Synergistic H ^* Generation and Substrate Adsorption Drives Efficient Electrocatalytic Hydrogenation of 4‐Nitrophenol Coupled with Glycerol Oxidation

ABSTRACT As a prevalent and highly hazardous organic contaminant in wastewater, the removal of 4‐nitrophenol (4‐NP) from the environment is of utmost urgency. Recently, electrocatalytic 4‐NP hydrogenation has been considered as an environmentally friendly strategy, which can not only remove 4‐NP from wastewater but also produce high‐value‐added product 4‐aminophenol (4‐AP). However, the electrocatalysis method still faces the challenge of low efficiency and the addition of reducing agents (e.g., H ₂ and NaBH ₄ ). Herein, a cooperative Ag/polydopamine catalyst was prepared by in situ immobilization of Ag nanoparticles on polydopamine (Ag/PDA), showing high electrocatalytic 4‐NP to 4‐AP performance with Faradaic efficiency (FE) of 98.4% and 4‐AP selectivity of 99.6%. Experimental results and theoretical calculations reveal that PDA can enhance the adsorption of 4‐NP ions and promote the generation and capture of reactive hydrogen species (H ^* ), enabling high reaction rate and selectivity. Moreover, PDA can also disperse and stabilize Ag nanoparticles on the catalyst. Finally, we design an integrated system of electrocatalytic 4‐NP hydrogenation coupled with glycerol oxidation, achieving the co‐production of 4‐AP and formate, further improving the economic efficiency of the system.