CoOx clusters-decorated IrO2 electrocatalyst activates NO3- mediator for benzylic C-H activation

作者：Ziyu Mi, Yuke Li, Chao Wu, Mingsheng Zhang, Xun Cao, Shibo Xi, Jia Zhang, Wan Ru Leow · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-58733-2 · 被引用次数：12 · 研究领域：Electrocatalysts for Energy Conversion、CO2 Reduction Techniques and Catalysts、Catalytic Processes in Materials Science

Electrochemical conversion of petrochemical-derived hydrocarbons to high-value oxygenates can utilize renewable energy and reduce carbon emissions. However, this involves the challenging activation of inert C(sp3)-H bonds at room temperature. Here, we introduce an electrocatalyst:mediator assembly in which CoOx clusters-decorated IrO2 electrocatalyst activates NO3- mediator to a highly reactive radical capable of abstracting a hydrogen atom from benzylic C-H. The interface between CoOx and IrO2 promotes NO3- activation by facilitating the desorption of NO3● radical for subsequent reaction. Our strategy is demonstrated through the selective oxidation of toluene to benzaldehyde with high Faradaic efficiency of 86( ±1)% at 25 mA/cm2, a factor of >3 times higher than the bare electrocatalyst. The electrocatalyst:mediator assembly is operated stably for 100 h, with minimal decline in performance. When translated into a flow system, a Faradaic efficiency of 60( ±4)% at 200 mA/cm2 was achieved. An electrocatalyst mediator system in which CoOx-cluster-decorated IrO2 activates the NO3- mediator into a reactive radical that abstracts a hydrogen atom from benzylic C-H is presented. This approach enables the electrochemical conversion of toluene to benzaldehyde with high Faradaic efficiency.