Theoretical studies of the CrOx/sSiO2 catalyst

The Phillips CrOx/SiO2 catalyst is one of the most commonly used system in the industrial production of high-density polyethylene (HDPE). This system has been extensively studied since decades, mainly by means of experimental techniques. However, the progress in determination of the nature of the chromium sites and understanding of surface reactions occurring has been rather not satisfying and many issues are still under debate. Among others, structure of the chromium oxide species on the surface of the reduced catalyst is not well defined. Likewise, the mechanism of the catalyst reduction and active site formation is not well established. Many experimental studies indicate that chromium exists on the surface of amorphous silica in a wide variety of different forms including monomeric, dimeric and polymeric species. Different oxidation states are also possible, as Cr(VI), Cr(V), Cr(IV), Cr(III), Cr(II) were detected. There is a general consensuses that Cr(VI) dominates at the surface after the catalyst preparation, while Cr(II) and Cr(III) are mainly formed after contact with a reducing agent, like ethylene or CO. Nevertheless, the detailed structure of these oxide species, as well as the active sites, is still strongly discussed. As experimental studies do not show a clear picture about the nature of silica-supported chromium catalyst, very helpful can be computational approach which can provide complementary information, not accessible by experimental techniques. In this short review we summarize the recent progress in the field of the Phillips (CrOx/SiO2) catalyst focusing on the most relevant theoretical papers that were published within last couple of years. We also highlight the need of applying advanced models if realistic theoretical description of the CrOx/SiO2 system is to be achieved. Additionally, different computational approaches in modeling of heterogenous catalysts are discussed