Direct Transformation of Glycerol to Propanal using Zirconium Phosphate-Supported Bimetallic Catalysts

Selective transformation of glycerol to propanal (PA) provides a feasible route towards the sustainable synthesis of high value-added chemicals. In this work, zirconium phosphate (ZrP) was studied as support and Ru and Co as metal sites for glycerol hydrogenolysis in a continuous-flow reactor. It was found that ZrP-supported Co-O species had a moderate selectivity to PA (49.5 %) in glycerol hydrogenolysis. Notably, once Ru species were doped into CoO/ZrP, the resulting catalyst exhibited not only an outstanding catalytic performance for glycerol hydrogenolysis to PA (a selectivity of 80.2 % at full conversion), but also a high stability at least a 50 h long-term performance. The spent catalyst could be regenerated by calcining in air to remove carbonaceous deposits. Characterization indicated that the acid sites on ZrP played a very critical role in the dehydration of glycerol into acrolein (AE), that the distribution of Co was uniform, basically consistent with that of Zr, P and Ru, and that an especially close contact between Co-O and Ru species was formed on Ru/CoO/ZrP catalyst. The further activity tests and characterizations confirmed that there was a strong interaction between the dispersed Co-O species and Ru(0)nanoparticles, which endowed Ru sites with high electronic density. This effect could play a role in facilitating the dissociation of H-2, and thus in promoting the hydrogenation reaction. Besides, DFT calculations suggested that the Co-O species can adsorb more strongly the C=C bond of the intermediate AE on a highly coordinatively unsaturated Co (Co-cus) site and thus lead to preferential hydrogenation at the C=C bond of AE to PA.