Formic Acid Electrooxidation on Platinum, Resolution of the Kinetic Mechanism in Steady State and Evaluation of the Kinetic Constants

Chialvo, María R. Gennero de; Luque, Gisela C.; Chialvo, Abel C.

doi:10.1002/slct.201801725

Cited by 14 publications

(12 citation statements)

References 29 publications

(73 reference statements)

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“…Although the calculation of rate coefficients at the standard potential k ±m 0 (T) is not possible using this methodology, it is possible to estimate k ±m (ϕ,T) as a function of the electrode potential and the temperature. 63 The value range for the rate coefficients at different temperatures and electrode potentials, between 0.40 and 0.80 V, is shown in Figure 1. In the case of the step r 2 , which is not an electrochemical one, the rate coefficient k 2 was modified according to Arrhenius-like dependence assuming an activation energy of 50 kJ mol −1 and using the equation…”

Section: Resultsmentioning

confidence: 99%

“…The data presented in Table can be expressed in terms of the following linear equations. Substituting these equations in the corresponding expressions for the rate coefficients, eq , the temperature dependence is explicit. Although the calculation of rate coefficients at the standard potential k ± m 0 ( T ) is not possible using this methodology, it is possible to estimate k ± m (ϕ, T ) as a function of the electrode potential and the temperature . The value range for the rate coefficients at different temperatures and electrode potentials, between 0.40 and 0.80 V, is shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…In electrochemical systems, the oscillatory dynamics strongly depends on the applied current besides the temperature, among other parameters. ,,,− On the other hand, the applied current density j is usually different in each galvanostatic experiment because it is adjusted by a normalization process to minimize the current effect on oscillatory characteristics and facilitate experimental comparison . Alternatively, the influence of temperature on the oscillatory behavior can be analyzed simultaneously with the effect of the applied current.…”

Section: Resultsmentioning

confidence: 99%

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Thorough Analysis of the Effect of Temperature on the Electro-Oxidation of Formic Acid

et al. 2020

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In this work, the effect of temperature on the electro-oxidation of formic acid on platinum was modeled and numerically investigated. Numerical simulations were carried out using an electrokinetic model recently validated through voltammetric and galvanostatic experiments. We show that the intrinsic electrocatalytic activity of the working electrode for the overall electrochemical reaction can hardly be interpreted from the apparent activation energy due to the complexity of the reaction scheme. A detailed analysis is possible through the estimation of the activation energies determined from the individual rate coefficients. By doing so, we observed that the direct pathway, with an activation energy of 91 kJ mol–1 at 0.40 V and 72 kJ mol–1 at 0.80 V, is the energetically easiest pathway for the formation of CO2 in the proposed reaction scheme. Regarding the self-organized potential oscillations under the galvanostatic regime, our model was able to reproduce experimentally observed results including the phenomena of temperature compensation and overcompensation. Importantly, we have introduced a formalism to classify the elementary steps that contribute to the increase and decrease of the oscillatory frequency in electrochemical systems. Our results shed light on the understanding of the temperature dependence of complex electrocatalytic reactions, and the developed methodology was proven to be robust and of general applicability.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Thorough Analysis of the Effect of Temperature on the Electro-Oxidation of Formic Acid

et al. 2020

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“…Even CO2RR induced CO formation by applying too cathodic potential (brown) 31 have been suggested. Recently, formate (yellow) 20,30,38,39 in various arrangements has gained attention as potential catalyst poisons.…”

Section: Figurementioning

confidence: 99%

Fundamental Reaction Limitations for Formic Acid Oxidation

Bagger

Jensen

Rashedi

et al. 2022

Preprint

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Electrocatalytic conversion of formic acid oxidation to CO2 and the related CO2 reduction to formic acid represent a potential closed carbon-loop based on renewable energy. However, formic acid fuel cells are inhibited by the formation of poisoning species during the reaction. Recent studies have elucidated how the binding of carbon and hydrogen on catalyst surfaces promote CO2 reduction towards CO and formic acid. This has also given fundamental insights to the reverse reaction, i.e. the oxidation of formic acid. In this work, simulations on multiple materials have been combined with formic acid oxidation experiments on electrocatalysts to shed light on the reaction and the accompanying catalytic limitations. We found that: (i) The desired principal reaction for efficient formic acid oxidation should progress through adsorbed carboxyl, *COOH, which should then be oxidized to CO2. (ii) *H adsorbed on the surface results in *CO formation and poisoning through a chemical disproportionation step. (iii) Catalysts are poisoned by formate and/or hydroxyl. Using these results, a framework for the reaction has been developed explaining the fundamental limitations and progressing our understanding.

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“…These could be HCOO ad , HCOO − , or [HCOOH] 2 , –COOH particles. It was nevertheless shown that the FAO takes place mainly through the HCOO ad pathway. For the direct oxidation of formic acid into CO 2 (Eq.…”

Section: Microstructural and Electrochemical Characteristics Of Pt/c mentioning

confidence: 99%

New Electrochemical Approach for the Synthesis of Pd‐PdO/C Electrocatalyst and Application to Formic Acid Electrooxidation

et al. 2019

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Pd‐PdO/C catalyst for formic acid electrooxidation has been synthesized via electrochemical dispersion of Pd foil electrodes under pulse alternating current conditions in NaCl aqueous electrolyte. About 35 wt% of the as‐prepared Pd‐PdO/C specimen is PdO as revealed by X‐ray diffraction. The microstructural characteristics and catalytic activity of the synthesized Pd/C catalyst have been compared with those of a Pt/C catalyst prepared under the same conditions. Pd nanoparticles of Pd‐PdO/C catalyst exhibit smaller average dimensions and narrower particle size distribution – 7.4±0.5 nm and 1.9±0.5 respectively for Pd and PdO particles. The process of ethanol electrooxidation on the catalyst was characterized by high overvoltage (up to 800 mV). The overvoltage of the formic acid electrochemical oxidation on Pd/C is 590 mV less than on Pt/C.

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Formic Acid Electrooxidation on Platinum, Resolution of the Kinetic Mechanism in Steady State and Evaluation of the Kinetic Constants

Cited by 14 publications

References 29 publications

Thorough Analysis of the Effect of Temperature on the Electro-Oxidation of Formic Acid

Thorough Analysis of the Effect of Temperature on the Electro-Oxidation of Formic Acid

Fundamental Reaction Limitations for Formic Acid Oxidation

New Electrochemical Approach for the Synthesis of Pd‐PdO/C Electrocatalyst and Application to Formic Acid Electrooxidation

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