C‒C Bond Cleavage Driven by Lattice Oxygen during Ethanol Oxidation Process

Abstract The capacity of C‒C bond cleavage determines the pathway selectivity during the ethanol oxidation process. Herein, ultra‐thin monodisperse PdCo nanosheets with an average diameter of 33 nm are successfully synthesized and the interface of Pd‐O‐Co is further constructed due to the introduction of lattice oxygen. Due to their ultra‐thin nanosheet structure, unique surface electronic structures driven by lattice oxygen, and alloying effect, the prepared PdCo/Pd‐O‐Co nanosheets (PdCo/Pd‐O‐Co NSs) show excellent ethanol oxidation reaction (EOR) activity and stability. The mass activity and specific activity of PdCo/Pd‐O‐Co NSs are 12.43 A mg⁻¹ and 22.01 mA cm⁻² for EOR, which exceeded PdCo nanosheets, Pd nanosheets and commercial Pd black. In situ FTIR spectroscopy and theoretical calculation identified that lattice oxygen introduced after square‐wave potential treatment can promote the cleavage of the C‒C bond. Through the introduction of lattice oxygen combined with lattice strain engineering, the PdCo/Pd‐O‐Co NSs surface is optimized to promote the generation of strong p‐d orbital hybridization, which led to the upward shift of the d‐band center and the electron delocalization effect, effectively promoting the C‒C bond cleavage and improving the anti‐poisoning ability.