A bilayer coating as an oxygen-transfer cascade for the electrochemical ambient conversion of methane to oxygenates.

Oxidation of methane at ambient conditions to useful oxygenates at a bilayer-coated electrode is demonstrated. The composition of the coating, a Mn porphyrin mediator layer on top of a N(OH)/NiOOH one, allows a cascade of oxygen transfer events upon applying a potential. It is shown, using (spectro)electrochemical techniques, density functional theory computations and product analytical methods, that formate and methanol accompanied by CO suppression can be observed at a certain potential range.

DFT and Empirical Considerations on Electrocatalytic Water/Carbon Dioxide Reduction by CoTMPyP in Neutral Aqueous Solutions*.

A combined experimental and density functional theory (DFT) investigation was employed in order to examine the mechanism of electrochemical CO reduction and H formation from water reduction in neutral aqueous solutions. A water soluble cobalt porphyrin, cobalt [5,10,15,20-(tetra-N-methyl-4-pyridyl)porphyrin], (CoTMPyP), was used as catalyst. The possible attachment of different axial ligands as well as their effect on the electrocatalytic cycles were examined.