Constrained-volume assembly of organometal confined in polymer to fabricate multi-heteroatom doped carbon for oxygen reduction reaction

The design and preparation of non-precious metal and carbon-based nanocomposites are critical to the development of efficient catalysts for technologies ranging from water splitting to fuel cell. Here, we present a constrained-volume self-assembly process for the one-step continuous precipitation-induced formation of soft colloidal particles, in which hydrophobic organoferrous compound, (Ph₃P)₂Fe(CO)₃, is encapsulated within poly(styrene-co-acrylonitrile) nanoparticles (NPs). The protective and confining polymer matrix ensures uniform carbonization and dispersion of (Ph₃P)₂Fe(CO)₃ within a carbon matrix after a pyrolysis process. The obtained carbon NPs are successfully co-doped with Fe, P and N with a relatively high surface area of ∼380 m² g⁻¹. The Fe-P-N-doped carbon catalyst exhibits high catalytic performance and stability toward oxygen reduction reaction in both alkaline and acidic electrolytes via a favorable four-electron pathway. Meanwhile, the catalytic capability of Fe-P-N-doped carbon can be tailored by the tunable nanostructures.