Bulk catalyst materials

The reactor volume is calculated from Mj and the bulk density of the catalyst material, (-r ) depends not only on composition and temperature, but also on the nature and size of the catalyst pellets and the flow velocity of the mixture. In a heterogeneous reaction where a solid catalyst is used, the reactor load is often determined by the term space velocity, SV. This is defined as the volumetric flow at the inlet of the reactor divided by the reaction volume (or the total mass of catalyst), that is... 

Analytical electron microscopy (AEM) permits elemental and structural data to be obtained from volumes of catalyst material vastly smaller in size than the pellet or fluidized particle typically used in industrial processes. Figure 1 shows three levels of analysis for catalyst materials. Composite catalyst vehicles in the 0.1 to lOim size range can be chemically analyzed in bulk by techniques such as electron microprobe, XRD, AA, NMR,... 

Figure 1. Three levels of analysis for catalyst materials, a) bulk analysis of an entire catalyst pellet, b) surface analysis and depth profiling from the surface inward, c) analytical electron microscopy of individual catalyst particles too small for analysis by other techniques.

In order to investigate how the support material affects heterogenous gold catalysts, we sought a synthetic technique that could be easily applied to a variety of realistic bulk support materials, regardless of the surface... 

The results presented in this paper therefore show that V and Mo species supported on alumina can give rise to a catalyst which has a high selectivity for the oxidation of propane to propene and a reasonable selectivity to acrolein and that both species are essential to give the optimal behaviour. Contrary to our previous observations and what observed for bulk catalysts [5], the presence of Nb and W seem to have little effect, perhaps because the methods used here restrict the active phase to a monolayer whereas previously prepared materials may have contained multilayer oxidic species. 

The catalyst activity depends not only on the chemical composition but also on the diffusion properties of the catalyst material and on the size and shape of the catalyst pellets because transport limitations through the gas boundary layer around the pellets and through the porous material reduce the overall reaction rate. The influence of gas film restrictions, which depends on the pellet size and gas velocity, is usually low in sulphuric acid converters. The effective diffusivity in the catalyst depends on the porosity, the pore size distribution, and the tortuosity of the pore system. It may be improved in the design of the carrier by e.g. increasing the porosity or the pore size, but usually such improvements will also lead to a reduction of mechanical strength. The effect of transport restrictions is normally expressed as an effectiveness factor q defined as the ratio between observed reaction rate for a catalyst pellet and the intrinsic reaction rate, i.e. the hypothetical reaction rate if bulk or surface conditions (temperature, pressure, concentrations) prevailed throughout the pellet [11], For particles with the same intrinsic reaction rate and the same pore system, the surface effectiveness factor only depends on an equivalent particle diameter given by... 

In the application of XAS to the study of fuel cell catalysts, the limitations of the technique must also be acknowledged the greatest of which is that XAS provides a bulk average characterization of the sample, on a per-atom basis, and catalyst materials used in low temperature fuel cells are intrinsically nonuniform in nature, characterized by a distribution of particle sizes, compositions, and morphologies. In addition, the electrochemical reactions of interest in fuel cells take place at the surface of catalyst par-... 

This loss of catalyst and contamination of product with benzene caused us to select the more stable tri(n-alkyl)tin iodides. These catalysts are not as active as the triaiyltin iodides but exhibit veiy good stability under normal reaction conditions. They are also readily prepared from industrially-available bulk starting materials. Tri(n-octyl)tin iodide [(n-Oc sSnl, referred to as "TOT"] can be prepared from three different starting materials although the iodide displacement is preferred ... 

In heterogeneous catalysis, the first tests on UPD were performed on bulk catalysts which allows, for the preparation of the bimetallic catalyst, easy control of the electrochemical potential by an external device (potentiostat). In the same way all electrochemical techniques, particularly the control of catalyst potential required for submonolayer deposition, can be extrapolated to metallic catalysts supported on conductive materials such as carbon or carbides [8]. 

FIGURE 6 Schematic representation of an oxide catalyst with its functional compartments in various structural states for high (back) and low (front) chemical potentials of oxygen. The arrows and the question mark indicate the complex distribution of oxygen in its dual role as a reactant at the surface and as a constituent of the catalyst material in the bulk. Its abundance is controlled by the presence of reducing species in the gas phase leading to a dependence of the results of XRD structural analysis on the availability of reducing gas-phase species. For details and references, see the text. 

A comparison of eqn 8.23 for arbitrary distribution of catalyst material with the formula 8.2 developed for bulk-species catalysts is instructive. Application of the latter to the cycle 8.14 yields... 

If all but an insignificant traction of the catalyst material were present as free catalyst, C, would practically equal C, so that the Christiansen numerator would equal that in eqn 8.2 for bulk catalyst cycles. The Christiansen denominator must then also equal the denominator in eqn 8.2. It does so if all terms except those of the first row are insignificant, i.e., if = Z>oo. 

So far, various studies focused on developing catalyst materials with improved ORR activity, but only few reported the stability and durability of ORR catalysts. The study of accelerated durability tests (ADT) in conjunction with electron microprobe analysis (BMPA), LEED, and XRD techniques on Pt-based al-loys ° observed hd metal dissolution, diffusion of 3bulk oxides on the surface, and migration and agglomeration of Pt. Yu et al. compared the durability and activity of PtCo/C with Pt/C catalysts. Throngh determination of the electrochemically active sniiace area, mass, and specific activities with respeet to the potential cycles, they found the overall cell performance of PtCo/C is higher than that of Pt/C. They also concluded that the observed dissolution of Co has no severe impact on the cell performanee or membrane conductance. Additionally, Popov et al studied the stabihty of Pt M/C for X = 1,3 and M = V, Fe, Ni, Co. ADT analyses revealed that Pt/C has the lowest activity when eompared to Pt-alloy catalysts, and that the metal dissolntion is lower for a Pt M ratio of 3 1 than compared to a 1 1 ratio. Also, Pt-Ni showed a lower dissolution rate than the other considered Pt-M alloys. 

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