Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post-Synthetic Modification of a UiO-66-Type Metal-Organic Framework

Alexander Kronast; Sebastian Eckstein; Peter T Altenbuchner; Konrad Hindelang; Sergei I Vagin; Bernhard Rieger

doi:10.1002/chem.201602318

Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post-Synthetic Modification of a UiO-66-Type Metal-Organic Framework

Chemistry. 2016 Aug 26;22(36):12800-7. doi: 10.1002/chem.201602318. Epub 2016 Aug 2.

Authors

Alexander Kronast¹, Sebastian Eckstein², Peter T Altenbuchner¹, Konrad Hindelang³, Sergei I Vagin¹, Bernhard Rieger¹

Affiliations

¹ Wacker-Lehrstuhl für Makromolekulare Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching bei München, Germany.
² Lehrstuhl für Technische Chemie II, Technische Universität München, Lichtenbergstrasse 4, 85747, Garching bei München, Germany.
³ Consortium für elektrochemische Industrie, Wacker Chemie AG, Zielstattstrasse 20, 81379, München, Germany.

PMID: 27483397
DOI: 10.1002/chem.201602318

Abstract

The highly porous and stable metal-organic framework (MOF) UiO-66 was altered using post-synthetic modifications (PSMs). Prefunctionalization allowed the introduction of carbon double bonds into the framework through a four-step synthesis from 2-bromo-1,4-benzenedicarboxylic acid; the organic linker 2-allyl-1,4-benzenedicarboxylic acid was obtained. The corresponding functionalized MOF (UiO-66-allyl) served as a platform for further PSMs. From UiO-66-allyl, epoxy, dibromide, thioether, diamine, and amino alcohol functionalities were synthesized. The abilities of these compounds to adsorb CO2 and N2 were compared, which revealed the structure-selectivity correlations. All synthesized MOFs showed profound thermal stability together with an increased ability for selective CO2 uptake and molecular gate functionalities at low temperatures.

Keywords: UiO-66; carbon dioxide sorption; gate effects; metal-organic frameworks; post-synthetic modification.