The impact of steam on the electronic structure of the selective propane oxidation catalyst MoVTeNb oxide (orthorhombic M1 phase)

The selective propane oxidation catalyst MoVTeNb oxide M1 was investigated by microwave conductivity, synchrotron X-ray photoelectron, soft X-ray absorption and resonant photoelectron spectroscopy under reaction conditions to identify the influence of steam on the electronic bulk and surface properties. Steam significantly increases both the conversion of propane and the selectivity to the target product acrylic acid. The increased catalytic performance comes along with a decreased conductivity, a modification of the surface chemical and electronic structure with an enrichment of covalently bonded V5+ species to the extent of Mo6+, a decreased work function and hence polarity of the surface and a modified valence band structure. The higher degree of covalency in metal oxide bonds affects the mobility of the free charge carriers, and hence explains the decrease of the conductivity with steam. Furthermore we could prove that a subsurface space charge region depleted in electrons and thus an upward bending of the electronic band structure are induced by the reaction mixture, which is however not dependent on the steam content

The role of carbon species in heterogeneous catalytic processes: an in situ soft x-ray photoelectron spectroscopy study

High pressure X-ray photoelectron spectroscopy (XPS) is used to characterize heterogeneous catalytic processes. The success of the new technique based on the possibility to correlate the catalytic activity and the electronic structure of an active surface. The dynamic character of a catalyst surface can be demonstrated impressively by this technique. In this contribution the basics of high pressure XPS will be discussed. Three examples of heterogeneous catalytic reactions are presented in this contribution. The selective hydrogenation of 1-pentyne over Pd based catalysts and the dehydrogenation of n-butane and the oxidation of ethylene over V based catalysts. It is shown, that the formation of subsurface carbons plays an important role in all the examples. The incorporated carbon changes the electronic structure of the surface and so controls the selectivity of the reaction. A change of the educts in the reaction atmosphere induces modifications of the electronic surface structure of the operation catalysts

The Influence of the Chemical Potential on Defects and Function of Perovskites in Catalysis

A Sm-deficient Sm0.96MnO3 perovskite was prepared on a gram scale to investigate the influence of the chemical potential of the gas phase on the defect concentration, the oxidation states of the metals and the nature of the oxygen species at the surface. The oxide was treated at 450°C in nitrogen, synthetic air, oxygen, water vapor or CO and investigated for its properties as a catalyst in the oxidative dehydrogenation of propane both before and after treatment. After treatment in water vapor, but especially after treatment with CO, increased selectivity to propene was observed, but only when water vapor was added to the reaction gas. As shown by XRD, SEM, EDX and XRF, the bulk structure of the oxide remained stable under all conditions. In contrast, the surface underwent strong changes. This was shown by AP-XPS and AP-NEXAFS measurements in the presence of the different gas atmospheres at elevated temperatures. The treatment with CO caused a partial reduction of the metals at the surface, leading to changes in the charge of the cations, which was compensated by an increased concentration of oxygen defects. Based on the present experiments, the influence of defects and concentration of electrophilic oxygen species at the catalyst surface on the selectivity in propane oxidation is discussed

The Energy Materials in-Situ Laboratory Berlin (EMIL) at BESSY II

The Helmholtz Center Berlin (HZB) and the Max-Planck Society (MPG) strengthen their research in renewable energies with the implementation of the joint Energy Material in-Situ Lab Berlin (EMIL) at the third generation light source BESSY II. The new facility is dedicated to the in-situ and in-system x-ray analysis of materials and devices for photovoltaic applications, (photo-) catalytic processes, energie conversion and storage. To obtain a comprehensive understanding of the involved materials, spectroscopic methods with x-rays from the soft- up to the hard x-ray regime reveal an almost complete picture of their chemical and electronic properties. The contribution presents the layout of the x-ray beamlines and their performance in terms of photon flux, energy resolution and spot sizes