Hydrogen Permeation as a Tool for Quantitative Characterization of Oxygen Reduction Kinetics at Buried Metal-Coating Interfaces

Vijayshankar, Dandapani; Bashir, Asif; Evers, Stefan; Rohwerder, Michael

doi:10.1016/j.electacta.2015.12.030

Cited by 14 publications

(19 citation statements)

References 20 publications

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“…17 Briefly, a double electrochemical cell with the one-side PVB coated Pd as the working electrode is sandwiched in-between the two individual cells (working electrode area = 0.3286 cm 2 ). Each independent cell consisted of a Luggin capillary that accommodated the Red Rod reference electrode and only the entry cell contained the Au foil as a counter electrode inside a glass shield.…”

Section: C780mentioning

confidence: 99%

“…Further, by monitoring the open circuit potential established as a result of this dynamic equilibrium between ORR and HOR at the exit side, the current-potential relationship (I(U) curve) can be quantitatively measured. By proving consistency 17 between the I(U) curve for ORR from this approach and that obtained from standard three electrode measurements on bare Pd surface in acid, alkaline and buffer electrolyte medium, the assumption of [H exit ] ≈ 0 was validated. Further, the rate determining step (rds) for ORR has been proved by earlier reports 20 to be the formation of the superoxide O − 2 , since H is not directly involved in this rds, i.e.…”

mentioning

confidence: 99%

“…Thus, at the exit side, a dynamic equilibrium between hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR) is established. It was proved 17 that once this dynamic equilibrium is established, one is able to obtain direct access to the oxygen reduction rate at the exit side from the known hydrogen uptake on the entry side. Further, by monitoring the open circuit potential established as a result of this dynamic equilibrium between ORR and HOR at the exit side, the current-potential relationship (I(U) curve) can be quantitatively measured.…”

mentioning

confidence: 99%

“…17 In this method, the classical Devanathan-Stachurski technique has been adapted, wherein hydrogen permeation from the back side of the sample is used to quantitatively measure the oxygen reduction rate at the metal/organic coating interface on the other side.…”

mentioning

confidence: 99%

“…[2][3][4] Recently, inspired by earlier work on controlling the potential on one side of a palladium membrane by applying a potential on the other side to control the defined hydrogen activity across the sample, [13][14][15][16] a new potentiometric approach using hydrogen permeation as a tool to measure interfacial oxygen reduction rates at this buried metal/organic coating interface has been developed. 17 In this method, the classical Devanathan-Stachurski technique has been adapted, wherein hydrogen permeation from the back side of the sample is used to quantitatively measure the oxygen reduction rate at the metal/organic coating interface on the other side.…”

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confidence: 99%

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Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Vijayshankar

Altin

Merola

et al. 2016

J. Electrochem. Soc.

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Corrosion driven delamination of coatings is crucially determined by the rate of the cathodic oxygen reduction reaction at the buried metal-organic coating interface. Quantitative measurement of this rate at such interfaces by conventional techniques is impeded due to the blocking of ion transport by the coating. A new approach where hydrogen permeation is used as a tool to measure the oxygen reduction rate underneath coatings has been recently introduced. This permeation based potentiometry approach measures the rate of the oxygen reduction reaction by correlating the open circuit potential established as a consequence of the dynamic electrochemical equilibrium between hydrogen oxidation and oxygen reduction reactions on the coated exit side with the hydrogen uptake rate on the entry side. In this work, the interfacial reaction kinetics of the oxygen reduction reaction causing delamination of the coating are investigated by this hydrogen permeation based potentiometric approach. Moreover, thus performed prolonged cathodic polarizations of the palladium/coating interface have been found to destroy the interface, just like it is the case in the cathodic delamination process. Initial results obtained on ultra-thin films of iron on palladium are also presented, showing that the technique is applicable also on technically more relevant metal surfaces. Corrosion driven degradation of the buried metal/organic coating interface is of utmost interest in the contemporary space of coatings science. Earlier studies have shown conclusively that the oxygen reduction reaction (ORR) plays a fundamental role in the destruction of this buried metal/organic coating interface. The role of the interface between organic coating and metal has been object of intense research over last decades. Leidheiser et al.1 pointed out the key role of the cathodic ORR for the degradation process and also showed that diffusion processes such as water and oxygen transport through the coating can influence this delamination rate. Stratmann and co-workers 2-4 proposed a detailed delamination mechanism for a basic polymer coating on steel where galvanic coupling between the defect site of metal dissolution (local anode) and delamination site of electrochemical oxygen reduction (local cathode) supported by cation migration along the polymer/metal interface lead to the progressive deadhesion of the polymer from the underlying metal based on comprehensive analysis of the local electrode potential at the metal/polymer interface using primarily the Scanning Kelvin Probe (SKP) technique along with complementary Auger electron spectroscopy and mechanical deadhesion tests. Fürbeth and Stratmann 5-7 extended their studies to coated zinc (or galvanized steel), which also involves anodic processes at the interface. Also other works by Brewis et al. 8 and Dickie et al. 9 show the importance of interfacial electrochemical reactions on metal/polymer adhesion. Up to now our knowledge about the reactions and how they are determined by the interface itself is too rest...

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Section: C780mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Vijayshankar

Altin

Merola

et al. 2016

J. Electrochem. Soc.

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Limiting Current Density of Oxygen Reduction under Ultrathin Electrolyte Layers: From the Micrometer Range to Monolayers

Zhong

Schulz²,

Wu³

et al. 2021

ChemElectroChem

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The oxygen reduction reaction (ORR) under ultrathin electrolyte layers is a key reaction in many processes, from atmospheric corrosion to energy conversion in fuel cells. However, the ORR current under ultrathin electrolyte layers is difficult to measure using conventional electrochemical methods. Hence, reliable data are scarce for the micrometer range and totally missing for the sub‐micrometer range of the electrolyte layer thickness. Here, we report a novel hydrogen‐permeation‐based approach to measure the ORR current underneath thin and ultrathin electrolyte layers. By using a Kelvin‐probe‐based measurement of the potential, which results from dynamic equilibrium of oxygen reduction and hydrogen oxidation, and the corresponding hydrogen charging current density, the full current‐potential relationship can be constructed. The results shed a new light on the nature of the limiting current density of ORR underneath ultrathin layers of electrolyte.

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Hydrogen loading and reduction of iron oxides on steel studied by XPS with an in situ cell

Wolfsjäger,

Duchoslav,

Kürnsteiner

et al. 2024

Applied Surface Science

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Hydrogen Permeation as a Tool for Quantitative Characterization of Oxygen Reduction Kinetics at Buried Metal-Coating Interfaces

Cited by 14 publications

References 20 publications

Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Probing the Buried Metal-Organic Coating Interfacial Reaction Kinetic Mechanisms by a Hydrogen Permeation Based Potentiometric Approach

Limiting Current Density of Oxygen Reduction under Ultrathin Electrolyte Layers: From the Micrometer Range to Monolayers

Hydrogen loading and reduction of iron oxides on steel studied by XPS with an in situ cell

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