In-situ nitrogen and Cr2O3 co-doped MOF-derived porous carbon supported palladium nanoparticles: A highly effective catalyst towards formic acid dehydrogenation

Fast and high selective dehydrogenation of formic acid (FA) is regarded as one of the most promising pathways to obtain the clean energy carrier: hydrogen. In this work, a nitrogen and Cr₂O₃ co-doped hierarchical carbon material has been successfully synthesized by in-situ pyrolysis of NH₂-MIL-101(Cr) in one step, followed by boiling in hot NaOH solution for surface etching. The activated carbon material is used to anchor the ultrafine Pd nanoparticles (2.18 nm) for formic acid dehydrogenation (FAD). As a result, the 5 wt% Pd@Cr₂O₃-NPCB-850 exhibits an excellent catalytic activity towards FAD: the turnover frequency (TOF) value is as high as 11 241 h⁻¹ at 333 K, and the selectivity of H₂ is up to 100%. The excellent catalytic performance is mainly attributed to the existence of N species and Cr₂O₃, which plays an important role of electron transfer and anti-aggregation. Our studies open a new methodology for convenient and fast syntheses of nitrogen and metal oxide co-doped activated carbon material, which also provides potential access for producing more highly effective catalysts for other catalytic reactions.