Hydrogen electrode reaction on electrodes of glassy carbon-supported ultrafine Pd particles in alkaline media

Tateishi, Naokazu; Yahikozawa, Kiyochika; Nishimura, Kinya; Takasu, Yoshio

doi:10.1016/0013-4686(92)87078-e

Cited by 45 publications

(36 citation statements)

References 12 publications

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“…Resembling oxidation peaks at potentials > 0.6 V RHE have already been reported in the literature for palladized palladium, 43 mesoporous Pd-films 73 or palladium-nanoparticles supported on glassy carbon, 46 and were related to the desorption of underpotentially deposited hydrogen. 46,73 Moreover, the small shoulder extending between ≈0.4 and ≈0.6 V RHE on the solid-line CV in Figure 7a has been assigned to H upd -desorption 45 or to the oxidation of absorbed hydrogen. 46 In the latter case, the small charge related to the shoulder would suggest that hydrogen absorption on this Pd/Au PC -surface is indeed very minor.…”

Section: −2supporting

confidence: 56%

“…2a) or others reported for nano-sized Pd-structures. 46,47 This difference may result from the higher RF Pd -value estimated for this third surface (≈1.6 cm Au , see Table II), which points at a non-pseudomorphic growth mechanism 78,79 resulting in a larger degree of coverage of the Au PC -substrate by a Pddeposit consisting of a larger number of adlayers. The latter appear to have an electrochemical behavior closer to that of bulk palladium, since in the subsequent HOR/HER-activity measurements plotted in Figure 10b (discussed in further detail below) the positive-going polarization curves display an oxidation peak at ≈0.7 V RHE that extends beyond the diffusion-limited current values.…”

Section: Preparation Of Palladium-on-gold Surfaces By Pd-plating Onmentioning

confidence: 90%

“…46,73 Moreover, the small shoulder extending between ≈0.4 and ≈0.6 V RHE on the solid-line CV in Figure 7a has been assigned to H upd -desorption 45 or to the oxidation of absorbed hydrogen. 46 In the latter case, the small charge related to the shoulder would suggest that hydrogen absorption on this Pd/Au PC -surface is indeed very minor. Next, we proceeded to H 2 -saturate the 0.1 M NaOH electrolyte while holding the Pd/Au PC -electrode at 0.6 V RHE , as we had done in the measurement on Pd PC (see above).…”

Section: −2mentioning

confidence: 97%

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Bulk-Palladium and Palladium-on-Gold Electrocatalysts for the Oxidation of Hydrogen in Alkaline Electrolyte

Henning

Herranz

Gasteiger

2014

J. Electrochem. Soc.

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The commercial feasibility of alkaline-exchange membrane fuel cells and electrolyzers passes by the development of hydrogen oxidation and evolution reaction (HOR/HER) catalysts featuring an activity and/or cost advantage over platinum, which remains the most active metal for these processes. Among these alternatives, Pd appears as a promising candidate, since its price is typically 2-3 fold lower than that of Pt. With this motivation, the first section of this study displays our attempts at quantifying the kinetic parameters of the HOR/HER on bulk Pd in 0.1 M NaOH, which were prevented by the simultaneous absorption of hydrogen into bulk palladium. We succeeded at circumventing this issue by depositing Pd-adlayers on a polycrystalline Au-substrate by galvanic displacement of underpotentially-deposited Cu or by electrochemical plating of Pd 2+ . The resulting surfaces appear to consist of three-dimensional Pd-structures of an unknown thickness that we believe to scale with the palladium coverage, θ Pd/Au . This last parameter is inversely proportional to the HOR/HER-activity of the Pd-on-Au surfaces, in agreement with numerous theoretical and experimental studies in acid media that correlate this effect to the tensile strain induced by the Au-substrate on the Pd-lattice. Proton-exchange membrane fuel cells (PEMFCs) fueled with hydrogen stored at 700 bar can attain energy densities in excess of 200 Wh · kg −1 (on a PEMFC system basis), making them excellent candidates for the propulsion of environmentally-benign, full range (≥ 300 miles) vehicles.1 However, the actual commercialization of PEMFC powered cars has been deterred by the lack of a hydrogen infrastructure and the high cost of the PEMFC. In this last respect, a significant fraction of the system's price is related to the costly platinum-based catalysts needed to catalyze the oxidation of hydrogen and the reduction of oxygen taking place at the FC anode and cathode, respectively.1-3 The kinetics of the oxygen reduction reaction (ORR) on Pt 4 are ≈7 orders of magnitude slower than those of the hydrogen oxidation reaction (HOR), 5 in agreement with the HOR 5 -and ORR 4 -exchange-current density (i 0 ) values of 4 ± 2 · 10 +2 mA · cmPt estimated by Neyerlin and coworkers (at 80• C and 100 kPa H 2 /air partial pressure). As such, the Pt-loading at the PEMFC's cathode (≈0.2-0.4 mg Pt · cm −2 ) is well above the ≤ 0.05 mg Pt · cm −2 required for the anodic HOR, and thus much research is being devoted to the development of more active and/or less expensive ORR catalysts.6-10 These include alloys of Pt with non-noble metals like Ni, Co or Cu (as well as their de-alloyed derivatives), and catalysts consisting of non-noble metal nanoparticles covered by one or a few monolayers of Pt (i.e., the so-called "core-shell" catalysts).Alternatively, operating a fuel cell in alkaline environment allows for the use a wider variety of potentially inexpensive, noblemetal free ORR-catalysts. Among these, certain materials based on Fe-, Co-and/or Cu-N 4 chelates (or equivalent no...

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Section: −2supporting

confidence: 56%

Section: Preparation Of Palladium-on-gold Surfaces By Pd-plating Onmentioning

confidence: 90%

Section: −2mentioning

confidence: 97%

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Bulk-Palladium and Palladium-on-Gold Electrocatalysts for the Oxidation of Hydrogen in Alkaline Electrolyte

Henning

Herranz

Gasteiger

2014

J. Electrochem. Soc.

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mentioning

confidence: 99%

“…[5,6] The electroadsorption of hydrogen over Pd(111) takes place through the surface reaction PdÀ H 2 O + 1 e À !PdÀH + OH À , which proceeds experimentally at 0.4 V versus the normal hydrogen electrode (NHE). [6] This reaction was found to be irreversible. This experimental irreversibility is consistent with the large hysteresis found in our simulations in which hydrogen does not electrodesorb from the surface back into H + ions, even at much higher potentials (at 0 K).…”

mentioning

confidence: 99%

Elucidation of the Electrochemical Activation of Water over Pd by First Principles

2006

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Elucidation of the Electrochemical Activation of Water over Pd by First Principles

2006

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Strukturänderungen, die bei der elektrokatalytischen Oxidation und Reduktion von Wasser an der Palladium(111)‐Wasser‐Grenzfläche ablaufen (siehe Bild), wurden mit Ab‐initio‐Methoden berechnet. Die Ergebnisse wurden verwendet, um ein elektrochemisches Phasendiagramm zu konstruieren, und sie belegen den Einfluss der Polarisation der Wasser‐Metall‐Grenzfläche auf die Oberflächeneigenschaften.

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Hydrogen electrode reaction on electrodes of glassy carbon-supported ultrafine Pd particles in alkaline media

Cited by 45 publications

References 12 publications

Bulk-Palladium and Palladium-on-Gold Electrocatalysts for the Oxidation of Hydrogen in Alkaline Electrolyte

Bulk-Palladium and Palladium-on-Gold Electrocatalysts for the Oxidation of Hydrogen in Alkaline Electrolyte

Elucidation of the Electrochemical Activation of Water over Pd by First Principles

Elucidation of the Electrochemical Activation of Water over Pd by First Principles

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