Selective CO2 uptake and inverse CO2/C2H2 selectivity in a dynamic bifunctional metal–organic framework

Wenbin Yang; Andrew J. Davies; Xiang Lin; Mikhail Suyetin; Ryotaro Matsuda; Alexander J. Blake; Claire Wilson; William Lewis; Julia E. Parker; Chiu C. Tang; Michael W. George; Peter Hubberstey; Susumu Kitagawa; Hirotoshi Sakamoto; Elena Bichoutskaia; Neil R. Champness; Sihai Yang; Martin Schröder

doi:10.1039/C2SC20443F

Selective CO₂ uptake and inverse CO₂/C₂H₂ selectivity in a dynamic bifunctional metal–organic framework†

Wenbin Yang,^a Andrew J. Davies,^a Xiang Lin,^a Mikhail Suyetin,^a Ryotaro Matsuda,^bc Alexander J. Blake,^a Claire Wilson,^a William Lewis,^a Julia E. Parker,^d Chiu C. Tang,^d Michael W. George,^a Peter Hubberstey,^a Susumu Kitagawa,^bc Hirotoshi Sakamoto,^bc Elena Bichoutskaia,^a Neil R. Champness,^a Sihai Yang*^a and Martin Schröder*^a

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* Corresponding authors

^a School of Chemistry, University of Nottingham, University Park, Nottingham, UK
E-mail: Sihai.Yang@nottingham.ac.uk, m.schroder@nottingham.ac.uk
Tel: +44 (0)115 9513452

^b ERATO Kitagawa Integrated Pores Project, Science and Technology Agency (JST), Kyoto Research Park Bldg#3, Shimogyo-ku, Kyoto, Japan

^c Institute for Integrated Cell-Material Science (iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto, Japan

^d Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire, UK

Abstract

The unique bifunctional porous metal–organic framework, [Co(HL^dc)]·1.5MeOH·dioxane, incorporates both free-standing carboxyl and pyridyl groups within its pores. Gas adsorption measurements on the desolvated framework reveal unusual selective CO₂ adsorption over C₂H₂ and CH₄ linked to a framework phase change from a narrow pore (np) to a large pore (lp) form, mediated by CO₂ uptake at 195 K. This phase transition has been monitored by in situ powder X-ray diffraction and IR spectroscopy, and modelled by Grand Canonical Monte Carlo simulations revealing that the reversible np to lp transition is linked to the rotation of pyridyl rings acting as flexible “pore gates”.

Chemical Science

Selective CO₂ uptake and inverse CO₂/C₂H₂ selectivity in a dynamic bifunctional metal–organic framework†

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Selective CO₂ uptake and inverse CO₂/C₂H₂ selectivity in a dynamic bifunctional metal–organic framework

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