Electrochemical Formation of Fe(IV)=O Derived from H2O2 on a Hematite Electrode as an Active Catalytic Site for Selective Hydrocarbon Oxidation Reactions

The high‐valence iron species (Fe(IV)=O) in the cytochrome P450 enzyme superfamily is generated via the activation of O2, and serves as the active center of selective hydrocarbon oxidation reactions. Furthermore, P450 can employ an alternate route to produce Fe(IV)=O, even from H2O2 without O2 activation. Meanwhile, Fe(IV)=O has recently been revealed to be the reactive intermediate during H2O oxidation to O2 on hematite electrodes. Herein, we demonstrated the generation of Fe(IV)=O on hematite electrodes during the electrochemical oxidative decomposition of H2O2 using in situ UV‐visible absorption spectra. The generation of Fe(IV)=O on hematite electrodes from H2O2 exhibited 100 mV lower overpotential than that from H2O. This is because H2O2 serves not only as the oxygen source of Fe(IV)=O, but also as the additional oxidant. Finally, we confirmed that the Fe(IV)=O generated on hematite electrodes can serve as the catalytic site for styrene epoxidation reactions. The generation of Fe(IV)=O on hematite electrodes during the electrochemical oxidative decomposition of H2O2 is demonstrated by in situ UV/Vis absorption spectroscopy. This process is found to exhibit a 100 mV lower overpotential than that involving H2O. The generated Fe(IV)=O selectively catalyzes styrene epoxidation reactions.