Catalysis/catalysts particle surface

Catalytic properties are dependent on physical form, principally the exposed surface area which is a function of particle size. Industrial PGM catalysts are in the form of finely divided powder, wine, or gauze, or supported on substrates such as carbon or alumina (see Catalysis Catalysts, supported). 

We have discussed here, very briefly, some recent observations of small particle surfaces and how these relate to geometrical catalytic effects. These demonstrate the general conclusion that high resolution imaging can provide a direct, structural link between bulk LEED analysis and small particle surfaces. Apart from applications to conventional surface science, where the sensitivity of the technique to surface inhomogenieties has already yielded results, there should be many useful applications in catalysis. A useful approach would be to combine the experimental data with surface thermodynamic and morphological analyses as we have attempted herein. There seems no fundamental reason why results comparable to those described cannot be obtained from commercial catalyst systems. 

The valence band structure of very small metal crystallites is expected to differ from that of an infinite crystal for a number of reasons (a) with a ratio of surface to bulk atoms approaching unity (ca. 2 nm diameter), the potential seen by the nearly free valence electrons will be very different from the periodic potential of an infinite crystal (b) surface states, if they exist, would be expected to dominate the electronic density of states (DOS) (c) the electronic DOS of very small metal crystallites on a support surface will be affected by the metal-support interactions. It is essential to determine at what crystallite size (or number of atoms per crystallite) the electronic density of sates begins to depart from that of the infinite crystal, as the material state of the catalyst particle can affect changes in the surface thermodynamics which may control the catalysis and electro-catalysis of heterogeneous reactions as well as the physical properties of the catalyst particle [26]. 

In catalysis active sites are operative that allow for an alternative reaction path. For a satisfactory catalyst this alternative pathway leads to higher rates and higher selectivity. In heterogeneous catalysis reactant molecules adsorb at active sites on the catalyst surface at the surface sites reactions occur and products are desorbed subsequently. After desorption, active sites are again available for reactant molecules and the cycle is closed. In homogeneous catalysis the situation is essentially identical. Here complexation and decomplexation occur. A complication in heterogeneous catalysis is the need for mass transfer into and out of the catalyst particle, which is usually porous with the major part of the active sites at the interior surface. 

A wide variety of solid materials are used in catalytic processes. Generally, the (surface) structure of metal and supported metal catalysts is relatively simple. For that reason, we will first focus on metal catalysts. Supported metal catalysts are produced in many forms. Often, their preparation involves impregnation or ion exchange, followed by calcination and reduction. Depending on the conditions quite different catalyst systems are produced. When crystalline sizes are not very small, typically > 5 nm, the metal crystals behave like bulk crystals with similar crystal faces. However, in catalysis smaller particles are often used. They are referred to as crystallites , aggregates , or clusters . When the dimensions are not known we will refer to them as particles . In principle, the structure of oxidic catalysts is more complex than that of metal catalysts. The surface often contains different types of active sites a combination of acid and basic sites on one catalyst is quite common. 

In situ dynamic surface structural changes of catalyst particles in response to variations in gas environments were examined by ETEM by Gai et al. (78,97). In studies of copper catalysts on alumina, which are of interest for the water gas shift reaction, bulk diffusion of metal particles through the support in oxygen atmospheres was shown (78). The discovery of this new catalyst diffusion process required a radical revision of the understanding of regeneration processes in catalysis. 

As the Beckmann rearrangement is believed to be a typical acid-catalysed reaction, many researchers have reported the relationship between the vapour phase reaction catalysis and the acidity of the catalysts tested on non-zeolitic catalysts - i2s- i3i. 318-334 and on zeolitic catalysts Another interesting point for the heterogeneous gas-phase Beckmann rearrangement is the location of the reaction on the catalyst and different studies have been published ° . The outer surface of the catalyst particle seems to be the most probable place for the Beckmann rearrangement supported by the traces of reagents, and notable amounts of by-products found only in the outer layers of the zeolite crystal. Development of new and more efficient catalysts have also been reported " . ... 

At one extreme diffusivity may be so low that chemical reaction takes place only at suface active sites. In that case p is equal to the fraction of active sites on the surface of the catalyst. Such a polymer-supported phase transfer catalyst would have extremely low activity. At the other extreme when diffusion is much faster than chemical reaction p = 1. In that case the observed reaction rate equals the intrinsic reaction rate. Between the extremes a combination of intraparticle diffusion rates and intrinsic rates controls the observed reaction rates as shown in Fig. 2, which profiles the reactant concentration as a function of distance from the center of a spherical catalyst particle located at the right axis, When both diffusion and intrinsic reactivity control overall reaction rates, there is a gradient of reactant concentration from CAS at the surface, to a lower concentration at the center of the particle. The reactant is consumed as it diffuses into the particle. With diffusional limitations the active sites nearest the surface have the highest turnover numbers. The overall process of simultaneous diffusion and chemical reaction in a spherical particle has been described mathematically for the cases of ion exchange catalysis,63 65) and catalysis by enzymes immobilized in gels 66-67). Many experimental parameters influence the balance between intraparticle diffusional and intrinsic reactivity control of reaction rates with polymer-supported phase transfer catalysts, as shown in Fig. 1. 

Macroporous68 71 > polymers present an additional diffusion step in catalysis. They have permanent pores created during synthesis in addition to the micropores, which are the spaces between chains in the polymer network filled by solvent in solvent-swollen form. Transport of a reactant from the surface of a macroporous catalyst particle to an active site may proceed first through the liquid-filled macropores to the internal surface of the catalyst particle and then through the polymer matrix. A mathematical treatment of catalysis kinetics of macroporous ion exchange resins is available 72). 

In chemical heterogeneous catalysis, it is common to use highly porous catalysts that come in particles of millimeter to centimeter size to increase the effective catalyst surface. In practical electrocatalysis, in particular applying electrocatalysis in fuel cells, it is also usual to use highly porous— although accounting for the low diffusion coefficients in liquid electrolytes compared to gases, 10 5 cm2/sec vs 1 cm2/sec, much smaller—catalyst particles. 

Influence of Metal Particle Size in Nickel-on-Aerosil Catalysts on Surface Site Distribution, Catalytic Activity, and Selectivity R. Van Hardeveld and F. Hartog Adsorption and Catalysis on Evaporated Alloy Films... 

The science of catalysis covers a large spectrum of phenomena. We observe—with some pride and joy—that this volume presents eight topics which, like the rainbow, form an almost systematic and complete sweep of the major classes of topics in catalysis. It spans from the most classical mechanistic study (P. W. Selwood), to a presentation of a hard practical application (M. Shelef et al). As we sweep across, we cover characterization studies of catalyst solids in terms of electronic (G. M. Schwab), surface chemical (H. A. Benesi and B. H. C. Winquist), as well as physicochemical and structural (F. E. Massoth) parameters, chemical reaction mechanisms and pathways (G. W. Keulks et al., and B. Gorewit and M. Tsutsui), and a topic on reactor behavior (V. Hlavacek and J, Votruba), which takes us from the single catalyst particle to the macroscopic total reactor operation. 

Catalyst particles generally consist of a metal deposited onto the surface of a support and are denoted by metal/support, e.g. Pd/C indicates palladium metal on a carbon support. Among the metals used for catalysis, Pd is often found to be the most active metal. (Augustine 1965) For example, in the aqueous hydrodechlorination of 1,1,2-trichloroethane, Pd catalysts achieved significantly more conversion than Pt or Rh catalysts. (Kovenklioglu et al. 1992) Catalyst supports can vary in shape, size, porosity and surface area typical materials include carbon, alumina, silica and zeolites. 

Attenuated total reflection (ATR) is sometimes used to measure the infrared spectra of catalysts inside a reactor. The infrared light is coupled into an ATR crystal, which can be either a flat plate (e.g., the wall of a reactor) or a cylindrical rod (surrounded by catalyst particles). The evanescent wave that protrudes outside the crystal when the infrared beam reflects on the inside of its surface is used for the measurement. A review of ATR in catalysis has been published by Biirgi and Baiker [11], and a catalytic cell to apply the method in situ inside a catalyst bed reported by Moser and co-workers [12]. An example of ATR is discussed later in this chapter. 

The support has an internal pore structure (i.e., pore volume and pore size distribution) that facilitates transport of reactants (products) into (out of) the particle. Low pore volume and small pores limit the accessibility of the internal surface because of increased diffusion resistance. Diffusion of products outward also is decreased, and this may cause product degradation or catalyst fouling within the catalyst particle. As discussed in Sec. 7, the effectiveness factor Tj is the ratio of the actual reaction rate to the rate in the absence of any diffusion limitations. When the rate of reaction greatly exceeds the rate of diffusion, the effectiveness factor is low and the internal volume of the catalyst pellet is not utilized for catalysis. In such cases, expensive catalytic metals are best placed as a shell around the pellet. The rate of diffusion may be increased by optimizing the pore structure to provide larger pores (or macropores) that transport the reactants (products) into (out of) the pellet and smaller pores (micropores) that provide the internal surface area needed for effective catalyst dispersion. Micropores typically have volume-averaged diameters of 50 to... 

Figure 3.3.14 Experimental ORR activity of dealloyed Pt-Cu and Pt-Ni core-shell nanoparticle ORR catalysts compared to a pure-Pt nanoparticle catalyst. All three catalyst particles are supported on a high surface area carbon material indicated by the suffix 1C. The shift of the j-E curve of the core-shell catalysts indicates the onset of oxygen reduction catalysis at a more anodic electrode potential (equivalent to a lower overpotential) and hence represents improved ORR reactivity compared to pure Pt.

Catalysts may be porous pellets, usually cylindrical or spherical in shape, ranging from 0.16 to 1.27 cm (Vm to Vi in) in diameter. Small sizes are recommended, but the pressure drop through the reactor increases. Among other shapes are honeycombs, ribbons, and wire mesh. Since catalysis is a surface phenomenon, a physical property of these particles is that the internal pore surface is nearly infinitely greater than the outside surface. 

In many cases of catalysis by metals the actual catalyst particles are supported. This capitalizes on the observation that only a small proportion of the metal atoms in the surface are catalytically active further a larger surface area is achieved for a given quantity of metal if it is dispersed on a high surface carrier. This also means that the catalyst is made in such a way that the support (frequently a metal oxide, though a wide variety of other matrices have been used) comprises the bulk of the material. This also has an obvious economic benefit since the actual (expensive) catalyst is diluted by a much cheaper material. Some support materials are inert - they play no role in the catalyses. 

In the catalysis community, it is generally accepted that there are two types of support materials for heterogeneous oxidation catalysts [84]. One variety is the reducible supports such as iron, titanium, and nickel oxide. These materials have the capacity to adsorb and store large quantities of molecules. The adsorbed molecules diffuse across the surface of the support to the catalyst particle where they are activated to a superoxide or atomically bound state. The catalytic reaction then takes place between the reactant molecules and the activated on the catalyst particle. Irreducible supports, in contrast, have a very low ability to adsorb O. Therefore, can only become available for reaction through direct adsorption onto the catalyst particle. For this reason, catalysts deposited on irreducible supports generally exhibit turnover frequencies that are much lower than those deposited on reducible supports [84]. More recent efforts in our laboratory are focused on characterizing catalyst support materials that are commonly used in industry. These studies are aimed at deciphering how specific catalyst and support material combinations result in superior catalytic activity and selectivity. 

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