Mixed-Ligand Assisted Direct Synthesis of Redox-Active UiO-66-(SH)2 Metal Organic Frameworks and Their Behavioural Pattern in Reductive and Oxidative Environments

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. 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 the performance study of the mixed-linker thiol MOFs under reductive and oxidative conditions. The rate of para-nitrophenolate hydrogenation under reductive conditions were mainly governed by the stability of the mixed-linker MOFs as catalyst supports. Whereas, post synthetic oxidation (PSO) was used to produce sulfonic acid tagged mixed-linker UiO-66 frameworks to probe the behavioral pattern in oxidative conditions of the parent mixed-linker thiol MOFs. The mixed-linker strategy was critical in preventing the frameworks from losing their crystallinity and porosity, upon oxidation. Thus, this work also paves the way for a general strategy to impart stability to thiol tagged UiO-66 framework having wide ranging applications.