In Situ Reconstructed Cu–Bi Interfacial Sites Enable Cooperative CO 2 and Nitrate Activation for Efficient Urea Electrosynthesis

ABSTRACT Electrochemical urea synthesis via co‐reduction of CO 2 and nitrate (NO 3 − ) offers a sustainable route for C─N bond formation but remains challenged by poor selectivity and competing side reactions. Here, we report a dual‐metal interfacial engineering strategy that enables C─N coupling by favoring a key NO─M 1 ─NO─CO─M 2 configuration. Using CuBi 2 O 4 as a model precursor, in situ electroreduction induces reconstruction into an electron‐enriched and low‐coordinated Cu─Bi interfacial structure. Operando Raman and surface‐enhanced infrared absorption spectroscopy, together with density functional theory calculations, reveal that these reconstructed dual‐metal interfaces enable cooperative adsorption of NO 3 − and CO 2 , favoring a spatially confined NO─Cu─NO─CO─Bi configuration. This proposed configuration lowers the overall activation barrier and converts the traditionally endergonic C─N coupling into an exergonic N─C─N coupling process, thereby redirecting the reaction pathway toward urea formation while suppressing nitrite and CO byproducts. As a result, the catalyst achieves a urea Faradaic efficiency of 32.7% at −0.4 V vs. RHE with a high yield rate of 2955.3 mg h −1 g −1 at −0.6 V vs. RHE under large current densities. This work provides insights into a generalizable interfacial‐site design for modulating reaction pathways in electrosynthetic C─N coupling systems.