Influence of the Molecular Structure on the Electrocatalytic Hydrogenation of Carbonyl Groups and H2 Evolution on Pd

We investigated the electrocatalytic hydrogenation (ECH) of model aldehydes and ketones over carbon-supported Pd in the aqueous phase. We propose reaction mechanisms based on kinetic measurements and on spectroscopic and electrochemical characterization of the working catalyst. The reaction rates of ECH and of the H2 evolution reaction (HER) vary with the applied electric potential following trends that strongly depend on the organic substrate. The intrinsic rates of hydrogenation and H2 evolution are influenced, in opposing ways, by the sorption of the reacting organic substrate. Strong interactions, that is, higher standard free energies of adsorption of the organic compound, induce high hydrogenation rates. The fast hydrogenation kinetics produces a hydrogen-depleted environment that kinetically hinders the HER and the bulk phase transition of Pd to a H-rich bulk Pd hydride, which is triggered by the applied potential in the absence of reacting organic compounds. As a consequence of strong organic–metal interactions, hydrogenation dominates at low overpotential. However, the coverages of organic substrates on the metal surface decrease, and the rates of H2 evolution surpass those of hydrogenation with increasingly negative electric potential. We determined the range of electric potential favoring hydrogenation on Pd and quantitatively deconvoluted the effects of the sorption of the organic compound, and of the rates of proton-coupled electron transfers, on the kinetics of both ECH and HER. The results indicate that electrocatalysis offers hydrogenation pathways for polar molecules which are different and, in some cases, faster than those dominating in the absence of an external electric potential.