Towards selective glycerol hydrodeoxygenation to 1,3-propanediol with effective Pt-WOx catalyst design: Insights from first principles

DFT simulations predicted the C-O bond cleavage in glycerol on Brønsted acidic Pt-WOx catalyst under a hydrogen atmosphere to be via a “protonation dehydration” mechanism. Interfacial Pt-WOx sites facilitate Brønsted acid (BA) site formation by hydrogen spillover and synergistic activity of Pt and WOx. At strong BA sites, selective formation of 1,3-PDO is likely due to the large difference of over 40 kJ/mol in primary and secondary C-O bond cleavage barriers. The secondary C-O bond cleavage has a linear relation with NH3 binding energy while there is a non-monotonic trend for the primary C-O cleavage. Hence, Brønsted acid strength is a potential descriptor for the catalyst activity and 1,3-PDO selectivity. Synthetic strategies enabling fine dispersion of WOx to trimeric units on the Pt nanoparticles, while preventing W doping and agglomeration of WOx to 3D WO3 on small Pt nanoparticles are desirable for high BA strength and thereby 1,3-PDO yield.