The issue of cathode passivation during cycling resulting in rapid capacity fading and premature battery death is a major challenge that hinders the applications of lithium–oxygen (Li–O 2 ) batteries. Here, a facile strategy of introducing a functional separator based on flexible amination SiO 2 /TiO 2 inorganic woven film (STON WF) is proposed to suppress the cathode passivation problem. The by-products, i.e. HCOOLi, CH 3 COOLi and Li 2 CO 3 can be selectively adsorbed on the STON WF separator preferably compared with the cathode and further proved by the density functional theory (DFT) calculations. Thus, benefiting from the separator, the Li–O 2 cells with super P carbon and catalyst-free cathode show enhanced electrochemical performance (5645 mA h g −1 at a current density of 200 mA g −1 ), good rate capability (discharge voltage of 2.43 V at a current density of 1.5 A g −1 ) and especially superior cycle stability up to 268 cycles. These findings present a promising approach to prevent the premature battery death.
O₂ and UV synergistically establish Cu + /Cu 2+ equilibrium for exceptional oxygen tolerance. • The catalyst shows self-adaptive redox behavior and self-recovery capability for long-term stability. • A dual-site synergy via Dewar-Chatt-Duncanson mechanism enhances both CO₂ adsorption and reduction. Photocatalytic CO₂ reduction represents a promising solar-driven technology for converting CO₂ into high-value chemicals. Nonetheless, its practical application is significantly hindered by challenges such as low CO₂ concentration, competitive O₂ reduction, and photocatalyst instability under industrial conditions. To address these issues, a Cu δ+ -functionalized TiO₂@SiO₂ aerogel (TS-3HF-1Cu δ+ ) was synthesized via sol-gel, HF etching, and photoreduction. This catalyst enables durable CO₂ reduction under simulated flue gas and dilute conditions. Experimental results indicate that TS-3HF-1Cu δ+ photocatalyst exhibits CO and CH₄ production rates 2.21 and 1.57 times higher, respectively, than those of TS-3HF. Theoretical calculations based on the Dewar-Chatt-Duncanson model reveal that, Cu 2+ with partially vacant d orbitals, serves as the adsorption site to enhance CO₂ uptake by accepting σ-donation from CO₂ during reduction reaction. In contrast, Cu + , characterized by occupied d orbitals, serves as the active sites to facilitate electron transfer via π-backdonation, activating CO₂ for further reduction. The complementary functionality between the two valence states endows the catalyst with improved cycling stability in oxygen-rich environments and self-recovery capability, thus achieving photocatalytic performance restoration after 96 h of air exposure. These findings highlight the strong potential of Cu δ+ -modified catalysts toward practical industrial photocatalytic CO₂ reduction. Self-adaptive Cu δ+ sites in TiO₂@SiO₂ aerogels drive robust CO₂ photoreduction via reversible Cu + /Cu 2+ valence cycles. Regulated by the Dewar-Chatt-Duncanson model, this dual-site mechanism optimizes σ-donation and π-backdonation, ensuring exceptional stability and “self-recovery” even in oxygen-rich industrial environments. Download: Download high-res image (237KB) Download: Download full-size image
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