Inducing Fe 3d Electron Delocalization and Spin-State Transition of FeN₄ Species Boosts Oxygen Reduction Reaction for...

Transition metal-nitrogen-carbon materials (M-N-Cs), particularly Fe-N-Cs, have been found to be electroactive for accelerating oxygen reduction reaction (ORR) kinetics. Although substantial efforts have been devoted to design Fe-N-Cs with increased active species content, surface area, and electronic conductivity, their performance is still far from satisfactory. Hitherto, there is limited research about regulation on the electronic spin states of Fe centers for Fe-N-Cs electrocatalysts to improve their catalytic performance. Here, we introduce Ti₃C₂ MXene with sulfur terminals to regulate the electronic configuration of FeN₄ species and dramatically enhance catalytic activity toward ORR. The MXene with sulfur terminals induce the spin-state transition of FeN₄ species and Fe 3d electron delocalization with d band center upshift, enabling the Fe(II) ions to bind oxygen in the end-on adsorption mode favorable to initiate the reduction of oxygen and boosting oxygen-containing groups adsorption on FeN₄ species and ORR kinetics. The resulting FeN₄-Ti₃C₂S_x exhibits comparable catalytic performance to those of commercial Pt-C. The developed wearable ZABs using FeN₄-Ti₃C₂S_x also exhibit fast kinetics and excellent stability. This study confirms that regulation of the electronic structure of active species via coupling with their support can be a major contributor to enhance their catalytic activity.