Electronic Regulation of Nickel Single Atoms by Confined Nickel Nanoparticles for Energy‐Efficient CO2 Electroreduction

Abstract Modulating the electronic structure of atomically dispersed active sites is promising to boost catalytic activity but is challenging to achieve. Here we show a cooperative Ni single‐atom‐on‐nanoparticle catalyst (NiSA/NP) prepared via direct solid‐state pyrolysis, where Ni nanoparticles donate electrons to Ni(i)−N−C sites via a network of carbon nanotubes, achieving a high CO current density of 346 mA cm −2 at −0.5 V vs RHE in an alkaline flow cell. When coupled with a NiFe‐based anode in a zero‐gap membrane electrolyzer, the catalyst delivers an industrially relevant CO current density of 310 mA cm −2 at a low cell voltage of −2.3 V, corresponding to an overall energy efficiency of 57 %. The superior CO 2 electroreduction performance is attributed to the enhanced adsorption of key intermediate COOH* on the electron‐rich Ni single atoms, as well as a high density of active sites.