Interfacial Engineering and Synergistic Effects on N–P-Doped Graphene-Supported NiAuPd Alloys for Enhanced Formic Acid Dehydrogenation

The rational design of efficient and selective catalysts for formic acid (FA) dehydrogenation is critical yet challenging for the development of hydrogen-based energy applications. Herein, ultrafine trimetallic NiAuPd nanoparticles (∼1.65 nm) supported on nitrogen–phosphorus-doped graphene (NPG) with excellent dispersibility have been successfully prepared. Remarkably, the optimized Ni0.2Au0.2Pd0.6/NPG catalyst exhibits exceptional catalytic activity and robust stability for additive-free FA dehydrogenation at 303 K, achieving 100% hydrogen selectivity and an unprecedented initial turnover frequency (TOF) of 10053.96 mol of Pd–1 h–1. The significant enhancement in catalytic activity can be attributed to the synergistic effects, including the optimized electronic structure and improved electron transfer facilitated by Ni incorporation, the precise control of particle size and dispersion by NPG support, and the strong metal–support interaction (SMSI) between the NiAuPd nanoparticles and the NPG substrate. Density functional theory (DFT) calculations further confirm that the optimal electronic environment induced by Ni incorporation promotes the rearrangement of H–COO* intermediates and reduces energy barriers (Ebar), thus enhancing the catalytic activity. This work provides a cost-effective strategy for designing high-performance catalysts and promoting hydrogen storage technologies.