A Titanium Silicalite‐1 (TS‐1) Catalyst with Abundant Active Ti‐VI Species for Efficient Conversion of Ethylene to Glycol

One‐pot synthesis of glycol from ethylene and H2O2 is simple and environmentally friendly, making it a potential alternative for glycol production. The key to the success of this is to have a bifunctional catalyst with both oxidative activity for ethylene in the presence of H2O2 and acidic centers for the subsequent hydration of ethylene oxide. Here, we propose a dual‐chemical post‐treatment regime to introduce acid centers in TS‐1 while simultaneously improve the oxidative activity. The study shows that the combined tetrapropylammonium hydroxide (TPAOH) + (NH4)2CO3 post‐treatment not only produces abundant Ti(OSi)2(OH)4 (Ti‐VI) species from Ti(OSi)4, but also creates numerous internal cavities within crystals of the post‐treated TS‐1. Ti‐VI possesses both high oxidative activity and acidic sites. The presence of internal cavities within TS‐1 crystals enhances the diffusion on the catalyst as well as increases the accessibility of Ti‐VI species. Consequently, when applied as a catalyst, the combined‐treated TS‐1 demonstrates an outstanding catalytic performance, achieving 98.6% conversion of H2O2 and 99.8% selectivity of EG, which is nearly 2 times of the conventional TS‐1. This study also unveils the formation mechanism of Ti‐VI during the post‐treatment.