Lead-Decorated Titanium Oxide Compound with a High Performance in Catalytic CO₂ Insertion to Epoxides

The CO₂ cycloaddition to epoxides is an efficient method for CO₂ capture and storage, important not only for reducing greenhouse gas emission but also for producing cyclic carbonates, which are valuable industrial materials. In this study, we report a novel high-nuclearity titanium oxide cluster (TOC) inlayed with main-group element Pb²⁺, H₂Ti₁₆Pb₉O₂₄(SA)₁₈(DMF)₁₀(OH₂)₂ (denoted as 1; SA = salicylate; DMF = N,N-dimethylformamide), which has the property of visible-light absorption and has shown high catalytic activities for cycloadditions of CO₂ under visible-light irradiation. The cluster was synthesized in a high yield in a facial solvothermal process. Its structure and electronic structure were characterized by single-crystal X-ray diffraction, density functional theory calculations, and complementary techniques. The cycloaddition reactions were performed under solvent-free conditions. While the catalytic activity due to the Lewis acidity was moderate, visible-light irradiation further folded the reaction rates. The turnover number reached 3400 with a turnover frequency of 120 h^-1. Mechanism studies indicated a synergistic effect of the Lewis acidity and photogenerated charge carriers. The performance of 1 in reversible I₂ uptake was also investigated. This study demonstrates the high potential of heterometal-decorated TOCs in the cost-effective and efficient CO₂ cycloaddition reaction under mild conditions.