Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells

Atomically dispersed and nitrogen coordinated single iron site (i.e., FeN₄) catalysts (Fe-N-C) are the most promising platinum group metal (PGM)-free cathode for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). However, current Fe-N-C catalysts are limited by the inferior exposure of active FeN₄ sites due to the inevitable agglomeration of particles in cathodes. Herein, we report a self-assembled strategy to synthesize the atomically dispersed FeN₄ site catalysts with a hierarchically porous matrix derived from dual-size Fe-doped ZIF-8 crystal precursors by using large particles to support small particles. The tailored structure is effective in mitigating the particle migration, agglomeration, and spatial overlap, thereby exposing increased accessible active sites and facilitating mass transport. The best performing catalyst composed of 100 nm “nucleated seed” assembled by 30 nm “satellite” demonstrates exceptional ORR activity in acidic electrolyte and membrane electrode assembly. This work provides new concepts for designing hierarchically porous catalysts with single metal atom dispersion via self-assembly of ZIF-8 crystal precursors with tunable particle sizes and nanostructures.