Efficient Electrosynthesis of Urea over Single‐Atom Alloy with Electronic Metal Support Interaction.

Urea electrosynthesis from carbon dioxide (CO2) and nitrate (NO3−) is an alternative approach to traditional energy‐intensive urea synthesis technology. Herein, we report a CuAu single‐atom alloy (SAA) with electronic metal support interaction (EMSI), achieving a high urea yield rate of 813.6 μg h−1 mgcat−1 at −0.94 V versus reversible hydrogen electrode (vs. RHE) and a Faradaic efficiency (FE) of 45.2 % at −0.74 V vs. RHE. In situ experiments and theoretical calculations demonstrated that single‐atom Cu sites modulate the adsorption behavior of intermediate species. Bimetallic sites synergistically accelerate C−N bond formation through spontaneous coupling of *CO and *NO to form *ONCO as key intermediates. More importantly, electronic metal support interaction between CuAu SAA and CeO2 carrier further modulates electron structure and interfacial microenvironment, endowing electrocatalysts with superior activity and durability. This work constructs SAA electrocatalysts with EMSI effect to tailor C−N coupling at the atomic level, which can provide guidance for the development of C−N coupling systems. [ABSTRACT FROM AUTHOR]