Single-crystal surface catalysts

Most of the published promotional kinetic studies have been performed on well defined (single crystal) surfaces. In many cases atmospheric or higher pressure reactors have been combined with a separate UHV analysis chamber for promoter dosing on the catalyst surface and for application of surface sensitive spectroscopic techniques (XPS, UPS, SIMS, STM etc.) for catalyst characterization. This attempts to bridge the pressure gap between UHV and real operating conditions. 

Propose a strategy for bridging the gap between the world of adsorption and reaction on well-defined single-crystal surfaces and the world of supported catalysts in high-pressure reactors. 

Structure Sensitivity over Re. As in the case of the Fe catalysts the rate of ammonia synthesis varies greatly over Re single crystal surfaces of different orientations. This phenomenon has been studied over the (0001), (loTo), (1120) and 0121) planes in a 3 1 Hp/N mixture at a total pressure of 20 atm. and a temperature or 870 K. Under these conditions these surfaces catalyze the reaction with relative rates of 1 94 920 2820 respectively, showing a range of activities even greater than that observed on Fe. 

Two examples of the application of transmission IR methods will be presented. The first, dealing with the chemisorption of CO on a Pd/S102 catalyst surface. Illustrates the first observation of a local stoichiometric surface species Interconversion process which occurs among chemisorbed CO species at high CO coverages. Evidence for the operation of the local stoichiometric process has been obtained on 75A Pd particles. These particles seem to show close similarities as well as to differ In some respects from a Pd(lll) single crystal surface Insofar as their Interaction with CO Is concerned. 

Rigby J, Kondratenkov M (2004) Arene Complexes as Catalysts. 7 181-204 Risse T, Freund H-J (2005) Spectroscopic Characterization of Organometallic Centers on Insulator Single Crystal Surfaces From Metal Carbonyls to Ziegler-Natta Catalysts. 16 117-149... 

Spectroscopic Characterization of Organometallic Centers on Insulator Single Crystal Surfaces From Metal Carbonyls to Ziegler-Natta Catalysts... 

Figure 3.7. In-situ reflection-absorption infrared (RAIRS) spectra as a function of catalyst temperature from a Pd(lll) single-crystal surface in the presence of a NO + CO gas mixture (240mbar, Pco/Pno = 1-5) [66]. The data clearly show the appearance of an isocyanate-related band at 2256 cm-1 at temperatures above 500 K. In-situ spectroscopic experiments such as these have proven indispensable to detect and identify key reaction intermediates for the catalytic reduction of NO on metal surfaces. (Figure provided by Professor Goodman and reproduced with permission from the American Chemical Society, Copyright 2003).

A question which has occupied many catalytic scientists is whether the active site in methanol synthesis consists exclusively of reduced copper atoms or contains copper ions [57,58]. The results of Szanyi and Goodman suggest that ions may be involved, as the preoxidized surface is more active than the initially reduced one. However, the activity of these single crystal surfaces expressed in turn over frequencies (i.e. the activity per Cu atom at the surface) is a few orders of magnitude lower than those of the commercial Cu/ZnO/ALO catalyst, indicating that support-induced effects play a role. Stabilization of ionic copper sites is a likely possibility. Returning to Auger spectroscopy, Fig. 3.26 illustrates how many surface scientists use the technique in a qualitative way to monitor the surface composition. 

This chapter deals with the study of structural properties of catalysts and catalytic model surfaces by means of interference effects in scattered radiation. X-ray diffraction is one of the oldest and most frequently applied techniques in catalyst characterization. It is used to identify crystalline phases inside catalysts by means of lattice structural parameters, and to obtain an indication of particle size. Low energy electron diffraction is the surface sensitive analog of XRD, which, however, is only applicable to single crystal surfaces. LEED reveals the structure of surfaces and of ordered adsorbate layers. Both XRD and LEED depend on the constructive interference of radiation that is scattered by relatively large parts of the sample. As a consequence, these techniques require long-range order. 

Carbon monoxide on metals forms the best-studied adsorption system in vibrational spectroscopy. The strong dipole associated with the C-O bond makes this molecule a particularly easy one to study. Moreover, the C-0 stretch frequency is very informative about the direct environment of the molecule. The metal-carbon bond, however, falling at frequencies between 300 and 500 cm1, is more difficult to measure with infrared spectroscopy. First, its detection requires special optical parts made of Csl, but even with suitable equipment the peak may be invisible because of absorption by the catalyst support. In reflection experiments on single crystal surfaces the metal-carbon peak is difficult to obtain because of the low sensitivity of RAIRS at low frequencies [12,13], EELS, on the other hand, has no difficulty in detecting the metal-carbon bond, as we shall see later on. 

Summarizing, infrared spectroscopy measures, in principle, force constants of chemical bonds. It is a powerful tool in the identification of adsorbed species and their bonding mode. Infrared spectroscopy is an in situ technique, which is applicable in transmission or diffuse reflection mode on real catalysts, and in reflection-absorption mode on single crystal surfaces. Sum frequency generation is a speciality... 

The aim of this chapter is to document how catalytic reactions can be promoted and regulated by the presence of coadsorbed species and by the design of active structures at catalyst surfaces. To clarify these issues, this chapter examines two classes of well-defined catalyst surfaces chemically designed surfaces and single-crystal surfaces. 

Fig. 2. (a) A comparison of the rate of methane synthesis over single crystal nickel catalysts and supported Ni/AliO, catalysts at 120 torr total reactant pressure. (From Rtf. 12.) (b) Atomic configuration of a Ni(100) surface, (c) Atomic configuration of a... 

---