Enhanced Fluorine Resistance and Catalytic Performance of the Zirconia-Supported Ru Single-Atom and WO x Cluster Catalysts for Elimination of the Typical Hydrofluorocarbon (HFC-134a)

Hydrofluorocarbons (HFCs) are potent greenhouse gases. Catalytic elimination faces a big challenge in improving the fluorine resistance of the catalysts. Herein, a ZrO₂-supported Ru single-atom and WOx cluster (Ru₁-WOx/ZrO₂) catalyst with Ru-O-Zr and W-O-Zr dual interfaces was prepared, featuring abundant oxygen vacancies and highly active Zr-WOx clusters, which collaboratively facilitated the activation of reactant molecules. Ru₁-WOx/ZrO₂ exhibited excellent catalytic activity (T90% = 434 °C at a space velocity of 20,000 mL g⁻¹ h⁻¹) and outstanding durability for the typical hydrofluorocarbon (1,1,1,2-tetrafluoroethane, HFC-134a) removal under humid conditions, which significantly outperformed most of the previously reported catalysts for HFC-134a removal. The atomically dispersed Ru₁ optimized the electronic structure of Zr and achieved the rational regulation of ZrO₂ crystal phase, thereby forming coordination-unstable Zr⁴⁺/Ruδ+ (0 < δ < 4) sites and three-dimensional distorted Zr-stabilized WOx clusters. The structure with abundant redox centers closely coupled with multiple acid centers facilitated the migration of fluorine and stimulated the interaction of water with the surface adsorbed or lattice oxygen species to generate highly reactive oxygen species. This work highlights the regulatory effect of the synergistic interaction between Ru₁ and WOx clusters on the catalyst surface, contributing to the development of high-performance catalysts for the removal of F-containing volatile organic compounds.