In Situ Spectroelectrochemical Studies on Anodic Oxidation of Copper in Alkaline Solution

Pyun, Chong-Hong; Park, Su‐Moon

doi:10.1149/1.2108333

Cited by 142 publications

(88 citation statements)

References 17 publications

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“…One possible explanation to account for these observations may involve the semi-conducting properties of the copper oxides. It is widely accepted that the passive films formed on copper in alkaline solutions, although complex in nature, consist of an overall duplex structure, with an inner layer of Cu 2 O and an outer layer of CuO, followed by Cu(OH) 2 at higher applied potentials [28,29]. Both Cu 2 O and CuO are well-known p-type semiconductors, with the defects arising from cation vacancies in the oxide lattice.…”

Section: Photo-induced Oxidation Of Glucose At the Composite Electrodementioning

confidence: 99%

Oxidation and photo-induced oxidation of glucose at a polyaniline film modified by copper particles

Farrell

Breslin

2004

Electrochimica Acta

116

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The oxidation and photo-induced oxidation of glucose at a copper-dispersed polyaniline film was studied in an alkaline hydroxide solution. It was found that the copper-dispersed polyaniline electrode was capable of oxidizing glucose at potentials between 0.2 and 0.75 V/(Ag|AgCl), with the rate of oxidation being higher than that observed at a bulk copper electrode. On irradiation of the composite with polychromatic UV light, a further increase in the rate of the glucose oxidation reaction was observed. Formate was identified as the main product of the glucose oxidation reaction under both light and dark conditions using 1 H NMR spectrometry. This suggests that illumination does not alter significantly the reaction pathway.

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Section: Photo-induced Oxidation Of Glucose At the Composite Electrodementioning

confidence: 99%

Oxidation and photo-induced oxidation of glucose at a polyaniline film modified by copper particles

Farrell

Breslin

2004

Electrochimica Acta

116

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“…[22][23][24][25] It is evident that in the entire range of potential window of aqueous electrolytes, different copper species are created and the Cu(II)/Cu(III) redox couple is generated at the anodic edge of the voltammograms in alkaline solutions. [22][23][24][25] Regarding the nature of Cu(III) entity, species ranging from copper oxy-hydroxide to Cu(III) radical have been proposed.…”

Section: Resultsmentioning

confidence: 99%

Electrooxidation and determination of etidronate using copper nanoparticles and microparticles-modified carbon paste electrodes

Heli¹,

Faramarzi²,

Jabbari³

et al. 2010

J. Braz. Chem. Soc.

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O comportamento eletroquímico e a determinação de um bisfosfonato, o etidronato de sódio, em três diferentes eletrodos de cobre: eletrodo de cobre policristalino (CE) e eletrodos de pasta de carbono modificados com micropartículas de cobre (m-CPE) e nanopartículas de cobre (n-CPE) foi investigado. Usando o eletrodo CE, os voltamogramas apresentaram um pico de corrente anódica, enquanto com m-CPE e n-CPE, foram observados dois picos de corrente de oxidação. A densidade de corrente anódica em 610 mV para n-CPE é cinco vezes maior do que para m-CPE. Isto está relacionado ao efeito do tamanho das nanopartículas de cobre. As correntes anódicas foram relacionadas à oxidação eletrocatalítica do etidronato via eletrogeração de espécies ativas de Cu(III) em um mecanismo EC'. Os valores para a constante de velocidade catalítica para o processo de oxidação e o coeficiente de difusão do etidronato foram 8,9 × 103 cm 3 mol -1 s -1 e 1,55 × 10 -6 cm 2 s -1 , respectivamente. Um procedimento sensível e rápido foi desenvolvido para a análise de etidronato, e os parâmetros analíticos correspondentes foram relatados. O etidronato foi determinado com um intervalo linear de 10,57 mmol L -1 e um limite de detecção de 200-2538 mmol L -1 . A exatitude foi checada pela aplicação do teste de recuperação nas amostras. O método amperométrico proposto foi aplicado à análise de comprimidos farmacêuticos comerciais e os resultados apresentaram concordância com os valores de literatura.The electrochemical behavior and determination of a bisphosphonate drug, sodium etidronate, on three different copper-based electrodes: polycrystalline copper electrode (CE) and copper microparticles-(m-CPE) and copper nanoparticles (n-CPE)-modified carbon paste electrodes was investigated. In the voltammograms recorded using CE, one anodic peak was appeared while, both m-CPE and n-CPE represented two anodic oxidation peaks. The anodic current density at 610 mV for n-CPE is >5 times higher that of m-CPE. This was related to the nanosize effect of copper nanoparticles. The anodic currents were related to the electrocatalytic oxidation of etidronate via the electrogenerated active species of Cu(III) in an EC' mechanism. The catalytic rate constant for the oxidation process and the diffusion coefficient of etidronate were obtained as 8.9×103 cm 3 mol -1 s -1 and 1.55×10 -6 cm 2 s -1 , respectively. A sensitive and time-saving sensing procedure was developed for the analysis of etidronate, and the corresponding analytical parameters were reported. Etidronate was determined with a limit of detection of 10.57 mmol L -1 with a linear range of 200-2538 mmol L -1. Accuracy was also checked by recovery test on spiked samples. The proposed amperometric method was applied to the analysis of commercial pharmaceutical tablets and the results were in good agreement with the declared values.

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“…Repeated cyclic voltammograms were completed at 100 mV s −1 in an argon-saturated 0.1 M KOH electrolyte in the scan range 0.05-1.2 V vs. RHE as an electrochemical break-in. 25 Voltammograms were also taken in an extended scan range (0.05-1.5 V vs. RHE) at 50 mV s −1 as a comparison to bulk polycrystalline Cu (BPCu). The electrochemically active surface areas (ECSAs) of Pd and Pt were determined by carbon monoxide oxidation volammograms since more than a monolayer of hydrogen adsorbed onto Pd during cyclic voltammograms.…”

Section: Methodsmentioning

confidence: 99%

Palladium Coated Copper Nanowires as a Hydrogen Oxidation Electrocatalyst in Base

Alia

Yan

2015

J. Electrochem. Soc.

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Palladium (Pd) nanotubes are synthesized by the spontaneous galvanic displacement of copper (Cu) nanowires, forming extended surface nanostructures highly active for the hydrogen oxidation reaction (HOR) in base. The synthesized catalysts produce specific activities in rotating disk electrode half-cells 20 times greater than Pd nanoparticles and about 80% higher than polycrystalline Pd. Although the surface area of the Pd nanotubes was low compared to conventional catalysts, partial galvanic displacement thrifted the noble metal layer and increased the Pd surface area. The use of Pd coated Cu nanowires resulted in a HOR mass exchange current density 7 times greater than the Pd nanoparticles. The activity of the Pd coated Cu nanowires further nears Pt/C, producing 95% of the mass activity. The commercial deployment of proton exchange membrane fuel cells (PEMFCs) is primarily limited by the cost of platinum (Pt) catalysts. Hydroxide exchange membrane fuel cells (HEMFCs) were recently developed as a potential alternative to PEMFCs as they can avoid the use of Pt group metal (PGM) catalysts, particularly at the cathode in the oxygen reduction reaction (ORR). [1][2][3][4][5] In both PEMFCs and HEMFCs, kinetic losses are primarily attributed to the cathode, where ORR on Pt requires an overpotential of approximately 0.3 V. In base, however, the hydrogen oxidation reaction (HOR) on Pt is two orders of magnitude slower than in acid.6,7 A reduction in HOR catalyst cost can significantly improve the commercial prospect of HEMFCs.Pd has previously been studied as a HOR catalyst and alternative to Pt in membrane electrode assemblies for PEMFCs and alkaline (liquid electrolyte) fuel cells. [8][9][10][11][12] Pd-based catalysts, including Pd-gold (Au) alloys, Pd-Pt alloys, and Pd modified polythiophene, have also been studied for catalyzing HORs in acid or gaseous environments. [13][14][15] Although fundamental studies of the kinetics of HOR on Pd in base are largely unavailable, recent rotating disk electrode (RDE) results provide insight, allowing for the design and electrochemical characterization of HOR catalysts in base. Shao-Horn et al. determined the HOR/hydrogen evolution reaction (HER) exchange current densities of carbon supported Pt (Pt/C) and bulk polycrystalline Pt (BPPt). Galvanic displacement has recently been used in the development of extended surface fuel cell catalysts. 17 Although most of the work into developing advanced geometry catalysts has focused on ORR in PEMFCs, Pt coated copper (Cu) nanowires (Pt/CuNWs) were recently studied as catalysts for HOR in base in RDE half-cells. 18Pt/CuNWs significantly exceeded the HOR mass and area exchange current densities of Pt/C, potentially benefitting from compressive strain and Cu surface impurities facilitating hydroxyl adsorption. 19,20 In this study, we galvanically displaced CuNWs with Pd, forming Pd coated CuNWs (Pd/CuNWs) and Cu templated Pd nanotubes (PdNTs (Cu)). These materials were investigated for HOR in base to: improve the HOR mass and area activiti...

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In Situ Spectroelectrochemical Studies on Anodic Oxidation of Copper in Alkaline Solution

Cited by 142 publications

References 17 publications

Oxidation and photo-induced oxidation of glucose at a polyaniline film modified by copper particles

Oxidation and photo-induced oxidation of glucose at a polyaniline film modified by copper particles

Electrooxidation and determination of etidronate using copper nanoparticles and microparticles-modified carbon paste electrodes

Palladium Coated Copper Nanowires as a Hydrogen Oxidation Electrocatalyst in Base

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