Paired Electrocatalytic Valorization of Phenolic Pollutants Into p ‐Benzoquinone and p ‐Aminophenol

ABSTRACT Electrocatalytic valorization of organic pollutants into value‐added chemicals offers a sustainable strategy for wastewater treatment and resource recovery; however, achieving high Faradaic and energy efficiency remains challenging. Herein, we report a bipolar electrocatalytic strategy integrating anodic phenol oxidation (PhOR) with cathodic p ‐nitrophenol reduction (NPRR) for simultaneously producing p ‐benzoquinone ( p ‐BQ) and p ‐aminophenol ( p ‐AP). The tailored Ni(OH) 2 /CeF 3 anode and Cu(OH) 2 /Ni(OH) 2 cathode achieve p ‐BQ and p ‐AP yields of 84.5% and 96.3%, respectively. Specifically, incorporation of CeF 3 induces the interfacial charge redistribution of Ni site and then facilitates Ni(OH) 2 reconstruction into active NiOOH. Operando x‐ray absorption fine structure (XAFS) reveals that the potential‐driven dynamic Ni–O evolution optimizes the binding strength of reaction intermediates to boost PhOR performance. The cathode with Cu and Ni sites favors the surface‐adsorbed H* formation for efficient NPRR via an indirect electron transfer pathway. The PhOR||NPRR system achieves an exceptional Faradaic efficiency of 129.3% with a low energy consumption of 1.06 kWh kg − 1 . The practical applicability was validated through the successful production of high‐purity p ‐BQ and p ‐AP from phenolic pollutants with respective recovery efficiency of 83.1% and 87.9%. This work provides a viable approach for facilitating a sustainable recovery of phenolic wastewaters.