Exploring the catalytic properties of supported palladium catalysts in the transfer hydrogenolysis of glycerol

• The transfer hydrogenolysis of glycerol is promoted by coprecipitated Pd-catalysts.
• The reaction solvent (2-propanol) was used as hydrogen-donor.
• Pd-Co and Pd-Fe ensembles have been identified as the active catalytic phases.
• CTH mechanism involves the glycerol dehydration and subsequent hydrogenation.

The transfer hydrogenolysis of glycerol promoted by supported palladium catalysts is reported. The reactions were carried out under mild conditions (453 K and 5 bar of N2) in absence of added hydrogen by using the reaction solvent, 2-propanol, as hydrogen source. The catalytic results are interpreted in terms of metal (Pd)–metal (Co or Fe) interaction that modifies the electronic properties of palladium and affords bimetallic PdM sites (M = Co or Fe), thus enhancing the catalytic properties of the systems in the conversion of glycerol as well as in the selectivity to 1,2-propanediol and 1-propanol. The transfer hydrogenolysis mechanism is here elucidated and involves the glycerol dehydration to 1-hydroxyacetone and the subsequent hydrogenation of 1-hydroxyacetone to propylene glycol.

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