Atomic Dispersion and Surface Enrichment of Palladium in Nitrogen-Doped Porous Carbon Cages Lead to High-Performance Electrocatalytic Reduction of Oxygen.

Metal-nitrogen-carbon (MNC) nanocomposites have been hailed as promising and efficient electrocatalysts toward oxygen reduction reaction (ORR), due to the formation of MNx coordination moieties. However, MNC hybrids are mostly prepared by pyrolysis of organic precursors along with select metal salts, where part of the MNx sites are inevitably buried in the carbon matrix. This limited accessibility compromises the electrocatalytic performance. Herein, we describe a wet-impregnation procedure by facile thermal refluxing, whereby palladium is atomically dispersed and enriched onto the surface of hollow, nitrogen-doped carbon cages (HNC) forming Pd-N coordination bonds. The obtained Pd-HNC nanocomposites exhibit an ORR activity in alkaline media markedly higher than that of metallic Pd nanoparticles, and the best sample even outperforms commercial Pt/C and relevant Pd-based catalysts reported in the literature. The results suggest that atomic dispersion and surface enrichment of palladium in a carbon matrix may serve as an effective strategy in the fabrication of high-performance ORR electrocatalysts.