Pulsed Oxidative–Reductive Electrolysis Over Dual Cu and Co Single‐Atom Sites for Urea Electrosynthesis

ABSTRACT Electrochemical C─N coupling of CO 2 with nitrogen species offers a sustainable route to urea and related chemicals but is constrained under steady‐state electrolysis by mismatched reaction kinetics. Here, pulsed oxidative–reductive electrolysis temporally coordinates CO 2 reduction and NH 3 oxidation, regulating the generation and coexistence of carbon‐ and nitrogen‐derived intermediates. Co/CuNC, containing atomically dispersed Co and Cu sites within a nitrogen‐doped carbon (NC), achieves a total C─N faradaic efficiency of 42 ± 4%, dominated by urea (20 ± 2%) and ethyl urea (16 ± 2%), with respective yield rates (YR) of 295 ± 25 and 50 ± 5 mmol h −1 g cat −1 . In situ synchrotron x‐ray absorption spectroscopy (XAS) reveals potential‐dependent changes in Cu and Co oxidation states and coordination environments, while in situ infrared spectroscopy identifies pulse‐regulated *CO and *NH x intermediates and suggests concurrent electrochemical and Wöhler‐type pathways. Density functional theory calculations reveal complementary site functions: Cu favors *NH 2 formation, whereas Co more strongly stabilizes *NH x and *CO intermediates, with *CO also accessible at Cu sites. These findings establish temporal coordination of reactant activation, intermediate populations, and active‐site states as a mode‐enabled strategy for accessing higher‐order C─N products.