Kinetics of formic acid dehydration on Pt electrodes by time-resolved ATR-SEIRAS

Laura Perez-Martinez, Enrique Herrero, Angel Cuesta Ciscar* (Corresponding Author)

*Corresponding author for this work

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The potential dependence of the rate of dehydration of formic acid to adsorbed CO (COad) on Pt at pH 1 has been studied on a polycrystalline Pt surface by time-resolved surface-enhanced infrared absorption spectroscopy in the attenuated total reflection mode (ATR-SEIRAS) with simultaneous recording of current transients after a potential step. A range of formic acid concentrations has been used to obtain a deeper insight into the mechanism of the reaction. Our experiments have allowed us to confirm that the potential dependence of the rate of dehydration has a bell shape, going through a maximum around the potential of zero total charge (pztc) of the most active site. The analysis of the integrated intensity and frequency of the bands corresponding to COL and COB/M shows a progressive population of the active sites on the surface. The observed potential dependence of the rate of formation of COad is consistent with a mechanism in which the reversible electroadsorption of HCOOad is followed by its rate-determining reduction to COad.
Original languageEnglish
Article number094705
Number of pages8
JournalThe Journal of Chemical Physics
Issue number9
Early online date9 Feb 2023
Publication statusPublished - 1 Mar 2023

Bibliographical note

L.P.-M. acknowledges a doctoral scholarship within the Leverhulme Centre for Doctoral Training in Sustainable Production of Chemicals and Materials (Grant DS-2017-073).


  • Formic acid dehydration
  • adsorbed CO
  • electrocatalysis


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