Selective Paired Electro‐Conversion of <i>p</i> ‐Nitrophenol and Benzyl Alcohol Boosted by Asymmetric Co–C–W Bridging

ABSTRACT Paired electrosynthesis technology provides an effective pathway for green upgrading of low‐cost organics to high‐value‐added chemicals. However, engineering interfacial catalysts with unique atomic bridges to achieve synergistic effects and understanding their bifunctional mechanisms remain challenging. Here, a unique atomic interfacial Co‐C‐W electron bridge catalyst (Co SAs/W x C) with a nanoflower‐spherical structure is designed as a bifunctional catalyst for p ‐nitrophenol electroreduction reaction ( p ‐NP ERR) and benzyl alcohol (Ph‐CH 2 OH) oxidation reaction (BAOR). In p ‐NP ERR, W x C facilitates water dissociation to generate *H and enhances *H coverage on Co‐centers via reverse hydrogen spillover, promoting the key hydrogenation step (─NO 2 * to ─NO*). The Co–C–W bridge modulates Co e g orbitals, optimizing the adsorption of intermediates (Ph‐CH 2 O*/Ph‐CHO*) and thereby lowering reaction energy barriers for BAOR. Remarkably, a low cell‐voltage of 1.324 V is required to achieve 50 mA cm −2 , with a Faradaic efficiency of ∼99% and high production rates of high‐value p ‐aminophenol and Ph‐COOH (0.74 and 1.12 mmol h −1 cm −2 , respectively) as potential drug precursors. Importantly, the well‐built Co–C–W bridge regulates the electronic structures of the catalyst and moderate adsorption and transfer behaviors of reaction intermediates, boosting both p ‐NP ERR and BAOR. This work provides new insights for developing highly‐efficient integrated systems in diverse energy and organic chemical conversion applications.