Electronic Structure Tuning in Cu–Co Dual Single Atom Catalysts for Enhanced COOH* Spillover and Electrocalytic CO 2 Reduction Activity

Abstract The development of efficient electrocatalysts for CO 2 reduction to CO is challenging due to competing hydrogen evolution and intermediate over‐stabilization. In this study, a Cu–Co dual single‐atom catalyst (CuCo‐DSAC) anchored on carbon black was synthesized via scalable pyrolysis. The catalyst achieves 98.5% CO Faradaic efficiency at 500 mA cm −2 , maintaining > 95% selectivity across a 400 mV window with < 6% decay over 48 h, which is superior to the corresponding single‐atom control samples. In situ spectroscopy and DFT calculations reveal a synergistic mechanism: Co sites activate CO 2 and stabilize *COOH intermediates, while adjacent Cu sites facilitate CO desorption by lowering the…