Probing the Surface of Noble Metals Electrochemically by Underpotential Deposition of Transition Metals

Mayet, Nolwenn; Servat, Karine; Kokoh, K. Boniface; Napporn, Têko W.

doi:10.3390/surfaces2020020

Cited by 45 publications

(45 citation statements)

References 100 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since it was difficult to unambitiously define the hydrogen region on our Pd films, the ECSA values using this procedure are not reported. Cu UPD has also been previously used to define the ECSA of both polycrystalline and single crystal electrodes [21][22][23]. Consistent with these reports, this technique was found to give ECSA values 150%-200% larger than that of the other methods.…”

Section: Electrochemical Surface Area Characterizationsupporting

confidence: 59%

Influence of Nanocrystalline Palladium Morphology on Alkaline Oxygen Reduction Kinetics

2019

View full text Add to dashboard Cite

The structure sensitivity of the alkaline oxygen reduction reaction (ORR) on palladium is of great interest as cost considerations drive the need to find a replacement for platinum catalysts. The kinetics of alkaline ORR were investigated on nanocrystalline palladium (Pd) films with domain sizes between 14 and 30 nm that were synthesized by electrodeposition from aqueous electrolytes. Ten Pd films were prepared under varying electrodeposition parameters leading to each having a unique texture and morphology. The sensitivity of initial alkaline ORR kinetics to the Pd surface structure was evaluated by measuring the kinetic current density and number of electrons transferred for each film. We show through scanning electron microscopy (SEM), x-ray diffraction (XRD), atomic force microscopy (AFM), and voltammetry from rotating disc electrodes (RDEs) that the fastest alkaline ORR kinetics are found on Pd surfaces with high surface roughness, which themselves are composed of fine grains. Such a study is useful for developing membrane electrode assemblies (MEAs) based on directly electrodepositing catalyst onto a conductive diffusion layer.

show abstract

Section: Electrochemical Surface Area Characterizationsupporting

confidence: 59%

Influence of Nanocrystalline Palladium Morphology on Alkaline Oxygen Reduction Kinetics

2019

View full text Add to dashboard Cite

show abstract

“…However, it would highly desirable to have some electrochemical surface probe to quantitatively evaluate the surface structure of these nanoparticles. In this sense, Cu UPD on Pd is an interesting process because it has been reported to be sensitive to the surface structure of the Pd electrodes (Chierchie and Mayer, 1988; Cuesta et al, 1999; Herrero et al, 2001; Vidal-Iglesias et al, 2006; Mayet et al, 2019). To evaluate this surface structure sensitivity, Figure 4 shows the Cu UPD profiles obtained in a 0.1 M H 2 SO 4 + 1 mM CuSO 4 + 1 mM NaCl solution with the three Pd basal planes (Pd(111), Pd(100), and Pd(110) and with a polyoriented Pd bead.…”

Section: Resultsmentioning

confidence: 99%

“…Among others, the use of pure electrochemical probes has been shown to be a powerful technique to successfully characterize the surface structure of different types of shape-controlled metal nanoparticles (Solla-Gullón et al, 2004, 2008a; Chen et al, 2012; Farias and Feliu, 2019; García-Cruz et al, 2019; Mayet et al, 2019). In addition, it is worth noting that this electrochemical surface structure characterization is (i) statistically representative, because thousands of nanoparticles are measured simultaneously, and (ii) performed in a similar environment than those that will be employed during the electrochemical reactions.…”

Section: Introductionmentioning

confidence: 99%

“…However, in the case of palladium, and despite some preliminary attempts (Jin et al, 2012; Solla-Gullon et al, 2015; Higuchi et al, 2018), a systematic analysis to qualitatively and quantitatively determine the presence of well-defined surface domains at the surface of different shape and size controlled Pd nanoparticles is still missing. This analysis will be based on the Cu UPD process on Pd which was reported to be highly sensitive to the surface structure as previously illustrated with Pd single crystal surfaces (Chierchie and Mayer, 1988; Cuesta et al, 1999; Vidal-Iglesias et al, 2006, 2007; Korzeniewski et al, 2012; Mayet et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Surface Structure Characterization of Shape and Size Controlled Pd Nanoparticles by Cu UPD: A Quantitative Approach

et al. 2019

View full text Add to dashboard Cite

The search for new surface sensitive probes that characterize the surface structure of shape and size-controlled nanoparticles is an interesting topic to properly understand the correlations between electrocatalytic properties and surface structure at the nanoscale. Herein, we report the use of Cu UPD to characterize, not only qualitatively but also quantitatively, the surface structure of different Pd nanoparticles with controlled particle shape and size. Thus, Pd nanoparticles with cubic, octahedral and rhombic dodecahedral shapes, that is, with preferential {100}, {111}, and {110} surface structures, respectively, were prepared. In addition, cubic Pd nanoparticles with different particles sizes and spherical (2–3 nm) Pd nanoparticles were also synthesized. Based on the Cu UPD results on Pd single crystals, a new approach is proposed to qualitatively and quantitatively determine the percentages of {100}, {111}, and {110} surface domains present at the surface of the different shape and size controlled Pd nanoparticles. The results reported clearly show the benefits of this Cu UPD to get detailed information of the surface structure of the nanoparticles according to their particle shape and size.

show abstract

“…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%

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

et al. 2019

View full text Add to dashboard Cite

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.

show abstract

Probing the Surface of Noble Metals Electrochemically by Underpotential Deposition of Transition Metals

Cited by 45 publications

References 100 publications

Influence of Nanocrystalline Palladium Morphology on Alkaline Oxygen Reduction Kinetics

Influence of Nanocrystalline Palladium Morphology on Alkaline Oxygen Reduction Kinetics

Surface Structure Characterization of Shape and Size Controlled Pd Nanoparticles by Cu UPD: A Quantitative Approach

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

Contact Info

Product

Resources

About