Simultaneously Enhanced Hydrophilicity and Stability of a Metal-Organic Framework via Post-Synthetic Modification for Water Vapor Sorption/Desorption

Tian-Yi Luo; Sunghwan Park; Tso-Hsuan Chen; Prerna; Roshan Patel; Xinyu Li; J Ilja Siepmann; Stavros Caratzoulas; Zhiyong Xia; Michael Tsapatsis

doi:10.1002/anie.202209034

Simultaneously Enhanced Hydrophilicity and Stability of a Metal-Organic Framework via Post-Synthetic Modification for Water Vapor Sorption/Desorption

Angew Chem Int Ed Engl. 2022 Nov 2;61(44):e202209034. doi: 10.1002/anie.202209034. Epub 2022 Sep 30.

Authors

Tian-Yi Luo¹, Sunghwan Park^{1

2}, Tso-Hsuan Chen³, Prerna^{4

5}, Roshan Patel^{4

5}, Xinyu Li⁴, J Ilja Siepmann^{4

5}, Stavros Caratzoulas³, Zhiyong Xia⁶, Michael Tsapatsis^{1

6}

Affiliations

¹ Department of Chemical and Biomolecular Engineering & Institute for NanoBioTechnology, Johns Hopkins University, 3400N. Charles Street, Baltimore, MD 21218, USA.
² School of Nano & Materials Science and Engineering, Kyungpook National University, 2559 Gyeongsang-daero, Sangju-si, Gyeongsangbuk-do, 37224, Republic of Korea.
³ Department of Chemical and Biomolecular Engineering and Catalysis Center for Energy Innovation, University of Delaware, Newark, DE 19716, USA.
⁴ Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, MN 55455, USA.
⁵ Department of Chemistry and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455, USA.
⁶ Applied Physics Laboratory, Johns Hopkins University, 11100 Johns Hopkins Road, Laurel, MD 20723, USA.

PMID: 35929949
DOI: 10.1002/anie.202209034

Abstract

With increasing demands for high-performance water sorption materials, metal-organic frameworks (MOFs) have gained considerable attention due to their high maximum uptake capacities. In many cases, however, high overall capacity is not necessarily accomplishing high working capacity under operating conditions, due to insufficient hydrophilicity and/or water stability. Herein, we present a post-synthetic modification (PSM) of MOF-808, with di-sulfonic acids enhancing simultaneously its hydrophilicity and water stability without sacrificing its uptake capacity of ≈30 mmol g^-1 . Di-sulfonic acid PSM enabled a shift of the relative humidity (RH) associated with a sharp step in water vapor sorption from 35-40 % RH in MOF-808 to below 25 % RH. While MOF-808 lost uptake capacity and crystallinity over multiple sorption/desorption cycles, the di-sulfonic acid PSM MOF-808 retained >80 % of the original capacity. PSM MOF-808 exhibited good hydrothermal stability up to 60 °C and high swing capacity.

Keywords: Hydrophilicity; Metal-Organic Framework; Post-Synthetic Modification; Sorption; Water Harvesting.

Abstract

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