Assembly-Foaming Synthesis of Hierarchically Porous Nitrogen-Doped Carbon Supported Single-Atom Iron Catalysts for Efficient Oxygen Reduction

Abstract

High-performance electrocatalysts are highly concerned in oxygen reduction reaction (ORR) related energy applications. However, facile synthesis of hierarchically porous structures with highly exposed active sites and improved mass transfer is challenging. Herein, we develop a novel assembly-foaming strategy for synthesizing hierarchically porous nitrogen-doped carbon supported single-atom iron catalysts. Incorporation of a Fe3+/histidine complex into the block copolymer F127/resol assembly system not only enables an assembly-foaming process forming hierarchical pores, but also promotes the creation of abundant nitrogen-coordinated single-atom Fe (FeNX) sites on well-graphitized carbon skeletons. The obtained materials possess interconnected macropores (1.5–11.5 µm), large mesopores (5–30 nm) and rich micropores, high surface areas (534–970 m2 g-1), large pore volumes (0.68–1.04 cm3 g-1) and rich FeNX sites. The optimized sample exhibits a superior ORR activity (onset potential 1.03 V and half-wave potential 0.89 V) to the commercial 20 wt% Pt/C catalyst, a high kinetic current density and excellent stability and methanol tolerance.The prominent performance stems from the coeffects of the hierarchical pore structure and the rich accessible FeNX sites. The significance of the pore structure is revealed by the positive linear relationship between the double-layer capacitances of the obtained materials and their ORR activities.

Keywords: Single-atom catalyst, hierarchical pore structure, soft templating, molecular foaming, Oxygen reduction reaction