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<p>A novel solvent-free synthesis for
Ce-UiO-66 metal-organic frameworks (MOFs) is presented. The MOFs are obtained
by simply grinding the reagents, cerium ammonium nitrate (CAN) and the
carboxylic linkers, in a mortar for few minutes with the addition of a small
amount of acetic acid (AcOH) as modulator (1.75 eq, o.1 ml). The slurry is then
transferred into a 1 ml vial and heated at 120°C for 1 day. The MOFs have been
characterized for their composition, crystallinity and porosity and employed as
heterogenous catalysts for the photo-oxidation reaction of substituted benzylic
alcohols to benzaldaldehydes under near ultraviolet light irradiation. The
catalytic performances, such as yield, conversion and kinetics, exceed those of
similar systems studied by chemical oxidation and using Ce-MOF as catalyst.
Moreover, the MOFs were found to be reusable up to three cycles without loss of
activity. Density functional theory (DFT) calculations gave an estimation of
the band-gap shift due to the different nature of the linkers used and provide
useful information on the catalytic activity experimentally observed.</p>
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Vanadium-catalyzed green oxidation of benzylic alcohols in water under air atmosphere
