Breaking the Scaling Relationship in C−N Coupling via the Doping Effects for Efficient Urea Electrosynthesis
Liyang Lv, Hao Tan, Hao Tan, Yuan Kong, Bing Tang, Qianqian Ji, Yuying Liu, Chao Wang, Zechao Zhuang, Huijuan Wang, Min Ge, Minghui Fan, Dingsheng Wang, Wensheng Yan, Wensheng Yan
Abstract
Abstract 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 0.39 Ru 0.61 O 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 SrRuO 3 . The oxygen vacancies weaken the adsorption of *CO and *NH 2 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 SrRuO 3 .