Behavior of Carbon Electrodes in Aqueous and Nonaqueous Systems

Panzer, R.E.; Elving, Philip J.

doi:10.1149/1.2404357

Cited by 82 publications

(33 citation statements)

References 13 publications

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“…The k8 app values for diamond and glassy carbon reported herein are 5 ± 10 times larger than some values reported in the literature. Panzer and Elving reported similar values for DE p at 0.1 V/s in 0.1 M LiClO 4 /CH 3 CN on glassy carbon [11]. The k8 app values reported for platinum are generally 2 ± 4 times larger than those observed for carbon electrodes.…”

Section: Resultsmentioning

confidence: 67%

Electron Transfer Kinetics of Ferrocene at Microcrystalline Boron‐Doped Diamond Electrodes: Effect of Solvent and Electrolyte

2003

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Cyclic voltammetric measurements were made using well-characterized microcrystalline boron-doped diamond thinfilm electrodes to test the material×s responsiveness for ferrocene as a function of scan rate, solvent, and electrolyte composition. Apparent heterogeneous electron transfer rate constants, k8 app , of 0.042 AE 0.015, 0.048 AE 0.015, and 0.008 AE 0.002 cm/s were observed in 0.1 M NaClO 4 /CH 3 CN, 0.1 M TBAClO 4 /CH 3 CN, and 0.1M TBAClO 4 /CH 2 Cl 2 , respectively. These rate constants, obtained using electrodes without any type of pretreatment, are similar to those observed for freshly polished glassy carbon. The results demonstrate that boron-doped diamond is a viable material for the electrochemical analysis of nonaqueous analytes.

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Section: Resultsmentioning

confidence: 67%

Electron Transfer Kinetics of Ferrocene at Microcrystalline Boron‐Doped Diamond Electrodes: Effect of Solvent and Electrolyte

2003

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“…Scan rates were varied from 20 to 400 mV s −1 . The BAS reference electrode was calibrated using the [Fe(CN) 6 ] 3− /[Fe(CN) 6 ] 4− couple, [16] at ionic strengths relevant to the present work (see below). Based on these data, reduction potentials, E 1/2 are reported relative to the normal hydrogen electrode (NHE) by addition of 250 mV to observed BAS electrode values.…”

Section: Electrochemistrymentioning

confidence: 99%

Ionic-strength dependence of electron-transfer reactions of Keggin heteropolytungstates: Mechanistic probes of O2 activation in water

Geletii

Weinstock

2006

Journal of Molecular Catalysis A: Chemical

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“…This value is close to the value, 2.55 × 10 −7 cm 2 s −1 , reported for the same redox system in (EMIM)(NTf 2 ). 26 The more viscous medium not only lowers the diffusion coefficient but it also reduces the electron-transfer kinetics. Tachikawa et al have shown that a linear relationship exists between the heterogeneous electron-transfer rate constant and η −1 .…”

Section: Resultsmentioning

confidence: 99%

Rapid Preparation of Room Temperature Ionic Liquids with Low Water Content as Characterized with a ta-C:N Electrode

Jarošová

Swain

2015

J. Electrochem. Soc.

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Room temperature ionic liquids (RTILs) provide an ionic, solvent-free medium for electrochemical reactions. RTILs are appreciated for their many unique properties; nevertheless, it is precisely these qualities that can be very easily debased by water and organic impurities. Water, as a major contaminant in hygroscopic RTILs, has a strong effect on the physical and electrochemical properties (e.g., viscosity and dielectric constant, hence the background voltammetric current, diffusion coefficient of redox analytes and electron-transfer kinetics). In this work, a simple and relatively rapid purification process was investigated that involves sparging ultrahigh purity Ar through the RTIL while being heated at 70 • C (so-called sweeping). A more conventional vacuum drying method at 80 • C was used for comparison. The electrochemical properties of two RTILs, [BMIM] [BF 4 ] and [EMIM] [BF 4 ], were assessed voltammetrically using a nitrogen-incorporated tetrahedral amorphous carbon (ta-C:N) thin-film electrode. We found the sweeping purification method to be superior to vacuum drying in terms of more timely and effective removal of water. In addition, we present for the first time some of the basic electrochemical properties of novel ta-C:N electrode in contact with a RTIL. Room temperature ionic liquids (RTILs) are pure salts with melting points near or below room temperature.1,2 Many ILs are composed of a bulky organic cation, like 1-ethyl-3-methylimidazolium, and a smaller inorganic anion, such as tetrafluoroborate. Equal numbers of positive and negative ions are present so the whole liquid is electrically neutral. Importantly, there is no solvent so the interfacial structure of an RTIL at an electrified interface is expected to be quite distinct from that of a typical aqueous electrolyte solution. It is also likely that the interfacial structure will depend on the carbon electrode microstructure and surface chemistry. 3 The conventional Gouy-Chapman-Stern model used to describe the electric double layer in aqueous or organic electrolytes is probably inappropriate for describing the interfacial structure in an ionic liquid. 4 In addition, the solution environment around a redox analyte will be different in an RTIL than in an aqueous electrolyte. How this environment affects electron-transfer kinetics and mechanisms at carbon electrodes is the focus of our ongoing research. RTIL properties useful for electrochemical applications include negligible vapor pressure, high thermal and chemical stability, moderate electrical conductivity, non-flammability and a wide working potential window or breakdown voltage. They are appreciated in many areas of chemistry and electrochemistry as a "green" 5-7 recyclable alternative to traditional organic solvents for batteries 8,9 and fuel cells. 10,11Depending on the electrode and the RTIL, the electrochemical potential window or breakdown voltage can be on the order of 5-6 V. 1,2,12,13 This is dependent on the purity of the RTIL because the nature and concentration of contaminants...

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Behavior of Carbon Electrodes in Aqueous and Nonaqueous Systems

Cited by 82 publications

References 13 publications

Electron Transfer Kinetics of Ferrocene at Microcrystalline Boron‐Doped Diamond Electrodes: Effect of Solvent and Electrolyte

Electron Transfer Kinetics of Ferrocene at Microcrystalline Boron‐Doped Diamond Electrodes: Effect of Solvent and Electrolyte

Ionic-strength dependence of electron-transfer reactions of Keggin heteropolytungstates: Mechanistic probes of O2 activation in water

Rapid Preparation of Room Temperature Ionic Liquids with Low Water Content as Characterized with a ta-C:N Electrode

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