Potential-dependent reconstruction kinetics probed by HER on Au(111) electrodes

Hermann, Johannes M.; Abdelrahman, Areeg; Jacob, Timo; Kibler, Ludwig A.

doi:10.1016/j.electacta.2020.136287

Cited by 11 publications

(10 citation statements)

References 51 publications

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“…The potential-dependent trend is in good agreement with previous reports . However, the absolute values of HER current density are different from literature data (Table S1), which are probably due to different amount of defects and extent of reconstruction of Au(111). − In this study, before measuring the j–E curves for HER in solutions with different pHs, we check the surface condition of Au(111) to make sure the quality of the Au(111) electrode is nearly the same. Specifically, we measure the base CVs of Au(111) in respective solutions of different composition as well as in 0.1 M H 2 SO 4 solution in a consecutive way; the representative CVs are shown in Figure S2 and S1.…”

Section: Resultssupporting

confidence: 87%

The pH-Induced Increase of the Rate Constant for HER at Au(111) in Acid Revealed by Combining Experiments and Kinetic Simulation

Liu,

Zhen,

Zhang

et al. 2023

Anal. Chem.

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Origins of pH effects on the kinetics of electrocatalytic reactions involving the transfer of both protons and electrons, including the hydrogen evolution reaction (HER) considered in this study, are heatedly debated. By taking the HER at Au(111) in acid solutions of different pHs and ionic concentrations as the model systems, herein, we report how to derive the intrinsic kinetic parameters of such reactions and their pH dependence through the measurement of j−E curves and the corresponding kinetic simulation based on the Frumkin−Butler− Volmer theory and the modified Poisson−Nernst−Planck equation. Our study reveals the following: (i) the same set of kinetic parameters, such as the standard activation Gibbs free energy, charge transfer coefficient, and Gibbs adsorption energy for H ad at Au(111), can simulate well all the j−E curves measured in solutions with different pH and temperatures; (ii) on the reversible hydrogen electrode scale, the intrinsic rate constant increases with the increase of pH, which is in contrast with the decrease of the HER current with the increase of pH; and (iii) the ratio of the rate constants for HER at Au(111) in x M HClO 4 + (0.1 − x) M NaClO 4 (pH ≤ 3) deduced before properly correcting the electric double layer (EDL) effects to the ones estimated with EDL correction is in the range of ca. 10 to 40, and even in a solution of x M HClO 4 + (1 − x) M NaClO 4 (pH ≤ 2) there is a difference of ca. 5× in the rate constants without and with EDL correction. The importance of proper correction of the EDL effects as well as several other important factors on unveiling the intrinsic pH-dependent reaction kinetics are discussed to help converge our analysis of pH effects in electrocatalysis.

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Section: Resultssupporting

confidence: 87%

The pH-Induced Increase of the Rate Constant for HER at Au(111) in Acid Revealed by Combining Experiments and Kinetic Simulation

Liu,

Zhen,

Zhang

et al. 2023

Anal. Chem.

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“…This is particularly relevant for structure-sensitive reactions, which can be employed to investigate the dynamics of structural changes. 34,43 From this perspective, the electrocatalytic activity of the nanostructured Au electrodes, obtained through cathodic corrosion in 10 M NaOH and 10 M KOH at various applied potentials, was evaluated with the FAOR and HER. The electrocatalytic behavior towards the FAOR is investigated by comparing the current-potential curves for the Au electrodes in 0.1 M HClO 4 + 0.1 M HCOOH at a scan rate of 10 mV s −1 , as shown in Fig.…”

Section: The Electrocatalytic Behavior Of Cathodically-corroded Au El...mentioning

confidence: 99%

“…For example, the electrocatalytic HER has been employed to probe the kinetics of potential-induced surface reconstruction of Au (111) in contact with either 0.1 M H 2 SO 4 or 0.1 M HClO 4 . 43 Similarly, FAOR has been used to examine the alterations upon adsorption and self-assembly of the 4-mercaptopyridine on Au(111), as well as to monitor the kinetics of surface oxidation of Au(111). 44,45 Furthermore, hydrogen and formic acid are ideal energy carriers, that have garnered considerable attention as prototype reactions in the advancement of sustainable energy technologies.…”

Section: Introductionmentioning

confidence: 99%

Metal deposition and electrocatalysis for elucidating structural changes of gold electrodes during cathodic corrosion

Elnagar¹,

Kibler²,

Jacob³

2023

Green Chem.

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“…While tailoring surface properties is used to design new catalysts, the (electro)catalytic response of an electrode surface sheds light on its surface structure. This is especially true for so-called structure-sensitive reactions, which can inversely be used to study dynamics of structural changes [48]. From both of these fundamental points of view, the electrocatalytic behavior of the nanostructured electrodes obtained by cathodic corrosion has been investigated towards the formic acid oxidation reaction (FAOR) and the hydrogen evolution reaction (HER).…”

Section: The Electrocatalytic Behavior Of Au After Cathodic Corrosionmentioning

confidence: 99%

An affordable option to Au single crystals through cathodic corrosion of a wire: Fabrication, electrochemical behavior, and applications in electrocatalysis and spectroscopy

Elnagar

Hermann

Jacob

et al. 2021

Electrochimica Acta

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Faceting and nanostructuring of polycrystalline gold electrodes by cathodic corrosion in concentrated potassium hydroxide electrolytes has been systematically studied at different electrode potentials. Current-potential curves for the restructured Au electrodes in 0.1 M H2SO4 show characteristic features of Au(111) facets in the double-layer and oxidation region.Thus, the modified Au electrodes adopt properties typically known for well-defined single crystal surfaces. Besides the preferential surface faceting, the electrochemically active surface area (EASA) is enhanced as a function of potential, concentration and time. Scanning electron micrographs show the formation of well-defined triangular pits and nanostructures with a specific orientation confirming the formation of (111)-facets. In this way, the behavior of single crystals is accompanied with the properties of nanoparticles which are of utmost interest in electrocatalysis and surface enhanced Raman spectroscopy (SERS). The electrocatalytic activity of the newly formed "Au(111)" surface from an Au wire has been tested towards the hydrogen evolution reaction (HER) and for the formic acid oxidation reaction (FAOR). The study of electrocatalytic reactions at these nanostructured electrodes allows to identify active centers, which are absent for extended single crystal surfaces.Adsorbed pyridine on the nanostructured Au electrodes directly shows SERS activity, while untreated polycrystalline Au is SERS-inactive. The use of cathodic corrosion of simple wires is a paradigm of SERS-applications in electrochemistry with clean Au electrodes that provide properties of Au(111) single crystals.

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Potential-dependent reconstruction kinetics probed by HER on Au(111) electrodes

Cited by 11 publications

References 51 publications

The pH-Induced Increase of the Rate Constant for HER at Au(111) in Acid Revealed by Combining Experiments and Kinetic Simulation

The pH-Induced Increase of the Rate Constant for HER at Au(111) in Acid Revealed by Combining Experiments and Kinetic Simulation

Metal deposition and electrocatalysis for elucidating structural changes of gold electrodes during cathodic corrosion

An affordable option to Au single crystals through cathodic corrosion of a wire: Fabrication, electrochemical behavior, and applications in electrocatalysis and spectroscopy

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