The use of bio-renewable resources, such as glycerol, a by-product from bio-diesel manufacture, can provide a viable way to make valuable products using greener technology. In particular, glycerol can be reduced to give 1,2-propanediol that can then be selectively oxidised to lactate, which has immense potential as a monomer for the synthesis of biodegradable polymers. We show that gold-palladium alloy catalysts can be very effective for the selective oxidation of 1,2-propanediol to lactate. Two supports, TiO2 and carbon, and two preparation methods, wet impregnation and sol-immobilisation, are contrasted. The addition of palladium to gold significantly enhances the activity and retains the high selectivity to lactate using O2 as oxidant (we observe 96% lactate selectivity at 94% conversion). Use of hydrogen peroxide is also possible but lower activities are observed as a result of the reaction conditions, but in this case no marked enhancement is observed on addition of palladium to gold. Comparison of the activity for C3 alcohols shows that the reactivity decreases in the order: glycerol > 1,2-propanediol > 1,3-propanediol ∼ 1-propanol > 2-propanol. The use of a sol-immobilisation preparation method as compared to impregnation leads to alloy catalysts with the highest activity for lactate formation from the oxidation of 1,2-propanediol; the origins of these activity trends are discussed. © 2009 The Royal Society of Chemistry.
Dimitratos, N., Lopez-Sanchez, J.A., Meenakshisundaram, S., Anthonykutty, J.M., Brett, G., Carley, A.F., et al. (2009). Selective formation of lactate by oxidation of 1,2-propanediol using gold palladium alloy supported nanocrystals. GREEN CHEMISTRY, 11(8), 1209-1216 [10.1039/b823285g].
Selective formation of lactate by oxidation of 1,2-propanediol using gold palladium alloy supported nanocrystals
Dimitratos, Nikolaos;Lopez-Sanchez, Jose Antonio;
2009
Abstract
The use of bio-renewable resources, such as glycerol, a by-product from bio-diesel manufacture, can provide a viable way to make valuable products using greener technology. In particular, glycerol can be reduced to give 1,2-propanediol that can then be selectively oxidised to lactate, which has immense potential as a monomer for the synthesis of biodegradable polymers. We show that gold-palladium alloy catalysts can be very effective for the selective oxidation of 1,2-propanediol to lactate. Two supports, TiO2 and carbon, and two preparation methods, wet impregnation and sol-immobilisation, are contrasted. The addition of palladium to gold significantly enhances the activity and retains the high selectivity to lactate using O2 as oxidant (we observe 96% lactate selectivity at 94% conversion). Use of hydrogen peroxide is also possible but lower activities are observed as a result of the reaction conditions, but in this case no marked enhancement is observed on addition of palladium to gold. Comparison of the activity for C3 alcohols shows that the reactivity decreases in the order: glycerol > 1,2-propanediol > 1,3-propanediol ∼ 1-propanol > 2-propanol. The use of a sol-immobilisation preparation method as compared to impregnation leads to alloy catalysts with the highest activity for lactate formation from the oxidation of 1,2-propanediol; the origins of these activity trends are discussed. © 2009 The Royal Society of Chemistry.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.