Revealing the Active Phase of Copper during the Electroreduction of CO in Aqueous Electrolyte by Correlating X-ray Spectroscopy and Electron Microscopy.

The variation in the morphology and electronic structure of copper during the electroreduction of CO into valuable hydrocarbons and alcohols was revealed by combining surface- and bulk-sensitive X-ray spectroscopies with electrochemical scanning electron microscopy. These experiments proved that the electrified interface surface and near-surface are dominated by reduced copper. The selectivity to the formation of the key C-C bond is enhanced at higher cathodic potentials as a consequence of increased copper metallicity. In addition, the reduction of the copper oxide electrode and oxygen loss in the lattice reconstructs the electrode to yield a rougher surface with more uncoordinated sites, which controls the dissociation barrier of water and CO. Thus, according to these results, copper oxide species can only be stabilized kinetically under CO reduction reaction conditions.