Microstructure Engineering of Fe/Fe₃C-Decorated Metal–Nitrogen–Carbon Mesoporous Nanospheres via a Self-Template Method for Enhancing Oxygen Reduction Activity

Abstract

We report a self-template and facile pyrolysis method to synthesize Fe/Fe₃C-decorated metal-nitrogen-carbon mesoporous nanospheres, of which preserved plum-like and hollow structures can be simply engineered via controlling the thickness of the outermost polydopamine layer in the precursors. The preserved plum-like structure is demonstrated to show a large electrochemically active surface area and facilitate fast charge transfer, in comparison with the hollow one. The catalytic activities of metal-nitrogen-carbon and nitrogen-doped carbon active sites in the outer carbon layer toward oxygen reduction are improved under the activation of the encased Fe species. Hence, preserved plum-like structures exhibit excellent catalytic kinetics toward the oxygen reduction reaction in alkaline media. The mass activity of 21.0 mA mg_catalyst^-1 at 0.9 V vs RHE is achieved and the half-wave potential is 50 mV more positive than that of the Pt/C catalyst with the same mass loading. Moreover, the outer carbon layer endows the tolerance of strong acidic and alkaline environments, resulting in good durability. Our study proposes a simple strategy for the rational design of novel transition metal carbide-based catalysts, making it a promising candidate for replacing platinum-group metal catalysts in low-temperature fuel cells.