The use of hydrated nickel–cobalt mixed oxide electrodes for oxidation of aliphatic and aromatic alcohols

Vijayabarathi, T.; Muzhumathi, S.; Noel, M.

doi:10.1007/s10800-006-9237-5

Cited by 13 publications

(6 citation statements)

References 18 publications

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“…The long-term applicability of alcohol oxidation to replace the OER in electrochemical applications requires the development of precious-metal-free catalyst systems that show high activity and high product selectivity for single value-added products. , Cobalt-based materials have shown particular promise as active catalysts for the AOR. ,− Ni-doped cobalt oxide (Co 2 NiO 4 ) has been reported as a particularly highly active for alcohol oxidation that is much more active than its Co 3 O 4 and NiO parent materials. , Specifically, Co 2 NiO 4 has been shown to operate with high activity for methanol (MeOH) oxidation, achieving current densities ≥10 mA cm –2 at ∼1.4 V vs reversible hydrogen electrode (RHE), approximately 0.2 V less positive than the onset of OER. − Co 2 NiO 4 has also shown promise as an electrocatalyst for the oxidation of 5-hydroxymethyl furfural (HMF), a biomass derivative, to 2,5-furandicarboxylic acid (FDCA), a useful polymerization feedstock. ,, …”

Section: Introductionmentioning

confidence: 99%

Electrochemical Oxidation of Primary Alcohols Using a Co₂NiO₄ Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

et al. 2022

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The electrochemical reduction of CO 2 and H 2 O to solar fuels remains a promising strategy for storing intermittent energy sources in the form of chemical bonds. These electrochemical reductions occurring at the cathode typically are coupled to the oxygen evolution reaction at the anode. The electrochemical oxidation of organic alcohols in the alcohol oxidation reaction is a promising alternative anode reaction that occurs at decreased operating potentials compared to the oxygen evolution reaction and that produces more valuable products than O 2 . Co 2 NiO 4 is a particularly promising catalyst for the oxidation of alcohols, able to promote alcohol oxidation at current densities of 10 mA cm −2 at potentials of only 1.42 V vs reversible hydrogen electrode (RHE) in alkaline aqueous conditions, significantly less positive than typical potentials required for the oxygen evolution reaction. In this work, we study the alcohol oxidation reaction by Co 2 NiO 4 for a series of straight-chain primary alcohols of increasing chain length from ethanol to n-pentanol. We show that the product distribution for alcohol oxidation depends on the alcohol chain length, changing from primarily aldehyde products for shorter-chain alcohols to primarily carboxylic acid products for longer-chain alcohols. These results suggest that alcohols are oxidized sequentially to first aldehydes and then carboxylic acids at Co 2 NiO 4 . During the oxidation of longer-chain alcohols, the aldehyde intermediates are retained at the catalyst surface for longer times, facilitating further oxidation to terminal carboxylic acid products. We also explored the potential-dependent activities and product distributions for nbutanol oxidation at Co 2 NiO 4 , and showed that alcohol oxidation is able to outcompete chloride oxidation in aqueous solutions containing Cl − at seawater concentrations. These studies provide further insight into the alcohol oxidation reaction at Co 2 NiO 4 and highlight its promise as an alternative anode reaction for the production solar fuels.

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Section: Introductionmentioning

confidence: 99%

Electrochemical Oxidation of Primary Alcohols Using a Co₂NiO₄ Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

et al. 2022

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“…Nickel is a low cost and mass produced material, showing inherent catalytic properties in a wide number of processes such as organic electrosynthesis [1][2][3][4], degradation of organic hazardous molecules [5], energy conversion in alkaline fuel cells [6,7], biosensing [8,9] and electroanalysis [10][11][12], among the most representative.…”

Section: Introductionmentioning

confidence: 99%

“…The electrocatalytic properties of nickel hydroxide -Ni(OH) 2 -and oxyhydroxideNiOOH-electrodes, obtained in alkaline medium under anodic polarization conditions, have been explored extensively for the oxidation of aliphatic and aromatic alcohols and amino compounds via the participation of Ni(III) species [1,3,4,[13][14][15][16][17][18][19][20][21][22]. In contrast, few studies have focused on the performance of Ni(OH) 2 /NiOOH couples in the electrooxidation of unsaturated alcohols (i.e., alken-1-ols or alkyn-1-ols) [1,3,23].…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic activity of Ni-doped nanoporous carbons in the electrooxidation of propargyl alcohol

García‐Cruz

Sáez

Ania

et al. 2014

Carbon

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Please cite this article as: García-Cruz, L., Sáez, A., Ania, C.O., Solla-Gullón, J., Thiemann, T., Iniesta, J., Montiel, V., Electrocatalytic activity of Ni-doped nanoporous carbons in the electrooxidation of propargyl alcohol, Carbon (2014), doi: http://dx.doi.org/10.1016/j.carbon. 2014.02.066 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Ni-doped nanoporous carbons provided similar propargyl alcohol conversions for very low metallic contents. Nanoparticulated Ni on various carbon supports gave rise to the highest electrocatalytic activity in terms of product selectivity, with a clear dependence on Ni content. The results point to the importance of controlling the dispersion of the Ni phase within the carbon matrix for a full exploitation of the electroactive area of the metal. Additionally, a change in the mechanism of the propargyl alcohol electrooxidation was noted, which seems to be related to the physicochemical properties of the carbon support as well. Thus, the stereoselectivity of the electrooxidative reaction can be controlled by the active nickel content immobilized on the anode, with a preferential oxidation to (Z)-3-(2-propynoxy)-2-propenoic acid with high Ni-loading, and to propiolic acid with low loading of active Ni sites. Moreover, the formation of (E)-3-(2-propynoxy)-2-propenoic acid was discriminatory irrespective of the experimental conditions and Ni loadings on the carbon matrixes.

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“…Ni-PbO 2 , 2% Ni-PbO 2 , PbO 2 and 4% Ni-PbO 2 , once again demonstrating that a certain amount of nickel doped PbO 2 anodes had larger specific surface area compared to the raw substrate [41].…”

Section: Cyclic Voltammetrymentioning

confidence: 82%

Electrochemical degradation of aspirin using a Ni doped PbO2 electrode

Xia

Dai

Chen

2015

Journal of Electroanalytical Chemistry

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The use of hydrated nickel–cobalt mixed oxide electrodes for oxidation of aliphatic and aromatic alcohols

Cited by 13 publications

References 18 publications

Electrochemical Oxidation of Primary Alcohols Using a Co₂NiO₄ Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

Electrochemical Oxidation of Primary Alcohols Using a Co₂NiO₄ Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

Electrocatalytic activity of Ni-doped nanoporous carbons in the electrooxidation of propargyl alcohol

Electrochemical degradation of aspirin using a Ni doped PbO2 electrode

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The use of hydrated nickel–cobalt mixed oxide electrodes for oxidation of aliphatic and aromatic alcohols

Cited by 13 publications

References 18 publications

Electrochemical Oxidation of Primary Alcohols Using a Co2NiO4 Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

Electrochemical Oxidation of Primary Alcohols Using a Co2NiO4 Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

Electrocatalytic activity of Ni-doped nanoporous carbons in the electrooxidation of propargyl alcohol

Electrochemical degradation of aspirin using a Ni doped PbO2 electrode

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Electrochemical Oxidation of Primary Alcohols Using a Co₂NiO₄ Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution

Electrochemical Oxidation of Primary Alcohols Using a Co₂NiO₄ Catalyst: Effects of Alcohol Identity and Electrochemical Bias on Product Distribution