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

Abstract 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(sp 3)-H bonds at room temperature. Here, we introduce an electrocatalyst:mediator...

Full description

Saved in:
Bibliographic Details
Main Authors: Ziyu Mi, Yuke Li, Chao Wu, Mingsheng Zhang, Xun Cao, Shibo Xi, Jia Zhang, Wan Ru Leow
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-58733-2
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Abstract 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(sp 3)-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.
ISSN:2041-1723