ChemInform Abstract: ELEKTROKATALYTISCHE RED. VON ADIPONITRIL

Томилов, А. П.; Kirilyus, I. V.; Andriyanova, I. P.

doi:10.1002/chin.197244117

Cited by 2 publications

(3 citation statements)

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“…Previous experimental studies have shown that low hydrogen overpotential electrocatalysts, such as Raney nickel and platinum or rhodium black, can effectively hydrogenate a variety of organic compounds, for example phenol to cyclohexanol [1], glucose to sorbitol [2,3], dinitriles to diamines and/or aminonitriles [4,5], and ketones and aldehydes to alcohols [6]. Similarly, flat sheet cathodes coated with Devarda copper or Raney nickel have been employed to hydrogenate nitroaromatics under potentiostatic conditions with high current efficiencies and near quantitative product yields [7,8].…”

Section: Introductionmentioning

confidence: 99%

The role of supporting electrolyte during the electrocatalytic hydrogenation of aromatic compounds

Pintauro

Bontha

1991

J Appl Electrochem

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The electrocatalytic hydrogenation of benzene, aniline, and nitrobenzene was investigated at a Raney nickel powder cathode. The single phase electrolyte consisted of t-butanol, water, and a hydrotropic salt, either sodium or tetraethylammonium p-toluenesulphonate (TEATS). The hydrogenation of benzene was achieved only in the latter case; the only product detected was cyclohexane. The highest current efficiency (73%) was obtained at 50 ~ C, 1.0 M benzene, 2.5 M TEATS, and at an apparent current density of 4.0 mAcm -2. Aniline was electrocatalytically hydrogenated to cyclohexylamine only in the presence of a quaternary ammonium ion supporting electrolyte (containing either Br-or p-toluenesulphonate anions), with product current efficiencies of ~ 40%. When nitrobenzene was hydrogenated with a sodium p-toluenesulphonate supporting electrolyte, only nitro group reduction was observed. When the supporting electrolyte was TEATS, both nitro group reduction and aromatic ring hydrogenation occurred.

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Section: Introductionmentioning

confidence: 99%

The role of supporting electrolyte during the electrocatalytic hydrogenation of aromatic compounds

Pintauro

Bontha

1991

J Appl Electrochem

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“…ECH in aqueous media have been reported mostly for unsaturated organic molecules, including the hydrogenation of aromatic compounds, − edible oils, − quinonemethides, , and other olefins. − The electroreduction of other oxygenated functional groups (i.e., ethers, ketones, and alcohols) has been studied extensibly, ,− while the ECH of nitrile groups has received less attention despite its important implications in chemical manufacturing. The conversion of adiponitrile (ADN) to hexamethylenediamine (HMDA) − is an example of a carbon–nitrogen bond hydrogenation that can be done electrochemically using Raney Nickel or palladium electrodes. This process can impact the annual production of nearly 2 Mt of HMDA, a chemical product used as a detergent, an insecticide, an emulsifying agent, and most importantly as a monomer in the manufacture of nylon-6,6. − It can be further coupled with already existing electrosynthetic routes to manufacture ADN, contributing to the electrification and intensification of the large-scale production of nylon-6,6.…”

Section: Introductionmentioning

confidence: 99%

“…Faradaic efficiencies between 50 and 60% were obtained toward ACN, which can be hydrolyzed to ε-aminocaproic acid, the precursor for nylon-6 . Other studies have reported faradaic efficiencies <60% for the electrohydrogenation of ADN to HMDA in aqueous electrolytes containing HCl, NaOH, or alcohols such as ethanol or methanol as cosolvents. This type of ECH often relies on the use of Raney nickel electrodes. − The limited faradaic efficiencies exhibited by these electrochemical reactions have hindered the viability of electrochemical HMDA production.…”

Section: Introductionmentioning

confidence: 99%

Controlling Selectivity in the Electrocatalytic Hydrogenation of Adiponitrile through Electrolyte Design

Blanco

Dookhith

Modestino

2020

ACS Sustainable Chem. Eng.

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Organic hydrogenations are key steps in the production of numerous valuable chemicals. Their requirement for high temperature, pressure, and compressed hydrogen has motivated the interest to develop safer electrocatalytic hydrogenation (ECH) routes in benign aqueous electrolytes. However, faradaic efficiencies in organic ECH tend to be greatly limited by competition with the hydrogen evolution reaction and low reactant solubility, which hinders the implementation of these more sustainable hydrogenation routes. Using the hydrogenation of adiponitrile to hexamethylenediamine (HMDA), a monomer used in the production of nylon-6,6, as a case study, we investigate the effect of reactant concentration, temperature, pH, and organic cosolvents on the ECH of nitrile groups with Raney nickel electrodes. Higher reactant concentrations, alkaline electrolytes, and mild temperature (40 °C) are key conditions that enhance the hydrogenation of organic substrates against hydrogen evolution. A maximum faradaic efficiency of 92% toward HMDA was obtained in aqueous electrolytes at −60 mA cm–2. The addition of an organic cosolvent is subsequently studied to evaluate the effect of enhanced reactant solubility, achieving a 95% faradaic efficiency at the same current density with 30% methanol by volume in water. The insights gained from this study are relevant for the design of energy efficient organic ECH and can help accelerate the implementation of sustainable chemical manufacturing.

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ChemInform Abstract: ELEKTROKATALYTISCHE RED. VON ADIPONITRIL

Cited by 2 publications

References 0 publications

The role of supporting electrolyte during the electrocatalytic hydrogenation of aromatic compounds

The role of supporting electrolyte during the electrocatalytic hydrogenation of aromatic compounds

Controlling Selectivity in the Electrocatalytic Hydrogenation of Adiponitrile through Electrolyte Design

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