Electrocatalytic conversion presents a promising alternative to conventional industrial catalysis.While aqueous-phase electrocatalysis has achieved notable advancements,oil-water immiscible systems remain challenging ...Electrocatalytic conversion presents a promising alternative to conventional industrial catalysis.While aqueous-phase electrocatalysis has achieved notable advancements,oil-water immiscible systems remain challenging due to restricted reaction flux at multiphase interfaces.To address the limitation,we engineered a biphasic reaction system featuring a tailored oil-water catalytic interface in cyclohexene oxidation reaction(COR).The system employed a catalyst-loaded porous electrode as an active phase domain,enabling spatial separation of cyclohexene(organic phase)and electrolyte(aqueous phase).The tailored oil-water interface enhanced the interfacial mass transfer of substrate-catalysts and facilitated the spontaneous migration of 2-cyclohexen-1-ol into the aqueous phase,thereby streamlining product separation.Notably,polyaniline(PANI)modification on Co_(3)O_(4)enhanced surface lipophilicity,promoting cyclohexene adsorption and accelerating the COR catalytic kinetics(Co^(3+)-O+cyclohexene-H+e-→Co^(2+)-OH+2-cyclohexen-1-ol).The synergistic effects of optimized interfacial engineering and catalyst functionalization achieved exceptional performance:a current density of 45 mA·cm^(-2)at 1.6 V vs.reversible hydrogen electrode(V_(RHE)),coupled with 96.2%selectivity and 82.9%Faradaic efficiency.This work establishes an innovative paradigm for electrocatalytic conversions in oil-water immiscible systems through rational interface design and catalyst surface modulation.展开更多
基金supported by the National Natural Science Foundation of China(No.22278380)China Postdoctoral Science Foundation(Nos.2024M762994 and GZC20232392)supported by the project of Yunnan Key Laboratory of Electromagnetic Materials and Devices,Yunnan University(No.ZZ2024009).
文摘Electrocatalytic conversion presents a promising alternative to conventional industrial catalysis.While aqueous-phase electrocatalysis has achieved notable advancements,oil-water immiscible systems remain challenging due to restricted reaction flux at multiphase interfaces.To address the limitation,we engineered a biphasic reaction system featuring a tailored oil-water catalytic interface in cyclohexene oxidation reaction(COR).The system employed a catalyst-loaded porous electrode as an active phase domain,enabling spatial separation of cyclohexene(organic phase)and electrolyte(aqueous phase).The tailored oil-water interface enhanced the interfacial mass transfer of substrate-catalysts and facilitated the spontaneous migration of 2-cyclohexen-1-ol into the aqueous phase,thereby streamlining product separation.Notably,polyaniline(PANI)modification on Co_(3)O_(4)enhanced surface lipophilicity,promoting cyclohexene adsorption and accelerating the COR catalytic kinetics(Co^(3+)-O+cyclohexene-H+e-→Co^(2+)-OH+2-cyclohexen-1-ol).The synergistic effects of optimized interfacial engineering and catalyst functionalization achieved exceptional performance:a current density of 45 mA·cm^(-2)at 1.6 V vs.reversible hydrogen electrode(V_(RHE)),coupled with 96.2%selectivity and 82.9%Faradaic efficiency.This work establishes an innovative paradigm for electrocatalytic conversions in oil-water immiscible systems through rational interface design and catalyst surface modulation.
