Direct Growth of Uniform Bimetallic Core‐Shell or Intermetallic Nanoparticles on Carbon via a Surface‐Confinement Strategy for Electrochemical Hydrogen Evolution Reaction

Abstract Due to the surface inhomogeneity of the solid supports, direct growth of uniform bimetallic nanoparticles (NPs) with controllable structure and size thereon is particularly challenging. Herein, a surface‐confinement strategy is reported to directly prepare ultrafine bimetallic PtM NPs (MFe, Cu, and Co) with structure of core‐shell or intermetallic compounds on an N functionalized carbon support (NC). It is found that the N species of NC support can atomically disperse metal cations of precursors, which largely renders uniform nucleation and growth of bimetallic NPs and fine structure modulation of them. In another regard, metal transfer is confined to a narrow region on NC via N‐mediation, hence greatly favoring localized particle growth and formation of ultrafine bimetallic NPs. Remarkably, the ultrafine 3.1 ± 0.7 nm intermetallic Pt₃Fe NPs on NC displayed excellent catalytic activity and durability toward electrochemical hydrogen evolution reaction.