Breaking the Scaling Relationship in C-N Coupling via the Doping Effects for Efficient Urea Electrosynthesis

Electrochemical C-N coupling reaction based on carbon dioxide and nitrate have been emerged as a new "green synthetic strategy" for the synthesis of urea, but the catalytic efficiency is seriously restricted by the inherent scaling relations of adsorption energies of the active sites, the improvement of catalytic activity is frequently accompanied by the decrease in selectivity. Herein, a doping engineering strategy was proposed to break the scaling relationship of intermediate binding and minimize the kinetic barrier of C-N coupling. A thus designed SrCo_0.39Ru_0.61O_3-δ catalyst achieves a urea yield rate of 1522 μg h^-1 mg_cat. ^-1 and faradic efficiency of 34.1 % at -0.7 V versus reversible hydrogen electrode. A series of characterizations revealed that Co doping not only induces lattice distortion but also creates rich oxygen vacancies (O_V) in the SrRuO₃. The oxygen vacancies weaken the adsorption of *CO and *NH₂ intermediates on the Co and Ru sites respectively, and the strain effects over the Co-Ru dual sites promoting the occurrence of C-N coupling of the two monomers instead of selective hydrogenating to form by-products. This work presents an insight into molecular coupling reactions towards urea synthesis via the doping engineering on SrRuO₃.