The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO2

Abstract A series of Cu/ZrO 2 catalysts with nominal CuO loadings of 5, 10, 18 and 31 wt.% was synthesized by co‐precipitation, characterized and applied in the hydrodeoxygenation of glycerol under mild reaction conditions (200 °C, 25 bar H 2 ). These catalysts were highly selective for the cleavage of C−O bonds while preserving C−C bonds leading to 95 % selectivity to 1,2‐propanediol. The conversion of glycerol was observed to be linearly correlated with the specific copper surface area derived from N 2 O frontal chromatography. The reaction was found to occur through the dehydration of glycerol to acetol followed by its hydrogenation to 1,2‐propanediol. Metallic copper was identified as the active site for both reactions suggesting the acid ZrO 2 sites to be blocked by water. Reusability studies showed that the catalyst was relatively stable and the conversion decreased by only 18 % after three cycles.