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 front cover artwork is provided by the group of Prof. Shuji Nakanishi. The image shows that Fe(lV)=O is generated from H2O2 on a hematite electrode and serve as the active center for selective styrene epoxidation. Read the full text of the Communication at 10.1002/cphc.201801207.

The Front Cover shows that Fe(lV)=O is generated by the oxidative decomposition of H2O2 on a hematite electrode and serves as the active center for selective styrene epoxidation. The generation of Fe(IV)=O from H2O2 exhibited lower overpotential than that from H2O. This work is the first demonstration that Fe(IV)=O on a hematite electrode is applied to hydrocarbon oxidation reactions. More information can be found in the Communication by K. Kamiya et al. on page 648 in Issue 5, 2019 (DOI: 10.1002/cphc.201801207).