A study of the adsorption of acetonitrile on a gold electrode from aqueous solutions using in situ vibrational spectroscopy

Faguy, Peter W.; Fawcett, W. Ronald; Liu, Guojun; Motheo, Artur J.

doi:10.1016/0022-0728(92)80462-d

Cited by 26 publications

(21 citation statements)

References 26 publications

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“…Some authors [17] reported a band at 2350 cm À1 and attributed it to the adsorption of acetonitrile. This has been confirmed in more recent studies, indicating that adsorption of CH 3 CN occurs at positive potentials on surfaces of polycrystalline platinum and gold [18]. Indeed, chemisorbed acetonitrile has a stretching vibration band at 2342 cm À1 unfortunately, such a band matches the position of the band corresponding to dissolved CO 2 [19][20][21].…”

Section: Spectroelectrochemical Studiessupporting

confidence: 59%

SNIFTIRS studies of the electrochemical oxidation of 1,3-dimethoxybenzene on platinum in acetonitrile/tetrabutilammonium electrolytes

Martínez

Hernández

Kalaji

et al. 2004

Journal of Electroanalytical Chemistry

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Section: Spectroelectrochemical Studiessupporting

confidence: 59%

SNIFTIRS studies of the electrochemical oxidation of 1,3-dimethoxybenzene on platinum in acetonitrile/tetrabutilammonium electrolytes

Martínez

Hernández

Kalaji

et al. 2004

Journal of Electroanalytical Chemistry

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“…Experiments demonstrate that on Au, acetonitrile weakly physisorbs with no evidence of chemisorption on the neutral and negatively charged electrode (corresponding to negative field strengths in Figure 5); 41,56,57,67,68 N-down linear chemisorption occurs only at positive electrode charge above approximately 8 μC cm −2 (corresponding to positive field in Figure 5). 41,69 In fact, Figure 5 demonstrates that Cu(211) shows the same qualitative behavior: no chemisorption at sufficiently negative electrostatic field, and linear, N-down chemisorption at sufficiently positive electrostatic field. Thus, our results for Ag and Cu are in agreement with available experimental data for group 11 (coinage) metals.…”

mentioning

confidence: 87%

“…34,38,41,50,54−57 Vibrational and X-ray photoelectron spectroscopy 41,56−61,61−71 corroborate that only weak adsorp-tion without chemical bonding occurs on Au, while at least two chemisorbed species are observed on Pt, Pd, and Ni surfaces: a "bridged" di-sigma-bonded species and a "linear" adsorption, oriented roughly normal to the surface plane and coordinated through the lone electron pair of the N atom, with distinct CN stretching frequency ranges. Potential and charge dependent spectra have also been observed, 5,41,46,63,69,72,73 providing evidence of potential and field dependence of adsorption configurations. But it is difficult to conclusively and unambiguously translate all of the available experimental evidence into a clear understanding of the atomic structure of the interface; this provides motivation for theoretical study of these interfaces.…”

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confidence: 88%

Acetonitrile Transition Metal Interfaces from First Principles

Ludwig

Singh

Nørskov

2020

J. Phys. Chem. Lett.

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Acetonitrile is among the most commonly used nonaqueous solvents in catalysis and electrochemistry. We study its interfaces with multiple facets of the metals Ag, Cu, Pt, and Rh using density functional theory calculations; the structures reported shed new light on experimental observations and underscore the importance of solvent–solvent interactions at high coverage. We investigate the relationship of potential of zero charge (PZC) to metal work function, reporting results in agreement with experimental measurements. We develop a model to explain the effects of solvent chemisorption and orientation on the PZC to within a mean absolute deviation of 0.08–0.12 V for all facets studied. Our electrostatic field dependent phase diagram agrees with spectroscopic observations and sheds new light on electrostatic field effects. This work provides new insight into experimental observations on acetonitrile metal interfaces and provides guidance for future studies of acetonitrile and other nonaqueous solvent interfaces with transition metals.

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“…14 Similar conclusions were reached by various investigators who used similar electrolytes but on different electrode materials. 10,15,16 It is important to investigate the possible pathways leading to the formation of this adduct under an oxidizing potential. From this work, it is known that a divided carbon electrode and the presence of BF 4 Ϫ are required and that, as far as the IR spectrum indicates the composition of the solutions in the vicinity of such an electrode does not evolve with time in the absence of an applied potential.…”

Section: Discussionmentioning

confidence: 99%

Infrared Spectroelectrochemical Studies of Divided Carbon Electrodes in Acetonitrile-Sodium Tetrafluoroborate Solutions

Backer

Berrier

Martinon

et al. 2005

J. Electrochem. Soc.

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Fourier transform infrared spectroelectrochemistry has been used to study the vibrational spectrum of a thin layer of the organic electrolyte in contact with a divided carbon supercapacitor electrode. Variations in the absorption of peaks characteristic of the solvent and of the support electrolyte during an anodic potential scan have been observed. The presence of adsorbed water was detected. The formation of a stable adduct of CH 3 CN and BF 3 under anodic potential was identified.Electrical energy produced by renewable sources such as wind power or photovoltaic devices is fluctuant by nature. In order to use it reliably, it is necessary to have a means of storing electricity. These storage devices are also of prime importance in systems where surges of power are frequent; e.g. applications such as transportation and regenerative braking.Storage of electrical energy can be accomplished in an elegant way through the use of lightweight capacitors. Recently, devices based on the use of the electrochemical double-layer capacitor ͑EDLC͒ have been developed: the supercapacitors. 1 Supercapacitors are intermediate systems between electrochemical batteries, which can store high energy associated with medium power values, and dielectric capacitors, which can deliver very high power during times of the order of a few milliseconds. Supercapacitors are used for energy storage over time periods ranging from seconds to minutes; their peak power is up to 10-20 times higher than that of batteries, but their energy density is 20-50 times lower.Their principle relies on the use of high specific area electrodes placed in an electrolyte and separated by a thin inert microporous membrane. This work focuses on organic electrolyte capacitors with electrodes manufactured using carbon dispersed in an aqueous solvent. To be useful, these devices must be able to remain charged in open-circuit conditions for great lengths of time. This implies that no irreversible reactions induced by the variation of the potential of each electrode should occur; thus, it is important to understand the mechanisms occurring during charge and spontaneous discharges.During the charge of the EDLC, several phenomena can occur. 2 An increase in the number of ions forming the double layer can be caused by the application of a voltage. A local increase in ionic concentration near the carbon surface, but not directly connected with the double layer, can also be produced if a current flows through the capacitor at or above the electrolyte potential range.Self-discharge processes are complex and involve mechanisms occurring on a short or a long time scale. When the supercapacitor is fully charged, its removal from the power supply induces a fast relaxation phenomenon. This process is reversible at short times. An irreversible process corresponding to faradaic reactions can also be observed on the same time scale. Another reason for self-discharge are the faradaic reactions of various groups at the surface of the carbon during ca. the first 500 h of use of the device...

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A study of the adsorption of acetonitrile on a gold electrode from aqueous solutions using in situ vibrational spectroscopy

Cited by 26 publications

References 26 publications

SNIFTIRS studies of the electrochemical oxidation of 1,3-dimethoxybenzene on platinum in acetonitrile/tetrabutilammonium electrolytes

SNIFTIRS studies of the electrochemical oxidation of 1,3-dimethoxybenzene on platinum in acetonitrile/tetrabutilammonium electrolytes

Acetonitrile Transition Metal Interfaces from First Principles

Infrared Spectroelectrochemical Studies of Divided Carbon Electrodes in Acetonitrile-Sodium Tetrafluoroborate Solutions

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