Cooperative catalysis at the metal-MOF interface: hydrodeoxygenation of vanillin over Pd nanoparticles covered with a UiO-66(Hf) MOF.

Cooperative catalysis has been demonstrated over metal-MOF hybrids for the conversion of vanillin (biomass based platform molecules) into value-added 2-methoxy-4-methylphenol. Over a Pd@UiO-66(Hf) core-shell catalyst, cooperativity between Brønsted acidic μ3-OH groups and Pd active sites present at the interface has rendered a catalytic performance of >99% vanillin conversion and >99% 2-methoxy-4-methylphenol selectivity at 90 °C under 3 bar H2 in water. An enhanced cooperative effect has been observed over a core-shell catalyst compared to a support catalyst.