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

Abstract Establishing a targeted switch for CO 2 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 Co x sites integrated into Pd metallene, which involves Co 1 /Pd single‐atom alloy (favoring CO) and Co 2 /Pd diatomic alloy (favoring formate). Transitioning from Co 1 /Pd to Co 2 /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 d z 2 band center and a nonlinear shift in preferred adsorption configurations of intermediates, dictating the C 1 pathways. Our finding reveals a desired switch in C 1 selectivity and robust stability within Co x /Pd system, providing a new perspective for fine‐tuning energy conversion processes through specific topological assembly.