Stabilization of Atomic CoO _<i>x</i> Clusters on Oxygen Vacancy-Rich TiO ₂ for Enhanced Photocatalytic CO ₂ to Methanol

This study utilizes cold plasma etching to create oxygen vacancies on TiO₂ nanosheets, which serve as anchoring sites to achieve atomic dispersion of CoO_<i>x</i> clusters. The synthesized catalyst exhibits exceptional performance in photocatalytic CO₂ to methanol, yielding 542.3 μmol·g^-1·h^-1 approximately three times higher than that of the nonplasma-treated samples. Comprehensive characterizations confirm the atomic dispersion of cobalt and strong metal-support interactions, which enhance charge separation/transfer kinetics. In situ DRIFTS analysis further elucidates the CO₂ to methanol reaction pathway via a *COOH intermediate. This work provides a valuable blueprint for designing efficient, atomically dispersed photocatalysts through vacancy-confined synthesis.