Strong Lewis acid-base interfacial regulation mechanism to reveal oxygen reduction activity origin of N,S-codoped carbon with PtNi particles.

[Display omitted] • Interfacial electronic structure of metal-support is regulated by heteratom doping. • N/S doping promotes the oxidation of Pt-Lewis acid center to a higher valence state. • S atom re-doping causes the d-band center of Pt to shift upward towards Fermi level. • High content of Ptx+ sites enhance the binding of Pt-Lewis acid to *OOH intermediate. • PtNi@N,S-HMCS with more Pt-Lewis acid shows high ORR activity and 4e- selectivity. Elucidating the mechanism of metal-support interface domain regulation is crucial for designing efficient fuel cell electrocatalysts. Herein, we propose an emerging strategy to enhance oxygen reduction reaction (ORR) activity and selectivity by regulating the Lewis alkalinity of carbon support to adjust the Lewis acidity of metal sites. The experimental results and density functional theory (DFT) simulations show that the introduction of N/S atoms into the carbon support structure will break the charge balance of the carbon skeleton and effectively regulate the charge distribution in the Pt-carbon interface domain, thus promoting the oxidation of the Lewis acid Pt atoms to a higher valence state Ptx+, so as to optimize the adsorption energy of oxygen-containing intermediates. Moreover, Bader charge analysis also verifies that N,S-HMCS, as a Lewis base, can receive more electrons from the Pt sites of Lewis acid, and the electron loss at Pt sites caused by N,S-HMCS strengthens interfacial electron effect. Meanwhile the strong electron adsorption ability of N/S atoms causes the d-band center of Pt atom orbital to shift upward to the Fermi level, which strengthens the binding of metal Lewis acid Pt sites with *OOH intermediates, and improves the 4-electron transfer mechanism. This research reveals the direct role of Lewis acid sites in ORR of fuel cell cathode, and provides a feasible way to guide the design of electrocatalysts with Lewis acid/base double centers. [ABSTRACT FROM AUTHOR]