Cerium-Organic Framework UiO-66(Ce) as a Support for Nanoparticulate Gold for Use in Oxidation Catalysis.

An optimised synthesis of the metal-organic framework (MOF) UiO-66(Ce) is reported using a modulator-free route, yielding ~5 g of material with high crystallinity and 22 % ligand defect. Two methods are developed for loading gold nanoparticles onto the MOF. The first uses a double-solvent method to introduce HAuCl onto UiO-66(Ce), followed by reduction under 5 % H in N, while the second is a novel one-pot method where HAuCl is added to the synthesis mixture, forming Au nanoparticles within the pores of the UiO-66(Ce) during crystallisation. Analysis using powder X-ray diffraction (PXRD), nitrogen adsorption isotherms, transmission electron microscopy and small-angle X-ray scattering (SAXS) reveals that the two-step double-solvent method yields gold crystallites on the external surface of the MOF particles that are visible by PXRD. In contrast, the one-pot method forms smaller gold crystallites, with a distribution of sizes centred on ~4 nm diameter as seen by SAXS, with evidence from PXRD for the smallest particles being present within the MOF structure. The Au-loaded UiO-66(Ce) materials are evaluated for the catalytic oxidation of vanillyl alcohol to vanillin at 60 °C. Our findings indicate that incorporating Au nanoparticles via the one-pot synthesis method, enhances redox activity, achieving 43 % conversion and 90 % selectivity towards vanillin.