Surface X-ray Scattering of Pd(111) and Pd(100) Electrodes during the Oxygen Reduction Reaction

Naito, Keita; Nakamura, Masashi; Sakata, Osami; Hoshi, Nagahiro

doi:10.5796/electrochemistry.79.256

Cited by 11 publications

(15 citation statements)

References 26 publications

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“…It was reported that there is substantial expansion in the inter layer spacing (5.3%) between d 12 and d 23 (d 12 and d 23 ; first and second, second and third, respectively) on Pd (100) surfaces while it is only 1.8% on Pd (111) surfaces in oxygen-saturated solution of 0.1 M HClO 4 . Therefore, the high degree of expansion with Pd (100) compared to Pd (111) may correspond to stronger interaction of oxygen with Pd (100) and hence leads to high activity (Naito et al, 2011). The ORR voltammograms over carbon-supported shape-controlled Pd nanoparticles suggest that there is 10-fold of higher ORR activity with Pd nanocubes compared to that of Pd octahedral in 0.1 M HClO 4 solution.…”

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

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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%

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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“…The voltammograms in O 2 saturated solution were reported in previous paper. 26 We measured SXS at 0.50 V (RHE) (the double layer region) in Ar saturated solution (Fig. 1), whereas the potential locates in the fully diffusion controlled region (limited current region) of the ORR in O 2 saturated solution.…”

Section: Resultsmentioning

confidence: 99%

“…Filled 4d orbital may contribute to the stabilization of (1 © 1) structure of Pd (110) and Pd(311) without the expansion of (111) terrace width. 26 On Pd(311), the interlayer spacings are expanded in O 2 saturated solution. The interlayer spacings below the fifth layer were the same as that of the bulk.…”

Section: Resultsmentioning

confidence: 99%

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Surface X-ray Scattering of Pd(110) and Pd(311) in Electrochemical Environments

et al. 2014

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“…31 Structures of adsorbed iodine were determined on Pd(111), Pd(100) and Pd(110) in 0.05 M H 2 SO 4 using STM, 32 however, real surface structures of bare Pd(100) and Pd(110) were not known in electrochemical environments. We determined real surface structures of Pd(111), Pd(100), Pd(110) 33 and Pd(311) 34 in 0.1 M HClO 4 using in-situ SXD. All the Pd surfaces examined have unreconstructed (1 © 1) structures.…”

Section: Introductionmentioning

confidence: 99%

Elucidation of Activity Enhancement Factors for the Oxygen Reduction Reaction on Platinum and Palladium Single Crystal Electrodes

Hoshi

Nakamura

2018

Electrochemistry

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This headline article focuses on the oxygen reduction reaction (ORR), cathodic reaction of fuel cells, on well-defined high index planes of Pt and Pd for the elucidation of factors enhancing the activity for the ORR. The surfaces with (111) terrace edge have high activity for the ORR on Pt electrodes. Pt(331) = 3(111)- (111) gives the highest activity for the ORR in the stepped surfaces of Pt. Incorporation of one kink atom among eleven step atoms further enhances the activity of Pt(331). On single crystal electrodes of Pd, however, terrace edge deactivates the ORR and wide (100) terrace enhances the activity. Effects of Pt oxides (PtOH and PtO) on the ORR have been examined using vibrational spectroscopy. Infrared reflection absorption spectroscopy (IRAS) shows that PtOH prevents the ORR on Pt electrodes. Nanoparticle surface enhanced Raman spectroscopy (NPSERS) indicates that PtO also blocks the ORR on Pt(100) of which ORR activity is the lowest. The ORR activity of Pt is also enhanced by the modification of the surfaces by amines with long alkyl chains such as octylamine (OA) and amine with pyrene ring (PA). Modification by OA/PA increases the ORR activity on n(111)-(111) surfaces of Pt with terrace atomic rows more than 7. The activity of flat Pt(111) is enhanced most remarkably by OA/PA. However, the ORR of Pt(100), of which surface is also composed of flat terrace, is deactivated significantly.

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Surface X-ray Scattering of Pd(111) and Pd(100) Electrodes during the Oxygen Reduction Reaction

Cited by 11 publications

References 26 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

Surface X-ray Scattering of Pd(110) and Pd(311) in Electrochemical Environments

Elucidation of Activity Enhancement Factors for the Oxygen Reduction Reaction on Platinum and Palladium Single Crystal Electrodes

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