207 resultados para reduction


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The electrochemical impedance spectroscopy (EIS) at different potentials has been used to study the oxygen reduction reaction (ORR) in 3.5% NaCl solution on glassy carbon (GC) electrode in this work. Results show that ORR consists of three two-electron reaction steps and both superoxide ion (O-2(-)) and hydrogen peroxide (H2O2), which are produced by ORR, obstruct the diffusion of oxygen to the surface of the electrode and make the EIS results change into a transmissive finite diffusion process with the real part contraction and a reflective finite diffusion process from a semi-infinite diffusion process. The values of electron transfer resistance (R-t) and diffusion resistance (R-d) were calculated from EIS. O-2(-) influenced strongly on the Rt values and induced a maximum at -0.45 V.

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The effects of marine environmental factors-temperature (T), dissolved oxygen (DO), salinity (S) and pH-on the oxidation-reduction potential (ORP) of natural seawater were studied in laboratory. The results show an indistinct relationship between these four factors and the ORP, but they did impact the ORP Common mathematical methods were not applicable for describing the relationship. Therefore, a grey relational analysis (GRA) method was developed. The degrees of correlation were calculated according to GRA and the values of T, pH, DO and S were 0.744, 0.710, 0.692 and 0.690, respectively. From these values, the relations of these factors to the ORP could be described and evaluated, and those of T and pH were relatively major. In general, ORP is influenced by the synergic effect of T, DO, pH and S, with no single factor having an outstanding role.

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Since the acceptance of the electrochemical rusting mechanism, oxygen reduction has been considered the main cathodic process, while H+ reduction has been overlooked for the past four decades because oxygen can be readily renewed due to the thin layer Of Solution film formed during atmospheric corrosion. This study shows that measurable hydrogen call be detected at the surface opposite to the corroding side of the specimen during wet-dry cycles, and a clear correlation exists between the quantities of hydrogen permeated through iron sheet and weight loss. Results Suggest the intrinsic importance of H+ reduction that merits further investigation. (c) 2004 Elsevier Ltd. All rights reserved.

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Cyclic voltammetry, electrochemical impedance spectroscopy, and rotating disk electrode voltammetry have been used to study the effect of chloride ions on the dissolved oxygen reduction reaction (ORR) on Q235 carbon steel electrode in a 0.02 M calcium hydroxide (Ca(OH)(2)) solutions imitating the liquid phase in concrete pores. The results indicate that the cathodic process on Q235 carbon steel electrode in oxygen-saturated 0.02 M Ca(OH)(2) with different concentrations of chloride ions contain three reactions except hydrogen evolution: dissolved oxygen reduction, the reduction of Fe(III) to Fe(II), and then the reduction of Fe(II) to Fe. The peak potential of ORR shifts to the positive direction as the chloride ion concentration increases. The oxygen molecule adsorption can be inhibited by the chloride ion adsorption, and the rate of ORR decreases as the concentration of chloride ions increases. The mechanism of ORR is changed from 2e(-) and 4e(-) reactions, occurring simultaneously, to quietly 4e(-) reaction with the increasing chloride ion concentration.

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Microwave effects have been shown to promote the activation of NOx molecules in the process of selective reduction of NO by CH4 over an In-Fe2O3/HZSM-5 catalyst and to enhance the water tolerance of this catalyst for NO reduction.

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Selective reduction of NO by CH4 on an In-Fe2O3/H-ZSM-5 catalyst was investigated in the presence of excess oxygen. Compared with In/H-ZSM-5, the In-Fe2O3/H-ZSM-5 catalyst with high Fe2O3 contents showed higher activity in a wide range of reaction temperatures. It was found that the addition of Fe2O3 yielded a promotion effect on CH4 activation. The influence of water vapor on NO conversion was also investigated. The activity of the In/H-ZSM-5 catalyst has been found to be strongly inhibited by water vapor, while the In-Fe2O3/H-ZSM-5 catalyst remained fairly active in the presence of 3.3% steam. (C) 2000 Elsevier Science B.V. All rights reserved.

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The catalytic performance of Ir-based catalysts was investigated for the reduction of NO under lean-burn conditions over binderless Ir/ZSM-5 monoliths, which were prepared by a vapor phase transport (VPT) technique. The catalytic activity was found to be dependent not only on the Ir content, but also on the ZSM-5 loading of the monolith. With the decreasing of the Ir content or the increasing of the ZSM-5 loading of the monolith, NO conversion increased. When the ZSM-5 loading on the cordierite monolith was raised up to ca. 11% and the metal Ir content was about 5 g/l, the NO conversion reached its maximum value of 73% at 533 K and SV of 20 000 h(-1). Furthermore, both the presence of 10% water vapor in the feed gas and the variation of space velocity of the reaction gases have little effect on the NO conversion. A comparative test between Ir/ZSM-5 and Cu/ZSM-5, as well as the variation of the feed gas compositions, revealed that Ir/ZSM-5 is very active for the reduction of NO by CO under lean conditions, although it is a poor catalyst for the C3H8-SCR process. This unique property of Ir/ZSM-5 makes it superior to the traditional three-way catalyst (TWC) for NO reduction under lean conditions. (C) 2001 Elsevier Science B.V. All rights reserved.

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The catalytic performance of silver-modified ZSM-5 catalysts in the selectively catalytic reduction (SCR) of NOx with methane was investigated. NO was selectively reduced by CH4 to N-2 in the presence of excess O-2, and the catalytic activity depended on both the activation of CH4 and the adsorption properties of NOx. Silver incorporated in ZSM-5 zeolite activated CH4 at low temperatures and lowered the "light-off" temperature for the CH4-SCR of NOx. Temperature-programmed (TP) spectroscopy studies depicted that surface nitrosyl species directly decomposed to N-2 in the absence of O-2. CH4 could not effectively reduce surface nitrosyl species, but might facilitate the direct decomposition of NO through the removal of surface oxygen. Surface nitrates were formed in NO and O-2 coexisting system and could be effectively reduced by CR4 to nitrogen. The priority of surface nitrates to O-2 in the reaction with CH4 clearly demonstrated that CH4 selectively and preferentially reduced the surface nitrate species to N-2 in the excess of oxygen. (C) 2002 Elsevier Science B.V. All rights reserved.

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Simultaneous NO reduction and CO oxidation in the presence of O-2,H2O and SO2 over Cu/Mg/AUO (Cu-cat), Ce/Mg/Al/O (Ce-cat) and Cu/Ce/Mg/Al/O (CuCe-cat) were studied. At low temperatures (<340 degreesC), the presence of O-2 or H2O enhanced the activity of CuCe-cat for NO and CO conversions, but significantly suppressed the activity of Cu-cat and Ce-cat, At high temperature (720 degreesC), the presence of O-2 or H2O had no adverse effect on the NO and CO conversions over these catalysts. The addition of SO2 to NO + CO + O-2 + H2O system had no effect on the, reaction of CO + O-2 over Cu-cat, but deactivated this catalyst for NO + CO and CO + H2O reactions; over Ce-cat, all of these reactions of NO + CO, CO + O-2 and CO + H2O were suppressed significantly; over CuCe-cat, NO + CO and CO + O-2 reactions were not affected while the reaction of CO + H2O was slightly inhibited. (C) 2002 Elsevier Science B.V. All rights reserved.

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The reduction behaviors of the supported platinum-iron catalysts and their comparison with supported iron catalysts were studied by TPR (temperature-programmed reduction)-in situ Fe-57 MBS (Mossbauer spectroscopy). The results indicated that the TPR processes of all Fe-containing catalysts were different from that of bulk alpha-Fe2O3. There were interactions between Pt, Fe and the gamma-Al2O3 or SiO2 support for the Pt-Fe/gamma-Al2O3 and Pt-Fe/SiO2 catalysts. All the iron-containing catalysts show that Fe3+ was highly dispersed on the support (gamma-Al2O3 and SiO2) before reduction. No Fe-0 was found in the reduction processes. The Fe3+ was reduced to Fe2+ in tetrahedral vacancy first for the reduction of the Pt-Fe/gamma-Al2O3 catalyst. No Fe2+ in octahedral vacancy was found in the reduction of the Pt-Fe/SiO2 catalyst. Adding Pt to Fe/support (gamma-Al2O3 or SiO2) could promote the reduction of the Fe species. (C) 1999 Elsevier Science B.V. All rights reserved.

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A kinetic model presented for the selective reduction of NO with CH4 over an InFe2O3/HZSM-5 catalyst by considering the process as a combination of two simultaneous reactions: NO+O2CH4 (reaction 1) and O-2+CH4 (reaction 2). Linear regression calculation was employed to find the kinetic parameters. It was found that although the activation energies of the two reactions were almost identical, the reaction rate constants were dramatically different, namely, k(1)much greater than k(2), indicating that the NO+O-2+CH4 reaction was more preferable to take place on the In-Fe2O3/HZSM-5 catalyst as compared with the O-2+CH4 reaction.