Gold nanoparticles supported on metal oxides as catalysts for the direct oxidative esterification of alcohols under mild conditions

•The catalysts were prepared by reduction method at room temperature.•The catalytic properties were studied at ambient temperature and pressure.•Gold nanoparticles showed superior catalytic activities.•The catalyst can be reused for 10 times.•This mechanism of esterification was proposed.

Gold nanoparticles supported on metal oxides were used to catalyze the direct oxidative esterification of alcohols; esters were obtained using molecular oxygen as an oxidant under ambient temperature and pressure. Higher activities for the reaction between the benzyl alcohol and methanol were obtained over Au/CeO2 and Au/ZrO2 than Au/TiO2 (anatase), Au/HT (hydrotalcite) and Au/Al2O3. These catalysts were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD), atomic absorption spectroscopy (AAS) and X-ray photoelectron spectroscopy (XPS). The distribution of gold nanoparticles was uniform; no change of chemical states occurred for supports and gold nanoparticles after the catalysts were reused 10 times. The oxidative esterification of various alcohols over these catalysts could also occur under optimized reaction conditions. The substituted benzyl alcohols and cinnamyl alcohols were more active than heterocyclic alcohols and aliphatic alcohols because their α-H could be eliminated more easily during the induction of adsorbed dioxygen. Self-oxidative esterification was available for benzyl alcohol in inert solvents with low polarity indexes. A reaction mechanism was proposed for the synthesis of esters from alcohols with molecular oxygen.

Graphical abstractThe interaction between oxygen atoms of alcohols and metal cations of supports and between hydrogen atoms of alcohol hydroxyl and oxygen anions of supports weakened the O–H bonds of the benzyl alcohol.Figure optionsDownload full-size imageDownload as PowerPoint slide