A Green and Efficient Electrocatalytic Route for the Highly‐Selective Oxidation of C–H Bonds in Aromatics over 1D Co3O4‐Based Nanoarrays

Electrocatalytic oxidation of C‐H bonds in hydrocarbons represents an efficient and sustainable strategy for the synthesis of value‐added chemicals. Herein, a highly selective and continuous‐flow electrochemical oxidation process of toluene to various oxygenated products (benzyl alcohol, benzaldehyde, and benzyl acetate) is developed with the electrocatalytic membrane electrodes (ECMEs). The selectivity of target products can be manipulated via surface and interface engineering of Co3O4‐based electrocatalysts. We achieved a high benzaldehyde selectivity of 90% at a toluene conversion of 47.6% using 1D‐Co3O4 nanoneedles (NNs) loaded on a microfiltration (MF) titanium (Ti) membrane, i.e, Co3O4 NNs/Ti. In contrast, the main product shifted to benzyl alcohol with a selectivity of 90.1% at conversion of 32.1% after modifying MnO2 nanosheets (NSs) on Co3O4 NNs/Ti (Co3O4@MnO2/Ti) catalyst. Moreover, benzyl acetate product can be obtained with selectivity of 92% at a conversion of 58.5% at high current density (> 1.5mA cm‐2), demonstrating that the pathway of toluene oxidation is readily maneuvered. DFT results reveal that modifying MnO2 on Co3O4 optimizes the electron structure of Co3O4@MnO2/Ti and modulates the adsorption behavior of intermediate species. This work demonstrates a sustainable, and continuous‐flow process for precise control over production selectivity of value‐added oxygenated derivatives in electrochemical oxidation of aromatic hydrocarbons.