Electrocatalytic oxidation of cyclohexanol on a nickel oxyhydroxide modified nickel electrode in alkaline solutions

Yi, Qingfeng; Zhang, Jingjing; Huang, Wu; Liu, Xiaoping

doi:10.1016/j.catcom.2006.10.009

Cited by 103 publications

(41 citation statements)

References 25 publications

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“…CV experiments were performed using an Autolab III potentiostat/galvanostat (Eco-Chemie). All Ni based anodes were previously pre-treated between -0.5 and +0.6 V versus the AgCl/Ag/ (3.5 M KCl) reference electrode for 100 cycles at a scan rate of 100 mV s -1 to obtain the catalytic form of NiOOH species [14,24,35,36] responsible for catalysing the electrooxidation of alcohols. All CV measurements were performed at 25 ± 1 ºC.…”

Section: Electrodes Characterisationmentioning

confidence: 99%

“…Therefore, the primary reaction involves the electrooxidation of PGA to PA throughout the regeneration of NiOOH species to Ni(OH)2 species (reaction 1 and 2) [35,51,52]. On the other hand, the electrooxidation of PGA can likely lead to the formation of Z-PPA isomer which proceeds through a hapto-propiolate complex with the NiOOH species on the surface via the triple bond of the alkyne moiety (reaction 3) as described in a tentative mechanism in [14].…”

Section: Preparative Electrooxidation Of Propargyl Alcoholmentioning

confidence: 99%

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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: Electrodes Characterisationmentioning

confidence: 99%

Section: Preparative Electrooxidation Of Propargyl Alcoholmentioning

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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“…The Ni(III) species is generated on the electrode surface at potentials in the region 0f 0.4 V to 0.5 V vs Ag/AgCl. The reactions are [6][7][8][9][10][11] …”

Section: Introductionmentioning

confidence: 99%

Utilization of Special Potential Scan Programs for Cyclic Voltammetric Development of Different Nickel Oxide-Hydroxide Species on Ni Based Electrodes

Pissinis¹,

Sereno²,

Marioli³

2012

OJPC

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Special potential scan programs were designed for cyclic voltammetric development of β-NiOOH or γ-NiOOH/ β-NiOOH mixtures on the surface of nickel or nickel-chromium (80:20) alloy electrodes in NaOH 0.10 M. The programs consisted on changing the anodic or cathodic switching limit to facilitate the chemical reactions taking place either between Ni(II) hydroxides or between Ni(III) oxides-hydroxides. The electrochemical charge density under the oxidative wave, observed at Ni or Ni-Cr electrode surfaces at approximately 0.48 V (vs SCE), remained almost constant with the number of cv cycles after approximately 600 cv cycles at 0.050 V/s. Thus, it can be suggested that a stable proportion of Ni(II)/Ni(III) oxides-hydroxides was obtained on the electrode surfaces. The relative amounts of β-NiOOH or γ-NiOOH species were calculated from the electrochemical charges under their reduction waves in the voltammetric experiments. Higher charge densities were always obtained with Ni-Cr alloy electrodes as compared to pure Ni electrodes. Linear relationships were obtained in our study on the dependence of the oxidative peak current with the square root of the scan rate at a scan rate range between 0.01 V/s and 0.16 V/s.

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“…To do this, the anode compartment was fed with a 1.0 M NaOH solution and then a current intensity was set to 0.3 A for 16 min to obtain the electrocatalytic NiOOH species [67]. Current intensity, charge passed and cell potential during the electrosynthesis were controlled and monitored using a Gw instek PSP-2010 power supply as current intensity source.…”

Section: Polarization Curves and Electrolysis Into A Pem Electrochemimentioning

confidence: 99%

High Performance of Alkaline Anion-Exchange Membranes Based on Chitosan/Poly (vinyl) Alcohol Doped with Graphene Oxide for the Electrooxidation of Primary Alcohols

García‐Cruz

Casado-Coterillo

Irabien

et al. 2016

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Mixed matrix membranes (MMM) based on chitosan (CS) and poly (vinyl) alcohol (PVA) with a 50:50 w/w ratio doped with graphene oxide (GO) are prepared by solution casting and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), water uptake, alcohol permeability, ion exchange capacity (IEC) and OHć onductivity measurements. The SEM analysis revealed a dense MMM where the GO nanosheets were well dispersed over the entire polymer matrix. The incorporation of GO increased considerably the thermal stability of the CS:PVA membrane. The GO-based MMM exhibited a low conductivity of 0.19 mS¨cm´1 in part because the GO sheets did not change the crystallinity of the CS:PVA matrix. The reinforced structure created by the hydrogen bonds between the GO filler and the CS:PVA matrix resulted to be a good physical barrier for alcohol permeability, achieving a coefficient of diffusion of 3.38ˆ10´7 and 2.43ˆ10´7 cm 2¨s´1 after 60 and 120 min, respectively, thus avoiding additional alcohol crossover. Finally, the electrochemical performance of the GO-based MMM in the electrooxidation of propargyl alcohol was investigated in a Polymer Electrolyte Membrane Electrochemical Reactor (PEMER) under alkaline conditions, through the polarization curve and the electrolysis reactions, showing a performance comparable to anion-exchange commercial membranes.

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Electrocatalytic oxidation of cyclohexanol on a nickel oxyhydroxide modified nickel electrode in alkaline solutions

Cited by 103 publications

References 25 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

Utilization of Special Potential Scan Programs for Cyclic Voltammetric Development of Different Nickel Oxide-Hydroxide Species on Ni Based Electrodes

High Performance of Alkaline Anion-Exchange Membranes Based on Chitosan/Poly (vinyl) Alcohol Doped with Graphene Oxide for the Electrooxidation of Primary Alcohols

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