No description available.

Methanol (MeOH) is a common external carbon source for wastewater denitrification, because of its low cost and low sludge yield. Ethanol (EtOH), on the other hand, is more expensive, but yields higher denitrification rates. This study introduces gasoline-denatured ethanol (dEtOH), which is now being produced in large quantities for the production of E10 gasoline, as an alternative carbon source. The gasoline added, as the denaturant, is known as "straight-run" gasoline; a lower grade material that contains mostly aliphatic compounds, but lacks the components that normally boost the octane rating, such as benzene, toluene, ethylbenzene and xylenes (BTEX). Herein are presented the results of using dEtOH, EtOH (95.5% ethanol-4.5% water) and MeOH for denitrification in lab-scale, sequencing batch reactors (SBRs). We also focused on the quantification of BTEX present in dEtOH solution and the inhibition potential of these compounds on both nitrification and denitrification. BTEX content in the dEtOH solution had low and consistent concentration. Ethylbenzene and o-xylene were not detected in the reactor. The removal rates of benzene, toluene and m-xylene were 3.1°1.4, 3.4°1.9 and 0.6°0.4 ?g/L·h, respectively. BTEX were not detected in the effluent and did not inhibit nitrification and denitrification. The denaturant did not affect biomass production or the settling properties of the sludge. The yield (COD/NOx-N) and denitrification rates of dEtOH were similar to those of EtOH and higher than those of MeOH. The cost of dEtOH ($0.91//lb NO??-N removed) is slightly higher than that of methanol ($0.74/lb NO??-N removed). Using dEtOH as an external carbon source is, therefore, very promising and utilities will have to decide if it is worth paying a little extra to take advantage of dEtOH's benefits. / Master of Science

Ionenspezifische Effekte treten in einer Vielzahl von wässrigen Lösungen aus Elektrolyten und größeren Molekülen wie Peptiden auf. Die Ionen bewirken dabei Änderungen in Eigenschaften wie z.B. der Viskosität, den Aktivitäten von Enzymen, der Stabilität von Proteinen und deren Ein- bzw. Aussalzverhalten. Typischerweise wird die ionenabhängige Ausprägung derartiger Effekte mithilfe der Hofmeister–Serie beschrieben, die ursprünglich Ionen nach ihrer Fähigkeit ordnete, die Löslichkeit von Hühnereiweis in Wasser zu steigern oder zu unterdrücken. Die empirische Abfolge der Ionen in der Hofmeister–Serie kann jedoch bis heute nicht zweifelsfrei erklärt werden. Trotz weitreichender Bemühungen, ein molekulares Verständnis dieses Phänomens zu schaffen, konnte bisher keine Einigung über die zugrundeliegenden Mechanismen und die genauere Bestimmung und Lokalisierung der Wechselwirkung erzielt werden. Die resonante inelastische Weichröntgenstreuung (RIXS) kombiniert die beiden Methoden der Röntgenemissions– (XES) und Röntgenabsorptionsspektroskopie (XAS). So können mit RIXS Informationen sowohl über die besetzten als auch die unbesetzten elektronischen Zustände gesammelt und zu einem umfassenden Bild der elektronischen Struktur des Systems verknüpft werden, was diese Methode zu einem vielversprechenden Werkzeug macht, etwas mehr Licht auf die Thematik zu werfen. Die in dieser Arbeit präsentierten Ergebnisse zielen deshalb darauf ab, ein verbessertes Verständnis der Wechselwirkungen zwischen Salzen und Peptiden in wässriger Lösung zu schaffen. Hierfür wird systematisch der Einfluss verschiedenster physikalischer Umgebungen auf die elektronische Struktur von kleinen Molekülen (Methanol und von Glycin abgeleitete Peptide) mittels Weichröntgenspektroskopie, unterstützt durch Dichtefunktionaltheorie (DFT) Rechnungen, untersucht. In einem ersten Schritt werden isolierte Moleküle ohne jeglicheWechselwirkung zu ihrer unmittelbaren Umgebung anhand von Methanol in der Gasphase als Modelsystem untersucht. Hierbei wird insbesondere der lokale und elementspezifische Charakter von RIXS demonstriert und die lokale elektronische Struktur von Methanols Hydroxyl– und Methylgruppe untersucht. Mithilfe von DFT–Rechnungen werden die beobachteten Emissionslinien in den XES–Spektren der Emission bestimmter Molekülorbitale zugeordnet und deren relative Emissionsintensitäten erläutert. Für eine resonante Anregung der ersten Resonanz an der Sauerstoff–K–Absorptionskante werden starke Isotopeneffekte beobachtet, die durch dynamische Prozesse an der Hydroxylgruppe erklärt werden können. Dies dient als hervorragendes Beispiel für mögliche Auswirkungen, die eine lokale Änderung in der Geometrie oder Symmetrie des Moleküls auf dessen elektronische Struktur haben kann. Im weiteren Verlauf dieser Arbeit wird das untersuchte Probensystem um die Aminosäure Glycin und deren kleinste Peptide Diglycin und Triglycin, vorerst in ihrer kristallinen Form als Festkörper, erweitert. Mithilfe von RIXS–Karten der Stickstoff– und Sauerstoff–K–Absorptionskanten wird erneut, unterstützt durch DFT–Rechnungen, ein umfassendes Bild der elektronischen Struktur der Moleküle gezeichnet. Ähnlich zum Fall von Methanol werden die Emissionsspektren an der Stickstoff–K–Kante stark von dynamischen Prozessen an der protonierten Aminogruppe der Moleküle beeinflusst. Zudem wird gezeigt, dass RIXS gezielt dazu verwendet werden kann, das Stickstoffatom in der Peptidbindung anzuregen und die elektronische Struktur in dessen lokaler Umgebung zu untersuchen. Desweiteren wird ein einfaches Baukastenprinzip für XES–Spektren dazu genutzt, die spektralen Anteile der Emission aus Übergängen an den beiden Stickstoffatomen in Diglycin zu isolieren. In wässriger Lösung kann eine leichte Veränderung der elektronischen Struktur der Moleküle durch die Wechselwirkung mit benachbarten Wassermolekülen, vermutlich an den geladenen funktionellen Gruppen, beobachtet werden. Die Auswirkungen auf die XES–Spektren sind jedoch eher gering. Deutlich größere Veränderungen werden beobachtet, wenn man den Protonierungszustand der Moleküle über den pH–Wert der Lösung manipuliert. Sowohl die Protonierung der Carboxylgruppe für kleine pH–Werte als auch die Deprotonierung der Aminogruppe in basischer Lösung führen zu starken Veränderungen in den RIXS–Karten. In einer umfangreichen Untersuchung der XES–Spektren von Glycin als Funktion des pH–Wertes wird gezeigt, dass sich die Änderungen jedoch nicht nur örtlich begrenzt auf die Umgebung der manipulierten funktionellen Gruppe, sondern auch auf die elektronische Struktur in weiter entfernten Bereichen des Moleküls auswirken. Als Beispiel für Systeme in denen Hofmeister–Effekte beobachtet werden, werden zu guter Letzt gemischte wässrige Lösungen aus Diglycin und verschiedenen Salzen untersucht. Um den Einfluss verschiedener Kationen auf die elektronische Struktur der Diglycin Moleküle zu erfassen wird eine Reihe unterschiedlicher Chloride verwendet, wohingegen eine Reihe von Kaliumsalzen für die Untersuchung verschiedener Anionen herangezogen wird. In beiden Fällen werden ionenspezifische Auswirkungen auf die XES–Spektren von Diglycin beobachtet, die qualitativ der Sortierung innerhalb der Hofmeister–Serie folgen. Die beobachteten Änderungen deuten dabei darauf hin, dass Kationen unterschiedlich stark mit dem Sauerstoff in der Peptidbindung und dessen unmittelbarer Umgebung wechselwirken, wohingegen Anionen eine gesteigerte Affinität zur Aminogruppe von Diglycin aufweisen. / Ion-specific effects occur in a huge variety of aqueous solutions of electrolytes and larger molecules like peptides, altering properties such as viscosity, enzyme activity, protein stability, and salting-in and salting-out behavior of proteins. Typically, these type of effects are rationalized in terms of the Hofmeister series, which originally orders cations and anions according to their ability to enhance or suppress the solubility of proteins in water. This empirical order, however, is still not understood yet. Quite some effort was made to gain a molecular level understanding of this phenomenon, yet no consensus has been found about the underlying mechanisms and the determination and localization of the interaction sites. Resonant inelastic soft x-ray scattering (RIXS) combines x-ray emission (XES) and absorption spectroscopies (XAS), probing the partial local density of states of both occupied and unoccupied electronic states and is thus a promising candidate to shed more light onto the issue. The studies presented in this work are directed towards an improved understanding of the interaction between salts and peptides. In order to address this topic, the impact of different physical environments on the electronic structure of small molecules (i.e., methanol and glycine derived peptides) is investigated systematically using soft x-ray spectroscopic methods, corroborated with density functional theory (DFT) calculations. In a first step, molecules without any interactions to the surrounding are investigated, using gas-phase methanol as a model system. Thereby, the local and element specific character of RIXS is demonstrated and used to separately probe the local electronic structure of methanol’s hydroxyl and methyl group, respectively. The attribution of the observed emission features to distinct molecular orbitals is confirmed by DFT calculations, which also quantitatively explain the different relative intensities of the emission features. For resonant excitation of the O K pre-edge absorption resonance, strong isotope effects are found that are explained by dynamical processes at the hydroxyl group. This serves as an excellent example for possible consequences of a local change in the geometric structure or symmetry of a molecule on its electronic structure. In the following, the sample system is expanded to the amino acid glycine and its smallest derived peptides diglycine and triglycine. As a first step, they are studied in their crystalline form in solid state. Again, a comprehensive picture of the electronic structure is developed by measuring RIXS maps at the oxygen and nitrogen K absorption edge, corroborated by DFT calculations. Similar to the case of methanol, dynamic processes at the protonated amino group of the molecules after exciting the nitrogen atom have a strong influence on the emission spectra. Furthermore, it is shown that RIXS can be used to selectively excite the peptide nitrogen to probe the electronic structure around it. A simple building block approach for XES spectra is applied to separate the contribution of the emission attributed to transitions into core holes at the peptide and the amino nitrogen, respectively. In the aqueous solution, the surrounding water molecules slightly change the electronic structure, probably via interactions with the charged functional groups. The effects on the x-ray emission spectra, however, are rather small. Much bigger changes are observed when manipulating the protonation state of the functional groups by adjusting the pH value of the solution. A protonation of the carboxyl group at low pH values, as well as a deprotonation of the amino group at high pH values lead to striking changes in the shape of the RIXS maps. In a comprehensive study of glycine’s XES spectra at varying pH values, changes in the local electronic structure are not only observed in the immediate surrounding of the manipulated functional groups but also in more distant moieties of the molecule. Finally, the study is extended to mixed aqueous solutions of diglycine and a variety of different salts as examples for systems where Hofmeister effects are observed. To investigate the influence of different cations and anions on the electronic structure of diglycine, two series of chlorine and potassium salts are used. Ion-specific effects are identified for both cases. Some of the changes in the x-ray emission spectra of diglycine in the mixed solutions qualitatively follow the Hofmeister series as a function of the used salt. The observed trends thereby indicate an increased interaction between the electron density around the peptide oxygen with the cations, whereas anions seem to interact with the amino group of the peptide.

<p> Poly(N-isopropylacrylamides) and copolymers of N-(isopropylacrylamide) and N(tetrahydrofurfurylacrylamide) bearing cholesterol substituents were prepared and their solution properties in water and in methanol were studied by dynamic light scattering, turbidity measurements and by fluorescence spectroscopy. These polymers were obtained in two steps: 1) preparation of a reactive polymer; and 2) coupling of cholesterol to the reactive polymer. In one case the reactive group (N-hydroxysuccinimide) was introduced at one chain end, in the other case, the same group was introduced randomly along the polymer chain. Reaction of an amino-terminated cholesteryl derivative with the reactive polymers led to modified polymers in which cholesterol was attached either to one chain end or to a small number of monomer units along the polymer chain. In the latter case, copolymers bearing pyrene and cholesterol were prepared as well. The copolymers were characterized by 1H NMR, IR and UV spectroscopy and their molecular weights were determined. </p> <p> Studies of the cholesterol-bearing polymers in aqueous solution by dynamic light scattering and fluorescence spectroscopy provided evidence for the formation of polymeric micelles via association of the cholesterol groups. Fluorescence probe and label experiments, using pyrene as a chromophore, gave strong indication that the micelle formation is controlled primarily by the cholesterol groups and only to a lesser extent by the architecture and composition of the polymer. </p> / Thesis / Master of Science (MSc)

No description available.

Excessive greenhouse gas emissions, like carbon dioxide, contribute to global warming and climate change. Methanol is hydrogenated from syngas and can react to produce hydrocarbons in a reaction known as methanol to hydrocarbons (MTH). Catalysts are vital in this reaction and are largely of zeolite origin. The zeolite typology, acidity, and reaction conditions donate the products produced and catalytic stability. Further, previous work shows increased catalytic stability and higher desired product selectivity when metal is incorporated onto the zeolite’s framework. We study the role of varying silica/alumina ratio (SAR) of beta zeolite via dealumination and incorporating titanium to understand their effect on product distribution, catalytic lifetime, and deactivation in the MTH reaction The samples maintained their structural integrity following the dealumination and metal incorporation. Techniques like XRD, N2 physisorption, ICP–OES, FTIR, and Raman spectroscopy are shown and discussed. They confirm the preservation of the zeolite structure following dealumination and metal incorporation. Pyridine-FTIR and ammonia TPD are used to understand the acidity character of the samples. Both show decreased acidity as the SAR increases. 27Al NMR and 1H NMR show the removal of extra framework 27Al as SAR increases and the presence of silanol nests in the dealuminated samples, respectively. A packed bed reactor in a PID setup with a UV-vis probe is used to test the catalytic activity and study the neutral and charged species formation, respectively. The catalytic activity results show a decrease in conversion as the SAR increases for the dealuminated samples. High propylene/ethylene ratio reaching up to 41.5 is observed for the 13M sample. Further, the UV-vis analysis shows the higher formation of bulkier hydrocarbons, like polyaromatics, as the reaction progresses. It is found that the parent sample deactivates quicker than the dealuminated samples as it presents stagnant UV-vis bands at the end of the reaction. The higher accumulation of polyaromatics and lower product formation of ethylene, in higher SARs, is related to the aromatic cycle hindrance and the dominance of the olefinic cycle products.

Three of Hampton Roads Sanitation District's (HRSD's) conventional activated sludge Water Resource Recovery Facilities (WRRFs) add methanol for post-anoxic denitrification: the Virginia Initiative Plant (VIP), Nansemond Plant (NP), and Army Base (AB). From 2017-2020, VIP averaged 0.49 ± 0.03 lb COD/lb N removed, while NP and AB averaged 1.48 ± 0.06 and 2.11 ± 0.15 lb COD/lb N, respectively. Significant methanol savings at VIP may result from post-anoxic denitrification using internal carbon that was stored in the anaerobic zone. An investigation into the factors affecting internal carbon-driven (internal C) denitrification was done via a series of batch tests. The capacity for internal C denitrification was demonstrated with sludge from all three WRRFs, despite not necessarily being used full-scale. For each WRRF, an increase in these rates correlated to higher phosphorus uptake rates, suggesting a dependence on the PAO population. Shorter aerobic times and more acetate in the anaerobic stage were shown to increase internal C denitrification rates to varying degrees, and this type of denitrification was only observed for bio-P biomass that was also nitrifying. Beyond internal carbon, other denitrification factors explored include moving the methanol dose point further into the anoxic zone, longer post-anoxic residence times, plug-flow conditions, solids residence time (SRT), and anoxic conditions prior to methanol dosing. Contributions from slowly biodegradable COD were minimal. Understanding the conditions that promote denitrification with internal carbon or other carbon sources would be required for effective strategies to achieve methanol savings at NP and AB that would rival those at VIP. / Master of Science / Three of Hampton Roads Sanitation District's (HRSD's) Water Resource Recovery Facilities (WRRFs) add methanol to facilitate denitrification in the post-anoxic zone: the Virginia Initiative Plant (VIP), Nansemond Plant (NP), and Army Base (AB). Significant methanol savings at VIP may result from denitrification using carbon that was stored in the biomass earlier in the treatment process. An investigation into the factors affecting this type of denitrification with internal carbon was done via a series of batch tests. All three WRRFs were able to use this internal carbon for denitrification in the batch tests, despite not necessarily using it full-scale. These denitrification rates were shown to relate to the performance of the biomass that is also responsible for phosphorus removal. Shorter aerobic times prior to the anoxic phase and more acetate in the stage where carbon is stored were shown to increase these denitrification rates, and this type of denitrification was only observed for biomass from WRRFs that implement nitrification. Beyond internal carbon, other denitrification factors explored include moving the methanol dose point further into the anoxic zone, longer post-anoxic residence times, plug-flow conditions, solids residence time (SRT), and anoxic conditions prior to methanol dosing. Contributions from carbon pushed downstream from overloading primary clarifiers was minimal. Understanding the conditions that promote denitrification with internal carbon or other carbon sources would be required for effective strategies to achieve methanol savings at NP and AB that would rival those at VIP.

Direct methanol fuel cells (DMFC) are appealing as a power source for portable devices as they do not require recharging with an electrical outlet. However, the DMFC technology is confronted with the high crossover of methanol fuel from the anode to the cathode through the currently used Nafion membrane, which not only wastes the fuel but also poisons the cathode platinum catalyst. With an aim to overcome the problems encountered with the Nafion membrane, this dissertation focuses on the design and development of new polymeric membrane materials for DMFC and a fundamental understanding of their structure-property-performance relationships. Several polymeric blend membranes based on acid-base interactions between an aromatic acidic polymer such as sulfonated ploy(ether ether ketone) (SPEEK) and an aromatic basic polymer such as heterocycle tethered poly(sulfone) (PSf) have been explored. Various heterochylces like nitro-benzimidazole (NBIm), 1H-Perimidine (PImd), and 5-amino-benzotriazole (BTraz) have been tethered to PSf to understand the influence of pKa values and the size of the hetrocycles. The blend membranes show lower methanol crossover and better performance in DMFC than plain SPEEK due to an enhancement in proton conductivity through acid-base interactions and an insertion of the heterocycle side groups into the ionic clusters of SPEEK as indicated by small angle Xray scattering and TEM data. The SPEEK/PSf-PImd blend membrane shows the lowest methanol crossover due to the larger size of the side groups, while the SPEEK/PSf-BTraz blend membrane shows the highest proton conductivity and maximum power density. To further investigate the methanol-blocking effect of the heterocycles, N,N’-Bis- (1H-benzimidazol-2-yl)-isophthalamide (BBImIP) having two amino-benzimidazole groups bonded to a phenyl ring has been incorporated into sulfonated polysulfone (SPSf) and SPEEK membranes. With two 2-amino-benzimidazole groups, which could greatly increase the proton transfer sites, and three phenyl rings, which are compatible with the aromatic polymers, the BBImIP/SPSf and BBImIP/SPEEK blend membranes show suppressed methanol crossover and increased fuel cell performance in DMFC. Novel sulfonated copolymers based on poly(aryl ether sulfone) (SPS-DP) that exhibit low methanol crossover have been synthesized and explored as a methanol-barrier center layer in a multilayer membrane configuration having SPEEK as the outer layers. These multilayer membranes exhibit better performance in DMFC than plain SPEEK and Nafion 115 membranes due to suppressed methanol crossover. To address the issue of incompatibility between the new hydrocarbon-based membranes synthesized and the Nafion ionomer used in the catalyst layer in fabricating membrane-electrode assemblies (MEAs), the MEAs have been fabricated with the SPEEK membranes and 10 to 30 % SPEEK ionomer in the catalyst layer. These MEAs exhibit better performance in DMFC compared to the MEAs fabricated with the SPEEK membranes and Nafion ionomer in the catalyst layer due to lower interfacial resistance. / text

Reductive functionalization of methyl ligands by 3d metal catalysts and two possible side reactions has been studied. Selective oxidation of methane, which is the primary component of natural gas, to methanol (a more easily transportable liquid) using organometallic catalysis, has become more important due to the abundance of domestic natural gas. In this regard, reductive functionalization (RF) of methyl ligands in [M(diimine)2(CH3)(Cl)] (M: VII (d3) through CuII (d9)) complexes, has been studied computationally using density functional techniques. A SN2 mechanism for the nucleophilic attack of hydroxide on the metal-methyl bond, resulting in the formation of methanol, was studied. Similar highly exergonic pathways with very low energy SN2 barriers were observed for the proposed RF mechanism for all complexes studied. To modulate RF pathways closer to thermoneutral for catalytic purposes, a future challenge, paradoxically, requires finding a way to strengthen the metal-methyl bond. Furthermore, DFT calculations suggest that for 3d metals, ligand properties will be of greater importance than metal identity in isolating suitable catalysts for alkane hydroxylation in which reductive functionalization is used to form the C—O bond. Two possible competitive reactions for RF of metal-methyl complexes were studied to understand the factors that lower the selectivity of C—O bond forming reactions. One of them was deprotonation of the methyl group, which leads to formation of a methylene complex and water. The other side reaction was metal-methyl bond dissociation, which was assessed by calculating the bond dissociation free energies of M3d—CH3 bonds. Deprotonation was found to be competitive kinetically for most of the 1st row transition metal-methyl complexes (except for CrII, MnII and CuII), but less favorable thermodynamically as compared to reductive functionalization for all of the studied 1st row transition metal complexes. Metal-carbon bond dissociation was found to be less favorable than the RF reactions for most 3d transition metal complexes studied. The first dinitrogen dicopper (I) complex has been characterized using computational and experimental methods. Low temperature reaction of the tris(pyrazolyl)borate copper(II) hydroxide {iPr2TpCu}2(µ-OH)2 with triphenylsilane under a dinitrogen atmosphere gives the µ -N2 complex, {iPr2TpCu}2(µ -N2). X-ray crystallography reveals an only slightly activated N2 ligand (N-N: 1.111(6) Å) that bridges between two iPr2TpCuI fragments. While DFT studies of mono- and dinuclear copper dinitrogen complexes suggest a weak µ-backbonding between the d10 CuI centers and the N2 ligand, they reveal a degree of cooperativity in the dinuclear Cu-N2-Cu interaction.

Selektivität zu erreichen ist eines der Hauptziele der Chemie. In der Katalyse wird allgemein von einem engen Zusammenhang zwischen der Selektivität und der Katalysatorstruktur ausgegangen - allerdings erschwert die komplexe mikroskopische Struktur realer Katalysatoren ein tiefergehendes Verständnis; daher wird versucht, weitergehende Erkenntnisse an strukturell vereinfachten Materialien zu gewinnen. Für diese Arbeit wurde hierzu ein Pd/Fe3O4-Modellkatalysator verwendet. Auf diesem System wurde die Selektivität in zwei katalytische Modellreaktionen untersucht. Die Reaktantenexposition erfolgte dabei über Molekularstrahlen im Hochvakuum, und die Reaktionsraten wurden massenspektrometrisch gemessen; Adsorbate wurden IR-spektroskopisch detektiert. - Zersetzung von Methanol: Es wird gezeigt, dass Methanol auf dem Oxid Fe3O4 sehr selektiv durch Reaktion mit Oberflächensauerstoff (Mars-van-Krevelen-Mechanismus) zu Formaldehyd und Wasser dehydrogeniert wird. Auf Pd-Metall zersetzt sich Methanol im wesentlichen sehr schnell zu Kohlenstoffmonoxid und Wasserstoff (bzw. zu Kohlenstoffablagerungen in einer Nebenreaktion). Es werden Experimente gezeigt, die darauf hindeuten, dass Diffusion von oxidgebundenem Methanol/Methoxy auf die Pd-Metallpartikel signifikant zur Gesamtaktivität des Modellkatalysators beiträgt. - Umsetzung von 2-Buten mit Deuterium: Zunächst wird gezeigt, dass die Erzielung katalytischer Aktivität kritisch von der dissoziativen Adsorption des Reaktanden Deuterium abhängt, die durch Kohlenwasserstoffadsorbate stark inhibiert wird; es war allerdings möglich, diese Limitierung experimentell zu umgehen. Darüberhinaus wird gezeigt, dass die Hydrierungsreaktion durch die Anwesenheit stark zersetzter Kohlenwasserstoffablagerungen selektiv induziert werden kann, während die alternative Reaktion (H/D-Austausch/Isomerisierung) auch in Abwesenheit dieser Spezies abläuft; mögliche Erklärungsmodelle werden diskutiert. Schließlich wird die mögliche Ursache für die unter bestimmten Reaktionsbedingungen beobachteten unterschiedlichen Reaktionsraten mit cis- und trans-2-Buten als Reaktanten diskutiert. / The achievement of selectivity is one of the main objectives in chemistry. For catalysis, selectivity is generally seen to be closely linked with catalyst structure; the complex microscopic structure of real catalysts, however, obstructs to obtain a deeper understanding; for this reason, structurally simplified materials are studied. For the current work, studies have been conducted on a Pd/Fe3O4 model catayst. On this system, the selectivity in two catalytic reactions has been examined. The exposure of the reactants was effected by molecular beams in high vacuum, and the reaction rates have been measured mass spectrometrically; additionally, adsorbates were detected by IR-spectroscopy. - Decomposition of Methanol: It is shown that on the oxide Fe3O4 methanol is dehydrogenated very selectively to formaldehyde and water by reaction with surface oxygen of the oxide (Mars-van-Krevelen mechanism). On Pd metal it is mainly decomposed very quickly to carbon monoxide and hydrogen (and, in a side reaction, to carbonaceous deposits). Experiments are shown indicating that the diffusion of oxide-related methanol and methoxy to the Pd metal-particles contributes significantly to the overall activity of the model catalyst. - Conversion of 2-Butene with Deuterium: At first it is shown that the catalytic activity depends critically on the dissociative adsorption of the reactant deuterium, which is strongly inhibited by hydrocarbon adsorbates; it was, however, possible to overcome this limitation experimentally. In addition, it is shown that the hydrogenation reaction can be selectively induced in the presence of strongly dehydrogenated carbonaceous deposits, whereas the alternative reaction (H/D-exchange/isomerisation) can proceed also without the presence of those species; possible models for explanation are discussed. Finally, the possible origin of the different reaction rates with cis- and trans-2-butene that were observed only under certain reaction conditions is discussed.