On the oxidation of alcohols and amines at nickel oxide electrodes: Mechanistic aspects

Robertson, P.M.

doi:10.1016/s0022-0728(80)80079-9

Cited by 132 publications

(42 citation statements)

References 7 publications

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“…It is also possible, as suggest by Hall et al, that the oxalate in the system can interact with the α-Ni(OH) 2 structure by forming a multilayered structure of oxalate-intercalated α-Ni(OH) 2 . Since the α-Ni(OH) 2 layer is limited to two ML [23], the presence of a multilayered structure with oxalate between the layers would result in more Ni available for the Ni(OH) 2 to NiOOH transition (Eq. 4); however, this was postulated to occur only with slow scan rates.…”

Section: Resultsmentioning

confidence: 99%

“…4 is unknown due to the process taking place in Eq. 3, and (iv) the extent of NiO x formation occurring concurrently with β-Ni(OH) 2 and NiOOH formation is also unknown. Regardless, there are several theoretical and estimated values for the expected charge density values associated with Eqs.…”

Section: Resultsmentioning

confidence: 99%

“…In each of these applications, the oxidation state of the electrode surface directly impacts the performance of the system. In electrocatalysis applications such as the oxidation of small organic molecules, it is often the surface oxide that participates directly in the reaction [1][2][3][4][5]. Thus, it is important not only to understand the oxide species that form on nickel in various electrochemical environments but also to develop strategies to control and optimize their growth.…”

Section: Introductionmentioning

confidence: 99%

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The Formation of Surface Oxides on Nickel in Oxalate-Containing Alkaline Media

2015

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The electrochemical formation of α-Ni(OH) 2 and NiOOH in the presence of adsorbed oxalate in alkaline media is studied under well-controlled experimental conditions that include the variation of the system temperature (T=−10 to 20°C), the scan rate (v=20, 150, and 200 mV s −1 ), and the concentration of supporting electrolyte (0.10 and 0.50 M KOH). The studies are carried out using cyclic voltammetry (CV) with polycrystalline bulk nickel and nickel foams. In situ infrared spectroscopy with voltammetry confirms the adsorption of oxalate to the surface of nickel in the 0.10 to 0.30 V potential window, concurrent with the formation of the α-Ni(OH) 2 species. The presence of oxalate in the system increases the charge density (Q) for the formation of both the α-Ni(OH) 2 and NiOOH surface oxides. The Q values calculated under various conditions indicate that the presence of oxalate in the system encourages the formation of a full single monolayer (ML) of NiOOH in the first CV scan. Measurements carried out at room temperature demonstrate that an increase in v decreases the Q values for NiOOH in the presence of oxalate to minimum values achieved at v ≥150 mV s −1 . An increase of KOH concentration results in the formation of a thicker layer of NiOOH both in the presence and absence of oxalate. The Q values of NiOOH reduction in conditions that favor the formation of one complete monolayer of NiOOH are used to calculate the specific surface areas of open-cell nickel foams. The calculation of electrochemical surface area using this method is discussed and evaluated with respect to calculations based on the charge of α-Ni(OH) 2 formation.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Formation of Surface Oxides on Nickel in Oxalate-Containing Alkaline Media

2015

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“…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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“…In recent years, the focus of research is towards finding cheaper alternative electrocatalysts and improving the overall cell performance. Non noble transition metal electrocatalysts such as copper [16], nickel [17][18][19][20][21][22][23][24] which oxidise methanol and other alcohols, offer good alternative electrocatalysts. The activity of nickel based electrocatalysts depends on the method of preparation of these electrodes.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Nickel Modified Carbon Fibre Electrodes and their Application for Methanol Oxidation

Risbud¹,

Baxter²,

Skyllas‐Kazacos³

2012

TOEFJ

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Nickel modified carbon fibre electrodes were prepared by electrochemical oxidation and partial reduction of a graphite fibre electrode with a slow linear potential sweep in 97% H 2 SO 4 solution followed by impregnation & ionexchange with Ni +2 species. The cyclic voltammetry of the modified electrode in an alkaline medium showed electrocatalytic activity towards methanol oxidation which is consistent with the behaviour of a polycrystalline nickel electrode in the same media. The electrode fabricated through the ion exchange with 0.1 M Ni solution provided the most significant response for solutions with lower methanol concentrations up to 0.5 M methanol while at higher concentrations of methanol, a poisoning effect was observed resulting in lower performance.

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On the oxidation of alcohols and amines at nickel oxide electrodes: Mechanistic aspects

Cited by 132 publications

References 7 publications

The Formation of Surface Oxides on Nickel in Oxalate-Containing Alkaline Media

The Formation of Surface Oxides on Nickel in Oxalate-Containing Alkaline Media

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

Preparation of Nickel Modified Carbon Fibre Electrodes and their Application for Methanol Oxidation

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