Supported metals, small particles impregnation

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. 

Cobalt-based catalysts are effective in the ethanol reformation to hydrogen. Many oxides have been used to prepare supported cobalt catalysts of low cobalt content (circa 1 wt%) by impregnation from a solution of Co2(CO)8 catalysts were used in the ethanol reformation as prepared [156]. The performance of the catalysts in the steam reforming of ethanol was related with the presence, under reaction conditions, of metallic (ferromagnetic) cobalt particles and oxidized cobalt species. An easy exchange between small metallic cobalt particles and oxidized cobalt species was found. Comparison of Co/ZnO catalysts prepared from Co2(CO)8 or from nitrate precursor indicated that the catalyst prepared from the carbonyl precursor was highly stable and more selective for the production of CO-free hydrogen... 

The various stages of the preparation and thermal treatments of supported metal catalysts arc very schematically illustrated in Fig. 3. A very similar presentation was earlier given by van Delft et al. [16]. Typically, the support is impregnated with a metal salt (sec Section A.2.2.1.1) which serves as the metal precursor and should be well dispersed. Small metal particles may be formed by either direct reduction under mild conditions or by reduction after an intermediate oxidation step. Mild oxidation will lead to thin oxide films spread out on the support or to small oxide particles, where particles and film may also coexist. More severe treatments in oxidative atmospheres can lead to the... 

Zeolites have been used for years as supports for metal catalysts [1-5]. Such catalysts are typically made by impregnation of the zeolite with an aqueous solution of a metal salt, followed by calcination and reduction in hydrogen. Because the metal particles in such catalysts are typically extremely small and nonuniform in size and shape, often being present both inside and outside the zeolite pore structure, their structures are not well understood. This structural complexity provides a fundamental motivation for preparing and investigating structurally simple zeolite-supported metals, those that are so small and uniform as to be nearly molecular in character and located almost entirely within the zeolite pores investigations of well-defined... 

Pd-Ag bimetallic catalysts supported on carbon xerogels have been used in the hydrodechlorination reaction of 1,2-dichloroethane [103,104], Pd and Ag were deposited by co-impregnation using a solution of palladium and silver nitrates. Metal particle size ranged from 2 to 5 nm in Pd catalysts but had a wider distribution (4 to 20 mn) in Ag catalysts. Bimetallic Pd-Ag catalysts showed small particle alloys of 3 to 4 nm. The bulk Ag content in this alloy was limited to about 50 wt%, which fixed the minimum Pd surface content of the alloy at about 10 wt%. Pd catalysts produced mainly ethane, whereas bimetallic Pd-Ag catalysts were selective for the production of ethylene. The ethylene selectivity increased with silver fraction at the alloy surface. 

The effect of 25 ppm SO2 with respect to the complete oxidation of methane over supported palladium catalysts has been examined. Pd nitrate was impregnated onto alumina, Ba-modified alumina and La-modified alumina by incipient wetness impregnation. The calculated metal loading was 2.5 wt%. Two different sets of catalysts have been prepared one calcined at 500 C and the other at 1000 C. The main purpose of these two calcinations temperatures was to obtain different metal particle sizes. The results show that the combustion activity is strongly affected by the nature of the support when large particles are present. On the other hand, the small Pd particles exhibit similar behavior regardless of the nature of the support. When SO2 is added to the gas stream, a strong deactivation is observed and the presence of additive to stabilize the support increases the loss of activity of the supported Pd particles. 

Electrodes consisting of supported metal catalysts are used in electrosynthesis and electrochemical energy conversion devices (e.g., fuel cells). Nanometer-sized metal catalyst particles are typically impregnated into the porous structure of an sp -bonded carbon-support material. Typical carbon supports include chemically or physically activated carbon, carbon black, and graphitized carbons [186]. The primary role of the support is to provide a high surface area over which small metallic particles can be dispersed and stabilized. The porous support should also allow facile mass transport of reactants and products to and from the active sites [187]. Several properties of the support are critical porosity, pore size distribution, crush strength, surface chemistry, and microstructural and morphological stability [186]. 

Nitrogen adsorption experiments showed a typical t)q5e I isotherm for activated carbon catalysts. For iron impregnated catalysts the specific surface area decreased fix>m 1088 m /g (0.5 wt% Fe ) to 1020 m /g (5.0 wt% Fe). No agglomerization of metal tin or tin oxide was observed from the SEM image of 5Fe-0.5Sn/AC catalyst (Fig. 1). In Fig. 2 iron oxides on the catalyst surface can be seen from the X-Ray diffractions. The peaks of tin or tin oxide cannot be investigated because the quantity of loaded tin is very small and the dispersion of tin particle is high on the support surface. 

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