Theoretical Investigation of Propylene Epoxidation Using H2 and O2 Over Titanosilicate-Supported Au Catalysts

Abstract

AbstractTitanosilicate-supported Au-cluster catalysts can be used to selectively synthesize propylene oxide from propylene using O2 and H2. However, the details of the catalytic reaction mechanism have not yet been elucidated. Thus, the reaction mechanism was investigated using density functional theory calculations. The calculation results revealed that active Ti-OOH forms on the surface Ti site, which is active as an oxidant and acts as an anchorage site for Au nanoclusters. The rate-determining step of propylene oxide synthesis on Au/titanosilicate is O insertion into propylene, with an activation energy of 1.37 eV. The propylene involved in this reaction is activated by adsorption on Au nanoclusters. Moreover, it was also found that the formation of Ti-OOH on Au/titanosilicate requires an activation energy of 0.48 eV, while it is barrierless on Au/anatase-TiO2. However, the decomposition energy of Ti-OOH on Au/titanosilicate is −0.16 eV, which is smaller than that on Au/anatase-TiO2 (−1.12 eV). The results indicate that Ti-OOH decomposes more readily on Au/titanosilicate than on Au/anatase-TiO2 but is easily regenerated because the reaction energy is significantly smaller than that on Au/anatase-TiO2. Therefore, these calculations are qualitatively in good agreement with the experimental results for Au/titanosilicate, which exhibited high catalytic activity at high temperatures. Graphical Abstract