Locating Gases in Porous Materials: Cryogenic Loading of Fuel-Related Gases Into a Sc-based Metal-Organic Framework under Extreme Pressures

Jorge Sotelo; Christopher H Woodall; Dave R Allan; Eugene Gregoryanz; Ross T Howie; Konstantin V Kamenev; Michael R Probert; Paul A Wright; Stephen A Moggach

doi:10.1002/anie.201506250

Locating Gases in Porous Materials: Cryogenic Loading of Fuel-Related Gases Into a Sc-based Metal-Organic Framework under Extreme Pressures

Angew Chem Int Ed Engl. 2015 Nov 2;54(45):13332-6. doi: 10.1002/anie.201506250. Epub 2015 Sep 11.

Authors

Jorge Sotelo¹, Christopher H Woodall², Dave R Allan³, Eugene Gregoryanz⁴, Ross T Howie⁴, Konstantin V Kamenev², Michael R Probert⁵, Paul A Wright⁶, Stephen A Moggach⁷

Affiliations

¹ EaStChem School of Chemistry and Centre for Science at Extreme Conditions, University of Edinburgh, David Brewster road, Joseph Black Building, Edinburgh EH9 3FJ (UK).
² School of Engineering and Centre for Science at Extreme Conditions, University of Edinburgh, Peter Gurthrie Tait Road, Erskine Williamson Building, Edinburgh EH9 3FD (UK).
³ Diamond Light Source, Harwell Campus, Didcot, OX11 ODE (UK).
⁴ School of Physics and Centre for Science at Extreme Conditions, University of Edinburgh, Peter Gurthrie Tait Road, Erskine Williamson Building, Edinburgh EH9 3FD (UK).
⁵ School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU (UK).
⁶ EaStCHEM School of Chemistry, Purdie Building, University of St. Andrews, St. Andrews KY16 9ST (UK).
⁷ EaStChem School of Chemistry and Centre for Science at Extreme Conditions, University of Edinburgh, David Brewster road, Joseph Black Building, Edinburgh EH9 3FJ (UK). smoggach@staffmail.ed.ac.uk.

PMID: 26358845
DOI: 10.1002/anie.201506250

Abstract

An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single-crystal of a porous metal-organic framework, is demonstrated to have considerable advantages over other gas-loading methods when investigating host-guest interactions. Specifically, loading the metal-organic framework Sc2BDC3 with liquefied CO2 at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH4 at 3-25 kbar demonstrates hyperfilling of the Sc2 BDC3 and two high-pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.

Keywords: X-ray crystallography; gas separation; high-pressure phases; metal-organic frameworks; structural science.