Windenergieausbau als Teil der Ökostromentwicklung

The new law for the support of electricity produced by renewable sources in Austria (Ökostromgesetz) which came into force with the beginning of 2003, shows its impacts already after the first months. Investments into wind power have increased considerably. These will be accompanied by activities for electricity production by biomass and biogas. The 4%-target quota will probably be reached earlier than the 2008 target period of the law.     

Structure of metal site in Cd-substituted His117Gly mutant of azurin with and without addition of imidazole derivatives

The present work uses 111mCd-perturbed angular correlations of gamma-rays (PAC) to investigate the structure of the metal site of the His117Gly mutant of Pseudomonas aeruginosa azurin in aqueous solution and the effect on the structure upon addition of the following exogenous ligands: imidazole, 4-methyl imidazole, 1-methyl imidazole, 2-methyl imidazole and histidine. The nuclear quadrupole interaction of cadmium bound to the mutant without addition of exogenous ligands shows a strong pH dependence with three different nuclear quadrupole interactions consistent with two pKa values at about 7.2 and 8.6 at 2 degrees C. Addition of the imidazole derivatives resulted in a significant change in the PAC spectrum showing that they coordinate. This is in accordance with observations by EPR for the same mutant with copper at the metal site [den Blaauwen, T. & Canters, G. W. (1993) J. Am. Chem. Soc. 115, 1121-1129]. However, whereas EPR and ultraviolet/visual absorption show that the characteristics of the wild-type copper protein are regained by addition of the imidazole derivatives with the exception of the possible bidentates (histidine and histamine), the comparison of the PAC results to model calculations shows that the cadmium ion must be fourfold coordinated in most cases, probably binding an additional water or hydroxide ligand. A fourfold coordination is in contrast to cadmium-substituted wild-type azurin where PAC data inferred a threefold coordination by a Cys and two His residues [Danielsen, E. Bauer, R., Hemmingsen, L., Andersen. M., Bjerrum, M. J., Butz, T., Tr?ger, W., Canters, G. W., Hoitink, C. W. G., Karlsson, G., Hansson, O. & Messerschmidt, A. (1995) J. Biol. Chem. 270, 573-580]     

Schätzung der modalen Parameter unter Berücksichtigung systematischer Fehler der Frequenzgänge

Zusammenfassung Aufgrund von Eingangs- und Ausgangsst?rungen des Me?systems sowie einer endlichen Frequenzaufl?sung treten stets systematische (Bias-) und zuf?llige Fehler bei gemessenen Frequenzg?ngen und deren Varianzen auf. Auf solchen Frequenzg?ngen und Varianzen beruhende Sch?tzungen der modalen Parameter sind damit ebenfalls systematisch verzerrt. Um die Genauigkeit und Sicherheit der modalen Parameter zu erh?hen, wird ein Sch?tzverfahren vorgestellt, in dem der Einflu? der Biasfehler auf die Sch?tzung n?herungsweise in einer diagonalen Wichtungsmatrix berücksichtigt wird. Es wird gezeigt, da? die systematischen Fehler Einflu? auf die Absch?tzung der statistischen Sicherheit der modalen Parameter haben. Anhand zweier Beispiele wird die Wirksamkeit des Sch?tzverfahrens demonstriert. Prof. Dr.-Ing. Dr.-Ing. E.h.H.K. T?nshoff: Dipl.-Ing.Z. Liu, Institut für Fertigungstechnik und Spanende Werkzeugmaschinen (IFW), Universit?t Hannover.     

Selectivity in Methanol Oxidation as Studied on Model Systems Involving Vanadium Oxides

Oxidation catalysts are modeled by oxide single crystals, thin oxide films, as well as supported oxide nanoparticles. We characterize the surface of those materials using a variety of surface sensitive techniques including scanning tunneling microscopy and spectroscopy, photoelectron spectroscopy, infrared spectroscopy, and thermal desorption spectroscopy. We find temperature dependent structural transformations from V₂O₅(001) to V₂O₃(0001) via V₆O₁₃(001). V₂O₃(0001) is found to be vanadyl terminated in an oxygen ambient and it loses the vanadyl termination after electron bombardment. It is shown that the concentration of vanadyl groups controls the selectivity of the methanol oxy-dehydrogenation towards formaldehyde. A proposal for the mechanism is made. The results on single crystalline thin films are compared with similar measurements on deposited vanadia nanoparticles. The experimental results are correlated with theoretical calculations and models.     

Preparation of Phase-Pure M1 MoVTeNb Oxide Catalysts by Hydrothermal Synthesis—Influence of Reaction Parameters on Structure and Morphology

This work presents a detailed investigation of the preparation of MoVTeNbO _x catalysts by hydrothermal synthesis. Phase-pure synthesis of M1 has been achieved applying the metals in a molar ratio Mo/V/Te/Nb = 1/0.25/0.23/0.12. Raman, UV/Vis spectroscopy, and SEM/EDX analysis show that the elements are inhomogeneously distributed in the initial suspension that is formed after mixing the metal salts in an aqueous medium. Iso- and heteropoly anions of molybdenum, free telluric acid as well as supra-molecular polyoxometalate clusters are observed in the solution, whereas all metals have been found in the precipitate. Complete rearrangement of molecular building blocks under hydrothermal conditions is essential for formation of phase-pure materials. Optimized synthesis conditions with respect to temperature and time result in the formation of a precursor consisting of nano-structured M1 characterized by an extended periodic organization in the [001] direction and a fairly homogeneous distribution of the elements. Residual ammonium containing supra-molecular species in the precursor result in the formation of phase mixtures during the subsequent crystallization by heat treatment in inert gas. Phase-pure M1 exhibits a distinct degree of flexibility with respect to the chemical composition that becomes obvious by incorporating Nb not exclusively into pentagonal bi-pyramidal units, but also into octahedral coordinated positions as shown by EXAFS. Anisotropic growth of the needle-like M1 crystals has been observed during the final heat treatment performed at 873–923 K in inert atmosphere disclosing a potential method to control the catalytic properties of MoVTeNbO _x catalysts.