Study of the kinetics of electrochemical reactions by thin-layer voltammetry

Lau, Arthur L. Y.; Hubbard, Arthur T.

doi:10.1016/s0022-0728(70)80148-6

Cited by 52 publications

(22 citation statements)

References 12 publications

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“…The [PtCl 4 ] 2− complex is an intermediate in the reduction of [PtCl 6 ] 2− to Pt 0 . Lau and Hubbard [ 38 ] found the reduction of [PtCl 4 ] 2− to Pt 0 to be a slow process and reported that the rate constant for the electro‐reduction of [PtCl 4 ] 2− was about an order of magnitude smaller than that of [PtCl 6 ] 2− electro‐reduction at equal chloride concentrations. This would result in much more [PtCl 4 ] 2− formed that can be immediately reduced, resulting in a build‐up of “excess” [PtCl 4 ] 2− close to the platinum surface.…”

Section: Resultsmentioning

confidence: 99%

Relation of the electrochemical interplay between H₂PtCl₆ and H₂O/H₃O⁺/H₂⁺ and the hydrogen‐evolution reaction

Kriek

Mogwase

Vorster

2021

Electrochemical Science Adv

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The electrodeposition of platinum from hexachloroplatinic acid solutions, on glassy carbon, was studied by developing multiple cyclic voltammetry transients. The development of an isopotential point, only observed under hydrogenevolution conditions, is postulated to be associated with the reduction of [PtCl 4 ] 2− to Pt 0 and the oxidation of the adsorbed molecular hydrogen ion (H 2 + ) ads species to (H 3 O + ) ads . The adsorption of H 2 + inhibits the continued reduction of [PtCl 4 ] 2− and the 'cleansing' of the platinum surface, that is, the removal of H 2 + through hydrogen evolution, results in the opening up of active sites to allow for the continued reduction of [PtCl 4 ] 2− on the return sweep, which results in an isopotential point (IPP). This IPP is not observed in the absence of hydrogen evolution, due to saturation of the surface by (H 2 + ) ads , and correlates with a model that explains the interplay between platinum chloride species, hydrogen containing species (H 2 O/H 3 O + /H 2 + ), and the hydrogenevolution reaction.

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Section: Resultsmentioning

confidence: 99%

Relation of the electrochemical interplay between H₂PtCl₆ and H₂O/H₃O⁺/H₂⁺ and the hydrogen‐evolution reaction

Kriek

Mogwase

Vorster

2021

Electrochemical Science Adv

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“…A transition from progressive to instantaneous nucleation has been observed by changing the electrolyte from perchlorate or sulfate to chloride. The latter, however, strongly inhibits Pt deposition as a result of competitive adsorption of chloride compared with the platinum chloro complexes and the consequent blocking of reduction sites. , For these reasons, sulfuric acid has been used here as the supporting electrolyte.…”

Section: Methodsmentioning

confidence: 99%

“…The latter, however, strongly inhibits Pt deposition as a result of competitive adsorption of chloride compared with the platinum chloro complexes and the consequent blocking of reduction sites. 29,30 For these reasons, sulfuric acid has been used here as the supporting electrolyte.…”

Section: Platinum Electrodeposition On Hopgmentioning

confidence: 99%

Substrate Structural Effects on the Synthesis and Electrochemical Properties of Platinum Nanoparticles on Highly Oriented Pyrolytic Graphite

et al. 2010

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Platinum nanoparticles have been prepared by potentiostatic multipulse electrodeposition with controlled nucleation and growth on freshly cleaved and electrochemically oxidized highly oriented pyrolytic graphite.The influence of the applied potential sequence on the size distribution was investigated. For short electrolysis times, the deposition of nanoparticles takes place via a progressive nucleation mechanism. A narrow size distribution was obtained by controlling independently the nucleation and growth steps, and particles with heights between 52 and 1.4 nm could be prepared by altering the pulse parameters. Anodic oxidation of the substrate had a large influence on the particle size, resulting in the preparation of particles 1.4 nm in height. XPS demonstrated that Pt particles of small size were readily oxidized. The rate of electrochemical methanol oxidation showed a dependence on the particle size, and no oxidation of methanol could be observed for the smaller sizes investigated.

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“…The interaction of hydrogen chloride on metal surfaces is of interest in a number of important fields. In electrochemistry, halogens adsorbed to metal electrodes can strongly influence electrochemical reactions and appear to be intimately involved in electron-transfer reactions of transition metal complexes. , In lubricants, chlorinated compounds are used as antiwear additives and are thought to decompose under tribological stress to produce metal chlorides, among other species . The detection of chlorinated species using thin-film chemical sensors is important in environmental testing and chemical warfare arenas, and remediation of chlorinated pollutants by metal catalysts is a field with great academic interest and several pilot industrial applications.…”

Section: Introductionmentioning

confidence: 99%

The Adsorption and Reaction of HCl on Pd(111)

et al. 2001

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HCl adsorbed onto clean Pd(111) produces three distinct HCl desorption states in thermal desorption spectroscopy (TDS), all of which are populated simultaneously, even at exposures as low as 0.33 L. One desorption state emanates from molecularly adsorbed HCl (220 K), while the other two (300 and 470 K) emanate from recombination of H plus Cl atoms. The lowest temperature recombinative peak (β at ∼300 K) belongs to recombination of chlorine adatoms with surface hydrogen. This reaction is competitive with the recombinative desorption of H2. Finally, the highest temperature peak with an onset at 470 K (α) is the recombination of the remaining Cl with hydrogen dissolved in the Pd crystal, which emerges from the bulk onto the surface at approximately 470 K. Some of the chlorine adatoms order on the Pd surface to yield a √3 × √3 R 30° overlayer structure at coverages as low as θ = 0.13 ML. This structure persists through a range of temperatures from 100 to 320 K, when initially adsorbed at 100 K. The order−disorder transition at ∼320 K is reversible.

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Study of the kinetics of electrochemical reactions by thin-layer voltammetry

Cited by 52 publications

References 12 publications

Relation of the electrochemical interplay between H₂PtCl₆ and H₂O/H₃O⁺/H₂⁺ and the hydrogen‐evolution reaction

Relation of the electrochemical interplay between H₂PtCl₆ and H₂O/H₃O⁺/H₂⁺ and the hydrogen‐evolution reaction

Substrate Structural Effects on the Synthesis and Electrochemical Properties of Platinum Nanoparticles on Highly Oriented Pyrolytic Graphite

The Adsorption and Reaction of HCl on Pd(111)

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Study of the kinetics of electrochemical reactions by thin-layer voltammetry

Cited by 52 publications

References 12 publications

Relation of the electrochemical interplay between H2PtCl6 and H2O/H3O+/H2+ and the hydrogen‐evolution reaction

Relation of the electrochemical interplay between H2PtCl6 and H2O/H3O+/H2+ and the hydrogen‐evolution reaction

Substrate Structural Effects on the Synthesis and Electrochemical Properties of Platinum Nanoparticles on Highly Oriented Pyrolytic Graphite

The Adsorption and Reaction of HCl on Pd(111)

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Resources

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Relation of the electrochemical interplay between H₂PtCl₆ and H₂O/H₃O⁺/H₂⁺ and the hydrogen‐evolution reaction

Relation of the electrochemical interplay between H₂PtCl₆ and H₂O/H₃O⁺/H₂⁺ and the hydrogen‐evolution reaction