Surface-enhanced IR absorption on platinum nanoparticles: an application to real-time monitoring of electrocatalytic reactions

Miki, Atsushi; Ye, Shen; Osawa, Masatoshi

doi:10.1039/b203392e

Cited by 379 publications

(436 citation statements)

References 16 publications

(37 reference statements)

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“…Formaldehyde is then nearly completely hydrated to methylene glycol, which will be oxidized to formic acid in solution, either directly (reaction 12) or through adsorbed formate (reaction 11 and 13). Finally, this scheme also explain the fact that formate was observed on platinum surfaces during the electrochemical oxidation of methanol (reactions 8-12), formic acid (reaction 13) and formaldehyde (reactions 10-13), as well as the fact that CO ads was found during the oxidation of formaldehyde and of formic acid (reactions 10, 11, and 16) by various authors [44,[49][50][51], substantiating the proposed reaction scheme.…”

Section: Methanol Electrooxidation On Ptsupporting

confidence: 53%

Mechanisms of Carbon Monoxide and Methanol Oxidation at Single-crystal Electrodes

et al. 2007

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The electrochemical oxidation of carbon monoxide and methanol on single-crystal noble metal electrodes has been studied using cyclic voltammetry, chronoamperometry, in situ FTIR spectroscopy, online electrochemical mass spectrometry, and theoretical methods. The oxidation of CO was found to be enhanced by steps and defects. Furthermore, the surface diffusion rate was found to have a significant influence on the kinetics of the oxidation process: for high diffusion rates, such as the oxidation of CO on platinum, the kinetics can be described by a mean field model, while for low diffusion rates, such as CO oxidation on rhodium in sulfuric acid, a nucleationand-growth model was found to be more suitable. Voltammetric and mass spectrometric measurements on the oxidation of methanol on platinum indicate that steps enhance the overall reaction rate. In general, the selectivity towards the direct oxidation pathway through soluble intermediates was found to be higher in the absence of strongly adsorbing anions. In both perchloric and sulfuric acid, this selectivity was also found to increase with increasing step density. In sulfuric acid, Pt(111) shows the highest relative contribution for the direct pathway of all surfaces studied in that electrolyte. Based on these results, a detailed reaction scheme for the electrochemical oxidation of methanol is presented.

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Section: Methanol Electrooxidation On Ptsupporting

confidence: 53%

Mechanisms of Carbon Monoxide and Methanol Oxidation at Single-crystal Electrodes

et al. 2007

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“…The Pt working electrode was a thin (ca. 50 nm) film formed on the total reflecting plane of a hemicylindrical Si ATR prism by a chemical deposition technique [28,29]. The electrode surface was very smooth by eye inspection and as shiny as well-polished bulk electrodes.…”

Section: Methodsmentioning

confidence: 99%

“…Experimental details of ATR-SEIRAS were given elsewhere [23,24,[26][27][28][29]. The Pt working electrode was a thin (ca.…”

Section: Methodsmentioning

confidence: 99%

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Kunimatsu

Senzaki

Samjeské

et al. 2007

Electrochimica Acta

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151

146

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Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm -1 . This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.

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“…Forty years ago, Capon and Parsons [1] summarized the results of earlier studies in the dual-path mechanism for HCOOH electrooxidation at noble metal electrodes, which has been widely accepted by the community. Nonetheless, the nature of the reactive intermediate for the direct pathway is still strongly debated in the literature, especially since adsorbed formate (HCOOads) has been detected by Osawa's group employing in situ Infrared (IR) spectro-electrochemistry [2] . This latter species has been proposed as candidate for the reactive intermediate species in numerous contributions [3][4][5][6][7][8] , while, oppositely, it has been considered as a site-blocking spectator species in other ones [9][10][11][12] .…”

Section: Introductionmentioning

confidence: 99%

Formic Acid Electrooxidation on Noble‐Metal Electrodes: Role and Mechanistic Implications of pH, Surface Structure, and Anion Adsorption

et al. 2014

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We have investigated the influence of the electrolyte pH on formic acid (HCOOH) electro-oxidation on both polycrystalline Pt and Au electrodes, and on single-crystalline Au electrodes in perchloric and sulphuric acid based electrolytes. On Au electrodes, the potentiodynamic oxidation currents are found to depend in a nonlinear way on the electrolyte pH, in a bell-shaped relation with a maximum of the catalytic activity at the pKa of HCOOH. On polycrystalline Pt electrodes, this feature is not observed and the catalytic activity increases steadily with increasing pH up to pH ≈ 5 followed by a plateau until pH 10, in contrast with recent observations [T. Joo et al., J. Amer. Chem. Soc., 135 (2013) 9991]. In addition, for Au surfaces, the reaction is only weakly influenced by the electrode surface structure, while for Pt structural effects are known to be considerable. Anion effects, in contrast, are much stronger for reaction on Au than for Pt electrodes. Also, it is shown that Pt group metal free Au electrodes do not oxidize molecular hydrogen under reaction conditions. The results are discussed in relation to findings in previous mechanistic studies. Most important, the activity is on both electrodes closely correlated with the concentration of HCOO -anions, for Au with both HCOO -and HCOOH concentrations. Based on these results, a number of mechanistic proposals put forward in earlier studies must be discarded, examples for mechanisms compatible with these results are discussed.

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Surface-enhanced IR absorption on platinum nanoparticles: an application to real-time monitoring of electrocatalytic reactions

Abstract: Molecules adsorbed on Pt nanoparticles prepared on Si by a chemical deposition technique exhibit extremely strong IR absorption, which enables fast time-resolved IR monitoring of electrocatalytic reactions.

Cited by 379 publications

References 16 publications

Mechanisms of Carbon Monoxide and Methanol Oxidation at Single-crystal Electrodes

Mechanisms of Carbon Monoxide and Methanol Oxidation at Single-crystal Electrodes

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Formic Acid Electrooxidation on Noble‐Metal Electrodes: Role and Mechanistic Implications of pH, Surface Structure, and Anion Adsorption

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