Defects Tune the Strong Metal-Support Interactions in Copper Supported on Defected Titanium Dioxide Catalysts for CO₂...

A highly active and stable Cu-based catalyst for CO₂ to CO conversion was demonstrated by creating a strong metal-support interaction (SMSI) between Cu active sites and the TiO₂-coated dendritic fibrous nano-silica (DFNS/TiO₂) support. The DFNS/TiO₂-Cu10 catalyst showed excellent catalytic performance with a CO productivity of 5350 mmol g^-1 h^-1 (i.e., 53,506 mmol g_Cu^-1 h^-1), surpassing that of almost all copper-based thermal catalysts, with 99.8% selectivity toward CO. Even after 200 h of reaction, the catalyst remained active. Moderate initial agglomeration and high dispersion of nanoparticles (NPs) due to SMSI made the catalysts stable. Electron energy loss spectroscopy confirmed the strong interactions between copper NPs and the TiO₂ surface, supported by in situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray photoelectron spectroscopy. The H₂-temperature programmed reduction (TPR) study showed α, β, and γ H₂-TPR signals, further confirming the presence of SMSI between Cu and TiO₂. In situ Raman and UV-vis diffuse reflectance spectroscopy studies provided insights into the role of oxygen vacancies and Ti³⁺ centers, which were produced by hydrogen, then consumed by CO₂, and then again regenerated by hydrogen. These continuous defect generation-regeneration processes during the progress of the reaction allowed long-term high catalytic activity and stability. The in situ studies and oxygen storage complete capacity indicated the key role of oxygen vacancies during catalysis. The in situ time-resolved Fourier transform infrared study provided an understanding of the formation of various reaction intermediates and their conversion to products with reaction time. Based on these observations, we have proposed a CO₂ reduction mechanism, which follows a redox pathway assisted by hydrogen.