Designing effective solid catalysts for biomass conversion: Aerobic oxidation of ethyl lactate to ethyl pyruvate

The direct oxidative dehydrogenation of lactates with molecular oxygen is a promising route for producing biobased pyruvates. But practical implementation of this route means high yields and mild conditions, which in turn require expensive noble-metal catalysts. Here we report a novel catalytic approach for efficient conversion of ethyl lactate to ethyl pyruvate. We show that vanadia supported on activated carbon acts synergistically with homogeneous pyridine-type additives, giving high conversion and selectivity. Control experiments and simulations show that the reaction follows a two-step pathway: first, the pyridine-lactate complex forms, followed by transfer to the vanadium active site where the oxidation occurs. Building on these results, we design a new solid catalyst where the vanadia sites are impregnated on a pyridine-rich carbonaceous support made from poly(4-vinylpyridine). This catalyst, made from abundant elements, combines the advantages of the homogeneous pyridine additive and the vanadia active site. The combination lowers local mass-transfer barriers and improves stability. The catalyst gives over 90% selectivity at 80% conversion at 130 [degree]C and 1 atm oxygen, and can be reused at least five times without losing activity.