Reaction kinetics studies of the conversions of formic acid and butyl formate over carbon-supported palladium in the liquid phase

► Pd/C is more active, selective, and stable than Ru/C for production of CO2/H2. ► Decomposition of formic acid favors decarboxylation, whereas butyl formate favors decarbonylation. ► The primary pathway can be coupled with water-gas shift to increase H2 selectivity. ► Ester hydrolysis leads to formic acid formation and subsequent production of CO2/H2.