Catalytic layer

Catalytic Support Body Monolithic Honeycomb Unit. The terms substrate and brick are also used to describe the high geometric surface area material upon which the active coating material is placed. Monolithic honeycomb catalytic support material comes in both ceramic and metallic form. Both are used in automobile catalysts and each possesses unique properties. A common property is a high geometric surface area which is inert and does not react with the catalytic layer. 

ActivatedL yer Loss. Loss of the catalytic layer is the third method of deactivation. Attrition, erosion, or loss of adhesion and exfoHation of the active catalytic layer aU. result in loss of catalyst performance. The monolithic honeycomb catalyst is designed to be resistant to aU. of these mechanisms. There is some erosion of the inlet edge of the cells at the entrance to the monolithic honeycomb, but this loss is minor. The peUetted catalyst is more susceptible to attrition losses because the pellets in the catalytic bed mb against each other. Improvements in the design of the peUetted converter, the surface hardness of the peUets, and the depth of the active layer of the peUets also minimise loss of catalyst performance from attrition in that converter. 

Control of emissions of CO, VOC, and NOj, is high on the agenda. Heterogeneous catalysis plays a key role and in most cases structured reactors, in particular monoliths, outperform packed beds because of (i) low pressure drop, (ii) flexibility in design for fast reactions, that is, thin catalytic layers with large geometric surface area are optimal, and (iii) attrition resistance [17]. For power plants the large flow... 

OS 41a] ]R 19] ]P 30] Ten different substrates (C4-C8 alcohols) were reacted with rhodium(I)-tris(fn-sulfophenyl)phosphane [110]. The variance in conversions (ranging from about 1-62%) determined was explained by differences in the solubility of the alcohols in the aqueous catalytic layer and by their different intrinsic activities. Chain length and steric/electronic effects of the different alcohols affected their reactivity in a well-known pattern (Figure 4.63). The results obtained correspond to the conversions achieved in a well-mixed traditional batch reactor (40 cm ). They further agreed with data from mono-phasic processing. 

The concept of a biocatalytic membrane electrode has been extended to the use of a tissue slice as the catalytic layer. An example of this approach is an electrode for AMP which consists of a slice of rabbit muscle adjacent to an ammonia gas electrode. NHj is produced by enzymatic action of rabbit muscle constituents on AMP The electrode exhibits a linear range of 1.4 x 10 to 1.0 x 10 M with a response time varying from 2.5 to 8.5 min, depending on the concentration. Electrode lifetime is about 28 days when stored between use in buffer with sodium azide to prevent bacterial growth. Excellent selectivity enables AMP to be determined in serum. 

Caillard A, Coutanceau C, Brault P, Mathias J, Leger JM. 2006. Structure of Pt/C and PtRu/C catalytic layers prepared by plasma sputtering and electric performance in direct methanol fuel cells (DMFC). J Power Sources 162 66-73. 

In PEMFCs, the membrane electrode assembly (MEA, Eig. 15.2a) is a multilayer sandwich composed of catalytic layers (CLs) where electrochemical reactions take place, gas-diffusion media providing access of gases to the CLs, and a proton exchange membrane (PEM) such as Nafion . The CL is a multiphase multicomponent medium comprising ... 

The necessity of having a post catalyst layer which can eliminate slipping ammonia (in addition, since CO and HC also must be eliminated, current catalytic SCR-urea systems applied to diesel engine emissions are composed typically of five catalytic layers, making the size of the catalytic converter quite large and therefore applicable essentially only to heavy-duty trucks and buses). 

The air gas-diffusion electrode developed in this laboratory [5] is a double-layer tablet (thickness ca.1.5 mm), which separates the electrolyte in the cell from the surrounding air. The electrode comprises two layers a porous, from highly hydrophobic, electrically conductive gas layer (from the side of the air) and a catalytic layer (from the side of the electrolyte). The gas layer consists of a carbon-based hydrophobic material produced from acetylene black and PTFE by a special technology [6], The high porosity of the gas layer ensures effective oxygen supply into the reaction zone of the electrode simultaneously the leakage of the electrolyte through the electrode... 

The catalytic layer of the air electrode is made from a mixture of the same hydrophobic material and porous catalyst [2]. It comprises hydrophobic zones through which the oxygen is transported in gas phase and zones containing catalyst where the electrochemical reduction of oxygen is taking place. It must be noted that the overall structure of the electrode is reproducible when various kinds of carbon-based catalysts are used. 

In Figure 4 we have presented the experimental Tafel plots of air electrodes with catalysts from pure active carbon and from active carbon promoted with different amounts of silver. The obtained curves are straight lines with identical slopes. It must be underlined that the investigated electrodes possess identical gas layers and catalytic layers, which differ in the type of catalyst used only. Therefore, the differences in the observed Tafel plots can be attributed to differences in the activity of the catalysts used. The current density a at potential zero (versus Hg/HgO), obtained from the Tafel plots of the air electrodes is accepted as a measure of the activity of the air gas-diffusion electrodes the higher value of a corresponds to higher activity of the air electrode. 

Experimental AE - I curves can be used for comparison of the air electrodes with respect to the transport hindrances. In order to illustrate this possibility in Fig. 9 are presented the AE - I curves for air electrodes with identical catalytic layers and gas layers differing in their thickness only. Apparently the hindrances in the transport of molecular oxygen will be higher in the electrodes with thicker gas layers. 

Figure 9. AE -1 curves of air electrodes with identical catalytic layer and gas layer with different thickness.

Unfortunately Nafion materials have not found commercial application as catalysts because of their extremely high cost. There were several attempts to use supported catalysts made by applying of low-molecular-weight Nafion polymer from solutions onto inert supports. However, such catalysts could only be used in very few reactions between nonpolar reagents in other cases the surface catalytic layer was easily washed away from the surface. 

An active, catalytic layer, comprising a three-dimensional porous structure composed of a mixture of hydrophilic carbon particles (Vulcan XC-72) supporting a finely dispersed catalyst, and a hydrophobic binder (PTFE). This layer faces the liquid side and can be visualised as being formed from many hydro-phobic channels (the route of the oxygen supply) and hydrophilic channels, required for the rapid removal of caustic released into the gap between the membrane and GDE. 

The porous hydrophobic film of previous electrode designs has now been substituted with a new layer based on a mixture of particles of hydrophobic carbon and PTFE binder. This mixture is very similar in composition to the catalytic layer. This particular modification provides several advantages ... 

Fernandez, R., Ferreira-Aparicio, P, and Daza, L. PEMFC electrode preparation Influence of the solvent composition and evaporation rate on the catalytic layer microstructure. Journal of Power Sources 2005 151 18-24. 

Figure 19.5. Process sequence for the lift-off process (the planarized metalhzation process) (a) a resist film is patterned on a dielectric film (b) dielectric patterning (c) a thin catalytic film layer (PVD or CVD Ti, Al) is deposited (d) a lift-off technique removes the excess material, leaving the catalytic layer in the trench only (e) electroless Cu deposition.

The hydrogen sensitivity of palladinm-oxide-semiconductor (Pd-MOS) strnctnres was first reported hy Lnndstrom et al. in 1975 [61]. A variety of devices can he nsed as field-effect chemical sensor devices (Fignre 2.6) and these are introdnced in this section. The simplest electronic devices are capacitors and Schottky diodes. SiC chemical gas sensors based on these devices have been under development for several years. Capacitor devices with a platinum catalytic layer were presented in 1992 [62], and Schottky diodes with palladium gates the same year [63]. In 1999 gas sensors based on FET devices were presented [64, 65]. There are also a few publications where p-n junctions have been tested as gas sensor devices [66, 67]. 

The gas response of the field-effect devices is determined by the catalytic properties of the contact material, which includes both the catalytic layer and the underlying material. The temperature plays a dominant role in the detection process because the origin of the gas response is found in the chemical reactions that take place on the sensor surface, and it is furthermore also influenced by the mass transport properties of the molecules in the gas phase. This permits arrays of sensors of a common design to be tailor-made for detection of a range of gases and for use in a range of applications... 

The electrodeposition offer the advantage of a fine control of the thickness of the catalytic layer, thus optimizing the electroactive area and the transparency of the cathode. A cathode that possesses both a remarkable catalytic activity and a partially porous structure with a large active area is important for limiting the concentration... 

The reactions take place only in active catalytic layer, the rates Rj are considered individually for each type of the converter (DOC, SCR, NSRC, TWC). The development of suitable reaction schemes and the evaluation of kinetic parameters are discussed generally in Section IV. The details for DOC, NSRC and SCR of NOx by NH3 are given in Sections V, VI and VII, respectively. The important species deposited on the catalyst surface are balanced (e.g. HC adsorption in DOC, oxygen and NOx storage in NSRC, NH3 adsorption in SCR). Heat transfer by radiation and homogeneous reactions... 

For the detailed study of reaction-transport interactions in the porous catalytic layer, the spatially 3D model computer-reconstructed washcoat section can be employed (Koci et al., 2006, 2007a). The structure of porous catalyst support is controlled in the course of washcoat preparation on two levels (i) the level of macropores, influenced by mixing of wet supporting material particles with different sizes followed by specific thermal treatment and (ii) the level of meso-/ micropores, determined by the internal nanostructure of the used materials (e.g. alumina, zeolites) and sizes of noble metal crystallites. Information about the porous structure (pore size distribution, typical sizes of particles, etc.) on the micro- and nanoscale levels can be obtained from scanning electron microscopy (SEM), transmission electron microscopy ( ), or other high-resolution imaging techniques in combination with mercury porosimetry and BET adsorption isotherm data. This information can be used in computer reconstruction of porous catalytic medium. In the reconstructed catalyst, transport (diffusion, permeation, heat conduction) and combined reaction-transport processes can be simulated on detailed level (Kosek et al., 2005). 

This methodology can be used for the calculation of local reaction rates and effectiveness factors in dependence on gas components concentrations, temperature and porous catalytic layer structure (cf. Fig. 9). The results can then be used as input values for simulations at a larger scale, e.g. the effective reaction rates averaged over the studied washcoat section can be employed as local reaction rates in the ID model of monolith channel. 

To model mass and energy transport in monolith systems, several approaches are discussed, leading from a representative channel spatially ID approach to 2D (1D+1D) modeling explicitly including washcoat diffusion. Correlations are given to describe heat and mass transfer between bulk gas phase and catalytic washcoat. For the detailed study of reaction-transport interactions in the porous catalytic layer, the spatially 3D model of the computer-reconstructed washcoat section can be employed. 

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