Pd-Modified Metal Organic Frameworks Synthesized via Mechanochemical Extrusion: Versatile Materials for Suzuki–Miyaura Cross-Coupling and Electrochemical Hydrogen Evolution Reaction

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 (j0). Overall, extrusion mechanochemistry enables robust, versatile Pd@MOF catalysts for both organic synthesis and energy-related applications.