Metal oxides, cluster deposition

Gas-phase metal oxide cluster cations have become increasingly interesting because of the possibility that a controlled reaction of size selected clusters might shed some light on condensed-phase catalysts. The possibility of producing small clusters in the condensed phase from deposition of gas-phase clusters has also been a driving force in the study of the reactivity of gas-phase ions. 

Few studies have also been reported with metal oxide clusters in mesoporous materials. MCM-41 modified by deposition of vanadium and titanium oxides exhibited catalytic activity for reduction of nitrogen oxides by NH3 [186]. 

With the advent of synthetic methods to produce more advanced model systems (cluster- or nanoparticle-based systems either in the gas phase or on planar surfaces), we come to the modern age of surface chemistry and heterogeneous catalysis. Castleman and coworkers demonstrate the large influence that charge, size, and composition of metal oxide clusters generated in the gas phase can have on the mechanism of a catalytic reaction. Rupprechter (Chap. 15) reports on the stmctural and catalytic properties of planar noble metal nanocrystals on thin oxide support films in vacuum and under high-pressure conditions. The theme of model systems of nanoparticles supported on planar metal oxide substrates is continued with a chapter on the formation of planar catalyst based on size-selected cluster deposition methods. In a second contribution from Rupprecther (Chap. 17), the complexities of surface chemistry and heterogeneous catalysis on metal oxide films and nanostructures, where the extension of the bulk structure to the surface often does not occur and the surface chemistry is often dominated by surface defects, are discussed. 

A different approach towards the incorporation of metal oxide clusters into zeo-litic pores via chemical vapor deposition has been studied extensively by Ozin et al. [236 - 240]. They developed a method denoted as intrazeolite metal carbonyl phototopotaxy . Metal carbonyls are used as precursors to obtain the occluded guest component because of their volatility, fitting molecular dimensions, ease of purification, ready availability, and facile and quantitative conversion to the respective metal oxide materials with minimal contamination by carbon [236, 240]. The metal carbonyl precursors are transformed into the metal oxides by photochemical oxidation. The term phototopotaxy is meant to indicate the similarity of this preparation method to epitactical growth of semiconducting oxide layers on planar surfaces commonly used to form low-dimensional quantum nanostructures for applications in electronic and optical devices [238]. 

In addition, the rate of Oz reduction, forming 02 by electron, is of importance in preventing carrier recombination during photocatalytic processes utilizing semiconductor particles. 02 formation may be the slowest step in the reaction sequence for the oxidation of organic molecules by OH radicals or directly by positive holes. Cluster deposition of noble metals such as Pt, Pd, and Ag on semiconductor surfaces has been demonstrated to accelerate their formation because the noble metal clusters of appropriate loading or size can effectively trap the photoinduced electrons [200]. Therefore, the addition of a noble metal to a semiconductor is considered as an effective method of semiconductor surface modification to improve the separation efficiency of photoinduced electron and hole pairs. 

The main characteristics of the various titanium oxide catalysts used in this chapter are summarized in Table 1. Titanium oxide thin film photocatalysts were prepared using an ionized cluster beam (ICB) deposition method [13-16]. In ICB deposition method, the titanium metal target was heated to 2200 K in a crucible and Ti vapor was introduced into the high vacuum chamber to produce Ti clusters. These clusters then reacted with O2 in die chamber and stoichiometric titanium oxide clusters were formed. Tlie ionized titanium oxide clusters formed by electron beam irradiation were accelerated by a high electric field and bombarded onto the glass substrate to form titanium oxide thin films. 

Oxide electrodes have been observed to be almost immune from poisoning effects due to traces of metallic impurities in solution [99]. This is undoubtedly due primarily to the extended surface area. It can be anticipated that the calcination temperature must have a sizable effect. But in addition, a different mechanism of electrodeposition must be operative. Chemisorption on wet oxides is usually weak because metal cations are covered by OH groups [479]. As a consequence, underpotential deposition of metals is not observed on Ru02, although metal electrodeposition does takes place. However, electrodeposited metals give rise to clusters or islands and not to a monomolecular layer like on Pt. Therefore, the oxide active surface remains largely uncovered even if metallic impurities are deposited [168]. Thus, the weak tendency of oxides to adsorb ions, and its dependence on the pH of the solution is linked to their favorable behavior observed as cathodes in the presence of metallic impurities. 

These catalysts are composed of one or several metallic active components, deposited on a high surface area support, whose purpose is the dispersion of the catalytically active component or components and their stabilization [23-27], The most important metallic catalysts are transition metals, since they possess a relatively high reactivity, exhibit different oxidation states, and have different crystalline structures. In this regard, highly dispersed transition clusters of metals, such as Fe, Ru, Pt, Pd, Ni, Ag, Cu, W, Mn, and Cr and some alloys, and intermetallic compounds, such as Pt-Ir, Pt-Re, and Pt-Sn, normally dispersed on high surface area supports are applied as catalysts. 

In those catalysts, the metal species were deposited in the form of salts or carbonyl clusters. Further, the modifications of the oxide surface with the multinuclear cobalt carbonyl cluster Co3(CO)9—CR (R = CH3 or Ph) have been reported (68). 

The complexity of the problem is increased by the fact that the point defects can be located at various sites, terraces, edges, steps, and kinks [11] and that they can be isolated, occur in pairs, or even in clusters . Furthermore, the concentration of the defects is usually low, making their detection by integral surface sensitive spectroscopies very difficult. A microscopic view of the metal/oxide interface and a detailed analysis of the sites where the deposited metal atoms or clusters are bound become essential in order to rationalize the observed phenomena and to design new materials with known concentrations of a given type of defects. 

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