Surface-enhanced IR spectroscopy investigation on the electro-oxidation of CO adlayer at a polycrystalline Pt film electrode in Cl−-containing HClO4

Peng, Bin; Yan, Yan-Gang; Cai, Wen‐Bin

doi:10.1016/j.electacta.2010.04.029

Cited by 10 publications

(9 citation statements)

References 31 publications

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“…Incidentally, OH stretching band at 3660 cm ¹1 of non-hydrogen-bonded water molecules co-adsorbed with CO, observed in the absence of chloride ions, 40,41 was not observed in the presence of 1.0 © 10 ¹4 M chloride ions or higher. A similar result has been obtained by Peng et al, 27 who have observed the interfacial free water coverage decreases by a factor of ca. 1/4 with 1 mM chloride ions during oxidation of adsorbed CO formed from CO gas.…”

Section: ¹1supporting

confidence: 76%

“…7(a2) and (b2). Peng et al 27 and Guillaume et al 43 have reported stabilization of adsorbed CO by chloride ion adsorption. We suppose that the reason for the stabilization is a strengthening of Pt-CO bond by chloride ion adsorption due to an increase in the electron back-donation from the metal to 2O* orbital of CO. 44 This is supported by the fact that the wavenumber of CO L decreased with increasing chloride ion concentrations, e.g., from 2071 to 2054 cm ¹1 at 0.50 V when the chloride ion concentration was increased from 1.0 © 10 ¹4 to 1.0 © 10 ¹1 M with 1.0 M methanol.…”

Section: ¹1mentioning

confidence: 99%

“…23, 24 Sobkowski et al 25,26 have reported that methanol adsorption is completely inhibited with 1 mol/L (M) chloride ions for 6 © 10 ¹2 M methanol by using 14 Clabeled methanol. Peng et al 27 have shown that the potential for oxidation of CO adlayer positively shifts in the presence of 1 mM chloride ions in a 0.1 M perchloric acid solution. They have also shown that chloride ion adsorption disrupts the interfacial free water structure on top of CO adlayer by surface-enhanced infrared absorption spectroscopy (SEIRAS).…”

Section: Introductionmentioning

confidence: 99%

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Regeneration Oscillation Observed during Oxidation of Methanol, Formic Acid, and Formaldehyde with Chloride Ions

et al. 2014

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A new type of oscillation, which we name regeneration oscillation, is investigated in detail. The regeneration oscillation is the ordinary potential oscillation with the higher turning potential lower than 0.85 V appearing repeatedly after the potential stays at a value higher than 1.0 V for a long time, of the order of 10 min or an hour. The oscillation has been observed during the oxidation of methanol, formaldehyde, and formic acid at 315 K when their concentrations are high, 1 or 10 mol/L (M), in the presence of high chloride ion concentrations, such as 10 −2 M, at a current far lower than the maximum current for the appearance of ordinary oscillation. The reason for the appearance of regeneration oscillation has been found by voltammetry and surface-enhanced infrared absorption spectroscopy to be due to the presence of two potentials for oxidizing adsorbed CO, one shifting to a value higher than 1.0 V and the other remaining unchanged, with increasing chloride ion concentration.

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Section: ¹1supporting

confidence: 76%

Section: ¹1mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Regeneration Oscillation Observed during Oxidation of Methanol, Formic Acid, and Formaldehyde with Chloride Ions

et al. 2014

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“…Nonetheless, tensile stress of the same magnitude is still observed. As surface H cannot be the origin of the tensile stress, this tensile stress response could be related to the removal of bridge and multibound CO, CO B , which has been previously observed with in situ ATR-FTIRS , and ATR-SEIRAS − studies. The peak intensity of CO B continuously decreased during the anodic scan, even before the onset of the prepeak.…”

Section: Results and Discussionmentioning

confidence: 65%

Electrochemical Surface Stress Development during CO and NO Oxidation on Pt

Zeng

Cohen³

et al. 2016

J. Phys. Chem. C

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The adsorbate-induced surface stress during the electrochemical oxidation of CO and NO on Pt is studied with in situ surface stress measurements and density functional theory (DFT) calculations. The changes in the surface stress response, Δstress, demonstrate the interplay between the adsorbed species during the oxidation process, which is determined by the coverage and the nature of the adsorbates. The oxidation of adsorbed CO, CO ads , shows a nonlinear surface stress response in both acidic and alkaline electrolytes, with the greatest tensile Δstress observed in the beginning of the oxidation where the CO coverage is the highest. Once a significant amount of CO is removed, OH starts to populate the surface and the Δstress becomes compressive. This surface stress development profilethe nonlinear stress development at high CO ads coverages and the inflection point due to coadsorption of CO and OHis further interrogated by DFT calculations. While a tensile to compressive switch in Δstress is observed during CO oxidation, the oxidation of another strongly bound diatomic adsorbate, NO ads , shows a continuous compressive Δstress. DFT calculations show that this behavior is attributed to the adsorption of the oxidation product, NO 3 − , which induces a similar magnitude of compressive Δstress compared to that of NO ads . Hence, the compressive Δstress from the oxide and hydroxide on the surface governs the surface stress response.

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“…4.2 kJ mol -1 ) 5 from bridge CO (CO B ) to atop CO (CO L ) during the formation of this coadsorbed adlayer at 0.1 V [10][11][12] (the data not shown). Another work 24 about a coadsorbed H 2 O free and CO co-structure at a Pt electrode in a Cl --containing solution also indicated that the H 2 O free probably adsorbed on the top of the CO adlayer through a strong chemical interaction.…”

Section: Resultsmentioning

confidence: 95%

Interfacial Water at a CO-Predosed Platinum Electrode: A Surface Enhanced Infrared Study with Strong Hydrogen Evolution Reaction Control

et al. 2011

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Surface-enhanced IR spectroscopy investigation on the electro-oxidation of CO adlayer at a polycrystalline Pt film electrode in Cl−-containing HClO4

Cited by 10 publications

References 31 publications

Regeneration Oscillation Observed during Oxidation of Methanol, Formic Acid, and Formaldehyde with Chloride Ions

Regeneration Oscillation Observed during Oxidation of Methanol, Formic Acid, and Formaldehyde with Chloride Ions

Electrochemical Surface Stress Development during CO and NO Oxidation on Pt

Interfacial Water at a CO-Predosed Platinum Electrode: A Surface Enhanced Infrared Study with Strong Hydrogen Evolution Reaction Control

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