Paderborn, Universiẗat-Gesamthochsch., Fachber. Maschinentechnik, Diss. 1985.

Zugl.: Berlin, Techn. Univ., Diss., 2009

Originally presented as the author's Thesis--Rheinish-Westfzalischen Technischen Hochschule Aachen. / Includes bibliographical references.

Universiẗat, Diss., 1998--Heidelberg.

Universiẗat, Diss., 2005--Bremen.

Die Schriftenreihe „Altersdatierung und Denitrifikation an Grundwassermessstellen“ informiert über die Auswertung der im Zeitraum von 2019 bis 2020 gewonnenen Stickstoffexzessdaten mittels N2-Ar-Methode, Tritium-Helium-Altersdaten im Grundwasser und hydrochemischen Messreihen. Die Auswertung dient dazu, die Evaluierung der Denitrifikationspotenziale in den Grundwasserleitern ausgewählter staatlicher Grundwassermessstellen unter dem Gesichtspunkt der vorherrschenden Nitratbelastungssituation im Grundwasser zu forcieren. Die räumliche Interpretation des untersuchten Datenbestandes ergab für die Landnutzungsform Ackerland die höchsten Nitratkonzentrationen und Denitrifikationsraten. Die Auswertung der Grundwasseraltersdaten mittels Tritium-Helium-Methode ergab für zirka 50 % der Grundwassermessstellen eine mittlere Verweilzeit des Grundwassers von 5 – 20 Jahren. Die Veröffentlichung richtet sich an Fach- und Vollzugsbehörden, an das interessierte Fachpersonal der Wasserversorgungsunternehmen sowie an Ingenieurbüros, die mit der Planung und Durchführung von Altersdatierungen im Grundwasser und der Bestimmung des Denitrifikationspotenzials im Grundwasserleiter betraut sind. Redaktionsschluss: 22.12.2021

To limit the environmental impact from fuel based transport of goods and mobility, the knowledge-based improvement of the hydrothermal long-term stability of Pd exhaust catalysts is demanded. Thus, the present study evaluates the performance of hydrothermally aged Pd/gamma-Al2O3 powder catalysts on lean CO oxidation (60-200°C) in the presence of H2O, and discusses structure-activity correlations. A decline in the number of Pd surface sites is quantified with growing aging temperature (650-950°C), and correlates with the decrease in the CO oxidation activity in transient state. However, unexpected shifts in the activation energy of the steady state CO oxidation are observed for the different aging temperatures and total time on stream. The characterization of the active Pd sites of the aged and non-aged catalysts before and after the CO oxidation indicate that the oxidation state of Pd changes during the lean and wet CO oxidation. The observed trends of the oxidation state of Pd correlate with the determined variations of the activation energy, successfully elucidating structure sensitivity of the CO oxidation at temperatures of 750°C or higher, and with changing total time on stream.:1 Introduction and aims 2 Fundamentals 2.1 Emissions from combustion engines 2.2 Diesel exhaust after-treatment systems 2.3 Pd catalysts for CO oxidation 2.3.1 Characterization and CO oxidation activity of Pd catalysts 2.3.2 Mechanism of the CO oxidation on Pd catalysts 2.3.3 Influence of H2O on the CO oxidation on Pd catalysts 2.3.4 Structure sensitivity of the CO oxidation on Pd catalysts 2.4 Thermal and hydrothermal aging of supported Pd catalysts 2.4.1 Sintering and phase transformations of γ-Al2O3 2.4.2 Sintering of Pd in supported catalysts 2.4.3 Kinetic modelling of the CO oxidation on aged Pd catalysts 3 Materials and methods 37 3.1 Preparation of the Pd/γ-Al2O3 catalyst 3.2 Hydrothermal aging of the catalyst 3.3 Performance of the catalytic CO oxidation 3.3.1 Temperature-programmed CO oxidation 3.3.2 Steady state CO oxidation 3.4 Characterization of the catalysts 3.4.1 N2 physisorption 3.4.2 Temperature-programmed desorption of H2 3.4.3 Scanning transmission electron microscopy 3.4.4 X-ray diffraction 3.4.5 X-ray photoelectron spectroscopy 4 Results and discussion 4.1 Transient CO oxidation activity of the non-aged and aged Pd/γ-Al2O3 catalysts 12 Contents 4.2 Quantification of the active sites of the non-aged and aged Pd/γ-Al2O3 catalysts 4.2.1 Number of Pd surface sites 4.2.2 Pd particle sizes 4.2.3 Pd crystallite sizes 4.2.4 Content of surface Pd 4.2.5 Comparative discussion of the quantification of the active sites 4.3 Investigation of the aging mechanism of the Pd/γ-Al2O3 catalysts 4.4 Steady state CO oxidation kinetics of the non-aged and aged Pd/γ-Al2O3 catalysts 4.4.1 Activation energy of the steady state CO oxidation and discussion of structure sensitivity 4.4.2 Dispersion of Pd after the steady state CO oxidation 4.4.3 Oxidation state of Pd after the steady state CO oxidation 4.4.4 Comparative discussion of the transient and steady state CO oxidation activity 4.5 Summarizing discussion of the structure-activity correlations of the nonaged and aged Pd/γ-Al2O3 catalysts for CO oxidation 5 Conclusions and outlook Bibliography List of Figures List of Tables A Annexes