Revisiting the Acetaldehyde Oxidation Reaction on a Pt Electrode by High-Sensitivity and Wide-Frequency Infrared Spectroscopy.

High-sensitivity and wide-frequency attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) is highly demanded in unraveling electrocatalytic processes at the molecular level. In this work, an in situ ATR-SEIRAS technique incorporating a micromachined Si wafer window, -polarized infrared radiation, and isotope labeling is extended to revisit the acetaldehyde oxidation reaction (AOR) on a Pt electrode in an acidic medium. New spectral features in the fingerprint region are detected, including ω(C-H) at 1078 cm and ν(C-C-O) at 919 cm for adsorbed acetaldehyde and δ(O-C-O) at 689 cm for adsorbed acetate, besides the other enhanced and clearly discriminated spectral signals at higher frequencies. Time-evolved and potential-dependent ATR-SEIRAS measurements together with advanced density functional theory calculations considering the coadsorption of CO and C species enable clarification of the structures and roles of surface C intermediates (η(C)-acetyl and η(H)-acetaldehyde), as reflected by the two bands at 1630 and 1663 cm, respectively, leading to updated pathways for the AOR on a Pt electrode.