Zirconium metal–organic frameworks incorporating tetrathiafulvalene linkers: robust and redox-active matrices for in situ confinement of metal nanoparticles

Abstract

Redox-active metal–organic frameworks (MOFs), with highly ordered porous structures and redox tunability, have attracted research interest in the fields of catalysis, energy storage, and electrochemical sensing. However, the chemical lability has limited the application scope of many redox-active MOFs. Herein, we selected stable Zr₆ inorganic nodes and redox-active tetrathiafulvalene (TTF)-based linkers to construct two robust, redox-active MOFs, namely compounds 1 ([Zr₆(TTFTB)₂O₈(OH₂)₈]) and 2 ([Zr₆(Me-TTFTB)_1.5O₄(OH)₄(C₆H₅COO)₆]) (TTFTB = tetrathiafulvalene tetrabenzoate; Me-TTFTB = tetrathiafulvalene tetramethylbenzoate). The structure and topology of the MOFs were controlled by tuning the linker conformation through steric effects, resulting in a variety of pore structures from microporous channels (compound 1) to hierarchically micro/mesoporous cages (compound 2). Compound 2 shows high porosity with a BET surface area of 1932 m² g⁻¹ and strong chemical stability in aqueous solutions with pH ranging from 1 to 12. Furthermore, the reductive TTF moieties allow for in situ generation and stabilization of ultra-small noble metal (Ag, Pd, and Au) nanoparticles by incubating MOFs in the respective metal salt solution. Single crystal structures, TEM images, and pore size distribution data from N₂ adsorption measurements indicated that the metal nanoparticles were mostly placed in the small cubic cavities of hierarchically porous compound 2, leaving the large cages open for substrate diffusion. As a proof of concept, Pd NPs@compound 2 was utilized as a heterogeneous catalyst for aerobic oxidation of alcohols, showing noteworthy activity and recyclability.