Atomically Dispersed Fe-N(4) Modified with Precisely Located S for Highly Efficient Oxygen Reduction

Immobilizing metal atoms by multiple nitrogen atoms has triggered exceptional catalytic activity toward many critical electrochemical reactions due to their merits of highly unsaturated coordination and strong metal-substrate interaction. Herein, atomically dispersed Fe-NC material with precise sulfur modification to Fe periphery (termed as Fe-NSC) was synthesized, X-ray absorption near edge structure analysis confirmed the central Fe atom being stabilized in a specific configuration of Fe(N(3))(N–C–S). By enabling precisely localized S doping, the electronic structure of Fe-N(4) moiety could be mediated, leading to the beneficial adjustment of absorption/desorption properties of reactant/intermediate on Fe center. Density functional theory simulation suggested that more negative charge density would be localized over Fe-N(4) moiety after S doping, allowing weakened binding capability to *OH intermediates and faster charge transfer from Fe center to O species. Electrochemical measurements revealed that the Fe-NSC sample exhibited significantly enhanced oxygen reduction reaction performance compared to the S-free Fe-NC material (termed as Fe-NC), showing an excellent onset potential of 1.09 V and half-wave potential of 0.92 V in 0.1 M KOH. Our work may enlighten relevant studies regarding to accessing improvement on the catalytic performance of atomically dispersed M-NC materials by managing precisely tuned local environments of M-N(x) moiety. [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s40820-020-00456-8) contains supplementary material, which is available to authorized users.