Hydrogen Peroxide Assisted Electrooxidation of Benzene to Phenol over Bifunctional Ni–(O–C 2 ) 4 Sites

Direct electrocatalytic oxidation of benzene has been regarded as a promising approach for achieving high‐value phenol product, but remaining a huge challenge. Here an oxygen‐coordinated nickel single‐atom catalyst (Ni–O–C) is reported with bifunctional electrocatalytic activities toward the two‐electron oxygen reduction reaction (2e − ORR) to H 2 O 2 and H 2 O 2 ‐assisted benzene oxidation to phenol. The Ni–(O–C 2 ) 4 sites in Ni–O–C ar proven to be the catalytic active centers for bifunctional 2e − ORR and H 2 O 2 ‐assisted benzene oxidation processes. As a result, Ni–O–C can afford a benzene conversion as high as 96.4 ± 3.6% with a phenol selectivity of 100% and a Faradaic efficiency (FE) of 80.2 ± 3.2% with the help of H 2 O 2 in 0.1  m KOH electrolyte at 1.5 V (vs RHE). A proof of concept experiment with Ni–O–C concurrently as cathode and anode in a single electrochemical cell demonstrates a benzene conversion of 33.4 ± 2.2% with a phenol selectivity of 100% and a FE of 44.8 ± 3.0% at 10 mA cm −2 .