Directed Urea‐to‐Nitrite Electrooxidation via Tuning Intermediate Adsorption on Co, Ge Co‐Doped Ni Sites

Abstract The electrochemical urea oxidation reaction (UOR) is an alternative to electrooxidation of water for energy–saving hydrogen (H 2 ) production. To maximize this purpose, design of catalysts for selective urea‐to‐nitrite (NO 2 – ) electrooxidation with increased electron transfer and high current is practically important. Herein, a cobalt, germanium (Co, Ge) co‐doped nickel (Ni) oxyhydroxide catalyst is reported first time that directs urea‐to‐NO 2 – conversion with a significant Faradaic efficiency of 84.9% at 1.4 V versus reversible hydrogen electrode and significantly boosts UOR activity to 448.0 mA cm −2 . Importantly, this performance is greater than for most reported Ni‐based catalysts. Based on judiciously combined synchrotron‐based measurement, in situ spectroscopy and density functional theoretical computation, significantly boosted urea‐to‐NO 2 – production results from Co, Ge co‐doping is demonstrated that optimizes electronic structure of Ni sites in which urea adsorption is altered as NO‐terminal configuration to facilitate CN cleavage for *NH formation, and thereby expedites pathway for urea to NO 2 – conversion. Findings highlight the importance of tuning intermediate adsorption behavior for design of high‐performance UOR electrocatalysts, and will be of practical benefit to a range of researchers and manufacturers in replacing conventional water electrooxidation with UOR for energy‐saving H 2 production.