The roles of different titanium species in TS-1 zeolite in propylene epoxidation studied by in situ UV Raman spectroscopy

Abstract

Titanium silicalite (TS-1) zeolites with different titanium species were synthesized and characterized by ultraviolet (UV)-Raman, ultraviolet visible (UV-Vis) diffuse reflectance spectroscopies and by the NH₃ temperature programmed desorption (NH₃-TPD) method. The roles of different titanium species in TS-1 samples have been investigated by gas chromatography-Raman spectrometry (GC-Raman) during the propylene epoxidation process. For the first time, a positive correlation was found among the concentration of framework Ti species, the amount of active intermediate Ti–OOH (η²) and the conversion of propylene by the in situ GC-Raman technique. The results give evidence that the framework titanium species is the active center and Ti–OOH (η²) is the active intermediate. The presence of extra-framework Ti species is harmful to propylene epoxidation. Furthermore, the amorphous Ti species has a more negative effect on the yield of propylene oxide (PO) than the anatase TiO₂. The NH₃-TPD results reveal that the amorphous Ti species are more acidic and thus should be mainly responsible for the further conversion of PO.