Hydrogen Overvoltage on Bright Platinum

Schuldiner, Sigmund

doi:10.1149/1.2779641

Cited by 55 publications

(45 citation statements)

References 6 publications

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“…current densities). [4][5][6] The discovery of active HER electrocatalysts comprised of inexpensive and earth-abundant materials is thus being vigorously pursued. [7][8][9] Ni metal and Ni alloys are effective HER catalysts in alkaline media, but are susceptible to chemical corrosion in acidic electrolytes.…”

Section: Supporting Information Placeholdermentioning

confidence: 99%

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Saadi¹,

Carim²,

Drisdell

et al. 2017

J. Am. Chem. Soc.

148

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Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogenevolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η, of −η < 100 mV at a current density of −10 mA cm −2 in 0.500 M H 2 SO 4 (aq). To obtain a chemical description of the material asprepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H 2 SO 4 (aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

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Section: Supporting Information Placeholdermentioning

confidence: 99%

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Saadi¹,

Carim²,

Drisdell

et al. 2017

J. Am. Chem. Soc.

148

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show abstract

“…The high degree of cleanliness of the Pt surfaces used in this work was confirmed by the large pseudocapacitance observed on the pulses obtained from the current interrupter (28,35).…”

Section: Discussionmentioning

confidence: 53%

“…The rate-determining step for the cathodic evolution of H2 on bright Pt is assumed to be the combination of adsorbed hydrogen atoms (Tafel mechanism) to form H2 molecules (33) H + H --> H2 [3] which gives a Tafel slope of RT/2F (28)1. If the presence of dermasorbed oxygen in the cathode surface makes a tighter bond between the adsorbed hydrogen and the metal surface, this effect would slow down the hydrogen combination reaction with the resultant inincrease in ~ and decrease in io.…”

Section: Discussionmentioning

confidence: 99%

On Dissolved Oxygen in Bulk Platinum

Hoare

1969

J. Electrochem. Soc.

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The hydrogen overvoltage was determined on the front side of a bright Pt foil in 2N H2SO4 solution while the solution on the back side was stirred with H2, N2, or 02. No change in the ~ was detected when the foil was connected as a diaphragm and when H2 stirring was replaced with 02 stirring on the back side. With the foil connected as a bielectrode, the ~ increased after an induction period depending on the thickness of the .foil when H2 stirring was" replaced with 02 stirring on the back side. These results indicate that under anodic polarization, oxygen can be dissolved in Pt. The dissolved oxygen can penetrate to the front side of the Pt foil where its presence as dermasorbed oxygen modified the catalytic activity of the Pt surface for the H2 evolution reaction. In the absence of anodization, oxygen sorbed from solution can penetrate the Pt lattice no further than the dermasorbed region.

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“…These investigators interpreted their results for active Pt as showing that the rate-controlling step was the diffusion of molecular hydrogen away from the electrode surface. The results given in this paper show that this diffusion-controlling mechanism is not likely since a change to the 0.040 slope could not be explained by such a diffusion-controlled step, Manuscript received Sept. 6,1960; revised manuscript received Dec. 7, 1960. This paper was prepared for delivery before the Indianapolis Meeting, April ~O-May 3, 1961.…”

Section: Discussionmentioning

confidence: 83%

Kinetics of Hydrogen Evolution at Zero Hydrogen Partial Pressure

Schuldiner¹

1961

J. Electrochem. Soc.

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Polarization curves for the hydrogen evolution reaction on platinum and rhodium were determined in 1M H2SO4 solution stirred rapidly with helium.Here the partial pressure of hydrogen gas above the solution was virtually equal to zero. Experimental results indicated that for both metals the ratedetermining step in the lowest current density range was primarily the electrochemical desorption of hydrogen atoms. As the current density increased the rate-determining step changed to one that was primarily controlled by atomic combination. Kinetic equations were derived and the calculated relationships compared favorably with the experimental results.When the partial pressure of hydrogen on an inert hydrogen electrode, e.g., Pt/H~, is dropped to zero, the reversible 2H++ 2e-= H~ reaction no longer occurs on the metal surface. If under these conditions the noble metal electrode is cathodized, hydrogen will be evolved, and if the hydrogen partial pressure above the solution is maintained virtually equal to zero, by sweeping out the evolved hydrogen with an inert gas, as fast as it is formed, the rate of the reverse ionization reaction will effectively be equal to zero. Breiter and Clamroth (1) used this fact to study the hydrogen evolution rate-determining steps on Pt and Au electrodes. In this investigation this technique, with rigorous control of electrode cleanliness and precision of potential measurements, was used to determine the rate-controlling steps on Pt and Rh electrodes.

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Hydrogen Overvoltage on Bright Platinum

Cited by 55 publications

References 6 publications

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

On Dissolved Oxygen in Bulk Platinum

Kinetics of Hydrogen Evolution at Zero Hydrogen Partial Pressure

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