Abstract
Electrochemical alcohol oxidation (EAO) is a compelling method for producing high-value carbonyl products. However, its industrial viability is hindered by suboptimal efficiency stemming from low reaction rates. Herein, we present a novel synergistic electrocatalysis approach that integrates an active electrode and aminoxyl radical to enhance the performance of EAO. The optimal aminoxyl radical (4-acetamido-TEMPO, ACT) and Ni0.67V0.33-layered double hydroxide (LDH) were screened as cooperative electrocatalysts by integrating theoretical predictions and experiments. The Ni0.67V0.33-LDH facilitates ACTH adsorption and activation via ketonic oxygen interactions, thereby enhancing selectivity and yield at high current densities. The electrolysis was scaled to demonstrate a 200 g synthesis of the steroid carbonyl product 8b resulted in a 91% yield and a productivity of 243 g/h. These results represent a promising method for accelerating electron transfer to enhance alcohol oxidation, highlighting its potential for practical electrosynthesis applications.