Mesoporous N-Doped Carbons Prepared with Thermally Removable Nanoparticle Templates: An Efficient Electrocatalyst for Oxygen Reduction Reaction

TLDR

Thermally removable FeO(OH) nanorod templates embedded in poly(2‑fluoroaniline) are pyrolyzed to yield self‑supported N‑doped mesoporous carbons with a surface area of 934.8 m² g⁻¹. The resulting Fe‑N/C-800 material exhibits superior oxygen‑reduction activity in 0.1 M KOH, with a +0.98 V onset potential, high diffusion‑limited current, electron transfer number > 3.95, excellent stability, and methanol tolerance, outperforming commercial Pt/C due to its high surface area and exposed N‑doped active sites.

Abstract

Thermally removable nanoparticle templates were used for the fabrication of self-supported N-doped mesoporous carbons with a trace amount of Fe (Fe-N/C). Experimentally Fe-N/C was prepared by pyrolysis of poly(2-fluoroaniline) (P2FANI) containing a number of FeO(OH) nanorods that were prepared by a one-pot hydrothermal synthesis and homogeneously distributed within the polymer matrix. The FeO(OH) nanocrystals acted as rigid templates to prevent the collapse of P2FANI during the carbonization process, where a mesoporous skeleton was formed with a medium surface area of about 400 m(2)/g. Subsequent thermal treatments at elevated temperatures led to the decomposition and evaporation of the FeO(OH) nanocrystals and the formation of mesoporous carbons with the surface area markedly enhanced to 934.8 m(2)/g. Electrochemical measurements revealed that the resulting mesoporous carbons exhibited apparent electrocatalytic activity for oxygen reduction reactions (ORR), and the one prepared at 800 °C (Fe-N/C-800) was the best among the series, with a more positive onset potential (+0.98 V vs RHE), higher diffusion-limited current, higher selectivity (number of electron transfer n > 3.95 at +0.75 V vs RHE), much higher stability, and stronger tolerance against methanol crossover than commercial Pt/C catalysts in a 0.1 M KOH solution. The remarkable ORR performance was attributed to the high surface area and sufficient exposure of electrocatalytically active sites that arose primarily from N-doped carbons with minor contributions from Fe-containing species.