Synergistic enhancement of electrochemical alcohol oxidation by combining NiV-layered double hydroxide with an aminoxyl radical.

Li, Suiqin; Wang, Shibin; Wang, Yuhang; He, Jiahui; Li, Kai; Gerken, James B; Stahl, Shannon S; Zhong, Xing et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Electrochemical alcohol oxidation (EAO) represents an effective method for the production of high-value carbonyl products. However, its industrial viability is hindered by suboptimal efficiency stemming from low reaction rates. Here, we present a synergistic electrocatalysis approach that integrates an active electrode and aminoxyl radical to enhance the performance of EAO. The optimal aminoxyl radical (4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl) and Ni<sub>0.67</sub>V<sub>0.33</sub>-layered double hydroxide (LDH) are screen as cooperative electrocatalysts by integrating theoretical predictions and experiments. The Ni<sub>0.67</sub>V<sub>0.33</sub>-LDH facilitates the adsorption and activation of N-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)acetamide (ACTH) via interactions with ketonic oxygen, thereby improving selectivity and yield at high current densities. The electrolysis process is scaled up to produce 200 g of the steroid carbonyl product 8b (19-Aldoandrostenedione), achieving a yield of 91% and a productivity of 243 g h<sup>-1</sup>. These results represent a promising method for accelerating electron transfer to enhance alcohol oxidation, highlighting its potential for practical electrosynthesis applications.