Impact of pretreatment and thiol modifiers on the partial oxidation of glutaraldehyde using Pd/Al2O3

Oxidative conversion of biomass-derived compounds to value-added chemicals is challenging due to the tendency of multi-functional reactants to overoxidize. Catalyst performance can be sensitive to both synthesis and pretreatment conditions. Additionally, coating the catalyst with self-assembled monolayers (SAMs) has shown promise in modulating activity and selectivity. Here, the liquid-phase partial oxidation of glutaraldehyde (GA) to glutaric semialdehyde (GSA) was investigated as a model reaction using a Pd/Al2O3 catalyst, with and without various thiolate SAM modifiers. Reductive pretreatment of the catalyst showed enhancement in the activity and a shortening of an apparent induction period relative to the untreated catalyst. The selectivity for GSA was further found to be sensitive to the identity of the SAM layers, with hydrophilic thioglycerol (TG) and thiolactic acid (TLA) coatings showing an enhancement in selectivity to GSA; the TG coating raised selectivity from - 60 % (on uncoated catalyst and catalysts coated with hydrophobic thiols) to - 80 % at identical conversion (- 30 %). However, the TG coating exhibited lower catalytic rates compared to UC and hydrophobically coated materials. Morphological and electronic causes were ruled out with various materials characterization techniques. Density functional theory (DFT) calculations suggested that hydrogen bonding stabilizes adsorption of GSA compared to the uncoated Pd surface. However, a large stabilization of glutaric acid (GAC) adsorption for TG-coated Pd was also predicted, likely leading to accumulation of this overoxidation product and lower overall rates. Inhibition of the rate of GA partial oxidation by GAC adsorption was then corroborated experimentally. Finding ways to stabilize the less-oxidized intermediates with more specificity is thus suggested as a strategy to improve rate and selectivity.