Catalytic active catalyst layer

Loss of catalytic activity Catalyst layer fracture... 

Aligned multiwall CNT arrays were synthesized as a basis for a microstructured catalyst, which was then tested in the Fischer-Tropsch reaction in a microchannel reactor [269]. Fabrication of such a structured catalyst first involved MOCVD of a thin but dense A1203 film on a FeCrAlY foam to enhance the adhesion between the catalyst and the metal substrate. Then, multiwall CNTs were deposited uniformly on the substrate by controlled catalytic decomposition of ethene. Coating the outer surfaces of the nanotube bundles with an active catalyst layer results in a unique hierarchical structure with small interstitial spaces between the carbon bundles. The microstructured catalyst was characterized by the excellent thermal conductivity inherent to CNTs, and heat could be efficiently removed from the catalytically active sites during the exothermic Fischer-Tropsch synthesis. 

The backspillover ions (O, Na, etc.) are each accompanied by their compensating (screening) charge in the metal, thus forming surface dipoles. Consequently, these surface dipoles form an "effective electrochemical double layer" on the gas-exposed, i.e., catalytically active, catalyst surface, in addition to the classical double layer which exists at the metal-solid electrolyte interface (Figure 13). 

This result could perhaps be interesting for coating purposes as elemental La can normally only be deposited in high-temperature molten salts, which requires much more diflBcult experimental or technical conditions. Furthermore La and Ce electrodeposition would be important as their oxides have interesting catalytic activity, for instance as oxidation catalysts. A controlled deposition of thin metal layers followed by a selective oxidation could perhaps produce catalytically active thin layers that would be of interest for fuel cells or waste gas treatment. 

Catalysis For technical reasons it can be necessary to have a catalytic active sohd material supported to improve, e.g., its mechanical stability and reduce its flow resistance when used in a flow reactor. The sol-gel fluorination synthesis provides a convenient way for depositing high surface area metal fluorides on supports. For example, HS-AIF3, which as fine powder makes problems when used as catalyst in flow systems, could be supported by Y-AI2O3 whereby its Lewis acidity and consequently its catalytic activity remains almost unchanged [64]. For other catalytic applications, like micro-reactor techniques, deposition of catalytically active thin layers of metal fluorides is also of interest. 

Catalytic Unit. The catalytic unit consists of an activated coating layer spread uniformly on a monolithic substrate. The catalyst predominantly used in the United States and Canada is known as the three-way conversion (TWC) catalyst, because it destroys aU three types of regulated poUutants HC, CO, and NO. Between 1975 and the early 1980s, an oxidation catalyst was used. Its use declined with the development of the TWC catalyst. The TWC catalytic efficiency is shown in Figure 5. At temperatures of >300° C a TWC destroys HC, CO, and NO effectively when the air/fuel mixture is close to... 

The higher activity of the catalyst [(mall)Ni(dppmo)][SbFg] in [BMIM][PFg] (TOF = 25,425 h ) relative to the reaction under identical conditions in CFF2C12 (TOF = 7591 h ) can be explained by the fast extraction of products and side products out of the catalyst layer and into the organic phase. A high concentration of internal olefins (from oligomerization and consecutive isomerization) at the catalyst is known to reduce catalytic activity, due to the formation of fairly stable Ni-olefin complexes. 

Recently, other authors when studying the activation of hydrogen by nickel and nickel-copper catalysts in the hydrogen-deuterium exchange reaction concentrated for example only on the role of nickel in these alloys (56) or on a correlation between the true nickel concentration in the surface layer of an alloy, as stated by the Auger electron spectroscopy, and the catalytic activity (57). 

Thus, as will be shown in this book, the effect of electrochemical promotion (EP), or NEMCA, or in situ controlled promotion (ICP), is due to an electrochemically induced and controlled migration (backspillover) of ions from the solid electrolyte onto the gas-exposed, that is, catalytically active, surface of metal electrodes. It is these ions which, accompanied by their compensating (screening) charge in the metal, form an effective electrochemical double layer on the gas-exposed catalyst surface (Fig. 1.5), change its work function and affect the catalytic phenomena taking place there in a very pronounced, reversible, and controlled manner. 

On the other hand, as already discussed in Chapter 11 in connection to the effect of metal-support interactions, it appears that a fully dispersed noble metal catalyst on porous YSZ is already at a NEMCA or electroche-mically-promoted state, i.e. it is covered by an effective double layer of promoting backspillover O2 ions. This can explain both the extreme catalytic activity ofZr02- and Ti02- supported commercial catalysts, as well as the difficulty so far to induce NEMCA on fully dispersed noble metal catalysts deposited on YSZ. 

A general theory based on the quantitative treatment of the reaction layer profile exists for pure redox catalysis where the crucial function of the redox mediator is solely electron transfer and where the catalytic activity largely depends only on the redox potential and not on the structure of the catalyst This theory is consistent... 

The recovery of petroleum from sandstone and the release of kerogen from oil shale and tar sands both depend strongly on the microstmcture and surface properties of these porous media. The interfacial properties of complex liquid agents—mixtures of polymers and surfactants—are critical to viscosity control in tertiary oil recovery and to the comminution of minerals and coal. The corrosion and wear of mechanical parts are influenced by the composition and stmcture of metal surfaces, as well as by the interaction of lubricants with these surfaces. Microstmcture and surface properties are vitally important to both the performance of electrodes in electrochemical processes and the effectiveness of catalysts. Advances in synthetic chemistry are opening the door to the design of zeolites and layered compounds with tightly specified properties to provide the desired catalytic activity and separation selectivity. 

In the case of a catalytic membrane reactor (CMR), the membrane is (made) intrinsically catalytically active. This can be done by using the intrinsic catalytic properties of the zeolite or by making the membrane catalytically active. When an active phase is deposited on top of a membrane layer, this is also called a CMR because this becomes part of the composite membrane. In addition to the catalytic activity of the membrane, a catalyst bed can be present (PBCMR). The advantages of a CMR are as follows ... 

As described in the previous section, the silica-alumina catalyst covered with the silicalite membrane showed exceUent p-xylene selectivity in disproportionation of toluene [37] at the expense of activity, because the thickness of the sihcahte-1 membrane was large (40 pm), limiting the diffusion of the products. In addition, the catalytic activity of silica-alumina was not so high. To solve these problems, Miyamoto et al. [41 -43] have developed a novel composite zeohte catalyst consisting of a zeolite crystal with an inactive thin layer. In Miyamoto s study [41], a sihcahte-1 layer was grown on proton-exchanged ZSM-5 crystals (silicalite/H-ZSM-5) [42]. The silicalite/H-ZSM-5 catalysts showed excellent para-selectivity of >99.9%, compared to the 63.1% for the uncoated sample, and independent of the toluene conversion. 

When NOj levels are measured electrochemicaUy, NO and NO2 can lead to opposing signals because NO is oxidized and NO2 tends to be reduced. Moreover, it is preferred to obtain a total NO, measurement instead of only one of the constituents. The latter can be achieved by catalytically equilibrating the feed with oxygen before contact with the sensor by coating an active zeolite layer on top or placing a active catalyst bed in front of the sensor. Both approaches have been demonstrated successfully with a Pt-Y zeohte as active catalyst [74, 75]. The additional advantage of the filter bed is a reduction in the cross-sensitivity with CO due to CO oxidation above 673 K. 

The platinum concentrations in the platinized carbon blacks are reported to be between 10 and 40% (by mass), sometimes even higher. At low concentrations the specific surface area of the platinum on carbon is as high as lOOm /g, whereas unsupported disperse platinum has surface areas not higher than 10 to 15m /g. However, at low platinum concentrations, thicker catalyst layers must be applied, which makes reactant transport to reaction sites more difficult. The degree of dispersion and catalytic activity of the platinum depend not only on its concentration on the carrier but also on the chemical or electrochemical method used to deposit it. 

A considerable decrease in platinum consumption without performance loss was attained when a certain amount (30 to 40% by mass) of the proton-conducting polymer was introduced into the catalytically active layer of the electrode. To this end a mixture of platinized carbon black and a solution of (low-equivalent-weight ionomeric ) Nafion is homogenized by ultrasonic treatment, applied to the diffusion layer, and freed of its solvent by exposure to a temperature of about 100°C. The part of the catalyst s surface area that is in contact with the electrolyte (which in the case of solid electrolytes is always quite small) increases considerably, due to the ionomer present in the active layer. 

On the surface of metal electrodes, one also hnds almost always some kind or other of adsorbed oxygen or phase oxide layer produced by interaction with the surrounding air (air-oxidized electrodes). The adsorption of foreign matter on an electrode surface as a rule leads to a lower catalytic activity. In some cases this effect may be very pronounced. For instance, the adsorption of mercury ions, arsenic compounds, or carbon monoxide on platinum electrodes leads to a strong decrease (and sometimes total suppression) of their catalytic activity toward many reactions. These substances then are spoken of as catalyst poisons. The reasons for retardation of a reaction by such poisons most often reside in an adsorptive displacement of the reaction components from the electrode surface by adsorption of the foreign species. 

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