Direct One-pot Synthesis of Highly Tunable Mixed-linker UiO-66-(SH)2 Metal-Organic Frameworks: Enroute Toward Robust Sulfonic Acid Tagged UiO-66 Architectures

05 September 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Synthesis, storage, and characterization of thiol functionalized metal-organic frameworks (MOFs) is highly challenging. However, they continue to be of great interest due to their broad spectrum of applications. In this work, for the first time, a solid solution approach has been adopted to dilute the thiol content in UiO-66-(SH)2 [Universitetet i Oslo] MOF by terephthalic acid linker without influencing its topology. Detailed characterization of the mixed-linker UiO-66-(SH)2 MOF samples have been performed using powder X-ray diffraction (PXRD), N2 sorption, X-ray photoelectron spectroscopy (XPS) and electron microscopy. The solid dilution had an overall impact on the crystallinity, defects, porosity and particle size of the UiO-66-(SH)2 framework. This study has the potential to significantly influence the syntheses of nanoscale thiol functionalized MOF materials and their applications in photocatalysis, water purification and drug delivery. This work also incorporates post synthetic oxidation (PSO) to produce sulfonic acid tagged mixed-linker UiO-66 frameworks. The solid dilution has been found to be critical in preventing the frameworks from losing their crystallinity and porosity, upon activation. Thus, this work also paves the way for a general strategy to impart stability to sulfonic acid tagged UiO-66 framework having wide ranging applications.

Keywords

Thiol MOFs
Solid dilution
Mixed-linker synthesis
UiO-66-(SH)2
Post synthetic modification
UiO-66-(SO3H)2.

Supplementary materials

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Title
Direct One-pot Synthesis of Highly Tunable Mixed-linker UiO-66-(SH)2 Metal-Organic Frameworks: Enroute Toward Robust Sulfonic Acid Tagged UiO-66 Architectures
Description
Synthesis, storage, and characterization of thiol functionalized metal-organic frameworks (MOFs) is highly challenging. In this work, for the first time, a solid solution approach has been adopted to dilute the thiol content in UiO-66-(SH)2 [Universitetet i Oslo] MOF by terephthalic acid linker without influencing its topology. The solid dilution had an overall impact on the crystallinity, defects, porosity and particle size of the UiO-66-(SH)2 framework. This study has the potential to significantly influence the syntheses of nanoscale thiol functionalized MOF materials and their applications in photocatalysis, water purification and drug delivery. This work also incorporates post synthetic oxidation (PSO) to produce sulfonic acid tagged mixed-linker UiO-66 frameworks. The solid dilution has been found to be critical in preventing the frameworks from losing their crystallinity and porosity upon activation. Thus, this work also paves the way for a general strategy to impart stability to sulfonic-acid tagged UiO-66 framework having wide-ranging applications.
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