Asymmetric Orbital Hybridization Triggered Electron Redistribution at the Cu‐In2O3 Interface Enables Energy‐Saving Coupled Urea Electrosynthesis

Abstract Urea electrosynthesis from aqueous co–electrolysis of CO 2 and NO 3 − offers a promising alternative to traditional Bosch–Meiser urea production, which however restricted by low urea synthesis efficiency and high energy input associated with cathodic and anodic overpotentials. Here, a Cu‐In 2 O 3 /C catalyst composed of Cu and In dual‐active‐sites with tailored electronic structure to boost ambient urea synthesis is reported. Detailed experimental and theoretical analyses reveal that the asymmetric Cu(3d)‐O(2p)‐In(5p) orbital hybridization effect allows electrons migrating from In 2 O 3 to Cu and triggers electron redistribution at the Cu‐In 2 O 3 interface, which significantly reduces the CO* and NH 2 * intermediate formation energy and C‐N coupling energy barrier and thereby enables selective urea synthesis on the Cu‐In 2 O 3 /C catalyst. Moreover, an energy‐saving coupled urea synthesis system by integrating with electro‐reforming of polyethylene terephthalate (PET) waste plastic to glycolic acid is demonstrated, which realize the simultaneous electrocatalytic upgrading of three kinds of wastes/pollutants into value‐added chemicals.