| Summary: | Abstract Catalytically active metals atomically dispersed on supports presents the ultimate atom utilization efficiency and cost‐effective pathway for electrocatalyst design. Optimizing the coordination nature of metal atoms represents the advanced strategy for enhancing the catalytic activity and the selectivity of single‐atom catalysts (SACs). Here, we designed a transition‐metal based sulfide‐Ni3S2 with abundant exposed Ni vacancies created by the interaction between chloride ions and the functional groups on the surface of Ni3S2 for the anchoring of atomically dispersed Pt (PtSA‐Ni3S2). The theoretical calculation reveals that unique Pt‐Ni3S2 support interaction increases the d orbital electron occupation at the Fermi level and leads to a shift‐down of the d ‐band center, which energetically enhances H2O adsorption and provides the optimum H binding sites. Introducing Pt into Ni position in Ni3S2 system can efficiently enhance electronic field distribution and construct a metallic‐state feature on the Pt sites by the orbital hybridization between S‐3p and Pt‐5d for improved reaction kinetics. Finally, the fabricated PtSA‐Ni3S2 SAC is supported by Ag nanowires network to construct a seamless conductive three‐dimensional (3D) nanostructure (PtSA‐Ni3S2@Ag NWs), and the developed catalyst shows an extremely great mass activity of 7.6 A mg−1 with 27‐time higher than the commercial Pt/C HER catalyst.
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