Selective Reduction of Phenol to Cyclohexanone with Electron Mediators via Off-Field Electrocatalysis

作者：Ben Chang, Qing‐Nan Wang, Chuchu Cheng, Shengqi Chen, Xiaolei Qu, Shihua Ye, Can Li · 发表于：ACS electrochemistry. · 年份：2025 · DOI：10.1021/acselectrochem.5c00410 · 被引用次数：2 · 研究领域：Catalysis for Biomass Conversion、Electrocatalysts for Energy Conversion、CO2 Reduction Techniques and Catalysts

High Resolution Image Download MS PowerPoint Slide Electrocatalytic hydrogenation offers a promising approach for biomass upgrading under mild conditions, yet its performance is often compromised by mass and electron transfer limitations, particularly at high current densities. Here, we introduce an off-field electrocatalytic (OFEC) system that uses V 2+ /V 3+ as electron mediators to reduce phenol, a representative biomass derivative, into cyclohexanone over Pt/TiO 2 catalysts, effectively decoupling the reaction from the electrode surface. This fluidized strategy delivers a 10-fold increase in turnover frequency (TOF) compared to that of the conventional electrocatalysis (3090 vs 290 h –1 ) while maintaining 94% cyclohexanone selectivity, underscoring the alleviation of transport bottlenecks. Crucially, Pt/TiO 2 effectively suppresses the secondary adsorption of cyclohexanone, thereby enhancing targeted selectivity. Furthermore, mechanistic studies reveal that electron transfer between mediators and phenol proceeds via a metal-mediated proton-coupled electron transfer (PCET) mechanism, enabling direct electron exchange at active sites while avoiding the poor conductivity of TiO 2 . Together, these findings establish a reaction paradigm for phenol hydrogenation at high current densities and provide a versatile platform for sustainable electrocatalytic biomass valorization.