Amino‐Modified Dual Support for Synergistic Stabilization of Ultrafine NiPd Nanoparticles as a Superior Dehydrogenation Catalyst

ABSTRACT The development of low‐cost and highly active heterogeneous catalysts is crucial for promoting formic acid (FA) as a practical hydrogen carrier for fuel cells. Herein, we report a novel strategy for the synthesis of ultrafine NiPd bimetallic nanoparticles (NPs) supported on amino‐modified dual support (NiPd/NH 2 ‐bNCG), which comprises bimetallic organic framework–derived nitrogen‐doped porous carbon and reduced graphene oxide. The optimized Ni 0.4 Pd 0.6 /NH 2 ‐bNCG catalyst exhibits excellent catalytic performance for FA dehydrogenation with 100% conversion and H 2 selectivity, reaching the high initial turnover frequency (TOF) value of 5444.7 mol H 2 mol catalyst −1 h −1 at 323 K without any additive. The superior activity is attributed to the synergistic effects of the strong metal–support interaction (SMSI) and the unique hierarchical porous structure of the dual support, which effectively confines and stabilizes the ultrafine NiPd NPs (1.6 nm). XPS analyses confirm electron transfer from the support to the metals and between Ni and Pd, creating an electron‐rich Pd active site. Moreover, the surface amino groups serve as proton transfer promoters, facilitating the O–H bond cleavage in FA. This work provides an efficient and economical catalyst design strategy for hydrogen storage and release via FA dehydrogenation.