Electrochemical reduction of molecular oxygen on platinum single crystals

Kadiri, F. El; Faure, R.; Durand, Robert

doi:10.1016/0022-0728(91)85468-5

Cited by 122 publications

(108 citation statements)

References 21 publications

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“…To this end, variations of metal surface crystallography and/or electronic properties by intermixing two or more metals has often been employed to delineated very impotent electrocatalytic trends. For example, it was demonstrated that the kinetics of the ORR on Pt(hkl) vary with the crystal face in a different manner depending on the electrolyte, suggesting that dependence of surface geometry arises primarily due to structure sensitive adsorption of specifically adsorbing anions [1][2][3][4][5] . To probe the electronic effects, the ORR kinetics was investigated on thin metal films grown epitiaxially on foreign metal substrates 6;7 .…”

Section: Introductionmentioning

confidence: 99%

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt₃Ni and Pt₃Co Alloy Surfaces

et al. 2002

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The oxygen reduction reaction (ORR) has been studied on polycrystalline Pt 3 Ni and Pt 3 Co alloys in acid electrolytes using the rotating ring disk electrode (RRDE) method. Preparation and characterization of alloy surfaces were performed in ultra high vacuum (UHV). Clearly defined surface composition was determined via low energy ion scattering (LEIS) spectroscopy. Polycrystalline bulk alloys of Pt 3 Ni and Pt 3 Co were prepared in UHV having two different surface composition: one with 75 % Pt and the other with 100 % Pt. The latter we call a "Pt-skin" structure and is produced by an exchange of Pt and Co in the first two layers. The base voltammetry in 0.1 M HClO 4 solution of the 75% Pt alloy surface indicated a decrease of H upd pseudocapacitance (ca. 30-40 µC/cm 2 ) consistent with the surface composition determined in UHV. With the exception of the "Pt-skin" surface on Pt 3 Ni, all the alloy electrodes exhibited stable i-E curves with repeated cycling between 0.05-1.0 V at all temperatures. Activities of Pt-alloys for the ORR were compared to the polycrystalline Pt in 0.5M H 2 SO 4 and 0.1M HClO 4 electrolytes in the temperature range of 293 < T < 333 K. It was found that the order of activity is dependent on the nature of anions of supporting electrolytes: in H 2 SO 4 the activity increased in the order Pt 3 Ni > Pt 3 Co > Pt; in HClO 4 , however, the order of activities at 333 K was "Pt-skin"> Pt 3 Co > Pt 3 Ni > Pt. The catalytic enhancement was greater in 0.1 M HClO 4 than in 0.5 M H 2 SO 4 , with the maximum enhancement observed for the "Pt-skin" on Pt 3 Co in 0.1 M HClO 4 being 3-4 times that for pure Pt. Catalytic enhancement of the ORR on Pt 3 Ni and Pt 3 Co vs. Pt was attributed to the inhibition of Pt-OH ad formation on Pt sites surrounded by "oxide" covered Ni and Co atoms beyond 0.8 V. Kinetic analyses of RRDE data revealed that kinetic parameters for the ORR and the production of H 2 O 2 on the Pt 3 Ni, Pt 3 Co and "Pt-skin" alloys are the same as on pure Pt: reaction order, m=1, two identical Tafel slopes in HClO 4 and a single Tafel slope in H 2 SO 4 , apparent activation energy, ≈ 21-25 kJ/mol. The fact that essentially the same kinetic parameters are assessed from the analysis of experimental results for the ORR on all three surfaces implies that the reaction mechanism on Pt 3 Ni and Pt 3 Co alloy surfaces is the same as one proposed for pure Pt, i.e., a "series" 4e -reduction pathway.

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Section: Introductionmentioning

confidence: 99%

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt₃Ni and Pt₃Co Alloy Surfaces

et al. 2002

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“…Figure 3 shows the CV of the 5-layer GNC electrode measured in a 0.1 M H 2 SO 4 solution after Pd deposition 6 . Hydrogen adsorption and desorption peaks, which were absent before Pd deposition, are observed between −200 and 0 mV, and surface oxide formation and reduction take place at a much more positive potential than before Pd deposition.…”

Section: Electrochemical Deposition Of Pd On the Surface Of Bare Gncsmentioning

confidence: 99%

“…Hydrogen adsorption and desorption peaks, which were absent before Pd deposition, are observed between −200 and 0 mV, and surface oxide formation and reduction take place at a much more positive potential than before Pd deposition. The amount of Pd 6 The CV in figure 3 has a background originating from dissolved oxygen within the multilayer. Although the solution was deaerated by passing Ar gas for more than 30 min, dissolved oxygen remained within the multilayer.…”

Section: Electrochemical Deposition Of Pd On the Surface Of Bare Gncsmentioning

confidence: 99%

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Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Harada

Noguchi

Zanetakis

et al. 2011

Science and Technology of Advanced Materials

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Multilayers of gold nanoclusters (GNCs) coated with a thin Pd layer were constructed using GNCs modified with self-assembled monolayers (SAMs) of mercaptoundecanoic acid and a polyallylamine hydrochloride (PAH) multilayer assembly, which has been reported to act as a three-dimensional electrode. SAMs were removed from GNCs by electrochemical anodic decomposition and then a small amount of Pd was electrochemically deposited on the GNCs. The kinetics of the oxygen reduction reaction (ORR) on the Pd modified GNC/PAH multilayer assembly was studied using a rotating disk electrode, and a significant increase in the ORR rate was observed after Pd deposition. Electrocatalytic activities in alkaline and acidic solutions were compared both for the GNC multilayer electrode and Pd modified GNC electrode.

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“…The ORR on Pt(111) has been looked at under electrochemical conditions in numerous experimental studies [5][6][7]; however, less attention has been given to the same reaction under non-electrochemical conditions [8][9][10][11][12][13][14]. The reactivity of hydrogen with pre-adsorbed atomic oxygen on Pt(111) was studied in the temperature range of 300-450 K using Auger electron spectroscopy (AES) [8].…”

Section: Introductionmentioning

confidence: 99%

Microkinetic Modeling of the Oxygen Reduction Reaction at the Pt(111)/Gas Interface

et al. 2014

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A microkinetic model of the oxygen reduction reaction (ORR) on Pt(111) under a gaseous H 2 and O 2 atmosphere is used to predict and explain which compositions of H 2 and O 2 lead to the fastest rate of water formation for temperatures between 600 and 900 K. For a stoichiometric (2:1) mixture of H 2 and O 2 the rate-determing step is found to transition from O H hydrogenation to O 2 H dissociation over this same temperature range. These results are explained in terms of the temperature dependence of the surface coverages of O H and H H and are shown to be consistent with kinetic models aimed at understanding the ORR under electrochemical conditions.

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Electrochemical reduction of molecular oxygen on platinum single crystals

Cited by 122 publications

References 21 publications

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt₃Ni and Pt₃Co Alloy Surfaces

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt₃Ni and Pt₃Co Alloy Surfaces

Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Microkinetic Modeling of the Oxygen Reduction Reaction at the Pt(111)/Gas Interface

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Electrochemical reduction of molecular oxygen on platinum single crystals

Cited by 122 publications

References 21 publications

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt3Ni and Pt3Co Alloy Surfaces

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt3Ni and Pt3Co Alloy Surfaces

Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Microkinetic Modeling of the Oxygen Reduction Reaction at the Pt(111)/Gas Interface

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Product

Resources

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Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt₃Ni and Pt₃Co Alloy Surfaces

Surface Composition Effects in Electrocatalysis: Kinetics of Oxygen Reduction on Well-Defined Pt₃Ni and Pt₃Co Alloy Surfaces