Congratulations to Maodi Zhang for her paper accepted by Journal of the American Chemical Society!
Direct ethanol fuel cells (DEFCs) relying on the complete C1 oxidation pathway face two linked barriers at the anode: the difficulty of C–C bond cleavage and *CO intermediate poisoning. While Pt-based alloys address the former, they are plagued by *CO-induced deactivation, and the mechanism of *CO clearance in alkaline electrolytes has remained elusive. Herein, we demonstrate that effective *CO detoxification plays a critical role in governing the selectivity toward the complete C1 pathway. Using a ternary Ag@Pt7Pd3 core–shell catalyst, we achieve a mass activity of 17.66 A mgPGM–1 with 90.5% retention after 5000 cycles. Through in situ electrochemical surface-enhanced Raman spectroscopy complemented by electronic structure analyses and theoretical calculations, we uncover a dual-mechanism detoxification pathway: Ag modulates the d-band center of Pt/Pd to enhance CO adsorption and activation, while adjacent Pd sites promote *OH formation, which subsequently executes nucleophilic attack on the activated *CO. This cooperative process efficiently removes *CO at low overpotentials, unlocking the C1 pathway and enabling sustained high performance. Our findings highlight the central role of *CO detoxification in steering reaction selectivity and enhancing device performance, thereby completing the key missing piece for enabling efficient DEFCs through the C1 pathway.
