In this review, we discuss the phenomenon of complementary macropore incorporation into mesoporous and/or microporous solids in order to enhance their catalytic performance in fuels and chemicals synthesis.

a b s t r a c tThe selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO 2 , ZnO, ␥-Al 2 O 3 , CeO 2 is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 • C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO 2 and ␥-Al 2 O 3 . In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature.

The influence of silica mesostructure upon the Pd-catalyzed selective oxidation of allylic alcohols has been investigated for amorphous and surfactant-templated SBA-15, SBA-16, and KIT-6 silicas. Significant rate enhancements can be achieved via mesopore introduction, most notably through the use of interconnected porous silica frameworks, reflecting both improved mass transport and increased palladium dispersion; catalytic activity decreases in the order Pd/KIT-6 ≈ Pd/SBA-16 > Pd/SBA-15 > Pd/SiO2. Evidence is presented that highly dispersed palladium oxide nanoparticles, not zerovalent palladium, are the catalytically active species.

Synergistic effects between alkali-free hydrotalcites and gold nanoparticles afford efficient heterogeneous catalysts for the cascade oxidation of 5-HMF to 2,5-FDCA.

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