Crafting Porous Carbon for Immobilizing Pd Nanoparticles with Enhanced Catalytic Activity for Formic Acid Dehydrogenation

Abstract The development of highly active heterogeneous catalytic systems that catalyze formic acid (FA) to generate CO‐free H₂ holds great promise for future energy demands, but is often limited by the low catalytic activity and stability of metal catalysts under ambient conditions. It is thus highly desirable to rationally design a catalyst to boost the catalytic performance. Herein, a general room‐temperature HNO₃‐treatment approach (RTHTA) is developed to accomplish surface modification of various porous carbon materials for immobilizing ultrafine palladium nanoparticles (Pd NPs). A significantly enhanced catalytic performance of the immobilized Pd NPs toward the selective dehydrogenation of FA is achieved, which gives a record‐high turnover frequency of 13333 h⁻¹ at 60 °C, corresponding to a calculated H₂ generation rate of 50.8 L H₂ min⁻¹ g_Pd⁻¹. The results presented here may provide insight into the formation and stabilization of highly active immobilized metal nanoparticles, as well as the enhanced catalytic performance of Pd NPs for catalytic dehydrogenation reactions.