Exploring the Reaction Pathways of Bioglycerol Hydrodeoxygenation to Propene over Molybdena‐Based Catalysts

The one‐step reaction of glycerol with hydrogen to form propene selectively is a particularly challenging catalytic pathway that has not yet been explored thoroughly. Molybdena‐based catalysts are active and selective to C−O bond scission; propene is the only product in the gas phase under the standard reaction conditions, and further hydrogenation to propane is impeded. Within this context, this work focuses on the exploration of the reaction pathways and the investigation of various parameters that affect the catalytic performance, such as the role of hydrogen on the product distribution and the effect of the catalyst pretreatment step. Under a hydrogen atmosphere, propene is produced primarily via 2‐propenol, whereas under an inert atmosphere propanal and glycerol dissociation products are formed mainly. The reaction most likely proceeds through a reverse Mars–van Krevelen mechanism as partially reduced Mo species drive the reaction to the formation of the desired product. Propylene dream: Green propylene can be formed selectively by glycerol hydrodeoxygenation over molybdena‐based catalysts. Reduced MoOx species drive the reaction towards the desired product.