Effect of water as a proton donor on the decay of anthracene and naphthalene anion radicals in aqueous mixtures of acetonitrile, dimethylformamide, and dimethyl sulfoxide

Jezorek, John R.; Mark, Harry B.

doi:10.1021/j100702a035

Cited by 44 publications

(26 citation statements)

References 8 publications

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“…It is already well-known that water is a very poor proton donor in DMF and Me2SO, to which it is very tightly hydrogen-bonded, and that it is a much better proton donor in acetonitrile, a poorer hydrogen-bond acceptor. 13 Finally, we note that the reduction potentials of unsaturated hydrocarbons are very similar in DMF and THF,14 in contrast to reported15 results for alkyl halides, sulfonates, and unsaturated carbonyl compounds.…”

Section: Methodsmentioning

confidence: 50%

Voltammetry in (toluene)3-tetrabutylammonium tetrafluoroborate, a novel liquid hydrocarbon electrolyte

Fry¹,

Touster²

1986

J. Org. Chem.

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Section: Methodsmentioning

confidence: 50%

Voltammetry in (toluene)3-tetrabutylammonium tetrafluoroborate, a novel liquid hydrocarbon electrolyte

Fry¹,

Touster²

1986

J. Org. Chem.

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“…Nevertheless, it is surprising that the solvent effects for 2 are so much more marked than for its positional isomer 3 . Since DMF and MeCN are isodielectric, [39,40] the extent of dimerization controlled by dipole‐dipole interactions [25] is likely to be similar in both solvents. However, DMF has a greater value of the Gutman donor number than MeCN [40] .…”

Section: Resultsmentioning

confidence: 99%

“…Since DMF and MeCN are isodielectric, [39,40] the extent of dimerization controlled by dipole‐dipole interactions [25] is likely to be similar in both solvents. However, DMF has a greater value of the Gutman donor number than MeCN [40] . This number recognizes the ability of a solvent to promote the ionization of compounds to form ion pairs, so we would expect greater stabilization of the dimer in DMF than in MeCN.…”

Section: Resultsmentioning

confidence: 99%

Decorating BODIPY with Electron‐Withdrawing NO Group: Spectroelectrochemical Consequences and Computational Investigation

et al. 2021

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4,4‐difluoro‐5,7‐dimethyl‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) and derivatives are an outstanding class of fluorescent dyes. Herein, we report on the introduction of a nitrosyl moiety into the BODIPY structure and its dramatic effect on the observed electrochemical reaction mechanism. 6‐Nitrosyl‐8‐phenyl‐BODIPY and its 5‐nitrosyl positional isomer, compounds 2 and 3, respectively, were obtained from the meso precursor, 8‐phenyl‐BODIPY (1), by nitrosation. Electrochemical studies for 1–3 are reported. Cyclic voltammetry and differential pulse voltammetry in degassed DMF or in MeCN (reduction+oxidation), both with n‐Bu4NPF6 (0.1 mol L−1), were obtained. Compound 1 displays the usual behaviour for 8‐phenyl substituted BODIPYs. The addition of the acceptor nitroso group in compounds 2 (in position β) and 3 (in position α), leads to a different profile. For all the compounds, the nitroso group greatly facilitates the reductions. For compound 3 (EpIc=−0.238 V), the first to be reduced is the nitroso group, due to the stability of the electrogenerated radical anion, along with non‐bonding interactions with the electronegative boron difluoride. This is different from compound 2 (EpIc=−0.351 V) with a β‐nitroso group, where the nitroso‐based facilitated reduction occurs in the substituted BODIPY core. Spectroelectrochemistry coupled with analysis through conceptual density functional theory (CDFT) corroborate the voltammetric results and explain the unexpected reactivity differences.

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“…35 Because acetonitrile does not hydrogen bond to water, radical anions (such as superoxide) generally have a short half-life in MeCN. 40 A dominant characteristic of superoxide ion is its ability to act as a strong Bronsted base via formation of HOO, which reacts with itself or a second superoxide ion. 35 Thus, the presence of even small molar quantities of water in a primarily acetonitrile based electrolyte solvent is mechanistically significant.…”

Section: Discussionmentioning

confidence: 99%

Progress toward Metal-Air Batteries: Mechanistic Investigation of the Effect of Water on the Oxygen Reduction Reaction at Carbon-Conductive Polymer-Silver Composite Air Electrodes

Lee

DeMayo

Takeuchi

et al. 2014

J. Electrochem. Soc.

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The oxygen reduction reaction (ORR) at the carbon-conductive polymer-silver (C-cp-Ag) composite electrode in non-aqueous electrolyte with small amounts of added water is the subject of this study. The contributions of the various components of the composite electrode were assessed by employing four electrodes: (1) glassy carbon (C), (2) polypyrrole coated glassy carbon (C-cp), (3) silver disk (Ag), and (4) carbon-polypyrrole-silver composite (C-cp-Ag). Notably, with 5000 ppm of water in non-aqueous solution, the ORR reaction at Ag and C-cp-Ag shows an n = 4 reduction, while ORR at C and C-cp display an n = 1 reduction. The results show that the use of a multilayer C-cp-Ag composite electrode provides the opportunity to achieve the four electron reduction of one O 2 molecule, with a low precious metal (Ag) loading. In metal air batteries, the cathode consists of the electroactive cathode material, oxygen (O 2 ) and the remainder of the inert electrode consisting of the current collector and oxygen reduction reaction (ORR) catalyst. Metal air batteries fall into a special category as the electroactive cathode material, oxygen (O 2 ), is available in excess from outside the battery. While the cathode current collector, the ORR catalyst and the oxygen reduction products all add mass, 1,2 metal air batteries still provide the opportunity for high energy densities relative to sealed battery technologies. 3,4 Notably, the structures and chemistries of the inert electrode (air electrode) can be varied to address ORR kinetic issues. Typically, a composite air electrode consists of an electrical conductor mixed with an ORR catalyst, often strengthened with a binder 5,6 and a support such as a metal mesh. 7,8 A disadvantage of the conventional air electrode fabrication strategy is that catalyst particles positioned within the electrode interior often have limited access to oxygen.With an earlier article, we introduced a new composite electrode paradigm for metal air batteries, and reported the preparation, characterization, and electrochemical activity of a carbon current collector-conductive polymer-silver (cc-cp-Ag) composite electrode. Enhanced oxygen reduction activity for our composite electrode was observed relative to coated glassy carbon or silver disk electrodes, at a low silver loading of < 0.3 mg cm −2 . Specifically, the role of the current collector toward the electrochemical reduction of oxygen, the role of the conductive polymer in improving the structural integrity of the composite electrode, and a quantitative study of the silver loading effect on ORR activity were all investigated. A notable advantage of the electrodeposition based strategy we developed is the ability to easily generate silver coated three-dimensionally structured composites via use of three dimensional electrically conductive substrates. Three dimensional electrodes can increase the active surface area, enabling reduction of more oxygen per unit planar area. This approach was utilized to prepare three-dimensionally structured carboncondu...

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Effect of water as a proton donor on the decay of anthracene and naphthalene anion radicals in aqueous mixtures of acetonitrile, dimethylformamide, and dimethyl sulfoxide

Cited by 44 publications

References 8 publications

Voltammetry in (toluene)3-tetrabutylammonium tetrafluoroborate, a novel liquid hydrocarbon electrolyte

Voltammetry in (toluene)3-tetrabutylammonium tetrafluoroborate, a novel liquid hydrocarbon electrolyte

Decorating BODIPY with Electron‐Withdrawing NO Group: Spectroelectrochemical Consequences and Computational Investigation

Progress toward Metal-Air Batteries: Mechanistic Investigation of the Effect of Water on the Oxygen Reduction Reaction at Carbon-Conductive Polymer-Silver Composite Air Electrodes

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