Boosting electrocatalytic alcohol oxidation: Efficient d–π interaction with modified <scp>TEMPO</scp> and bioinspired structure

Abstract Aminoxyl radicals electrocatalysis presents a sustainable method for oxidizing alcohols into high‐value products. Nonetheless, the requirement for high doses of aminoxyl radicals diminishes product purity and economic viability. This study synthesized methylimidazole‐functionalized 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl derivative (MIAcNH‐TEMPO) with a strongly electron‐withdrawing imidazole group and combined it with bioinspired nickel‐supported carbonaceous octopus tentacles for effective electrooxidation of alcohols, achieving high current density of 200 mA cm −2 , selectivity of 99%, and turnover frequency of 26,490 h −1 . In situ experiments and theoretical calculations indicated that the synergistic effect of Ni‐3d xz orbitals on the tentacle surface interacting with the π orbitals of MIAcNH‐TEMPO creates a strong d–π interaction, which effectively facilitating the creation of a locally intermediate‐enriched microenvironment, decreased the required quantity of aminoxyl radicals. Moreover, the high aqueous solubility of MIAcNH‐TEMPO reduces the difficulty of separation process. Scale‐up experiments conducted in a continuous flow electrolyzer showcased the potential of this strategy for practical applications.