On the behavior of CO oxidation on shape-controlled Pt nanoparticles in alkaline medium

Farias, Manuel J. S.; Vidal‐Iglesias, Francisco J.; Solla-Gullón, José; Herrero, Enrique; Feliu, Juan M.

doi:10.1016/j.jelechem.2013.07.017

Cited by 26 publications

(23 citation statements)

References 45 publications

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“…Electrochemical techniques offer detailed information on the surface structure of shape-controlled metal nanoparticles based on a large number of nanoparticles that are available on the electrode surface (Solla-Gullón et al, 2004, 2008; Chen et al, 2012; Farias et al, 2014; García-Cruz et al, 2019; Mayet et al, 2019). Voltammograms characteritic of low-index planes on the surface of Pt nanoparticles in both acidic and alkaline electrolytes were recently reported in the literature (Vidal-Iglesias et al, 2012; Devivaraprasad et al, 2014; Jukk et al, 2017).…”

Section: Structure Sensitivity Of Orr With Single Crystal Electrodes mentioning

confidence: 99%

“…Thus, many research groups investigated electrooxidation of organic molecules (formic acid, carbon monoxide, methanol etc. ), hydrogen evolution, and oxygen reduction on low-index crystallographic planes of Pt and Pd (Housmans and Koper, 2003; Hoshi et al, 2006; Solla-Gullón et al 2008; Grozovski et al, 2010; Farias et al, 2014). In particular, the kinetics of ORR was found to be dependent on the exposed crystallographic planes ({hkl}) as reported with single crystal Pt and Pd surfaces and on electronic factors decided by the surface, subsurface and bulk compositions (Marković et al, 1994, 1995, 1997; Stamenkovic et al, 2002, 2006; Kondo et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

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Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

et al. 2019

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Shape-controlled precious metal nanoparticles have attracted significant research interest in the recent past due to their fundamental and scientific importance. Because of their crystallographic-orientation-dependent properties, these metal nanoparticles have tremendous implications in electrocatalysis. This review aims to discuss the strategies for synthesis of shape-controlled platinum (Pt) and palladium (Pd) nanoparticles and procedures for the surfactant removal, without compromising their surface structural integrity. In particular, the electrocatalysis of oxygen reduction reaction (ORR) on shape-controlled nanoparticles (Pt and Pd) is discussed and the results are analyzed in the context of that reported with single crystal electrodes. Accepted theories on the stability of precious metal nanoparticle surfaces under electrochemical conditions are revisited. Dissolution, reconstruction, and comprehensive views on the factors that contribute to the loss of electrochemically active surface area (ESA) of nanoparticles leading to an inevitable decrease in ORR activity are presented. The contribution of adsorbed electrolyte anions, in-situ generated adsorbates and contaminants toward the ESA reduction are also discussed. Methods for the revival of activity of surfaces contaminated with adsorbed impurities without perturbing the surface structure and its implications to electrocatalysis are reviewed.

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Section: Structure Sensitivity Of Orr With Single Crystal Electrodes mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

et al. 2019

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“…An additional characteristic of the voltammograms is that they contain, aside from the prevawe, a shoulder at low potentials followed by a peak at higher potentials. The general shape is almost independent of the shape of the nanoparticles, although the ratio of the different peaks and the exact peak position depends on the specific shape [75]. It Another difference with the acidic conditions is the small effect of the support in the stripping voltammogram.…”

Section: Co Oxidation On Pt Nanoparticles In Alkaline Mediamentioning

confidence: 99%

“…Finally, the presence of two peaks is the result of a nucleation and growth model. As the effect of different scan rates and partial stripping indicates [75], both peaks are interconnected. Peak potentials have the same scan rate dependence.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Understanding CO oxidation reaction on platinum nanoparticles

Arán‐Ais

Vidal‐Iglesias

Farias

et al. 2017

Journal of Electroanalytical Chemistry

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To understand how the CO oxidation reaction proceeds on nanoparticles, which have complex surface structures, the behavior of the nanoparticles for the reaction has to be related to that of single crystal electrodes with a well-defined surface structure.However, the direct extrapolation of the results is not possible because significant differences in the behavior between both type of surfaces are observed. In single crystal electrodes in both acidic and alkaline media, the reaction initiates on defects on the CO adlayer. These defects can be already present on the surface, as surface defects or steps, or generated during the formation of the CO adlayer. In the case of steps, the oxidation starts on the lower part of the step. The only difference between the reaction behavior between acidic and alkaline solutions is the lower mobility of the CO in alkaline solutions, which generates adlayers with higher number of defects and give rise to multiple stripping peaks in stepped surfaces. Using these results, the differences of the behavior between single crystal electrodes and nanoparticles can be rationalized. In spite of the fact that nanoparticles have small ordered domains, the presence of sites in which the reaction is initiated, equivalent to the site in the lower part of the step, is almost negligible, and thus, the oxidation reaction takes place at higher potential values A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT2 than in stepped surfaces with similar domain size. Also the effect of nanoparticle agglomeration in the oxidation has been rationalized.nanomaterials [8][9][10][11][12][13][14][15][16][17]. Regarding the electrochemical characterization of Pt surfaces, this type of studies has been mainly performed in acid medium. It is important to bear in mind that for this purpose, it has to be considered that the nanoparticles are not perfect surfaces, showing different type of sites on their surfaces. In addition, and unlike single crystal basal planes, which present ideal infinite terraces, nanoparticles possess shorter and narrower ordered domains. Even in the case of stepped surfaces where the width of the terrace is controlled, the length of the terrace is ideally infinite. The first manuscript where CO oxidation was evaluated with shape-controlled nanoparticles was reported by

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“…In the present case, it was found that the contrasting balances in activity of different sites caused by changing the (electro)chemical (solution) environment of a Pt catalyst was related to the type of site, and seemed to be influenced by the surface scale of the catalyst in question. From comparison of the voltammetric profiles for CO oxidation on shapecontrolled Pt nanoparticles in acid72 and alkaline73,74 solutions, it can be concluded that changing the solution pH from acidic to alkaline is accompanied by the promotion of all types of catalytic sites at nanoparticle surfaces. Hence, the contrasting balances in catalytic activity at low coordinated sites on extended Pt surfaces, compared to the (111) terraces, indicate that low coordinated sites on a stepped surface present different catalytic behavior, compared to low coordinated sites on a Pt nanoparticle.The solution pH also appeared to have different effects on the HUPD binding energy, depending on the site at stepped Pt surfaces.…”

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confidence: 99%

Site-specific catalytic activity of model platinum surfaces in different electrolytic environments as monitored by the CO oxidation reaction

Farias

Mello

Tanaka

et al. 2017

Journal of Catalysis

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Stepped Pt surfaces having different width (111) terraces interrupted by (110) or (100) monoatomic steps were employed to evaluate the catalytic activity towards CO oxidation at specific sites of these surfaces in HClO4, H2SO4, and H3PO4 solutions, as well as in phosphate buffer and alkaline solution. The catalytic activity at the (111) terraces was sensitive to the nature of the anions derived from the electrolyte dissociation, while no effect on catalytic activity was detected at the monoatomic steps. For the same stepped surface, a change in solution pH, passing from acid to alkaline solutions, had contrasting effects on catalytic activity at the (111) terraces and the step sites, with the catalytic activity of the (111) terraces improving, while catalytic activity at the step sites deteriorated. It was found that the release of CO surface sites occurred preferentially from the (111) terraces of the Pt(s)-[(n-1)(111)×(110)] series, while from Pt(s)-[(n)(111)×(100)] surfaces, (111) terrace and (100) step sites were released simultaneously.

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On the behavior of CO oxidation on shape-controlled Pt nanoparticles in alkaline medium

Cited by 26 publications

References 45 publications

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

Electrocatalysis of Oxygen Reduction Reaction on Shape-Controlled Pt and Pd Nanoparticles—Importance of Surface Cleanliness and Reconstruction

Understanding CO oxidation reaction on platinum nanoparticles

Site-specific catalytic activity of model platinum surfaces in different electrolytic environments as monitored by the CO oxidation reaction

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