Systematic Thiol Decoration in a Redox-Active UiO-66-(SH)2 Metal-Organic Framework: A Case Study under Oxidative and Reductive Conditions.

Abstract

The practical applicability of thiolated metal-organic frameworks (MOFs) remains challenging due to their low crystallinity and transient stability. Herein, we present a one-pot solvothermal synthesis process using varying ratios of 2,5-dimercaptoterephthalic acid (DMBD) and 1,4-benzene dicarboxylic acid (100/0, 75/25, 50/50, 25/75, and 0/100) to prepare stable mixed-linker UiO-66-(SH)2 MOFs (ML-U66SX). For each variant, the effects of different linker ratios on the crystallinity, defectiveness, porosity, and particle size have been discussed in detail. In addition, the impact of modulator concentration on these features has also been described. The stability of ML-U66SX MOFs was investigated under reductive and oxidative chemical conditions. The mixed-linker MOFs were used as sacrificial catalyst supports to highlight the interplay of template stability on the rate of the gold-catalyzed 4-nitrophenol hydrogenation reaction. The release of catalytically active gold nanoclusters originating from the framework collapse decreased with the controlled DMBD proportion, resulting in a 59% drop in the normalized rate constants (9.11-3.73 s-1 mg-1). In addition, post-synthetic oxidation (PSO) was used to further probe the stability of the mixed-linker thiol MOFs under harsh oxidative conditions. Following oxidation, the UiO-66-(SH)2 MOF underwent immediate structural breakdown, unlike other mixed-linker variants. Along with crystallinity, the microporous surface area of the post-synthetically oxidized UiO-66-(SH)2 MOF could be increased from 0 to 739 m2 g-1. Thus, the present study delineates a mixed-linker strategy to stabilize the UiO-66-(SH)2 MOF under harsh chemical conditions through meticulous thiol decoration.