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In Situ X-Ray Photoelectron Spectroscopy Studies of Gas/Solid Interfaces at Near-Ambient Conditions Hendrik Bluhm, Michael Havecker, Axel-Knop-Gericke, Maya Kiskinova, Robert Schlogl, and Miquel Salmeron Abstract X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst’s chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, i.e., in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces. Introduction One of the main goals in catalysis research is to find a direct correlation between the structure and chemical composition of a catalyst and its catalytic activity and selectivity. This requires the investigation of catalysts under realistic operating pressures, where the chemical composition and structure of the catalyst are monitored simultaneously with its catalytic activity. A number of spectroscopies have been combined with methods that monitor catalytic performance (for recent surveys, see References 1 and 2). Among the techniques

In SituX-Ray Photoelectron Spectroscopy Studies of Gas-Solid Interfaces at Near-Ambient Conditions