Supported-Metal Samples

A large variety of problems related to the nature of the adsorption processes have been studied by infrared spectroscopy. The most extensive and productive application of this method has been in studies of chemisorption on supported-metal samples. Spectra of physically adsorbed molecules have provided important information on the interaction of these molecules with the surface of the adsorbent. Experimental developments have reached a state where it is evident that the infrared techniques are adaptable to practically all types of samples which are of interest to catalytic chemists. Not only are the infrared techniques applicable to studies of chemisorption and physical adsorption systems but they add depth and preciseness to the definitions of these terms. 

Interpretation of the spectra of chemisorbed molecules presents some difficulties because the surface compounds formed during chemisorption have no exact counterparts among conventional compounds. Although some general principles can be applied, interpretations of the spectra of unknown species are usually based on empirical comparison with spectra of compounds of known structure. Experience has shown, however, that these difficulties are more philosophical than practical. Interpretations of spectra of chemisorbed molecules by comparison with the spectra of compounds of known structure have produced results which are self-consistent and reasonable in a wide range of applications. 

Chemisorption on Supported-Metal Samples 1. Experimental Considerations 

The details of the sample preparation and studies of the nature of the supported-metal samples have been described in a paper dealing with the effect of surface coverage on the spectra of carbon monoxide chemisorbed on platinum, nickel, and palladium (1). The samples consist of small particles of metal dispersed on a nonporous silica which is produced commercially under the names Cabosil or Aerosil.f This type of silica is suitable as a support because it is relatively inert and has a small particle size (150-200 A.). The small particle size is important because it reduces the amount of radiation which is lost by scattering. A nonporous small particle form of gamma-alumina, known as Alon-C, is also available. This material is not so inert as the silica and will react with gases such as CO and CO2 at elevated temperatures. 

The concentration of metal in the reduced sample is usually 9.2 wt. %. Higher concentrations have been tried. It appears, however, that the ad- 

---

Supported Metal Samples Prepared by Deposition-Precipitation with NaOH... 

Jiang X-Z, Hayden TF, Dumesic JA. Evidence for slow uptake of hydrogen by titania-supported metal samples consequences for estimating metallic surface areas. J Catal. 1983 83 168. 

The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

Interest, because of their nonuniformity and will not be discussed further. Schmidt ( ) and Baker (11) have elaborated on the platlnum-slllca mobility question and the strength of metal-support Interactions. Sample C, Pt on alumina, was used as a reference for the H/Pt measurements, and beyond that Is of little relevance In these discussions. 

Samples of high area powders and of supported metals may be applied to the CaF2 support plate by a spraying technique, previously described In detall(ll). In Figure 1, we show a half plate design In which a supported metal deposit, produced by H2 reduction of metal Ions held on the support, occupies one half of the plate while the pure support occupies the other half. 

There are no known examples of supported clusters dispersed in crystallo-graphically equivalent positions on a crystalline support. Thus, no structures have been determined by X-ray diffraction crystallography, and the best available methods for structure determination are various spectroscopies (with interpretations based on comparisons with spectra of known compoimds) and microscopy. The more nearly uniform the clusters and their bonding to a support, the more nearly definitive are the spectroscopic methods however, the uniformities of these samples are not easy to assess, and the best microscopic methods are limited by the smallness of the clusters and their tendency to be affected by the electron beam in a transmission electron microscope furthermore, most supported metal clusters are highly reactive and... 

Much remains to be done to develop the chemistry of organic hgands on supported metal clusters, and substantial progress is to be expected as the samples are well suited to characterization, by IR, NMR, and neutron scattering (F. Li, J. Eckert, and B.C. Gates, unpubhshed results) spectroscopies, as well as density functional theory. 

In Section 2 the general features of the electronic structure of supported metal nanoparticles are reviewed from both experimental and theoretical point of view. Section 3 gives an introduction to sample preparation. In Section 4 the size-dependent electronic properties of silver nanoparticles are presented as an illustrative example, while in Section 5 correlation is sought between the electronic structure and the catalytic properties of gold nanoparticles, with special emphasis on substrate-related issues. 

Structure and morphology of supported metal nanoparticles may differ drastically, depending on (i) their size, (ii) their interaction with support, (iii) the (electro)chemical environment, and, (iv) since very often particles do not attain equUibrium shapes, also on the preparation conditions and sample prehistory. 

Electrocatalytic activity of supported metal particles has been investigated on surfaces prepared in an ultrahigh vacuum (UHV) molecular beam epitaxy system (DCA Instruments) modified to allow high throughput (parallel) synthesis of thin-film materials [Guerin and Hayden, 2006]. The system is shown in Fig. 16.1, and consisted of two physical vapor deposition (PVD) chambers, a sputtering chamber, and a surface characterization chamber (CC), all interconnected by a transfer chamber (TC). The entire system was maintained at UHV, with a base pressure of 10 °mbar. Sample access was achieved through a load lock, and samples could be transferred... 

Transmission IR (TIR) spectroscopy if the solid in question is IR transparent over an appreciable range of wavelength. This is often used on supported metal catalysts, where the large metallic surface area permits a high concentration of adsorbed species to be sampled. The sample consist typically of 10-100 mg of catalyst, pressed into a self-supporting disk of approximately 1 cm2 and a few tenths of a mm in thickness. The support particles should be smaller than the wavelength of the IR radiation, otherwise scattering losses become important. 

It is also observed in Fig. 5.3 that Pd(II) ions are partly adsorbed on AI2O3 before ultrasonic irradiation the concentration of Pd(II) just before irradiation becomes ca. 0.8 mM, although 1 mM Pd(II) was added in the sample solution. From a preliminary adsorption experiment, the rate of Pd(II) adsorption on A1203 was found to be slow compared with those of Pd(II) reduction in the presence of alcohols. Therefore, it is suggested that the sonochemical reduction of Pd(II) in the presence of alcohols mainly proceeds in the bulk solution. The mechanism of the Pd/Al203 formation is also described in the section of sonochemical synthesis of supported metal nanoparticles. 

The use of EM (except in the special case of SEM) demands that the catalyst, whether mono-or multi-phasic, be thin enough to be electron transparent. But, as we show below, this seemingly severe condition by no means restricts its applicability to the study of metals, alloys, oxides, sulfides, halides, carbons, and a wide variety of other materials. Most catalyst powder preparations and supported metallic catalysts, provided that representative thin regions are selected for characterization, are found to be electron transparent and thus amenable to study by EM without the need for further sample preparation. 

---