorption.

MeSH terms

Adsorption
Bandages
Carbon Dioxide*
Cold Temperature*
Temperature

Substances

Carbon Dioxide

Abstract

MeSH terms

Substances

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