Changes in the electrochemical response of noble metals produced by square-wave potential perturbations

Chialvo, Abel C.; Triaca, Walter Enrique; Arvía, Alejandro Jorge

doi:10.1016/s0022-0728(83)80114-4

Cited by 144 publications

(92 citation statements)

References 30 publications

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“…0.5 kHz. The reciprocal of this figure was associated with the half-life time of adsorbed OH species on platinum produced in the early stages of underpotential electro-oxidation of water (25,26 where the freshly formed Pt* atom occupies, in principle, a new equilibrium position in the metal lattice, according to Pt* --> Pt(lattice) [4] The reaccommodation reaction [4] depends on the number of degrees of freedom of Pt* atoms on the metal surface. Hence, the first layers of metal atoms under the fast periodic potential perturbation behave as a dynamic surface structure where the metal atoms move on the electrode surface, from initial metastable positions at the polycrystalline metal towards a certain equilibrium configuration.…”

Section: Discussionmentioning

confidence: 99%

A Study of the Optimal Conditions for the Development of Preferred Oriented Platinum Surfaces by Means of Fast Square Wave Potential Perturbations

Triaca

Kessler

Canullo

et al. 1987

J. Electrochem. Soc.

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Changes in the voltammetric response of polycrystalline platinum in the direction expected for preferred oriented surface electrodes are achieved after applying a fast repetitive square wave potential signal covering the potential range of H-and O-electroadsorption/electrodesorption. The influence of the characteristics of the square wave potential signal on the voltammetric response of the modified platinum surfaces is systematically studied to establish the optimal conditions for obtaining surface structures with determined preferred orientations.Recently, it was found that changes in the voltammetric response of polycrystalline platinum electrodes in the direction expected for preferred oriented surface electrodes can be achieved by using a fast repetitive square wave potential signal (RSWPS) within the potential range of H-and O-electroadsorption/electrodesorption in acid solution (1). Similar results were earlier obtained by applying a fast triangular potential signal to a polycrystalline platinum electrode in acid electrolyte at room temperature (2, 3). After applying the fast potential perturbation the electroae surface modifications were voltammetrically followed at a low potential sweep rate in the H-and O-electroadsorption/electrodesorption potential range by using an acid electrolyte. These changes in the electrode surface can also be seen through SEM for a relatively low magnification factor (4). The change from the initial polycrystalline platinum surface to the preferred oriented surface is independent of the shape of the periodic potential perturbation, but it is extremely sensitive to its frequency and potential limits (1, 2, 5). Thus, depending on the preset parameters of the potential perturbation either the platinum (100) preferred oriented surface or the platinum (111) preferred oriented surface are obtained (1-5).In the present work the influence of the RSWPS characteristics on the voltammetric response at low potential sweep rate of the resulting platinum surfaces is systematically studied to establish the optimal conditions for obtaining surface structures with a determined preferred orientation. ExperimentalRuns were made in 1M H2SO4 at 25~ with commercially available polycrystalline platinum wire shaped working electrodes of ca. 0.10 cm 2 geometric area. Previous to each experiment the working electrode was electropolished with ac (50 Hz; 10-15V) in a slightly acid (HC1) saturated CaC12 solution. Later, the electrode was repeatedly rinsed with triply distilled water and kept in water for lh before use. The potential of the working electrode was measured against a RHE in the acid electrolyte. A large area platinum counterelectrode (ca. 50 cm 2) concentrically surrounding the working electrode was used. The electrochemical cell and the instrumentation have been described elsewhere (1, 5). The distortion of the RSWPS, which was due to the proper risetime of the electrochemical setup, was less than 5% at frequencies lower than 6 kHz.After the pretreatment, the working electrode was subjected ...

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Section: Discussionmentioning

confidence: 99%

A Study of the Optimal Conditions for the Development of Preferred Oriented Platinum Surfaces by Means of Fast Square Wave Potential Perturbations

Triaca

Kessler

Canullo

et al. 1987

J. Electrochem. Soc.

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“…Indeed the triangular wave is most convenient as changes in the current vs. potential response, the voltammogram, can be employed during the oxide growth reaction to monitor changes in redox behavior associated with the latter. 86 That said, Arvia and co-workers 87 contend that a repetitive square wave potential pulse is very effective for the controlled generation of relatively thick hydrated metal oxy-hydroxide films.…”

Section: Hydrous Oxide Electrodesmentioning

confidence: 99%

Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes

Doyle

Godwin

Brandon

et al. 2013

Phys. Chem. Chem. Phys.

521

565

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This paper presents a review of the redox and electrocatalytic properties of transition metal oxide electrodes, paying particular attention to the oxygen evolution reaction. Metal oxide materials may be prepared using a variety of methods, resulting in a diverse range of redox and electrocatalytic properties. Here we describe the most common synthetic routes and the important factors relevant to their preparation. The redox and electrocatalytic properties of the resulting oxide layers are ascribed to the presence of extended networks of hydrated surface bound oxymetal complexes termed surfaquo groups. This interpretation presents a possible unifying concept in water oxidation catalysis -bridging the fields of heterogeneous electrocatalysis and homogeneous molecular catalysis. In contextOver the past 50 years considerable research efforts have been devoted to the realisation of efficient, economical and renewable energy sources. Metal oxide materials have played a large part in this drive with demonstrated applications at both the research and commercial level. Their use in areas such as batteries, fuel cells and water electrolysis has resulted in the development of materials with a diverse range of structural and chemical properties. In all cases, understanding the fundamental electrochemistry of the material can be invaluable for rational design and optimisation. This review focuses on the redox, charge transport and electrocatalytic properties of transition metal oxide electrodes as they pertain to the electrolytic splitting of water. Particular emphasis is placed on the nature of the active surface which is interpreted in terms of hydrated interlinked oxymetal complexes termed surfaquo groups. In this way, the review seeks to bridge the gap between heterogeneous electrocatalysis and homogeneous molecular catalysis for water oxidation, areas of considerable modern interest and activity.

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“…Many studies have been performed for platinum thin films, which show their strong dependence on the surface free energy of each substrate [9][10][11]. Platinum layers of controlled roughness are grown by defined annealing and etching processes [12] and from the application of different electrode potential programs in strong acid or alkaline solutions [13,14]. Crystalline orientations can be obtained using fast repetitive potential signals through a mechanism of platinum faceting, which obeys a pulsating diffusion layer condition for the dissolution and redeposition processes [13,14].…”

Section: General Aspects Of Platinum and Platinum Oxide Electrochemicmentioning

confidence: 99%

“…Platinum layers of controlled roughness are grown by defined annealing and etching processes [12] and from the application of different electrode potential programs in strong acid or alkaline solutions [13,14]. Crystalline orientations can be obtained using fast repetitive potential signals through a mechanism of platinum faceting, which obeys a pulsating diffusion layer condition for the dissolution and redeposition processes [13,14]. Different types and morphologies of platinum oxides can be formed depending on the experimental conditions (symmetry of the wave, upper and lower potentials, frequency, and electrolyte).…”

Section: General Aspects Of Platinum and Platinum Oxide Electrochemicmentioning

confidence: 99%

Catalytic effects on methanol oxidation produced by cathodization of platinum electrodes

Díaz

Zinola

2007

Journal of Colloid and Interface Science

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Changes in the electrochemical response of noble metals produced by square-wave potential perturbations

Cited by 144 publications

References 30 publications

A Study of the Optimal Conditions for the Development of Preferred Oriented Platinum Surfaces by Means of Fast Square Wave Potential Perturbations

A Study of the Optimal Conditions for the Development of Preferred Oriented Platinum Surfaces by Means of Fast Square Wave Potential Perturbations

Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes

Catalytic effects on methanol oxidation produced by cathodization of platinum electrodes

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