The CrOx/SiO2/Si(100) catalyst – a surface science approach to supported olefin polymerization catalysis

Depositing catalytically active particles onto flat, thin and oxidic support forms an attractive way to make supported catalyst suitable for surface science characterization. Here we show how this approach has been applied to the Phillips (CrO_x/SiO₂) ethylene polymerization catalyst. The model catalyst shows a respectable polymerization activity after thermal activation in dry air (calcination). Combining the molecular information from X‐ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) we can draw a molecular level of the activated catalyst that features exclusively monochromate species, which are anchored to the silica support via ester bonds with the surface silanol groups. These surface chromates form the active polymerization site upon contact with ethylene. Upon increasing calcination temperature we observe a decrease in chromium coverage as some of the surface chromate desorbs from the silica surface. Nevertheless, we also find an increasing polymerization activity of the model catalyst. We attribute this increase in catalytic activity to the isolation of the supported chromium, which prevents dimerization of the coordinatively unsaturated active site. Diluting the amount of chromium to 200 Cr‐atoms/nm² of silica surface enables the visualisation of polyethylene produced by a single active site.