Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction

Abstract
Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e. Eu3+, Tb3+ and Y3+) fcu metal‒organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cut-off ideal for selective adsorption kinetics separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in-situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the RE-fcu-MOF plat-form, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded nota-ble gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol and butanol/water pair systems.

Citation
Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction 2015:150331183830008 Journal of the American Chemical Society

Publisher
American Chemical Society (ACS)

Journal
Journal of the American Chemical Society

DOI
10.1021/ja5131403

PubMed ID
25825923

Additional Links
http://pubs.acs.org/doi/abs/10.1021/ja5131403

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