Revealing the Effect of Electronic Configuration in Cux Species on CO₂ Photoreduction Characteristic Products

As of the present time, the in‐depth study of the structure‐activity relationship between electronic configuration and CO 2 photoreduction performance is often overlooked. Herein, a series of Cu x species modified CeO 2 nanodots are constructed in situ by flame spray pyrolysis (FSP) to achieve an efficient photocatalytic CO 2 ‐to‐C 2 conversion with an electron utilization of up to 142.5 µmol g −1 . Through an in‐depth study of the electronic behavior and catalytic pathways, it is found that the Cu 0 /Cu + species in the coexistence state of Cu 0 /Cu + /Cu 2+ can optimize the energy band structure, photocurrent stability, and provide a kinetic basis for the active surface catalytic reaction process that requires the conversion of multiple electrons into C 2 products, which ultimately enhances the CO 2 ‐to‐C 2 H 6 photoreduction by 3.8‐fold and that for CO 2 ‐to‐C 2 H 4 photoreduction by 5.2‐fold. Besides, the Cu 2+ species in the coexistence state of Cu 0 /Cu + /Cu 2+ are able to regulate the electronic behavior and the choice of the catalytic pathway, enabling the transitions between CO 2 ‐to‐C 2 H 6 and CO 2 ‐to‐C 2 H 4 . This work indicates that electronic configuration optimization is an effective strategy to significantly enhance the CO 2 photoreduction performance and provides new ideas for the design and synthesis of high‐performance heterostructure photocatalysts.