Nitrogen‐doped carbon‐armored copper–nickel alloy electrocatalytic C–N coupling for urea synthesis

Abstract Excessive CO 2 and NO x emissions surpass Earth's capacity, driving environmental degradation. Electrocatalytic CO 2 and NO 3 − co‐reduction offers a sustainable route to value‐added chemicals like urea, addressing emissions and advancing green synthesis. However, copper‐based catalysts, while efficient in CO 2 ‐to‐hydrocarbon and nitrate‐to‐ammonia conversion, show limited activity for C–N coupling reactions. To address this, we developed a nitrogen‐doped carbon nanotube‐coated CuNi alloy catalyst (CuNi@C) leveraging bimetallic synergy to achieve a Faradaic efficiency (FE) of 32.8% for urea synthesis from CO 2 and NO 3 − at −0.6 V (vs. RHE), with stable performance over 26 h. In situ ATR‐SEIRAS and DFT calculations revealed that bridge adsorption of *CO induced a Stark effect, promoting C–N bond formation, while a unique hydrogen‐bonding network suppressed HER. *NHO and *CO were identified as key intermediates in the C–N coupling process.