Radioactive labeling study of sulfate/bisulfate adsorption on smooth gold electrodes

Zelenay, Piotr; Rice-Jackson, L.M.; Wiȩckowski, Andrzej

doi:10.1016/0022-0728(90)87403-7

Cited by 53 publications

(26 citation statements)

References 17 publications

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“…It should be noted that interpretation of present EQCM data in sulfuric acid solution is consistent with the literature data obtained by EQCM, 18 radiotracer, [19][20][21] , FTIR, 22,23 STM, 25 and UHV 26 studies on polycrystalline and single-crystal gold electrode.…”

supporting

confidence: 90%

Electrochemical Quartz Crystal Microgravimetry of Gold in Perchloric and Sulfuric Acid Solutions

Jusys¹,

Bruckenstein

1999

Electrochem. Solid-State Lett.

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Formation of oxidized surface films at a gold electrode in sulfuric acid medium during anodization was studied using the electrochemical quartz crystal microbalance (EQCM) technique. The oxidation process consists of two single-electron steps. Forming a surface OH species from adsorbed water is the first step. Generating a surface O species from the OH species is the second step. The second step is accompanied by a concerted place exchange reaction involving the surface O species and gold atoms below the surface, and rehydration of the gold surface. The reduction of the surface retraces the oxidation processes. During the faradaic processes, sulfate species are adsorbing on (or desorbing from) the gold surface, but produce no detectible mass change. They have C 3v symmetry on the surface in the relevant potential region and compete for five surface gold atoms with five adsorbed water, OH and/or O moieties. In the double-layer region, mass changes are caused by the adsorption/desorption of sulfate species. Changing frequency-potential responses accompany cyclic potential scans because of roughening of the gold electrode's surface caused by sulfate-induced gold dissolution and redeposition processes.The electrochemical quartz crystal microbalance (EQCM) is sufficiently sensitive to measure mass changes accompanying the adsorption of an oxygen monolayer on gold in HClO 4 solution. 1 A mechanism for oxygen electrosorption on gold was proposed on the basis of these EQCM data. Surprisingly, only a few other EQCM studies of oxide formation on gold are reported in the literature, 2,3 and their results are contradictory. Consequently we thought it worthwhile to undertake comparative EQCM measurements of the oxygen adsorption/desorption on gold in both H 2 SO 4 and HClO 4 solutions. Our motivation was to understand EQCM results better in the light of literature data on similar systems: other studies of electrochemical behavior of gold in sulfuric acid solutions were carried out by employing electrochemistry combined with various in situ and ex situ techniques, including radiotracer, Fourier transform infrared spectroscopy (FTIR), and ultraviolet high vacuum (UHV) techniques. These are discussed below.Experimental EQCM apparatus and protocol.-The EQCM apparatus used in the present study used the DQCM circuit described by Bruckenstein et al. 4 Gold-sputtered AT-cut quartz crystals with a 10 MHz fundamental frequency (from International Crystal Manufacturing Company, Inc., Oklahoma City, OK, USA) were affixed to the bottom of the electrochemical cell by silicone rubber adhesive. 1,5 Before all experiments, the crystal face that had the gold-sputtered working electrode to be exposed to the acid electrolytes was cleaned with a freshly prepared H 2 SO 4 /HNO 3 mixture (1:1) for a few minutes. Then this crystal face was extensively rinsed with deionized Millipore water, and finally dried in a stream of nitrogen. Only the circular gold electrode (geometric area 0.22 cm 2 ) on the crystal face was sensitive to mass changes. The g...

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supporting

confidence: 90%

Electrochemical Quartz Crystal Microgravimetry of Gold in Perchloric and Sulfuric Acid Solutions

Jusys¹,

Bruckenstein

1999

Electrochem. Solid-State Lett.

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“…1b). This frequency shift is due to changes in the double layer structure, adsorption of submonolayer of hydroxyl species [30] and eventually some (bi)sulfate adsorption [31,32]. When the potential is scanned in the range of 0.3-0.6 V a minor anodic peak is observed around 0.5 V (Fig.…”

Section: Apparatus and Proceduresmentioning

confidence: 91%

Electrode passivation caused by polymerization of different phenolic compounds

Ferreira

Varela

Torresi

et al. 2006

Electrochimica Acta

225

106

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“…CO poisoning in methanol electrooxidation anodes, coverages of oxides and related species during ORR operation, and the adsorption of sulfates, halides, and other counterions, have been the subject of extensive studies in the experimental literature. 14,52,53,[138][139][140][141][142][143][144][145][146][147][148][149][150][151][152] Analogous studies have been carried out to a lesser extent in the computational community, describing effects ranging from the requisite ensemble of free sites for methanol electrooxidation on platinum to the specific adsorption of halides. One example in which joint experimental and computational studies have succeeded in teasing out the details of these complex surface structures and their impact on the catalysis concerns the elucidation of the structure of highcoverage carbon monoxide molecules near platinum defects, of central importance to the electrochemical oxidation of CO. 153 However, these are only the first examples of the work that is needed to understand the tremendous complexity of covalently adsorbed species on electrocatalytic surfaces; many other electrochemical reactions, such as the electrooxidation of platinum surfaces and the reaction chemistries of alcohols and complex biomolecules on surfaces, can depend sensitively on surface coverages, and improvements in both experimental and computational approaches to the study of these and related problems are urgently needed.…”

Section: Some Future Directions In Surface Electrochemistrymentioning

confidence: 99%

The road from animal electricity to green energy: combining experiment and theory in electrocatalysis

Greeley

Marković

2012

Energy Environ. Sci.

236

200

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Advances in the field of electrocatalysis over the past several decades have been driven both by improvements in fundamental techniques for probing the solid-liquid electrochemical interface and by the technological imperative to develop enhanced low temperature electrocatalytic devices. In this review, we describe how a synergistic interaction between fundamental science and technological progress has resulted in both the emergence of greatly enhanced understanding of electrocatalytic systems and the development of practically improved electrocatalysts. Since it is not possible to summarize in detail all relevant developments in this broad field in such a brief space, we focus selectively on the early historical development of the field and on the use of trends-based analyses to describe the properties of electrocatalytic materials in terms of relatively simple catalytic properties, or descriptors. We begin by discussing aspects of the historical development of ''reversible fuel cells'' in acidic media, including topics relevant both to fuel cells, wherein hydrogen and oxygen are converted to water with concomitant production of electricity (electrons), and to electrolyzers, wherein electrons are used to initiate water splitting to yield hydrogen and oxygen. We then show how this development has stimulated the development of in situ and ex situ surface sensitive probes and spectroscopic methods capable of elucidating fundamental (atomic-/molecular-level) chemical and electronic properties of electrode-electrolyte interfaces. We further discuss how enhanced computational approaches, that can accurately calculate covalent bonding interactions in these systems, have contributed to the growth of a synergistic experimental/computational approach to electrochemical surface science that has resulted in a highly successful paradigm for the understanding of reactivity trends across a space of different metals, alloys, and metal oxides; this work, in turn, has spurred the development of alternative energy systems for efficient conversion and storage of chemical energy. We conclude with a discussion of some further needs for methodological developments and future research directions.

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Radioactive labeling study of sulfate/bisulfate adsorption on smooth gold electrodes

Cited by 53 publications

References 17 publications

Electrochemical Quartz Crystal Microgravimetry of Gold in Perchloric and Sulfuric Acid Solutions

Electrochemical Quartz Crystal Microgravimetry of Gold in Perchloric and Sulfuric Acid Solutions

Electrode passivation caused by polymerization of different phenolic compounds

The road from animal electricity to green energy: combining experiment and theory in electrocatalysis

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