Systematic Pore Hydrophobization to Enhance the Efficiency of an Amine-Based MOF Catalyst

Submitting author affiliation:
Kansas State University, Manhattan, United States

Beilstein Arch. 2025, 20252. https://doi.org/10.3762/bxiv.2025.2.v1

Published 16 Jan 2025

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Abstract

We systematically hydrophobicized an amine-based metal-organic framework (MOF) catalyst and applied the functionalized MOFs to the Knoevenagel condensation reaction. A well-defined MOF material composed of both amine- and hydroxyl-bearing linkers was reacted with a series of aliphatic isocyanates (isopropyl, tert-butyl, n-hexyl, and tetradecyl) and, incongruously, was found to preferentially react at the hydroxyl groups. This selective functionalization yielded MOFs in which the catalytically active amines are confined within highly hydrophobic pores, reminiscent of many enzyme active sites. We determined that systematically increasing the hydrophobicity of the pores results in a commensurate increase of catalyst efficiency.

Keywords: metal-organic frameworks; supramolecular catalysis; post-syhnthesis modification

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Matseketsa, P.; Gadzikwa, T. Beilstein Arch. 2025, 20252. doi:10.3762/bxiv.2025.2.v1

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