Surface science techniques

The implementation of high-pressure reaction cells in conjunction with UFIV surface science techniques allowed the first tme in situ postmortem studies of a heterogeneous catalytic reaction. These cells penult exposure of a sample to ambient pressures without any significant contamination of the UFIV enviromnent. The first such cell was internal to the main vacuum chamber and consisted of a metal bellows attached to a reactor cup [34]- The cup could be translated using a hydraulic piston to envelop the sample, sealing it from... 

B1.23.9 ROLE OF SCATTERING AND RECOILING AMONG SURFACE SCIENCE TECHNIQUES... 

Unlike traditional surface science techniques (e.g., XPS, AES, and SIMS), EXAFS experiments do not routinely require ultrahigh vacuum equipment or electron- and ion-beam sources. Ultrahigh vacuum treatments and particle bombardment may alter the properties of the material under investigation. This is particularly important for accurate valence state determinations of transition metal elements that are susceptible to electron- and ion-beam reactions. Nevertheless, it is always more convenient to conduct experiments in one s own laboratory than at a Synchrotron radiation focility, which is therefore a significant drawback to the EXAFS technique. These focilities seldom provide timely access to beam lines for experimentation of a proprietary nature, and the logistical problems can be overwhelming. 

X-ray photoelectron spectroscopy (XPS), which is synonymous with ESCA (Electron Spectroscopy for Chemical Analysis), is one of the most powerful surface science techniques as it allows not only for qualitative and quantitative analysis of surfaces (more precisely of the top 3-5 monolayers at a surface) but also provides additional information on the chemical environment of species via the observed core level electron shifts. The basic principle is shown schematically in Fig. 5.34. 

In general the group of the late Professor Gopel pioneered the use of surface science techniques in solid state electrochemistry. 

Why are typical surface science techniques such as low-energy electron diffraction, scanning tunneling and atomic force microscopy generally unsuitable for studying supported catalysts ... 

Although much progress has been made toward understanding the nature and probable catalytic behavior of active sites on CoMo/alumlna catalysts, much obviously remains to be accomplished. Detailed explanation of the acidic character of the reduced metal sites evidently most important In HDS, and presumably In related reactions, must await the Increased understanding which should come from studies of simplified model catalysts using advanced surface science techniques. Further progress of an Immediately useful nature seems possible from additional Infrared study of the variations produced In the exposed metal sites as a result of variations In preparation, pretreatment, and reaction conditions. 

Understanding and controlling oxide surfaces are the key issues for the development of industrial oxide catalysts, but oxide surfaces are in general heterogeneous and complicated, and hence have been little studied so as to put them on a scientific basis by traditional approaches. While studies of the structure of surfaces have focused on metals and semiconductors over the past thirty years, the application of surface science techniques to metal oxides has blossomed only within the last decade[l-3]. 

By surface science techniques, Mullins and Overbury showed that the presence of reduced ceria might create new active sites for NO dissociation [82], The degree of decomposition is increased and the onset temperature for decomposition is reduced when Rh is supported on reduced ceria (Rh/CeOj compared to Rh on oxidized ceria (Rh/Ce02) NO dissociation being self-inhibiting. 

In accord with the fact that XPS has become a standard surface science technique but has not been appreciated adequately in electrochemistry, it is the scope of this review chapter to bring XPS nearer to those who work on electrochemical problems and convince electrochemists to use XPS as a complementary technique. It is not the intention to treat fundamental physical and experimental aspects of photoelectron spectroscopies in detail. There are several review articles in the literature treating the basics and new developments in an extensive and competent way [9,13], In this article basic aspects are only addressed in so far as they are necessary to understand and... 

Like most surface science techniques, conventional in situ STM studies have been carried out in UHV on model catalysts consisting of extended planar surfaces. When extrapolating the information obtained in UHV surface science studies to real-world catalysis, two issues have generally concerned the catalysis community, namely, the pressure and material gaps. 

The phenomenon appears to be due to formation and destruction of some type of surface silver oxide during oxygen pumping to and from the catalyst respectively. The use of in situ surface science techniques should prove very useful for the elucidation of the exact nature of this surface oxide. 

In this chapter we introduce and discuss a number of concepts that are commonly used in the electrochemical literature and in the remainder of this book. In particular we will illuminate the relation of electrochemical concepts to those used in related disciplines. Electrochemistry has much in common with surface science, which is the study of solid surfaces in contact with a gas phase or, more commonly, with ultra-high vacuum (uhv). A number of surface science techniques has been applied to electrochemical interfaces with great success. Conversely, surface scientists have become attracted to electrochemistry because the electrode charge (or equivalently the potential) is a useful variable which cannot be well controlled for surfaces in uhv. This has led to a laudable attempt to use similar terminologies for these two related sciences, and to introduce the concepts of the absolute scale of electrochemical potentials and the Fermi level of a redox reaction into electrochemistry. Unfortunately, there is some confusion of these terms in the literature, even though they are quite simple. 

Methods that investigate the interface as such are called in situ methods. In ex situ methods the electrode is pulled out of the solution, transferred to a vacuum chamber, and studied with surface science techniques, in the hope that the structure under investigation, such as an adsorbate layer, has remained intact. Ex situ methods should only be trusted if there is independent evidence that the transfer into the vacuum has not changed the electrode surface. They belong to the realm of surface science, and will not be considered here. 

EELS is not suited for investigating catalysts but is, just as RAIRS, a typical surface science technique. We compare the two techniques on a number of points ... 

The good agreement between electrochemical and UHV data, documented in Figure 4, is a very important result, because it proves for the first time that the microscopic information which one obtains with surface science techniques in the simulation studies is indeed very relevant to interfacial electrochemistry. As an example of such microscopic information, Figure 5 shows a structural model of the inner layer for bromide specific adsorption at a halide coverage of 0.25 on Ag 110 which has been deduced from thermal desorption and low energy electron diffraction measurements /12/. Qualitatively similar models have been obtained for H2O / Br / Cu( 110) /18/and also for H2O/CI /Ag 110. ... 

The chemisorption and thermal decomposition of ethylene over platinum (111) surfaces have been extensively studied by several groups using a range of modern surface science techniques (1-3 ). Chemisorption at low temperatures is molecular, with the... 

In non-electrochemical heterogeneous catalysis, the interface between the catalyst and the gas phase can often be characterized using a wide variety of spectroscopic probes. Differences between reaction conditions and the UHV conditions used in many studies have been probed extensively 8 as have differences between polycrystalline and single-crystalline materials. Nevertheless, the adsorbate-substrate interactions can often be characterized in the absence of pressure effects. Therefore, UHY based surface science techniques are able to elucidate the surface structures and energetics of the heterogeneous catalysis of gas phase molecules. 

Carbon monoxide oxidation is a relatively simple reaction, and generally its structurally insensitive nature makes it an ideal model of heterogeneous catalytic reactions. Each of the important mechanistic steps of this reaction, such as reactant adsorption and desorption, surface reaction, and desorption of products, has been studied extensively using modem surface-science techniques.17 The structure insensitivity of this reaction is illustrated in Figure 10.4. Here, carbon dioxide turnover frequencies over Rh(l 11) and Rh(100) surfaces are compared with supported Rh catalysts.3 As with CO hydrogenation on nickel, it is readily apparent that, not only does the choice of surface plane matters, but also the size of the active species.18-21 Studies of this system also indicated that, under the reaction conditions of Figure 10.4, the rhodium surface was covered with CO. This means that the reaction is limited by the desorption of carbon monoxide and the adsorption of oxygen. 

---