Pt Single Atoms Supported on N‐Doped Mesoporous Hollow Carbon Spheres with Enhanced Electrocatalytic H2‐Evolution Activity

Abstract The electronic metal–support interaction (EMSI) plays a crucial role in catalysis as it can induce electron transfer between metal and support, modulate the electronic state of the supported metal, and optimize the reduction of intermediate species. In this work, the tailoring of electronic structure of Pt single atoms supported on N‐doped mesoporous hollow carbon spheres (Pt 1 /NMHCS) via strong EMSI engineering is reported. The Pt 1 /NMHCS composite is much more active and stable than the nanoparticle (Pt NP ) counterpart and commercial 20 wt% Pt/C for catalyzing the electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 40 mV at a current density of 10 mA cm −2 , a high mass activity of 2.07 A mg −1 Pt at 50 mV overpotential, a large turnover frequency of 20.18 s −1 at 300 mV overpotential, and outstanding durability in acidic electrolyte. Detailed spectroscopic characterizations and theoretical simulations reveal that the strong EMSI effect in a unique N 1 −Pt 1 −C 2 coordination structure significantly tailors the electronic structure of Pt 5d states, resulting in promoted reduction of adsorbed proton, facilitated H−H coupling, and thus Pt‐like HER activity. This work provides a constructive route for precisely designing single‐Pt‐atom‐based robust electrocatalysts with high HER activity and durability.