Electrochemical Synthesis of Urea: Co‐Reduction of Nitrite and Carbon Dioxide on Binuclear Cobalt Phthalocyanine

Abstract Exploration of molecular catalysts with the atomic‐level tunability of molecular structures offers promising avenues for developing high‐performance catalysts for the electrochemical co‐reduction reaction of carbon dioxide (CO 2 ) and nitrite (NO 2 − ) into value‐added urea. In this work, a binuclear cobalt phthalocyanine (biCoPc) catalyst is prepared through chemical synthesis and applied as a C─N coupling catalyst toward urea. Achieving a remarkable Faradaic efficiency of 47.4% for urea production at –0.5 V versus reversible hydrogen electrode (RHE), this biCoPc outperforms many known molecular catalysts in this specific application. Its unique planar macromolecular structure and the increased valence state of cobalt promote the adsorption of nitrogenous and carbonaceous species, a critical factor in facilitating the multi‐electron C─N coupling. Combining highly sensitive in situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) with density functional theory (DFT) calculations, the linear adsorbed CO (CO L ) and bridge adsorbed CO (CO B ) is captured on biCoPc catalyst during the co‐reduction reaction. CO B , a pivotal intermediate in the co‐reduction from CO 2 and nitrite to urea, is evidenced to be labile and may be attacked by nitrite, promoting urea production. This work demonstrates the importance of designing molecular catalysts for efficient co‐reduction of CO 2 and nitrite to urea.