High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to γ-valerolactone.

The catalytic hydrogenation of levulinic acid, a key platform molecule in many biorefinery schemes, into γ-valerolactone is considered as one of the pivotal reactions to convert lignocellulose-based biomass into renewable fuels and chemicals. Here we report on the development of highly active, selective and stable supported metal catalysts for this reaction and on the beneficial effects of metal nano-alloying. Bimetallic random alloys of gold-palladium and ruthenium-palladium supported on titanium dioxide are prepared with a modified metal impregnation method. Gold-palladium/titanium dioxide shows a marked,~27-fold increase in activity (that is, turnover frequency of 0.1 s(-1)) compared with its monometallic counterparts. Although ruthenium-palladium/titanium dioxide is not only exceptionally active (that is, turnover frequency of 0.6 s(-1)), it shows excellent, sustained selectivity to γ-valerolactone (99%). The dilution and isolation of ruthenium by palladium is thought to be responsible for this superior catalytic performance. Alloying, furthermore, greatly improves the stability of both supported nano-alloy catalysts.