Evgueni Kleimenov

In Situ Surface Analysis in Selective Oxidation Catalysis: n-Butane Conversion Over VPP

In situ analysis of the surface of a working selective oxidation catalyst is an essential yet rarely conducted experiment in attempts to derive structure–function relationships. The case study of n-butane oxidation over vanadyl pyrophosphate (VPP) is used to develop a general working hypothesis and to illustrate that the molecular properties of the substrate sets boundary conditions on the surface chemical properties of the catalyst. Experiments using in situ X-ray photoelectron spectroscopy (XPS) and in situ low-energy X-ray absorption spectroscopy are used to derive compositional, electronic, and geometric structural information of the surface of the working VPP. These data allow the conclusion that a surface phase different from VPP must be present covering at least part of the active material. The recent data together with literature observations are used to derive a scenario explaining the function of VPP as a unique catalytic system.

Chapter 4 X‐Ray Photoelectron Spectroscopy for Investigation of Heterogeneous Catalytic Processes

Abstract X‐ray photoelectron spectroscopy (XPS) is commonly applied for the characterization of surfaces in ultrahigh vacuum apparatus, but the application of XPS at elevated pressures has been known for more than 35 years. This chapter is a description of the development of XPS as a novel method to characterize surfaces of catalysts under reaction conditions. This technique offers opportunities for determination of correlations between the electronic surface structures of active catalysts and the catalytic activity, which can be characterized simultaneously by analysis of gas‐phase products. Apparatus used for XPS investigations of samples in reactive atmospheres is described here; the application of synchrotron radiation allows the determination of depth profiles in the catalyst, made possible by changes in the photon energy. The methods are illustrated with examples including methanol oxidation on copper and ethene epoxidation on silver. Correlations between the abundance of surface oxygen species and yields of selective oxidation products are presented in detail. Further examples include CO adsorption and methanol decomposition on palladium and CO oxidation on ruthenium.

Adsorbate coverages and surface reactivity in methanol oxidation over Cu(110): An in situ photoelectron spectroscopy study

The adsorbate species present during partial oxidation of methanol on a Cu(110) surface have been investigated in the 10(-5) mbar range with in situ x-ray photoelectron spectroscopy and rate measurements. Two reaction intermediates were identified, methoxy with a C 1s binding energy (BE) of 285.4 eV and formate with a C 1s BE of 287.7 eV. The c(2x2) overlayer formed under reaction conditions is assigned to formate. Two states of adsorbed oxygen were found characterized by O 1s BEs of 529.6 and 528.9 eV, respectively. On the inactive surface present at low T around 300-350 K formate dominates while methoxy is almost absent. Ignition of the reaction correlates with a decreasing formate coverage. A large hysteresis of approximately 200 K occurs in T-cycling experiments whose correlation with adsorbate species was studied with varying oxygen and methanol partial pressures. The two branches of the hysteresis differ mainly in the amount of adsorbed oxygen, the methoxy species, and a carbonaceous species. Methoxy covers only a minor part of the catalytic surface reaching at most 20%. Above 650 K the surface is largely adsorbate-free.