Improving the Stability of Non‐Noble‐Metal M–N–C Catalysts for Proton‐Exchange‐Membrane Fuel Cells through M–N Bond Length and Coordination Regulation

An effective and universal strategy is developed to enhance the stability of the non-noble-metal M-N_x /C catalyst in proton exchange membrane fuel cells (PEMFCs) by improving the bonding strength between metal ions and chelating polymers, i.e., poly(acrylic acid) (PAA) homopolymer and poly(acrylic acid-maleic acid) (P(AA-MA)) copolymer with different AA/MA ratios. Mössbauer spectroscopy and X-ray absorption spectroscopy (XAS) reveal that the optimal P(AA-MA)-Fe-N catalyst with a higher Fe³⁺ -polymer binding constant possesses longer FeN bonds and exclusive Fe-N₄ /C moiety compared to PAA-Fe-N, which consists of ≈15% low-coordinated Fe-N₂ /N₃ structures. The optimized P(AA-MA)-Fe-N catalyst exhibits outstanding ORR activity and stability in both half-cell and PEMFC cathodes, with the retention rate of current density approaching 100% for the first 37 h at 0.55 V in an H₂ -air fuel cell. Density functional theory (DFT) calculations suggest that the Fe-N₄ /C site could optimize the difference between the adsorption energy of the Fe atoms on the support (E_ad ) and the bulk cohesive energy (E_coh ) relative to Fe-N₂ /N₃ moieties, thereby strongly stabilizing Fe centers against demetalation.