Pd-Modified Metal Organic Frameworks Synthesized via Mechanochemical Extrusion: Versatile Materials for...

Extrusion-based mechanochemistry offers a sustainable route for materials synthesis. Here, we report the preparation of Pd-modified metal-organic frameworks (UiO-66, UiO-66-NH₂, and MOF-801) via continuous-flow twin-screw extrusion. The resulting amorphous Pd@MOF materials contain quasi-spherical Pd nanoparticles whose dispersion is strongly influenced by the functional groups of the parent MOFs, with UiO-66-NH₂ providing superior stabilization. The catalysts were evaluated in two applications: the Suzuki-Miyaura cross-coupling reaction and the electrochemical hydrogen evolution reaction (HER). Optimization of the Suzuki-Miyaura conditions afforded improved temperature and time parameters compared to literature examples, delivering higher TOFs and meeting CHEM21 First Pass sustainability criteria. A substrate scope analysis, including aryl bromides and chlorides, further confirmed their efficiency, while recycling studies demonstrated catalyst stability. In HER, the highly dispersed Pd nanoparticles maximized active-site availability, with 5Pd@UiO-66-NH₂-2-200 showing the best performance. The presence of amino groups in the UiO-66-NH₂ support provided an electron-rich environment that enhanced the intrinsic kinetic rate (j ₀). Overall, extrusion mechanochemistry enables robust, versatile Pd@MOF catalysts for both organic synthesis and energy-related applications.