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Unveiling the Electrooxidation of Urea: Intramolecular Coupling of the N−N Bond
Author(s) -
Chen Wei,
Xu Leitao,
Zhu Xiaorong,
Huang YuCheng,
Zhou Wang,
Wang Dongdong,
Zhou Yangyang,
Du Shiqian,
Li Qiling,
Xie Chao,
Tao Li,
Dong ChungLi,
Liu Jilei,
Wang Yanyong,
Chen Ru,
Su Hui,
Chen Chen,
Zou Yuqin,
Li Yafei,
Liu Qinghua,
Wang Shuangyin
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202015773
Subject(s) - chemistry , nucleophile , intramolecular force , electron transfer , photochemistry , amine gas treating , inorganic chemistry , catalysis , organic chemistry
The nitrogenous nucleophile electrooxidation reaction (NOR) plays a vital role in the degradation and transformation of available nitrogen. Focusing on the NOR mediated by the β‐Ni(OH) 2 electrode, we decipher the transformation mechanism of the nitrogenous nucleophile. For the two‐step NOR, proton‐coupled electron transfer (PCET) is the bridge between electrocatalytic dehydrogenation from β‐Ni(OH) 2 to β‐Ni(OH)O, and the spontaneous nucleophile dehydrogenative oxidation reaction. This theory can give a good explanation for hydrazine and primary amine oxidation reactions, but is insufficient for the urea oxidation reaction (UOR). Through operando tracing of bond rupture and formation processes during the UOR, as well as theoretical calculations, we propose a possible UOR mechanism whereby intramolecular coupling of the N−N bond, accompanied by PCET, hydration and rearrangement processes, results in high performance and ca. 100 % N 2 selectivity. These discoveries clarify the evolution of nitrogenous molecules during the NOR, and they elucidate fundamental aspects of electrocatalysis involving nitrogen‐containing species.