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Dynamics of the Interaction of Formic Acid with a Polycrystalline Pt Film Electrode: a Time-Resolved ATR-FTIR Spectroscopy Study at Low Potentials and Temperatures

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Abstract

Aiming at more insights into the interaction of formic acid with a Pt electrode, we have studied the dynamics of formic acid interaction with a polycrystalline Pt film electrode in the potential range around the onset of the reaction, from 0.0 to 0.4 V (reversible hydrogen electrode (RHE)), by a combination of electrochemical and in situ IR spectroscopy transient measurements. The measurements were performed under well-defined mass transport conditions; IR spectra were acquired in an attenuated total reflection (ATR) configuration with a time resolution of up to 25 ms (rapid scan mode). To slow down the reaction kinetics and thus stabilize short-living adsorbed intermediates, measurements were performed at ambient and low reaction temperatures (3 °C). Kinetic H/D isotope effects, introduced by using deuterated formic acid, were explored to learn more about the contribution of C–H bond splitting in the rate-determining step in formic acid dehydration (COad formation). Rapid scan ATR-FTIRS measurements show no measurable time delay between the appearance of the bands related to adsorbed bridge-bonded formate species and adsorbed CO at higher potentials (>0.1 V) and no detectable formate signals at low potentials (≤0.1 V), although COad is still formed even at 0.0 V. Adsorption of HCOOH species at low potentials (0.0–0.1 VRHE) is indicated by a band developing at around 1720 cm−1, which is isotope shifted upon deuteration of the C–H bond. Consequences of these and other observations, including the observation of a bell-shaped potential dependence of the initial rate for COad formation in the potential range 0.0–0.4 V or distinct kinetic H/D isotope effects in the rate constants for COad formation, on the mechanistic understanding of the formic acid–Pt interaction are discussed.

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Acknowledgements

We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft via Research Unit FOR 1376 (projects JU 2781/2-1 and JU 2781/2-2).

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  1. Institute of Surface Chemistry and Catalysis, Ulm University, Albert-Einstein-Allee 47, D-89081, Ulm, Germany

    Z. Jusys & R. J. Behm

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Correspondence to R. J. Behm.

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Jusys, Z., Behm, R.J. Dynamics of the Interaction of Formic Acid with a Polycrystalline Pt Film Electrode: a Time-Resolved ATR-FTIR Spectroscopy Study at Low Potentials and Temperatures. Electrocatalysis 8, 616–629 (2017). https://doi.org/10.1007/s12678-017-0392-8

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