Authors: Can‐Jun Zou, Zi‐Yu Du, Wei Tang, Qiong Liu, Xing‐Biao Liu, Jin‐Chao Dong, Ping‐Ping Fang, Jian‐Feng Li
Published: 2025-05-30
Source: Full article
AbstractThe electrochemical conversion of CO2 into multicarbon products represents a pivotal yet challenging target, particularly for metal catalysts that predominantly yield C1 products. Herein, this challenge is addressed through sulfur‐induced electronic modulation of Ag‐based catalysts, steering the CO2 reduction pathway toward ethanol production. By constructing atomically engineered Ag/Ag2S nanowires (NWs) via a controlled sulfurization strategy, a remarkable Faradaic efficiency (FE) of 75% for ethanol at −0.95 V, along with exceptional stability over 14 h of high‐performance metrics surpassing most reported Ag‐based systems is achieved. Operando electrochemical surface‐enhanced Raman spectroscopy (EC‐SERS) and density functional theory (DFT) calculations unveil that the Ag/Ag2S heterointerface synergistically regulates interfacial water networks and stabilizes key *CO intermediates, thereby accelerating CO2 activation, proton‐coupled electron transfer, and asymmetric C‐C coupling. Furthermore, sulfurization‐induced dual effects‐optimized hydrogen‐bond interactions and enriched K⁺ confinement are identified as critical drivers for tailoring the local microenvironment to favor ethanol selectivity. This work not only demonstrates a rational atomic interface design for C2 product orientation but also deciphers the dynamic interplay between catalyst electronic structure and interfacial species, offering a molecular‐level roadmap for advanced CO2 conversion systems.