Nonredox trivalent nickel catalyzing nucleophilic electrooxidation of organics

作者：Yuandong Yan, Ruyi Wang, Qian Zheng, Jiaying Zhong, Weichang Hao, Shicheng Yan, Zhigang Zou · 发表于：Nature Communications · 年份：2023 · DOI：10.1038/s41467-023-43649-6 · 被引用次数：154 · 研究领域：Electrocatalysts for Energy Conversion、Advanced battery technologies research、Electrochemical Analysis and Applications

Abstract A thorough comprehension of the mechanism behind organic electrooxidation is crucial for the development of efficient energy conversion technology. Here, we find that trivalent nickel is capable of oxidizing organics through a nucleophilic attack and electron transfer via a nonredox process. This nonredox trivalent nickel exhibits exceptional kinetic efficiency in oxidizing organics that possess the highest occupied molecular orbital energy levels ranging from −7.4 to −6 eV (vs. Vacuum level) and the dual local softness values of nucleophilic atoms in nucleophilic functional groups, such as hydroxyls (methanol, ethanol, benzyl alcohol), carbonyls (formamide, urea, formaldehyde, glucose, and N-acetyl glucosamine), and aminos (benzylamine), ranging from −0.65 to −0.15. The rapid electrooxidation kinetics can be attributed to the isoenergetic channels created by the nucleophilic attack and the nonredox electron transfer via the unoccupied e g orbitals of trivalent nickel (t 2g 6 e g 1 ). Our findings are valuable in identifying kinetically fast organic electrooxidation on nonredox catalysts for efficient energy conversions.