Fluorine‐Doped Carbon Support Enables Superfast Oxygen Reduction Kinetics by Breaking the Scaling Relationship

Abstract It is well‐established that Pt‐based catalysts suffer from the unfavorable linear scaling relationship (LSR) between *OOH and *OH (ΔG(*OOH)=ΔG(*OH)+3.2±0.2 eV) for the oxygen reduction reaction (ORR), resulting in a great challenge to significantly reduced ORR overpotentials. Herein, we propose a universal and feasible strategy of fluorine‐doped carbon supports, which optimize interfacial microenvironment of Pt‐based catalysts and thus significantly enhance their reactive kinetics. The introduction of C−F bonds not only weakens the *OH binding energy, but also stabilizes the *OOH intermediate, resulting in a break of LSR. Furthermore, fluorine‐doped carbon constructs a local super‐hydrophobic interface that facilitates the diffusion of H 2 O and the mass transfer of O 2 . Electrochemical tests show that the F‐doped carbon‐supported Pt catalysts exhibit over 2‐fold higher mass activities than those without F modification. More importantly, those catalysts also demonstrate excellent stability in both rotating disk electrode (RDE) and membrane electrode assembly (MEA) tests. This study not only validates the feasibility of tuning the electrocatalytic microenvironment to improve mass transport and to break the scaling relationship, but also provides a universal catalyst design paradigm for other gas‐involving electrocatalytic reactions.