Unraveling the Synergistic Effect of Hollow Sea Urchin-like Ag-Co₃O₄ Heterostructures in Electrochemical Dehydrogenation Reactions: Interface-Enhanced Electron Transfer and Desorption Process

Enhancing electron transfer rates and regulating the adsorption/desorption behavior of intermediates are critical for optimizing electrochemical energy conversion. Partial substitution of Co³⁺ by Ag in Co₃O₄ enhances the polarization of Co-O bonds, leading to charge redistribution at the Co-O-Ag interfaces and promoting the formation of oxygen vacancies. These structural features serve as efficient electron transport channels and provide additional active sites, significantly improving the reaction kinetics for electrochemical dehydrogenation. Specifically, the charge transfer coefficient increases from 0.118 to 0.152. Moreover, the modification of the d-band center in Ag-Co₃O₄ heterostructures enhances the electron occupancy in the antibonding orbitals of Co atoms, facilitating the desorption of radical intermediates from Ag-Co₃O₄. This promotes equilibrium between intermediate adsorption and desorption, optimizing the oxidative dehydrogenation process. Seven substrates achieved efficient dehydrogenation with a Faradaic efficiency of 94.73% and a conversion rate of 93.27%. The in situ generated interfacial state of Ag⁺·O·Co³⁺ serves as the key active species throughout the entire catalytic process. Our study elucidates the unique catalytic mechanisms of Ag-Co₃O₄ heterostructures, offering strategies for optimizing adsorption/desorption behaviors and electron transfer pathways in electrochemical reactions.