Shielding effect‐engineered single‐crystalline Ti‐rich nanosized aggregated <scp>TS</scp>‐1 for 1‐hexene epoxidation

Abstract Titanosilicate with H 2 O 2 stands out as a highly consequential oxidized catalytic system, prized for its user‐friendly operation, mild conditions, and eco‐friendly attributes. However, a synthesis strategy for large surface area titanosilicalites approaching the theoretical lowest Si/Ti ratio without extra‐framework Ti species remains an ongoing challenge. In this study, we successfully synthesized single‐crystalline Ti‐rich nanosized aggregated TS‐1 by shielding effect with a Si/Ti polymer. This polymer demonstrated effectiveness in restraining TiO 2 species by regulating the proximity of Si/Ti species in Ti‐Diol‐Si polymers. The polymer not only facilitated the synthesis of single‐crystalline Ti‐rich TS‐1 but also exploited the chain length of PEG, functioning as a shielding cage by hydrogen bonds, to synthesize nanosized aggregated TS‐1 (TS‐1‐PEG400). This TS‐1‐PEG400 exhibited superior conversion (~60%), selectivity (~90%), and stability in 1‐hexene epoxidation. This study not only establishes a synthesis pathway for Ti‐rich TS‐1 but also holds the potential to enhance related industrial oxidation reactions involving titanosilicates and H 2 O 2 .