Mechanism of Pd/C-catalyzed hydrogenation of furfural under hydrothermal conditions.

• Mechanism of Pd/C-catalyzed hydrogenation of furfural in H 2 O was established. • Deuterium labeling is one of the techniques used to study the reaction mechanism. • Aqueous-phase furfural hydrogenation is realized through four pathways. • Mechanism includes reductive and acid-catalyzed furan ring opening reactions. Catalytic hydrogenation of furfural under hydrothermal conditions is of great importance and has recently attracted huge attention as an approach to obtaining a wide range of valuable chemicals from a renewable source. However, the data concerning the reaction mechanism of aqueous-phase furfural hydrogenation are very scarce, and it is still not clear which reactions lead to various carbonyl compounds, such as cyclopentanone, 4-oxopentanal, 5-hydroxy-2-pentanone. Herein, we present the results of an experimental study of the mechanism of reactions occurring in the furfural hydrogenation under hydrothermal conditions over the 1% Pd/CNTs catalyst. The following approaches have been used to study the reaction mechanism: hydrogenation of key intermediates formed upon the furfural conversion, and isotopic labeling experiments using D 2 O as a tracer in hydrogenation of furfural, which provides direct evidence of the occurring reactions. It was found that the furfural hydrogenation process is realized through four pathways including various reductive and acid-catalyzed furan ring opening reactions. The methods and approaches used in the present work, as well as the results obtained, can be useful in studying the mechanism of aqueous-phase hydrogenation of a wide range of oxygen-containing substrates in the presence of catalysts of different compositions. [ABSTRACT FROM AUTHOR]