Electrocatalytic hydrogenation of ketones and of α- and β-diketones on Raney metal electrodes

Cheong, Amoy Kam; Bolduc, Yvon; Lessard, Jean

doi:10.1139/v93-232

Cited by 11 publications

(4 citation statements)

References 25 publications

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“…The ECH of the conjugated double bond was much less selective in trans-cinnamaldehyde (entries 16 and 17: selectivities of 56 and 5 1% for conversion rates of 69 and loo%, respectively) than in trans-phenylbutenone (100% selectivity at 87% conversion in entry 15), in agreement with the fact that the carbonyl group of an aldehyde is less hindered and more reactive than that of a ketone. Aldehydes have indeed been shown to be hydrogenated more readily than ketones in both catalytic (18) and electrocatalytic (3) hydrogenations. double bond hydrogenation can be increased to 100% by decreasing the current density, and the efficiency can be increased to loo%, also by both increasing the concentration of the substrate and decreasing the current density.…”

Section: Resultsmentioning

confidence: 99%

“…(Y=Z)M with chemisorbed hydrogen (reaction [3]). There is Electrocatalytic hydrogenation (ECH) of unsaturated organic molecules in aqueous or mixed aqueous-organic media has been carried out since the beginning of the century.'…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, the formation of chemisorbed hydrogen by reduction of water on a low hydrogen overvoltage cathode requires a less negative potential than the electronation of most functional groups of organic chemistry (with the exception of the nitro group family). Furthermore, the formation, for instance, of dimerization products in the electrohydrogenation of carbonyl compounds may be avoided since reactive intermediates such as radical anions and radicals are not produced (3,9). However, an advantage of the EP process is the possibility of controlling the product selectivity by potentiostatic reduction.…”

Section: Introductionmentioning

confidence: 99%

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Electrocatalytic hydrogenation of conjugated enones on nickel boride, nickel, and Raney nickel electrodes

Mahdavi¹,

Chambrion²,

Binette³

et al. 1995

Can. J. Chem.

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Abstract:The selectivity of the electrocatalytic hydrogenation (ECH) of conjugated enones to the corresponding carbonyl compounds has been investigated in aqueous methanol under constant current at nickel boride, fractal nickel, and Raney nickel electrodes made of pressed powders. The influence of various parameters (water percentage, pH, concentration of substrate, and current density) on the selectivity of the carbon-carbon double bond hydrogenation was studied with cyclohex-2-en-I-one at nickel boride electrodes. Under given electrolysis conditions, fractal nickel electrodes were found to give the highest selectivity. The selectivity of the ECH of a variety of conjugated enones at fractal nickel electrodes was determined under electrolysis conditions that gave the best selectivity with cyclohexenone at nickel boride electrodes.Key words: electrocatalytic hydrogenation, a,P-unsaturated ketones, selective hydrogenation, nickel based cathodes.RCsume : Nous avons fait l'ttude de la stlectivite de l'hydrogtnation Clectrocatalytique (HEC) d'tnones conjugutes en cttones saturtes correspondantes dans le methanol-eau 5 courant constant sur des tlectrodes de borure de nickel, nickel fractal et nickel de Raney fabriqutes par pressage de poudres. L'influence de divers paramktres (le pourcentage d'eau, le pH, la concentration du substrat et la densitt du courant) sur la stlectivitt a t t t ttudite avec la cyclohex-2-tn-1-one sur tlectrodes de borure de nickel. Sous des conditions d'Clectrolyse donnCes, la stlectivite s'est averCe la plus Clevte avec les tlectrodes de nickel fractal et celles-ci ont t t t utilistes pour une Ctude de la sClectivitC de I'HEC de diverses cttones conjugCes sous les conditions d'Clectrolyse ayant donnt la meilleure stlectivitt dans le cas de la cyclohextnone.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrocatalytic hydrogenation of conjugated enones on nickel boride, nickel, and Raney nickel electrodes

Mahdavi¹,

Chambrion²,

Binette³

et al. 1995

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

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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.…”

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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Porous N‐Doped Carbon‐encapsulated Iron as Novel Catalyst Architecture for the Electrocatalytic Hydrogenation of Benzaldehyde

Pota,

Costa de Oliveira,

Schröder

et al. 2024

ChemSusChem

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Carbon porous materials containing nitrogen functionalities and encapsulated iron‐based active sites have been suggested as electrocatalysts for energy conversion, however their applications to the hydrogenation of organic substrates via electrocatalytic hydrogenation (ECH) remain unexplored. Herein, we report on a Fe@C:N material synthesized with an adapted annealing procedure and tested as electrocatalyst for the hydrogenation of benzaldehyde. Using different concentrations of the organic, and electrolysis coupled to gas chromatography experiments, we demonstrate that it is possible to use such architectures for the ECH of unsaturated organics. Potential control experiments show that ECH faradaic efficiencies >70% are possible in acid electrolytes, while maintaining selectivity for the alcohol over the pinacol dimerization product. Estimates of product formation rates and turnover frequency (TOF) values suggest that these carbon‐encapsulated architectures can achieve competitive performance in acid electrolytes relative to both base and precious metal electrodes.

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Electrocatalytic hydrogenation of ketones and of α- and β-diketones on Raney metal electrodes

Cited by 11 publications

References 25 publications

Electrocatalytic hydrogenation of conjugated enones on nickel boride, nickel, and Raney nickel electrodes

Electrocatalytic hydrogenation of conjugated enones on nickel boride, nickel, and Raney nickel electrodes

Controlling Selectivity in the Electrocatalytic Hydrogenation of Adiponitrile through Electrolyte Design

Porous N‐Doped Carbon‐encapsulated Iron as Novel Catalyst Architecture for the Electrocatalytic Hydrogenation of Benzaldehyde

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