Rational Tuning of Zirconium Metal-Organic Framework Membranes for Hydrogen Purification

Behnam Ghalei; Kazuki Wakimoto; Chih Yi Wu; Ali Pournaghshband Isfahani; Takuma Yamamoto; Kento Sakurai; Masakazu Higuchi; Bor Kae Chang; Susumu Kitagawa; Easan Sivaniah

doi:10.1002/anie.201911359

Rational Tuning of Zirconium Metal-Organic Framework Membranes for Hydrogen Purification

Angew Chem Int Ed Engl. 2019 Dec 19;58(52):19034-19040. doi: 10.1002/anie.201911359. Epub 2019 Nov 7.

Authors

Affiliations

¹ Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida-Honmachi, Sakyo Ku, 606-8501, Kyoto, Japan.
² Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
³ Department of Chemical and Materials Engineering, National Central University, Taoyuan City, 32001, Taiwan, ROC.

PMID: 31602745
DOI: 10.1002/anie.201911359

Abstract

The effect of organic ligands on the separation performance of Zr based metal-organic framework (Zr-MOF) membranes was investigated. A series of Zr-MOF membranes with different ligand chemistry and functionality were synthesized by an in situ solvothermal method and a coordination modulation technique. The thin supported MOF layers (ca. 1 μm) showed the crystallographic orientation and pore structure of original MOF structures. The MOF membranes show excellent selectivity towards hydrogen owing to the molecular sieving effect when the bulkier linkers were used. The molecular simulation confirmed that the constricted pore apertures of the Zr-MOFs which were formed by the additional benzene rings lead to the decrease in the diffusivity of larger penetrants while hydrogen was not remarkably affected. The gas mixture separation factors of the MOF membranes reached to H₂ /CO₂ =26, H₂ /N₂ =13, H₂ /CH₄ =11.

Keywords: hydrogen; membranes; metal-organic frameworks; molecular simulation; separation.