Heterogeneous redox catalysis with titanium/chromium(III) oxide + TiO2 composite anodes

Beck, F.; Schulz, H.

doi:10.1016/0013-4686(84)85011-2

Cited by 72 publications

(11 citation statements)

References 58 publications

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“…All CVs in the presence of reactants were quite similar, showing an oxidation peak E$ in the +0.5-+0.6V region and an oxidation peak current directly proportional to the reactant concentration in the millimolar range. A peak current was observed instead of a plateau even at low scan rates; this last behavior is what should be expected if the number of catalytic sites remains constant at the electrode surface during the potential scan [42]. At bare glassy carbon, all the examined compounds exhibit a very slow oxidation rate owing to the very high overpotentials involved.…”

Section: Catalytic Oxidation At a Nickel-based Chemicallymentioning

confidence: 62%

Electrode modification with a poly(Ni^II‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

1995

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The voltammetric behavior in alkaline solution of a nickel-based chemically modified electrode (Ni-CME) prepared by oxidative electropolymerization of a nickel-tetraazaannulene complex (Ni"L) was investigated. After electrochemical deposition of the (Ni"L), film in dichloromethane on a conducting substrate, the modified electrode was continuously cycled in alkaline solution until a steady voltammetric profile was obtained. Although upon electrochemical treatment in basic solutions the nickel-nitrogen tetracoordination of the (NiI'L), film is probably lost, the nickel species remain entrapped inside the polymeric skeleton and exhibit stable redox behavior resembling that of the nickel hydroxide ele'ctrode. This makes it possible to prepare very thin films of nickel-based modified electrodes. In cyclic voltammetry experiments the Ni-CME exhibits a pH dependence of the peak potentials typical of the a-Ni (OH)2/y-NiOOH redox process, and a separation between anodic and cathodic peak potentials of 64mV at pH 13.2 and 10 mV s-'. The redox catalysis at Ni-CMEs of representative compounds that are not easily electrooxidized, such as choline, cadaverine, y-amino butyric acid (GABA), benzyl alcohol, and glycine, is demonstrated. The good stability of these nickel-based modified electrodes makes them attractive in analytical applications.

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Section: Catalytic Oxidation At a Nickel-based Chemicallymentioning

confidence: 62%

Electrode modification with a poly(Ni^II‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

1995

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“…k" could be evaluated from a plot of In kf vs. E. It has been recognized [40] that in mediated electrocatalysis three current-controlling factors should be taken into account: ( 1) the mass transport of the analyte to the electrode surface, as manifest in the limiting Current id; (2) the rate of eleCtrOn transfer between the analyte and the active sites of the mediator; (3) the self-electron exchange rate of the mediator at the applied potential. The rate for the chemical step in an oxidative mediated electrode process can be expressed as:…”

Section: Kinetic Data Analysismentioning

confidence: 99%

Electrochemical characteristics of conductive carbon cement as matrix for chemically modified electrodes

Huang

Pot

Kok

1995

Analytica Chimica Acta

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Electrochemical characteristics of conductive carbon cement as matrix for chemically modified electrodes Huang, X.; Pot, J.J.; Kok, W.T. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. AbstractConductive carbon cement (CCC) was evaluated as matrix material for the preparation of electrodes bulk-modified with electrocatalysts. For pure CCC electrodes the background current characteristics were examined. In acidic or neutral phosphate buffers the useful electrode potential range was from -0.3 to + 1.0 V vs. SCE, while in 0.1 mol l-' NaOH it was from -0.3 to + 0.7 V. The electrochemical reversibility of CCC electrodes was examined by measuring the standard rate constants for the reduction of hexacyanoferrate( III) and the oxidation of hydroquinone, using cyclic voltammetry (CV) and rotating disk experiments. The reversibility of a CCC electrode was comparable with that of a freshly polished glassy carbon electrode and better than that of carbon paste electrodes. CCC was used as matrix for the preparation of electrodes bulk-modified with cuprous oxide and cobalt phthalocyanine (CoPC). With a C&O-CCC electrode the oxidation potential of glucose, which shows sluggish kinetics at unmodified carbon electrodes, was strongly reduced. The kinetics of the mediated glucose oxidation has been studied with a rotating disk electrode. It was shown that at glucose concentrations higher than approximately 1 mmol 1-l the electrochemical regeneration of the catalyst becomes rate-determining. The Cu@-CCC modified electrode has been applied with a constant potential in flow-injection analysis for the determination of glucose. The long-term stability of the electrode was studied; repeated injections of a glucose solution during a period of 6 h yielded a relative standard deviation of the peak height of 1.8% (n = 57). In CV experiments the electrocatalytic activity of CoPC was shown for the oxidation of various compounds such as penicillamine, hydrazine and bile acids. Application of the CoPC-CCC electrode for the detection of bile acids in flow-through detection with a constant or pulsed potential failed, due to a rapid deactivation of the electrode.

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“…Activated adsorption or coordination, possibly due to interaction at the same adatom or adion sites, may still be important but for most organics the oxidation apparently does not occur until the adatom is oxidized. An interfacial redox cycle, widely postulated [3] and quantitatively described [4] for oxide electrode systems, is assumed to operate in many cases.…”

Section: Introductionmentioning

confidence: 99%

The importance of superficial (adatom) surface oxidation in the electrocatalytic behaviour of noble metals in aqueous media

Burke

O'Leary

1989

J Appl Electrochem

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The conventional, activated chemisorption, model of electrocatalysis is unable to explain fully the surprisingly high level of activity of gold anodes in base for certain organic electrooxidation reactions or even the ability of platinum to catalyse certain oxygen insertion reactions, e.g. methanol or formaldehyde oxidation in acid, at low potentials (in the hydrogen or double layer region) where the surface is considered usually to be oxygen-free. It was demonstrated that such behaviour can be rationalized by postulating the involvement of a quite low coverage of hydrous oxide species, generated at low potential at adatom sites, which act as mediators or catalysts in many electrooxidation reactions. The converse situation was also shown to arise, i.e. the reduction of certain species, e.g. HNO3 or NO;-, which requires the involvment of adatoms, was shown to be inhibited as long as the latter existed in the oxidized, hydrous oxide, form. An appreciation of hydrous oxide electrochemistry was shown to be very useful in interpreting electrocatalytic effects at noble metal electrodes in aqueous media.

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Heterogeneous redox catalysis with titanium/chromium(III) oxide + TiO2 composite anodes

Cited by 72 publications

References 58 publications

Electrode modification with a poly(Ni^II‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

Electrode modification with a poly(Ni^II‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

Electrochemical characteristics of conductive carbon cement as matrix for chemically modified electrodes

The importance of superficial (adatom) surface oxidation in the electrocatalytic behaviour of noble metals in aqueous media

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Heterogeneous redox catalysis with titanium/chromium(III) oxide + TiO2 composite anodes

Cited by 72 publications

References 58 publications

Electrode modification with a poly(NiII‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

Electrode modification with a poly(NiII‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

Electrochemical characteristics of conductive carbon cement as matrix for chemically modified electrodes

The importance of superficial (adatom) surface oxidation in the electrocatalytic behaviour of noble metals in aqueous media

Contact Info

Product

Resources

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Electrode modification with a poly(Ni^II‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I

Electrode modification with a poly(Ni^II‐tetramethyldibenzotetraaza[14]annulene) film. Electrochemical behavior and redox catalysis in alkaline solutions. I