Supported catalysts, electronic state metallic particles

Suppose you prepared an iron oxide catalyst supported on an alumina support. Your aim is to use the catalyst in the metallic form, but you want to keep the iron particles as small as possible, with a degree of reduction of at least 50%. Hence, you need to know the particle size of the iron oxide in the unreduced catalyst, as well as the size of the iron particles and their degree of reduction in the metallic state. Refer to Chapters 4 and 5 to devise a strategy to obtain this information. (Unfortunately for you, it appears that electron microscopy and X-ray diffraction do not provide useful data on the unreduced catalyst.)... 

As described above, XAS measurements can provide a wealth of information regarding the local structure and electronic state of the dispersed metal particles that form the active sites in low temperature fuel cell catalysts. The catalysts most widely studied using XAS have been Pt nanoparticles supported on high surface area carbon powders,2 -27,29,so,32,33,38-52 represented as Pt/C. The XAS literature related to Pt/C has been reviewed previ-ously. In this section of the review presented here, the Pt/C system will be used to illustrate the use of XAS in characterizing fuel cell catalysts. 

The goal of catalyst development is to understand how the chemical and physical properties of the catalyst affect its activity and selectivity for a desired reaction. For a supported metal, the variables affecting its function are the metal composition, the metal particle size, the particle shape, the structure of the metal surface, the oxidation state of the metal, the composition of the support, and the presence of promoters or poisons. These variables influence catalytic activity by altering both the structure and electronic state of the metal. The relative importance of the structure effect versus the electronic effect has been a question that catalyst researchers have long sought to answer. 

The term electron deficiency was introduced by Dalla Betta and Bou-dart to account for the anomalously high hydrogenation activity of small Pt particles in zeolite Y (50). The electron deficiency was ascribed to an electron transfer from small Pt particles to the zeolite. X-Ray absorption has been applied to measure the Pt Lm white line area as an indication of the electron deficiency because the white line is related to the number of unoccupied electronic states in the 5d and the 6j bands (273). For reduced Pt/NaHY it appeared that the white line area, and hence the electron deficiency of Pt particles, are closely related to the proton concentration of the zeolites. For example, the relative white line areas for Pt/H4gY, Pt/ H19Y, and Pt foil are 1.6, 1.2, and 1, respectively. White line areas at the Liii X-ray absorption threshold to determine the if-band occupancy of supported metal catalysts were first reported by Lytle 274). The use of the white line area as an indication for electron deficiency has been questioned by Lewis, who argues that a decrease of the metal particle size will also lead to an increase of the white line area (275). 

There is no single interpretation to explain the effects of particle size, alloying, and metal-support interaction on the chemisorption and catalytic properties of supported metal particles. Depending on the particle size, the nature of co-metal and support, and the nature of the reaction, the change of chemisorption and catalytic properties can be interpreted in terms of geometric features, electronic modifications, and/or mixed sites. This is due to the formation of various adsorbed species and intermediates. Moreover, in many cases, the promotion of catalytic properties will be directly related to the method of catalyst preparation, which affects the architecture of the active site, with respect to chemical and electronic states of components and topology. 

H2 chemisorption. Both Rh/R-Ti02 and Rh/A-Ti02 show a decrease in H2 chemisorption when the reduction and evacuation temperature is increased, while at the same time the slope of the chemisorption vs. In t curve decreases. The decrease in H2 chemisorption is of course due to the gradual transition of the Rh particles into the SMSI state. Whatever the explanation for this state, an electronic interaction between metal particles and support or a covering of the metal particles by the support, in this SMSI state the metal particles are unable to adsorb H2. The decreased slope of the H/Rh-ln t curve can be explained in several ways, such as slow H2 chemisorption on Rh because of an activated process, dependence on metal dispersion, or an effect related to the support. The experiments in which H2 chemisorption was started around 200°C proved that the time dependence is indeed due to a slow adsorption at room temperature, but the experiment with Rh/Si(>2 showed that there is no kinetic limitation in the H2 chemisorption on the metal part of the catalyst. In accordance with this conclusion, no effect of rhodium dispersion on the time dependence of the H2 chemisorption was observed for catalysts in the normal state (cf. Figure 1 curves A, B and F). 

In a recent publication Dumeslc c.s. described adsorption and desorption measurements of H2 on Ni/Ti(>2 and Pt/Ti(>2 catalysts, which showed that a larger amount of H2 could be desorbed (after 15-20 h equilibration of these catalysts under about 40 kPa H2) than could be directly adsorbed (32). In agreement with our conclusions their explanation was that, apart from a fast H2 adsorption on the metal, hydrogen apparently also adsorbed slowly on the Ti02 support via a spillover process from metal to support. These authors noticed that the amounts of H2 desorbed from the M/Ti(>2 catalysts in the SMSI state were in fair agreement with metal particle sizes determined by X-ray line broadening and electron microscopy and suggested that H2 desorption could be used to estimate metal... 

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