Unraveling the Nature of Active Sites in Ethanol Electro-oxidation by Site-Specific Marking of a Pt Catalyst with Isotope-Labeled 13CO

This works deals with the identification of preferential site-specific activation at a model Pt surface during a multiproduct reaction. The (110)-type steps of a Pt(332) surface were selectively marked by attaching isotope-labeled 13CO molecules to them, and ethanol oxidation was probed by in situ Foureir transfrom infrared spectroscopy in order to precisely determine the specific sites at which CO2, acetic acid, and acetaldehyde were preferentially formed. The (110) steps were active for splitting the C–C bond, but unexpectedly, we provide evidence that the pathway of CO2 formation was preferentially activated at (111) terraces, rather than at (110) steps. Acetaldehyde was formed at (111) terraces at potentials comparable to those for CO2 formation also at (111) terraces, while the acetic acid formation pathway became active only when the (110) steps were released by the oxidation of adsorbed 13CO, at potentials higher than for the formation of CO2 at (111) terraces of the stepped surface.M.J.S.F. is grateful to PNPD/CAPES (Brazil). A.A.T. acknowledges CAPES (PROCAD-2013) and CNPq (309066/2013-1). J.M.F. thanks the MINECO (Spain) project-CTQ2013-44083-P