982 resultados para JACOBSEN CATALYST
Resumo:
The Aquivion short-side-chain (SSC) perfluorosulfonic acid (PFSA) ionomer was adopted in catalyst layers (CL) of polymer electrolyte membrane water electrolysers (PEMWE) instead of long-side-chain (LSC) Nafion ionomer. The effects of SSC ionomer content in CL for oxygen evolution reaction were studied in half cell with cyclic voltammetry and steady state linear sweep. In a single cell test the MEA with SSC-PFSA Aquivion ionomer exhibited better thermal stability than the one with LSC-PFSA Nafion ionomer at 90 °C. The cell voltage at a current density of 1 A cm was 1.63 V at 90 °C using the SSC-PFSA Aquivion ionomer binder, Nafion 117 membrane, and without back pressurizing. In a continuous operation the cell voltage degradation rate of the MEA using Aquivion ionomer binder was only about 0.82 mV h.
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Bimetallic catalyst system of ruthenium oxide (RuO) and niobium oxide (NbO) was prepared using the Adams method and the hydrolysis method. Physical and electrochemical characterizations of the catalysts were studied using X-ray diffraction (XRD), Scanning electron microscopy (SEM), cyclic voltammogram (CV) and polarization measurements. NbO addition to RuO was found to increase the stability of RuO. In Adams method the sodium nitrate was found to be forming complex with NbO at high temperature reaction. This makes Adams method unsuitable for the synthesis of RuO -NbO bimetallic system. Hydrolysis method on other hand does not have this problem. But a proper mixture of two oxides was not obtained in hydrolysis method. A lower crystallite size for bimetallic system was obtained with Adams method compared to hydrolysis method. RuO prepared by Adams method had higher activity compared to the hydrolysis counterpart in electrolyzer operation with nafion membrane. A cell voltage of 1.62 V was obtained with RuO (A) at 1 A/cm. A higher stability for RuNbO(A) compared to RuO(A) was observed in continuous cyclic voltammogram and electrolyzer cell test. Copyright © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Resumo:
Antimony doped tin oxide (ATO) was studied as a support material for IrO2 in proton exchange membrane water electrolyser (PEMWE). Adams fusion method was used to prepare the IrO2-ATO catalysts. The physical and electrochemical characterisation of the catalysts were carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder conductivity, cyclic voltammetry (CV) and membrane electrode assembly (MEA) polarisation. The BET surface area and electronic conductivity of the supported catalysts were found to be predominantly arisen from the IrO2. Supported catalyst showed higher active surface area than the pristine IrO2 in CV analysis with 85% H3PO4 as electrolyte. The MEA performance using Nafion®−115 membrane at 80 °C and atmospheric pressure showed a better performance for IrO2 loading ≥60 wt.% than the pristine IrO2 with a normalised current density of 1625 mA cm−2 @1.8 V for the 60% IrO2-ATO compared to 1341 mA cm−2 for the pristine IrO2 under the same condition. The higher performance of the supported catalysts was mainly attributed to better dispersion of active IrO2 on electrochemically inactive ATO support material, forming smaller IrO2 crystallites. A 40 wt.% reduction in the IrO2 was achieved by utilising the support material.
Resumo:
A density functional theory study of methanol dehydrogenation over stepped Pt(2 1 1) surfaces without and with Ru modification was carried out to understand fuel catalytic reactions on Pt-based catalysts. Two main pathways of the CH3OH dehydrogenation were examined: the O–H pathway which was initiated by O–H bond scission to form the methoxy (CH3O) intermediate followed by sequential cleavage of C–H bonds to CO, and the C–H pathway which was initiated by C–H bond scission to form the hydroxymethyl (CH2OH) followed by two C–H bond cleavages to COH and then CO. Possible crossover reactions between the O–H and C–H pathways were also computed. Compared to flat Pt(1 1 1), stepped Pt(2 1 1) increases the adsorption energies of intermediates, making no significant contribution to decreasing the reaction barriers of most elementary steps involved, except in the first hydrogen scission. However, on the Ru-modified surface, a significant reduction was found in reaction barriers for the first step of the C–H bond scission and a number of further dehydrogenation steps crossing over to the O–H pathway, with the most facile paths identified. Our data reveals the complexity of methanol catalytic reaction processes at the atomic level and contributes to a fundamental understanding of fuel reactions on Pt-based catalysts.
Resumo:
The ability of a gold palladium bimetallic catalyst to selectively oxidise toluene has been used to enhance the hydrocarbon selective catalytic reduction of NOx, a reaction in which the interaction of partial oxidation intermediates is considered important. The combination of gold with palladium has a synergistic effect, producing a catalyst that is more active for NOx conversion than the arithmetic sum of the corresponding mono-metallic materials. Three regimes in the conversion profile of the AuPd catalyst are proposed relating to production and consumption of toluene derived species, such as benzaldehyde and benzonitrile. The possible role of these reaction intermediates in the toluene HC-SCR reaction is examined. Using 15NO, the formation of N2 and N2O is observed via the direct interaction between the nitrogen atom of benzonitrile and 15NO. The higher activity of the bimetallic catalyst for the NOx reduction reaction by toluene is discussed in the context of these partial oxidation intermediates.
Resumo:
Many kinetic models have appeared in literature in past decades using two main approaches: the traditional global kinetics approach, or the more complex micro-kinetics approach. Whether global or micro-kinetics, kinetic models have been based on experimental data obtained at the end of the monolith. The experimental procedure using end pipe analysis may give an accurate overview of the reaction mechanisms that occur; however, the lack of information from within the catalyst can ultimately lead to inaccuracies in the kinetic model and parameters used.
Using SpaciMS, a spatially resolved experimental technique developed at the Queen's University Belfast, information from within the catalyst can be obtained. This minimally invasive technique provides detailed information of the gas concentration and temperature profile from inside the catalytic monolith. This paper presents a kinetic model and simulations validated against experimental data obtained from three positions inside the catalyst monolith at 2, 14, and 26 mm in, using data from the SpaciMS. Also, simulations of end pipe analysis, using a commercial reactor, for the CO oxidation are presented and analyzed. The simulations presented are for varying concentrations of both CO and O2 (0.5 % and 1 % CO, 0.5 % and 2 % O2) for both the global and micro-kinetic approach.
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Mathematical modelling has become an essential tool in the design of modern catalytic systems. Emissions legislation is becoming increasingly stringent, and so mathematical models of aftertreatment systems must become more accurate in order to provide confidence that a catalyst will convert pollutants over the required range of conditions.
Automotive catalytic converter models contain several sub-models that represent processes such as mass and heat transfer, and the rates at which the reactions proceed on the surface of the precious metal. Of these sub-models, the prediction of the surface reaction rates is by far the most challenging due to the complexity of the reaction system and the large number of gas species involved. The reaction rate sub-model uses global reaction kinetics to describe the surface reaction rate of the gas species and is based on the Langmuir Hinshelwood equation further developed by Voltz et al. [1] The reactions can be modelled using the pre-exponential and activation energies of the Arrhenius equations and the inhibition terms.
The reaction kinetic parameters of aftertreatment models are found from experimental data, where a measured light-off curve is compared against a predicted curve produced by a mathematical model. The kinetic parameters are usually manually tuned to minimize the error between the measured and predicted data. This process is most commonly long, laborious and prone to misinterpretation due to the large number of parameters and the risk of multiple sets of parameters giving acceptable fits. Moreover, the number of coefficients increases greatly with the number of reactions. Therefore, with the growing number of reactions, the task of manually tuning the coefficients is becoming increasingly challenging.
In the presented work, the authors have developed and implemented a multi-objective genetic algorithm to automatically optimize reaction parameters in AxiSuite®, [2] a commercial aftertreatment model. The genetic algorithm was developed and expanded from the code presented by Michalewicz et al. [3] and was linked to AxiSuite using the Simulink add-on for Matlab.
The default kinetic values stored within the AxiSuite model were used to generate a series of light-off curves under rich conditions for a number of gas species, including CO, NO, C3H8 and C3H6. These light-off curves were used to generate an objective function.
This objective function was used to generate a measure of fit for the kinetic parameters. The multi-objective genetic algorithm was subsequently used to search between specified limits to attempt to match the objective function. In total the pre-exponential factors and activation energies of ten reactions were simultaneously optimized.
The results reported here demonstrate that, given accurate experimental data, the optimization algorithm is successful and robust in defining the correct kinetic parameters of a global kinetic model describing aftertreatment processes.
Resumo:
A simple catalyst system composed of Pd(OAc)2, phosphomolybdic acid and tetrabutylammonium acetate oxidises a range of alcohols efficiently, with turnover numbers (TONs) of up to 10 000.
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An acid-functionalized ionic liquid was entrapped within a silica gel to yield a recyclable liquid phase catalyst for the dehydration of rac-1-phenyl ethanol. Hot filtration tests showed that the activity was within the gel. Comparison with an analogous SILP system revealed fundamental differences in the properties and behavior of the materials.
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The kinetics of hydrodeoxygenation of waste cooking oil (WCO) is investigated with unsupported CoMoS catalysts. A kinetic model is established and a comprehensive analysis of each reaction pathway is carried out. The results show that hydrodecarbonylation/decarboxylation (HDC) routes are the predominant reaction pathways in the elimination of oxygen, with the rate constant three times as high as that of hydrodeoxygenation (HDO). However, the HDC activity of the CoMoS catalyst deactivates due to gradual loss of sulfur from the catalyst. HDO process is insensitive to the sulfur deficiency. The kinetic modeling shows that direct hydrodecarbonylation of fatty acids dominates the HDC routes and, in the HDO route, fatty acids are transferred to aldehydes/alcohols and then to C-18 hydrocarbons, a final product, and the reduction of acids is the rate limiting step. The HDO route via alcohols is dominant over aldehydes due to a significantly higher reaction rate constant. The difference of C-18/C-17 ratio in unsupported and supported catalysts show that a support with Lewis acid sites may play an important role in the selectivity for the hydrodeoxygenation pathways and promoting the final product quality