985 resultados para delay reduction


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The reduction of RE3+ to RE2+ (RE=Eu, Sm and Tm) in SrB6O10 prepared in air by high-temperature solid state reaction was observed. The luminescent properties of Eu2+ and Tm2+ show f-d transition and Sm2+ shows f-f transition at room temperature. Three crystallographic sites for Sm2+ in matrix are available. Vibronic transition of D-5(0)-F-7(0) of Sm2+ was studied. The coupled phonon energy about 108 cm(-1), was determined: from the vibronic transition. Due to the thermal population from D-5(0) level, (D1-FJ)-D-5-F-7 (J=0, 1, 2) transitions of Sm2+ were observed at room temperature. A charge compensation mechanism is proposed as a possible explanation.

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Two series of mixed oxides, CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: hi) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H-2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al: Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.

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A series of layered mixed oxides La4BaCu5-xMnxO13+lambda(x = 0-5) was prepared, characterized and used as catalysts for NO+CO reaction. It was found that all the samples were single phase having a structure with five-layered-perovskite. La4BaCu2Mn3O13+lambda showed the highest activity in the title reaction, this could be attributed to the synergetic effect between Cu and Mn. The results of TPR, TPD and excess oxygen investigations confirmed that the Cu ion would be the active center. The displacement of the Cu ion by Mn caused the Cu ion to be more easily reducible and more content of excess oxygen, and it was beneficial to the activity of the catalyst. The reaction mechanism was also proposed.

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Photoelectrochemical reduction of nitrite and nitrate was studied on the surface of an electrochemically roughened silver electrode. The dependence of the photocurrent on photon energy, applied potential, and concentration of nitrite was determined. It was concluded that the photoelectrochemical reduction proceeds via a photoemission process followed by the capture of hydrated electrons by electron accepters. The excitation of plasmon resonances in nanosize metal structures produced during the roughening procedure resulted in the enhancement of the photoemission process. Ammonia was detected as one of the final products in this reaction. Mechanisms for the photoelectrochemical reduction of nitrite and nitrate are proposed.

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This paper reports a new observation of the abnormal reduction of Eu3+ --> Eu2+ in Sr2B5O9Cl when prepared in air at high temperature. A model based on the nature of substitution defects is proposed to explain this abnormal reduction. Electrons, which reduced the Eu3+ ions, are created by the substitution of cations first and then transferred to the target Eu3+ ions via tetrahedral berate anion groups. Codoping experiments are designed and performed. The results of these experiments support the model proposed. (C) 1999 Academic Press.

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Catalysts with spinel structure derived from Hydrotalcite-like Compounds (HTLcs) containing cobalt have been investigated in NO catalytic reduction by Co. It was found that catalysts with spinel structures derived from HTLcs had obviously higher activity than that prepared from general methods. A two-step reaction was observed during the reaction curse: NO was first reduced to N2O by Co, and with the increase of temperature, the N2O was reduced to N-2. The reactivity of the catalysts studied increased with the amount of cobalt-content in the catalyst, and decreased with the calcination temperature. The crystal defect would play an important role in the reaction.

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A novel organic-inorganic composite film was formed by attaching Keegin-type heteropolyanion, SiW12O404- (devoted briefly as SiW12), on a glassy carbon electrode derivatized by 4-aminophenyl group. The composite film has an ionic bonding character between SiW12 and the surface amino group, which greatly improves the Blm stability and exhibits a more reversible electrochemical behavior. The modified electrode offers an excellent and stable electrocatalytic response for the reduction of nitrite. Possible mechanism was provided for the reaction of nitrite with SiW12O404-/aminophenyl composite film.

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Composite membrane modified electrodes were prepared by electrochemical deposition of platinum particles in a poly(o-phenylenediamine) (PPD) him coated on glassy carbon (GC) electrodes. The modified electrodes showed high catalytic activity towards the reduction of oxygen and hydrogen peroxide. A four-electron transfer process predominated the reduction process. The pH dependence and the stability of the electrodes were also studied.

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Cyclic voltammetry and in-situ microscopic FTIR spectroelectrochemistry were used for the electrochemical and vibrational characterizations of the reduction process of K3Fe (CN)(6) in polyethylene glycol(PEG) with LiClO4 as supporting electrolyte at a Pt microelectrode. The rate of electron transfer is a function of the concentration of the supporting electrolyte. The redox potentials and cyclic voltammetric currents vary with Li/O molar ratio. The bl-situ spectroelectrochemistry shows that the infrared spectra are influenced by the concentration of LiClO4. The bridging cyanide groups with a structure Fe-I-C drop N ... Fe-I-C drop N are formed during the reduction process of K3Fe (CN)(6). There may be an activated complex between the Lif cation and the complex anion.

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The reduction of Eu3+ to Eu2+ in SrB6O10 prepared in air by a high-temperature solid state reaction was studied. The luminescent properties of Eu2+ in this matrix show f-d broad band emission peaking at about 386 and 432 nm at room temperature. A charge compensation mechanism is proposed as a possible explanation. The luminescence of Eu3+ with f-f transitions was studied in this sample and reflected that the Eu3+ ion occupied a site with non-centro-symmetry. The ESR spectrum was used to detect the existence of Eu2+ in the samples. (C) 1998 Elsevier Science S.A.

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This paper presents a microelectrode voltammetric determination of heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of 7,7,8',8 '-tetracyanoquinodimethane (TCNQ) in polyelectrolytes. The diffusion coefficients are estimated using cyclic voltammetry under linear diffusion conditions, and the heterogeneous electron transfer rate constants are obtained under mixed linear and radial diffusion in the polyelectrolyte. k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction for reduction of TCNQ are obtained. On the other hand, the dependencies of D and k(s) of TCNQ on the size and charge of the counterion are compared in the polyelectrolyte. (C) 1998 Elsevier Science Ltd. All rights reserved.

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A series of sample having the stoichiometry La4BaCu5-xMnxO12 (x = 0 similar to 5) were prepared, characterized by XRD, IR and H-2 - TPR and used as catalyst for NO + CO reaction. It was found that they have 5 - layered ABO(3) - type structure. The results of H-2 - TPR showed that the Cu ion was more easily reduced while a part of them was replaced by Mn ions. Their catalytic behavior to NO + CO reaction was investigate, La4BaCu2Mn3O12 showed the highest catalyst activity for the reaction than the others. The reaction mechanism is discussed:the activity of the catalysts could be attributed to the Cu ions, but it was improved when Mn ions took the place of some Cu ions.

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The mixed oxides, including LaBa2Cu3O7, LaBaCu2O5, La4BaCu5O12 with perovskite structure, were prepared. The catalysts were characterized by means of chemical analysis, XRD, H-2-TPR. It was found that their structures were layered ABO(3) perovskite structure and they were the active catalysts for the NO reduction by CO. The existence of Cu3+ is an important factor to give the catalysts a high activity for the NO reduction by CO.

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An electrode modified with a polybasic lanthanide heteropoly tungstate/molybdate complex K10H3[Nd(SiMo7W4O39)(2)] entrapped into polypyrrole (PPy) film, denoted as Nd(SiMo7W4)(2)-PPy, exhibits three couples of two-electron redox waves in pH 1-5 buffer solutions. The redox waves are surface-controlled at lower scan rates and diffusion-controlled at higher scan rates. The effects of pH on the electrochemical behavior of Nd(SiMo7W4)(2) in PPy film were investigated in detail and compared with that of Nd(SiMo7W4)(2) in aqueous solution. The various charge states of PPy during its redox process have peculiar effects on the relationship between pH and formal potentials of Nd(SiMo7W4)(2)-PPy at different acidities. The Nd(SiMo7W4)(2)-PPy cme can remarkably catalyze the electrochemical reduction of bromate with good stability. (C) 1997 Elsevier Science Ltd.

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Oxidation-reduction properties of horseradish peroxidase (HRP) have been investigated by using direct electrochemical methods. Two successive separated distinct one-electron processes of HRP were obtained and the related physiological processes were described. The monolayer coverage of HRP at the electrode surface is about 50 pmol/cm(2). UV-Vis spectrophotometry and stable amperometry prove that the enzyme electrode possesses catalytic activity for H2O2 in the absence of a mediator and it might offer an opportunity to build the third generation of biosensors for analytes, such as H2O2, glucose and cholesterol etc. (C) 1997 Elsevier Science S.A.