f-p-d Orbital Hybridization Promotes Hydroxyl Intermediate Adsorption for Electrochemical Biomolecular Oxidation and Identification

The rational design of efficient hydroxyl intermediate (*OH) adsorption catalysts for dopamine electrooxidation still faces a major challenge. To address this challenge, a CeO2-loaded CuO catalyst inspired by the f-p-d orbital hybridization strategy is designed to achieve efficient *OH adsorption and improve dopamine oxidation. The experimental results and theoretical calculations demonstrate that the f-p-d orbital hybridization regulates the electron distribution at the Ce–O–Cu interface, which facilitates electron transfer and optimizes the adsorption of *OH, thereby promoting dopamine oxidation. The designed electrochemical sensor exhibits excellent catalytic activity and sensitivity, reaching a limit of detection of 3.22 nM. This work provides a promising approach for designing highly active electrocatalysts with orbital hybridization for dopamine oxidation.