Establishing a Robust Nonlinear Targeted Switch for C1 Electroproduction in Atomic Alloy Cox/Pd Bimetallenes

Establishing a targeted switch for CO2 conversion under electric drive is essential for achieving carbon‐balance by enabling selective chemicals. However, engineering the topological assembly of active sites to precisely regulate the competing pathways for various intermediates has been plagued by unclear structure‐function relationships. To tailor the CO/formate pathways, herein we established a robust nonlinear targeted switch with tunable active Cox sites integrated into Pd metallene, which involves Co1/Pd single‐atom alloy (favoring CO) and Co2/Pd diatomic alloy (favoring formate). Transitioning from Co1/Pd to Co2/Pd atomic alloy bimetallenes resulted in a nonlinear, high‐contrast flip in selectivity, surpassing 94% for CO and formate productions in both H‐cell and flow cell. Furthermore, the superior selectivity and current efficiency for CO (> 80 %) and formate (> 88%) were consistently maintained at ‐150 mA cm‐2 over continuous 200 h. Theoretical simulations and in‐situ spectroscopy analyses unveiled that appropriate adjacent metal site combinations (Pd‐Pd, Pd‐Co and Co‐Co) lead to tunable dz2 band center and a nonlinear shift in preferred adsorption configurations of intermediates, dictating the C1 pathways. Our finding reveals a desired switch in C1 selectivity and robust stability within Cox/Pd system, providing a new perspective for fine‐tuning energy conversion processes through specific topological assembly.