On the effectiveness of partial oxidation of propylene by gold: A density functional theory study

The catalytic effectiveness of extended gold surfaces on the partial oxidation of olefins containing an allylic C–H bond is studied by means of periodic density functional calculations applied to slab models representing Au(1 1 1). Results show that the H-stripping, leading to an adsorbed allyl and OH radicals is by far more probable than the one leading to the formation of oxametallacycle intermediates, which is the necessary step towards the partial oxidation of propylene. Our observations suggest that the failure of extended gold surfaces arises from the high sensitivity of the molecular mechanism toward changes in the basic character of adsorbed oxygen, in line with previous findings.

Graphical abstractThe two different OMMP intermediates – OMMP1 (left) and OMMP2 (right) – involved in the primary chemistry of propylene partial oxidation on Au(1 1 1).Figure optionsDownload full-size imageDownload high-quality image (138 K)Download as PowerPoint slide