Application of the SPE method to organic electrochemistry—VII. The reduction of nitrobenzene on a modified Pt-nafion

Ogumi, Zempachi; Inaba, Masaaki; Ohashi, Shigeru; Uchida, Masaya; Takehara, Zen‐ichiro

doi:10.1016/0013-4686(88)85030-8

Cited by 60 publications

(24 citation statements)

References 7 publications

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“…for the N-acetyl-L-cysteine production from the electroreduction of N,N-diacetyl-L-cysteine [5] and the synthesis of 1-phenylethanol from the electroreduction of acetophenone [6,7] under acidic conditions. Moreover, pioneering work performed by Ogumi and co-workers on the electrochemical hydrogenation of olefinic double bonds [8] and the reduction of nitrobenzene [9] was performed using a Nafion membrane-based SPE, within a similar configuration to PEMER, in which the product purification operations were then reduced. To the best of our knowledge and from a synthetic point of view, there are few works dealing with the electrooxidation of alcohols within a configuration similar to PEMER and/or filter-press electrochemical cell under alkaline conditions [10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor Under Alkaline Conditions − a Case Study With the Electrooxidation of Alcohols

García‐Cruz

Casado-Coterillo

Irabien

et al. 2016

Electrochimica Acta

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A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nano-particulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA -a membrane generally used in alkaline fuel cells-in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm -2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.

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Section: Introductionmentioning

confidence: 99%

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor Under Alkaline Conditions − a Case Study With the Electrooxidation of Alcohols

García‐Cruz

Casado-Coterillo

Irabien

et al. 2016

Electrochimica Acta

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“…SPE reactors have been examined previously for organic electrochemical syntheses (both oxidation and reduction reactions). Most of the published work on reduction reactions was carried out by Ogumi and co-workers who studied, for example, the electrohydrogenation of nitrobenzene to aniline by using a Cu-Pt cathode/Nafion ® membrane/Pt anode MEA (14) and the reduction of cyclooctene, α-methyl stylene, and diethyl maleate at a Pt cathode/Nafion ® membrane/Pt anode MEA (15) (Nafion is a registered trademark of E.I. DuPont de Nemours & Co., Inc., Wilmington, DE).…”

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The electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. I. Reactor design and operation

Hong

Pintauro

et al. 1998

J Americ Oil Chem Soc

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A new electrochemical method has been devised and tested for the moderate temperature/atmospheric pressure hydrogenation of edible oils, fatty acids, and fatty acid methyl esters. The method employed a solid polymer electrolyte (SPE) reactor, similar to that used in H 2 /O 2 fuel cells, with water as the source of hydrogen. The key component of the reactor was a membrane-electrode-assembly, composed of a RuO 2 powder anode and either a Pt-black or Pd-black powder cathode that were hot-pressed as thin films onto the opposing surfaces of a Nafion cation-exchange membrane. During reactor operation at a constant applied current, water was back-fed to the RuO 2 anode, where it was oxidized electrochemically to O 2 and H + . Protons migrated through the Nafion membrane under the influence of the applied electric field and contacted the Pt or Pd cathode, where they were reduced to atomic and molecular hydrogen. Oil was circulated past the back side of the cathode and unsaturated triglycerides reacted with the electrogenerated hydrogen species. The SPE reactor was operated successfully at a constant applied current density of 0.10 A/cm 2 and a temperature between 50 and 80°C with soybean, canola, and cottonseed oils and with mixtures of fatty acids and fatty acid methyl esters. Reaction products with iodine values in the range of 60-105 were characterized by a higher stearic acid content and a lower percentage of trans isomers than those produced in a traditional hydrogenation process. JAOCS 75, 917-925 (1998). FIG. 1. Principles of operation of a solid polymer electrolyte (SPE) reactor during the electrohydrogenation of an oil.

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“…To improve the selectivity and current efficiency for AN, Cu modified Pt [18,19] and carbon supported Cu electrodes [20] have been studied for the electrochemical reduction of nitrobenzene in the literature. Only AN is detected for the product of the reduction reaction and the maximum current efficiency is reported to be close to 100% [19].…”

Section: Preparative Electrolysismentioning

confidence: 99%

Promotion of the electrochemical hydrogenation of nitrobenzene at hydrogen storage alloys studied using a solid electrolyte method

Jiang

2006

J Appl Electrochem

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The electrocatalytic properties of an AB 5 -type hydrogen storage alloy towards the electrochemical hydrogenation of unsaturated organic compounds have been studied by a solid electrolyte method using electrochemical hydrogenation of nitrobenzene as a model reaction. Voltammetric studies reveal that the kinetics of the nitrobenzene electro-reduction on the hydrogen storage alloy electrode is similar to that on a Ni electrode. Aniline and p-aminophenol are produced as the reaction products. Compared to the Ni electrode, the production of aniline is considerably promoted on the hydrogen storage alloy electrode. Modifying the alloy surface with a thin layer of Cu enhances the reaction selectivity and current efficiency for aniline formation. Compared to a Cu electrode, the electrochemical hydrogenation of nitrobenzene to aniline is promoted on the Cu-modified alloy electrode. The hydrogenation promotion effect is attributed to the chemical reaction between nitrobenzene and metal hydrides that are electrochemically generated in situ. Hydrogen storage alloys therefore make it possible to intensify the electrochemical hydrogenation process of unsaturated organic compounds.

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Application of the SPE method to organic electrochemistry—VII. The reduction of nitrobenzene on a modified Pt-nafion

Cited by 60 publications

References 7 publications

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor Under Alkaline Conditions − a Case Study With the Electrooxidation of Alcohols

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor Under Alkaline Conditions − a Case Study With the Electrooxidation of Alcohols

The electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. I. Reactor design and operation

Promotion of the electrochemical hydrogenation of nitrobenzene at hydrogen storage alloys studied using a solid electrolyte method

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