Redirecting Charge Distribution and Spatial Proximity of Co−O−Cu Motif with 4f−2p−3d Orbital Hybridization for High‐Efficiency Urea Electrosynthesis

ABSTRACT Electrocatalytic CO 2 /NO 3 − co‐reduction to access urea typically relies on the tailored two‐site catalysts, with the complexity of C/N‐intermediate generation and C─N coupling that limit urea synthesis efficiency. Here, a 4f (Ce)−2p (O)−3d (Co) orbital hybridization maneuver is demonstrated to customize a spin‐polarized Co‐site and a relatively electron‐rich Cu‐site for generating *NH 2 and *CO species to undergo C─N coupling to access urea, respectively, delivering a production rate of 2612.4 µg mg −1 h −1 at −0.27 V RHE , with an ultrahigh Faradaic efficiency (85.7%). Mechanistic investigations elucidate that the 4f−2p−3d motif enables the high‐spin Co 2+ (t 2g 5 e g 2 ) translation toward…

• NN
  National Natural Science Foundation of China

  Awards: 22478087, 22368014