Iron atom–cluster interactions increase activity and improve durability in Fe–N–C fuel cells

Simultaneously increasing the activity and stability of the single-atom active sites of M–N–C catalysts is critical but remains a great challenge. Here, we report an Fe–N–C catalyst with nitrogen-coordinated iron clusters and closely surrounding Fe–N₄ active sites for oxygen reduction reaction in acidic fuel cells. A strong electronic interaction is built between iron clusters and satellite Fe–N₄ due to unblocked electron transfer pathways and very short interacting distances. The iron clusters optimize the adsorption strength of oxygen reduction intermediates on Fe–N₄ and also shorten the bond amplitude of Fe–N₄ with incoherent vibrations. As a result, both the activity and stability of Fe–N₄ sites are increased by about 60% in terms of turnover frequency and demetalation resistance. This work shows the great potential of strong electronic interactions between multiphase metal species for improvements of single-atom catalysts.