A silica-supported palladium oxide catalyst (PdO@MCM-41) selectively cleaves ether linkages in lignin model compounds and alkali lignin via intramolecular hydrogen transfer

Abstract

Lignin is a potential renewable feedstock for the production of aromatic chemicals but due to the recalcitrant nature of its aryl ether bonds (C–O), and recondensation of depolymerized products, it is challenging to produce aromatic compounds with selectivity in high yield. Here we present that a heterogeneous catalyst containing highly dispersed palladium oxide (PdO) particles supported on mesoporous silica (MCM-41) catalyzes oxidant-free oxidation (dehydrogenation) of hydroxyl group at α-carbon of β-O-4 linkage in lignin model compounds and alkali lignin. The catalyst was synthesized via a molecular approach utilizing molecular designed dispersion of palladium diketonate complex followed by calcination. The oxidized lignin models provide high individual yields of monomeric products such as phenol (97%) at moderate temperature (120 °C) through intramolecular hydrogen transfer in green solvents (ethanol and water). The process, therefore, doesn't require any external oxidant, or reductant for cleaving the most abundant β-O-4 linkage of lignin model compounds and tolerates electron donating or withdrawing substitutes at the benzene ring. The approach was successfully extended to alkali lignin where 89% of lignin oil was produced from alkali lignin containing high yield (26 wt%) of monomeric products such as vanillin (2 wt%), benzaldehyde (12 wt%) and benzoic acid (12 wt%).