Ultrafine Pd nanoparticles on amine-functionalized carbon nanotubes for hydrogen production from formic acid

Formic acid is a promising hydrogen source and liquid organic hydrogen carrier because of its high hydrogen density. To produce hydrogen from formic acid, catalytic dehydrogenation of formic acid over Pd-based catalysts has been investigated. Here, a highly active catalyst is rationally designed. Carbon nanotubes without micropores were adopted as a support to facilitate the mass transport of reactants or products. Pd particles were made as small as possible to provide a large number of active sites and to alleviate the activation barrier for hydrogen desorption. Amine functional groups were introduced into carbon nanotubes to generate formate anions by capturing protons from formic acid. Based on this design, ultrafine Pd nanoparticles (1.76 nm) on amine-functionalized carbon nanotubes were successfully synthesized. This catalyst demonstrated remarkable activity for the formic acid dehydrogenation reaction, with a high turnover frequency value of 2560 h⁻¹ at 30 °C.