Elucidating the alloying effect of PdAg/CNT catalysts on formic acid dehydrogenation with kinetic isotope effect

Abstract

Formic acid has emerged as a promising liquid hydrogen carrier for addressing the transport and storage issues of hydrogen, owing to its high hydrogen density (4.4 wt.%) and easy-handling liquid phase. Therefore, the conversion of formic acid into hydrogen and vice versa is a significant technique. Despite the development of various metal alloy catalysts for efficient production of hydrogen from formic acid, it remains unclear how the metal alloy affects formic acid dehydrogenation from the mechanistic perspective. This study addresses this gap by investigating the alloy effect of Pd and Ag on formic acid dehydrogenation, using PdAg alloy nanoparticles supported on carbon nanotube catalysts. The PdAg alloy, analyzed using multiple characterization methods, demonstrated enhanced catalytic activity, which was maximized at a Pd:Ag molar ratio of 7:3. More importantly, temperature-dependent and kinetic isotope effect experiments demonstrated that the electronic modification of Pd by Ag improved its activity by promoting the cleavage of the CH bond of formic acid. The results suggest that the kinetic isotope effect would be a potent technique for elucidating the alloying effect, as well as providing a deeper understanding of the mechanism.