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Insight into the reduction of pyruvic acid to lactic acid over Cu{110}: the crucial role of intramolecular tunneling in direct hydrogenation.

This work presents results from density functional theory calculations which are used to elucidate the reduction of pyruvic acid to lactic acid by direct hydrogenation over Cu{110} in vacuo. We propose a plausible pathway from reactants to products that crucially relies upon an intramolecular tunneling step to circumvent energetically unfavorable hydrogen exchange with the surface. The conclusions are further augmented by analyzing the electron density and frontier orbitals of key reaction intermediates. This reveals the origin of the predicted activity to be intimately linked to the electronic structure, which in turn is dependent upon the asorption geometry of pyruvic acid. Through the use of equilibrium thermodynamics, we are able to show the influence of temperature and pressure on the reaction profile. Importantly showing, that as the temperature is raised at low pressure (1 x 10(-10) mbar), so the rate-determining step switches from being the carbonyl reduction to the reprotonation of the carboxylate group (leading to the desorption of lactic acid). At ambient pressure of 1 bar, the influence of temperature on the relative barrier heights is much less significant. This is an important step in attempting to bridge the so-called "pressure gap" and opens up the possibility of understanding the reactivity of small biologically relevant molecules at metal surfaces.