Comparative evaluation of surface structure specificity of kinetics of UPD and OPD of H at single-crystal Pt electrodes

Conway, B. E.; Barber, J.; Morin, Sylvie

doi:10.1016/s0013-4686(98)00214-x

Cited by 115 publications

(120 citation statements)

References 34 publications

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“…Resulting Faradayic currents and current densities (normalized vs active surface area) recorded during BCV at 100 mV s [53,54] The active Pt surface area was determined by integrating the H-upd current in the negativegoing potential scan and subtracting the double-layer contribution. The corresponding H-upd charge was converted into the active Pt surface area by assuming a H-upd monolayer charge on polycrystalline Pt of 210 mC cm À2 [55] and a hydrogen coverage at the onset of bulk evolution of 0.77 monolayer.…”

Section: Electrochemical Characterizationmentioning

confidence: 99%

Oscillatory behaviour in Galvanostatic Formaldehyde Oxidation on Nanostructured Pt/Glassy Carbon Model Electrodes

et al. 2010

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The electrocatalytic oxidation of formaldehyde, which results in CO(2) and HCOOH formation, was investigated under galvanostatic conditions on nanostructured Pt/glassy carbon (GC) electrodes fabricated by employing colloidal lithography (CL). The measurements were performed on structurally well-defined model electrodes of different Pt surface coverages under different applied currents (current densities) and at constant electrolyte transport in a thin-layer flow cell connected to a differential electrochemical mass spectrometry (DEMS) setup to monitor the dynamic response of the reaction selectivity under these conditions. Periodic oscillations of the electrode potential and the CO(2) formation rate appear not only for a continuous Pt film, but also for the nanostructured Pt/GC electrodes when a critical current density is exceeded. The critical current density for achieving regular oscillation patterns increased with decreasing Pt nanodisk density. Lower oscillation frequencies of the electrode potential and lower CO(2) formation rate for nanostructured Pt/GC electrodes compared to continuous Pt film at similar applied current densities suggest that transport processes play an essential role. Moreover, from the simple periodic response of the nanostructured electrodes it follows that all individual Pt disks in the array oscillate in synchrony. This result is discussed in terms of the different modes of spatial coupling present in the system: global coupling, migration coupling and mass transport of the essential chemical species, and the coverage of corresponding adsorbates.

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Section: Electrochemical Characterizationmentioning

confidence: 99%

Oscillatory behaviour in Galvanostatic Formaldehyde Oxidation on Nanostructured Pt/Glassy Carbon Model Electrodes

et al. 2010

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“…We follow the kinetic analysis of Conway et al [87]. The HER/HOR on Pt can be considered to proceed via the following steps with the rate constants indicated:…”

Section: H Opd On the Anodementioning

confidence: 99%

Operando XAS Techniques: Past, Present, and Future

Roth

Ramaker

2010

Fuel Cell Science

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“…[8][9][10][11][12][13] Photovoltaic cells can be conjugated with electrolysers 1,2 to generate hydrogen from water. 14-18 When electrochemically splitting water into hydrogen and oxygen, extremely acidic [19][20][21][22][23][24][25][26] or alkaline [22][23][24][25][26][27][28] pH conditions are favored because higher electrocatalytic activities are generally obtained compared with those at neutral pH. [29][30][31] The fundamental issue regarding the hydrogen evolution reaction (HER) and oxygen evolution reaction under neutral pH conditions is reactant switching: hydronium and hydroxyl ions are the reactants at acidic and alkaline pH, respectively, whereas to attain substantial reaction rates at neutral pH, water molecule must act as the reactant.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Hydrogen Evolution under Densely Buffered Neutral pH Conditions

Takanabe

2015

J. Phys. Chem. C

104

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Under buffered neutral pH conditions, solute concentrations drastically influence the hydrogen evolution reaction (HER). The iR-free HER performance as a function of solute concentration was found to exhibit a volcano-shaped trend in sodium phosphate solution at pH 5, with the maximum occurring at 2 M. A detailed microkinetic model that includes calculated activity coefficients, solution resistance, and mass-transport parameters accurately describes the measured values, clarifying that the overall HER performance is predominantly governed by mass-transport of slow phosphate ions (weak acid). In the HER at the optimum concentration of approximately 2 M sodium phosphate at pH 5, our theoretical model predicts that the concentration overpotential accounts for more than half of the required overpotential. The substantial concentration overpotential would originate from the electrolyte property, suggesting that the proper electrolyte engineering will result in an improved apparent HER performances.

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Comparative evaluation of surface structure specificity of kinetics of UPD and OPD of H at single-crystal Pt electrodes

Cited by 115 publications

References 34 publications

Oscillatory behaviour in Galvanostatic Formaldehyde Oxidation on Nanostructured Pt/Glassy Carbon Model Electrodes

Oscillatory behaviour in Galvanostatic Formaldehyde Oxidation on Nanostructured Pt/Glassy Carbon Model Electrodes

Operando XAS Techniques: Past, Present, and Future

Electrocatalytic Hydrogen Evolution under Densely Buffered Neutral pH Conditions

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