Spin-regulated Fe-N-C catalyst enabled by adjusting coordination nitrogen species for robust oxygen reduction

Fe-N-C catalysts have emerged as a promising substitute for the expensive Pt/C to boost the oxygen reduction reaction (ORR). However, conventional Fe-N₄ active sites, which generally feature a low-spin configuration, strongly adsorb oxygen intermediates and necessitate structural optimization of the active sites for improved performance. Herein, graphitic nitrogen (N_GC) adjacent to the Fe-N₄ centers is straightforwardly introduced to modulate the spin state of Fe-N-C catalysts after elucidating the influence of nitrogen species on the Fe-N₄ sites. Theoretical calculations demonstrate that the adjacent N_GC can effectively regulate the spin state of the active Fe sites, which enables electron filling from Fe to the anti-bonding <i>π*</i> orbital of oxygen species and optimizes the *OH desorption for accelerated ORR. Inspired by this, such catalysts are cost-effectively prepared by a rational combination of electrospinning and controlled thermal annealing using inexpensive precursors. The optimal catalyst shows superior ORR activity to the benchmark Pt/C, and excellent durability, with a minor voltage decay of 11 mV after 10 000 cycles. The spin-state-promoted performance enhancement is confirmed by a series of <i>in-situ</i> characterizations. The remarkable performance of the optimized catalyst is further confirmed in Zn-air batteries (ZABs) with a peak power density of 225 mW cm^-2. Moreover, quasi-solid ZABs using this catalyst realize excellent performance even under bending conditions and successfully power electronic devices, including a mobile phone and an electronic watch. This work correlates the spin state of catalysts and oxygen reduction performance, providing an alternative strategy for regulating the performance of electrocatalysts as well as promoting their application in wearable electronics.