Glycerol and fructose are molecules that are readily available in substantial quantities fromthe biomass. In this work dehydration routes for valorization of these compounds wereinvestigated. Therefore, zirconia and titania based catalysts, and calcium phosphate materialswere prepared and evaluated in the glycerol dehydration in gas phase. Niobia-ceria mixedoxides and mesoporous Nb2O5-MeO2 (M = Ce, Zr, Ti) mixed oxides were prepared andtested in fructose dehydration reaction in aqueous phase. The surface acid-base properties ofthe studied catalysts were correlated to their catalytic performance.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Cement has been used in the world, presenting a wide versatility. However, due to its chemical nature, it is subject to several types of chemical damages, especially for agents of acidic nature. With the purpose of increase its life-time, new cement slurries have been modified with the addition of specific additives. The objective of this work is to modify cement slurries with epoxy resins, which promote higher resistance of those materials in relation to acid attacks. Three cement slurries were synthesized with epoxy resins (GY, PY-1 and PY-2) and a standard slurries, which was composed by cement and water (w/c = 0,5). The syntheses were performed according to the API recommendations. After 30 days of hydration, the samples were characterized by XDR, FTIR and thermal analysis (TG and DSC). The slurries characterization has suggested the presence of low amounts of portlandita (Ca(OH)2) in the slurry with the higher content of polymerized epoxy resin. The hydration processes of the cement slurries were studied by heat-conduction microcalorimetry. The energetic and enthalpic hydration data were all exothermic in nature. It was verified that the addition of the polymers delayed the processes of hydration of the slurries, decreasing the flow of heat released as a function of the amount of added resin. The cumulative heat release curves have shown the presence of multilinearity of the kinetic processes. The hydration microcalorimetric data were well fitted to the multistep Avrami kinetic model. A kinetic study of HCl interaction with the new slurries were performed by the batch methodology at 25, 35, 45 e 55°C. The Avrami kinetic model also appears to be the most efficient in describing the kinetic isotherms. It was observed that the kinetic constants of interaction of the acid with the slurries increased with the increase of temperature and decreased as a function of the amount of resin added in the slurries. The speed of reaction of the cement slurries with HCl was determined from the kinetic parameters obtained by the Avrami model. Speed reaction in the order of 10-3 mol.g.h-1 were found for the standard slurry and of the order of 10-5 mol.g.h-1 for the slurries with the epoxy resins. In general, the analysis of the kinetic parameters indicated that increasing the resin amount in the composition of the slurries reduced the reaction speed and increased the resistance of those slurries to the acid attack. / O cimento é um dos materiais mais utilizados no mundo, apresentando uma larga versatilidade. No entanto, devido à sua natureza química, está sujeito a vários tipos de desgastes, especialmente por agentes de natureza ácida. Com a finalidade de prolongar o tempo de vida útil desse material, buscam-se novas formulações de pastas de cimento através da adição de aditivos específicos. O objetivo deste trabalho é a modificação de pastas de cimento com resinas epóxi, as quais promovem maior resistência desses materiais frente aos ataques ácidos. Foram sintetizadas três pastas de cimento com resinas epóxi (GY, PY-1 e PY-2) e uma pasta padrão, composta de cimento e água. Para preparação utilizaram-se dois tipos de resinas epóxi, uma do tipo bisfenol-A e seu endurecedor de isoforonodiamina (GY) e outra, uma combinação do bisfenol-F e do bisfenol-A com endurecedor de poliamidoamina (PY-1 e PY-2). Após 30 dias de hidratação, as amostras foram caracterizadas por DRX, FTIR e por análise térmica (TG e DSC). A caracterização das pastas sugeriu a presença de baixas quantidades de portlandita (Ca(OH)2) nas composições com maior porcentagem de resina epóxi. Os processos de hidratação das pastas de cimento foram estudados por calorimetria isotérmica. Os dados energéticos de entalpia de hidratação foram todos de natureza exotérmica. Foi verificado que a adição do polímero retardou o processo de hidratação das pastas, reduzindo o fluxo de calor liberado em função da porcentagem de resina adicionada. As curvas de liberação do fluxo de calor mostraram a presença de vários processos cinéticos distintos. Os dados de hidratação foram bem ajustados ao modelo cinético de Avrami. O estudo cinético de interação de HCl com as pastas de cimento foi realizado pelo método de batelada nas temperaturas de 25, 35, 45 e 55°C. O modelo cinético de Avrami também foi o que mais se mostrou eficiente em descrever as isotérmicas cinéticas. Foram observados que as constantes cinéticas de interação do ácido com as pastas aumentaram com o aumento da temperatura, e diminuíram em função do aumento da quantidade de polímero adicionado nas pastas. A velocidade de reação das pastas de cimento com o HCl foi estimada a partir dos parâmetros cinéticos obtidos pelo modelo de Avrami. Foram verificados valores de velocidade de reação da ordem de 10-3 mol.g.h-1 para a pasta padrão e da ordem de 10-5 mol.g.h-1 para as pastas aditivadas. Em geral, a análise dos parâmetros cinéticos indicou que o aumento da porcentagem de resina na composição das pastas reduziu a velocidade de reação e, aumentou a resistência dessas pastas ao ataque ácido.

A estabilidade térmica em função do pH para três formas da hemoglobina extracelular gigante do anelídeo Glossoscolex paulistus (HbGp), monitorada atraves de DSC, CD e absorção óptica, e estudada no presente trabalho. Estes estudos possibilitaram a determinação de parâmetros importantes do processo de desnaturação e dissociação da proteína oligomerica em pH ácido, neutro e alcalino. A HbGp se mostrou mais estável no pH ácido do que em pH neutro e alcalino. No meio alcalino a HbGp sofre dissociação oligomérica gerando subunidades tais como o dodecâmero, o trímero e o monômero. Além disso, as técnicas de DSC, dicroísmo circular (CD) e absorção óptica permitiram o monitoramento da desnaturação da estrutura protéica global, da estrutura secundária e do centro ativo da HbGp, em função da temperatura. Por DSC foi determinado que o mecanismo do processo de desnaturação térmica da HbGp é irreversível. As variações de entalpia calorimétrica, ΔHcal, e de van Hoff, ΔHvH, nas formas oxi-, meta- e cianometa-HbGp são bem distintas, em todos os pHs estudados, indicando que o processo de desnaturação é bastante complexo, sugerindo que o pico de transição deve ser composto por varias transições. A ordem de estabilidade apresentada pela HbGp em termos dos valores de temperatura de transição (Tm) foi a seguinte: cianometa- > oxi- > meta- no intervalo de pH 5,0 a 8,0. Os valores de ΔHcal no pH 7,0 para a oxi-HbGp, meta-HbGp e cianometa-HbGp foram de 25 ± 4, 20 ± 2 e 56 ± 4 MJ/mol, respectivamente. Os valores de energia de ativação (Ea) obtidos no pH 7,0 para a oxi- e cianometa-HbGp foram de 673 ± 99 e 780 ± 105 KJ/mol, e no pH 8,0 de 897 ± 106 e 850 ± 201 KJ/mol, respectivamente. Esses valores de energia de ativação são condizentes com os reportados na literatura para outras hemoglobinas. Nos estudos realizados por CD a oxi-HbGp forma hemicromo no pH 6,0 e 7,0, em temperaturas superiores a 40 °C, e se dissocia em meio alcalino. A oxi-HbGp apresenta temperatura crítica (Tc) nas regiões das hélices-α e do grupo heme praticamente idêntica nos vários pHs estudados. A cianometa-HbGp possui maior quantidade de estrutura secundária do que a oxi-HbGp, e maiores valores de temperatura crítica (Tc), sendo bem mais estável que a oxi-HbGp, assim como o observado por DSC. Por absorção óptica o comportamento térmico da HbGp é similar ao do CD, sendo observado ainda, além da formação de hemicromo, a presença de espécies pentacoordenadas no pH neutro e alcalino. / The thermal stability as a function of the pH, for three forms of the extracellular giant hemoglobin of the annelid Glossoscolex paulistus (HbGp) was monitored by DSC, CD and optical absorption in the present work. These studies allowed the determination of important parameters characterizing the denaturation and dissociation at acid, neutral and alkaline pH values. HbGp was shown to be more stable in acid pH as compared to neutral and alkaline pH values. In alkaline medium, HbGp presents oligomeric dissociation generating smaller subunits such as the dodecamer, the trimer and the monomer. Besides that, the techniques of the DSC, circular dichroism (CD) and optical absorption spectroscopy allowed to monitor, respectively, the denaturation of the global protein structure, of the secondary structure and of the active center of the hemoglobin, as a function of the temperature. By DSC it was determined that the mechanism of the thermal denaturation of the HbGp is irreversible. The variations of calorimetric and van Hoff enthalpies, in the oxy- and cyanomet-HbGp forms, are quite different, for all studied pH values, indicating that the process of denaturation is complex, characterized by a transition peak composed by several contributions. The order of stability presented by the HbGp in terms of the transition temperature values (Tm) was the following: cyanomet-> oxy- for pH from 5.0 to 8.0. The values of ΔHcal at pH 7.0 for the oxy-HbGp, met-HbGp and cianomet-HbGp were 25 ± 4, 20 ± 2 and 56 ± 4 MJ/mol, respectively. The activation energy values (Ea) obtained at pH 7.0 for the oxy- and cyanomet-HbGp were 673 ± 99 and 780 ± 105 KJ/mol, and at pH 8.0 they were 897 ± 106 and 850 ± 201 KJ/mol, respectively. Those energy values are consistent with data reported in the literature for other hemoglobins. In the studies carried out by CD for oxy-HbGp formation of hemichrome was observed at pH 6.0 and 7.0, at temperatures above 40 °C. In alkaline medium the oligomeric dissociation is observed. Oxy-HbGp presents critical temperatures (Tc), which are practically identical in the spectral regions of the polypeptide and of the heme groups for all studied pH values. The cyanomet-HbGp own larger quantity of secondary structure than oxy-HbGp, and higher values of critical temperatures (Tc), being more stable than oxy-HbGp, in agreemente with DSC data. Optical absorption spectroscopy shows thermal behavior of HbGp similar to that observed by CD. Besides the formation of the hemichrome species upon heating, the presence of penta-coordinate species at neutral and alkaline pH values was observed.

This work is focused on the study of interaction between hyaluronan and high-biocompatible amphiphilic molecules. Using fluorescent probe method, screening of the interaction of cationic lipid 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP), mixture of this cationic lipid with zwitterionic lipid, 1,2-dipalmitoyl-sn-glycero-3-phosphochloline (DPPC), with hyaluronan, both native and hydrophobically modified was carried out. Results showed the self-aggregation of DPPC and DPTAP independently on lipids ratio in the mixture and the interaction of DPTAP and DPPC/DPTAP aggregates with hyaluronan at specific ratio of DPTAP and hyaluronan concentration. Physical properties of formed membranes and the influence of cholesterol were also investigated at different DPPC and DPTAP concentration ratio. Last but not least, the non-ionic surfactant-DPPC systems were studied, namely, the size of the formed aggregates, the thermodynamics of solubilisation and the interaction with native hyaluronan.

This master thesis deals with the using of microcalorimetry in the study of hydration of biopolymers. Lactose has been selected together with the other biopolymers although it is not among biopolymers but disaccharides. Selected biopolymers are alginate, dextrane, chitosan and hyaluronan of two molecular weights. Lactose has been selected for these purposes mainly because it is a model example to determine whether or not the reaction to moisture between the other samples and the saturated salt solution occurs. The biopolymer hydration study, as opposed to the commonly used perfusion calorimetry method using the possibility of measuring with adjustable moisture has been used an isothermal microcalorimetry method where at two constant temperatures the reaction of the sample to the different moisture released by the saturated salt solution was monitored.

Over the last years, varieties of technologies for biofilm analysis were developed and established. They work on different principles and deliver information about biofilms on different information levels. In this work, chip-calorimetry was applied as an analytical tool that measures heat produced from biofilms. Any change of metabolism in biofilms is reflected by a changed heat flow. The heat, which is the integral of the heat flow vs. time, is quantitatively related to the growth stoichiometry of the biofilm, as described by the Hess’ Law. The heat flow is related to the growth kinetics with the reaction heat as proportionality factor. The results from the calorimetric measurement thus, deliver general information about growth stoichiometry and kinetics. The other interpretation of calorimetric results bases on the assumed proportionality between heat flow and oxygen consumption rate (- 460 kJ/mol ). This ratio is called oxycaloric equivalent. Because in case of aerobic growth the majority of oxygen is consumed in catabolic processes during the electron transport phosphorylation, calorimetry is assumed to provide information about the catabolic side of the metabolism. The newly developed chip-calorimeter applied in this work is much more suitable for biofilm studies compared to conventional microcalorimeters due to the flow-through design of the calorimetric chamber. The measurement of undisturbed growing biofilms and the comparison with conventional biofilm analysis tools (i.e. plate counts, confocal laser scanning microscopy (CLSM), and the determination of intermediates’ concentrations (e.g. ATP)) demonstrate the proper functionality of the calorimetric method and the related cultivation procedure by delivering measurement results in the range of literature values. However, when the biofilms were challenged with antimicrobial agents i.e. antibiotics, bacteriophage, and predatory bacteria, the calorimetric results surprisingly deviated from the reference analyses. By combining the results of the calorimetric and reference analyses, additional information about the antimicrobial effects on biofilms can be acquired. Combination of heat measurement and plate counts, which is one of the most conventional approaches, demonstrated that antimicrobials (especially the bactericidal acting kanamycin) could cause the loss of culturability while the cells were still metabolically active. The measurement of ATP content resulted in values out of the typical range, which indicated that antimicrobial treatments disturbed the cellular ATP regulation and the ATP concentration was no longer linearly correlated to the cell number. ATP measurements are therefore not suitable for antimicrobial susceptibility testing. The comparison of heat profiles with the biovolume determined by quantification of microscopic images shows an elevated cell specific heat production rate after the introduction of some antimicrobials (antibiotics and bacteriophage). In case of antibiotics, this can be explained as a consequence of the bacterial defense mechanisms. Most of the described defense mechanisms against antibiotics need biological energy and therefore drive the electron transport phosphorylation (ETP). In case of biofilm treatments with bacteriophage, the trigger of increasing ETP might be the synthesis of phage proteins, hull material, and genetic information molecules. In aerobic conditions, oxygen is used as terminal electron acceptor. Elevated ETP leads therefore to an increase in oxygen consumption, which correlates to the heat production using oxycaloric equivalent as a factor. These correlations explain the increase of cell specific heat productions as biofilms were challenged by antibiotics and bacteriophage. However, also a decrease of specific heat production was observed (in case of predatory bacteria). Here, the predatory bacteria activity caused various damages in host cells, including the interruption of ETP. With these experiments, chip-calorimetry was demonstrated as a promising complementary tool in biofilm research, which provides deeper insights about metabolic activity and alterations. It benefits from the noninvasive handling and the online, real-time measurement that allow the method to be applied for monitoring purposes. Furthermore, its miniaturized dimension allows easy integration in more complex analytic systems and also reduces experiment costs with minimal media/chemical consumption. This thesis also demonstrates the potential development of chip-calorimetry to be more suitable for routine analyses. The use of superparamagnetic beads as matrix to grow biofilms allows regulated transfer of biofilm samples into and from the measurement chamber. This was an initial step towards automation and higher-throughput analysis. One further outcome of the thesis is based on the highly interesting fact about the elevated heat production rate of the host cells induced by the phage infection observed in the chip- calorimetric experiments. The volume specific detection limit of the chip-calorimeter is lower compared to a commercial microcalorimeter. Thus, the infection effect of phages was additionally measured in microcalorimeter to get better quantitative information about the thermal effect of the infection. The results showed that the immediate heat increase after the addition of phage into the solution of the host cells appeared to be quantitatively related to the infection factor, MOI (Multiplicity of Infection). Unfortunately, microcalorimetric measurements in closed ampoules are often subjected to the oxygen limitation. Thus, this problem of microcalorimetric measurement has been addressed. The combination of experimental results and mathematical modeling showed that the rate of metabolism in the static ampoules is defined by the diffusion rate of oxygen into media. This factor has to be considered while designing biological experiments in closed calorimetric measuring chambers and interpreting the calorimetric results for their biological meaning. Some possible solutions to overcome the oxygen bioavailability problem are e.g. to design the experiments with low biomass, or by using media with elevated density to float the biomass at the interface to air and thus to reduce the diffusion path.

Afin de répondre aux demandes des industriels de nouveaux matériaux poreux sont testés pour de nouvelles applications ou pour améliorer les procédés existants. Les adsorbants de types Metal Organic Frameworks(MOFs) ont des structures construites à partir d'unités inorganiques reliées entre elles par des ligands organiques. La possibilité de varier ces deux entités, offre une grande diversité de structures avec des cavités de tailles contrôlées. L'objectif de cette thèse a été d'évaluer les performances des MOFs pour l'adsorption de composés organiques et de comprendre les mécanismes d'adsorption. Les deux problématiques sélectionnées sont d'intérêt pour l'industrie pétrochimique. La séparation du para-xylène des autres isomères du xylène et de l'éthylbenzene, permets de répondre à la demande de matière première pour la synthèse du polytéréphtalate d'éthylène. L'adsorption des composés azotés et soufrés (teneur fixée par des législations), permets la purification de carburants. Notre étude thermodynamique est basée sur la réalisation d'isothermes d'adsorption et la détermination d'enthalpies d'adsorption par microcalorimétrie en phase liquide. L'adsorption des vapeurs des xylènes purs a été étudiée pour comprendre l'effet du solvant. Une grande variété de comportement a été observée selon les structures des MOFs. Nous avons par exemple mis en évidence l'effet de l'empilement moléculaire des isomères du xylène sur la sélectivité des MOFs. Nous avons démontré que la flexibilité des MOFs intervient sur les interactions au cours de l'adsorption des xylènes. Nous avons mis en évidence une sélectivité des MOFs possédant un centre métallique insaturé en faveur des composés azotés / In order to meet the industrials requirements, new porous materials are tested for new applications or to improve existing processes. The Metal Organic Frameworks (MOFs) are hybrids crystalline compounds made up of clusters (or chains) of metal ions coordinated by organic linkers to form three dimensional structures. The ability to vary these two entities offers to MOFs a wide variety of organized structure with pore sizes controlled. The aim of this thesis was to evaluate the MOF performances for the adsorption of organic compounds and also understand the related adsorption mechanism. The two selected issues are of interest for the petrochemical industry. The para-xylène separation from the other xylene isomers (ortho, meta) and ethylbenzene, allows to meet the demand for raw materials in the polyethylene terephthalate (PET) synthesis. The nitrogen and sulphur compounds adsorption allows the purification of fuels (sulphur content set by legislation). We present a thermodynamic study of adsorption from solution based on the determination of adsorption isotherms by depletion method and adsorption enthalpies by microcalorimetry. The pure xylenes vapour adsorption was also studied to understand the solvent effect. A wide variety of behaviour has been observed depending on MOF structures. For example we demonstrated the effect of xylene isomers molecular packing on MOF selectivity. Furthermore we have shown that the MOF structure flexibility influence the interactions involved during xylene isomers adsorption. We also demonstrated that MOF with unsaturated metallic centres present selectivity for nitrogen compounds (Lewis acid/base).

La synthèse de nitriles gras à partir de ressources renouvelables est un domaine qui attire depuis quelques temps les industries de la parfumerie, des polymères et des biocarburants pour avion. Ce travail de thèse s’est plus particulièrement intéressé à réduire de 100°C la température de travail pour les procédés en phase liquide et gaz, au moyen de catalyseurs plus efficaces. Le procédé en phase liquide a été étudié en terme de catalyse homogène et les formes actives à base de zinc ou indium ont été plus particulièrement détaillées ; des conditions ont été établies pour obtenir une réduction de 50°C de la température de travail. Le procédé en phase gaz a été étudié en terme de catalyse hétérogène, les catalyseurs obtenus ou synthétisés étant caractérisés par microcalorimétrie d’adsorption ; des corrélations entre la conversion de l’ester et l’acidité du lit catalytique ont été trouvées à 300°C, et des conditions expérimentales ont été développées pour obtenir une conversion totale à une température réduite de 100°C sur des catalyseurs choisis / The production of fatty nitriles from renewable sources has lately become attractive for the perfume, polymer and aviation biofuel industry. The present work investigated both liquidand gas-phase processes in the aim of developing catalysts working at 200°C, this is 100°C lower than the state-of-the-art. Homogeneous catalysis was described with zinc and indium based species for the liquid-phase process, succeeding in reducing by 50°C the operating temperature. Heterogeneous catalysts with acid-base features were characterized by adsorption calorimetry and tested in the gas-phase process, leading to correlations between acidity and ester conversion at 300°C, while conditions were found on selected catalysts in order for the process to perform the complete conversion of esters into nitriles at 200°C

Die effiziente Nutzung der begrenzten Ressourcen auf der Erde ist ein entscheidender Faktor für ein nachhaltiges Leben. Die Entwicklung besserer Katalysatoren kann dabei einen wesentlichen Beitrag leisten. Ein umfassendes Verständnis der katalytischen Reaktivität würde es ermöglichen, spezifische katalytische Eigenschaften zu konzipieren und zu kontrollieren. In diese Arbeit wurde die Korrelation der Katalysatoroberfläche mit den Adsorptionswärmen von Molekülen aus der Gasphase untersucht. Insbesondere wurde die Adsorptionwärme von CO auf Pd-Partikeln als Funktion der Partikelgröße mittels gut charakterisierte Modelkatalysatorsysteme, eisenoxidgeträgerte Pd-Partikel, und UHV-Einkristalladsorptionskalorimetrie bestimmt. Es konnte die langjährige Kontroverse, wie sich die Adsorptionswärme von CO auf Pd mit der Partikelgröße ändert, aufgelöst werden. Die Adsorptionswärmen wurden für CO auf geträgerten Pd-Partikeln mit mittleren Größen zwischen 1.8 und 8 nm, sowie Pd(111) untersucht. Es zeigte sich dabei, dass die Anfangsadsorptionsenergie mit abnehmender Partikelgröße kleiner wird. Das Mikrokalorimeterexperiment besteht aus einer Präparationskammer und einer Kalorimetriekammer, die sowohl die Präparation und Charakterisierung von geträgerten metallischen Nanopartikeln, als auch Adsorptionsenergiemessungen ermöglichen. Das Kalorimeter basiert auf dem Design von Campbell et al. und nutzt eine pyroelektrische Folie als Detektor. Es wurden Verbesserungen in Bezug auf Ausrichtung, Temperaturstabilität und Vibrationsisolation implementiert. Ein gepulster Molekularstrahl wird eingesetzt, um die Oberfläche einem stabilen und homogenen Fluss von Gasphasenmolekülen auszusetzten. Desweiteren erlaubt ein In situ Reflektivitätsmessaufbau die Bestimmung der optischer Eigenschaften von Modelkatalysatoroberflächen, was entscheidend für eine akkurate Energiekalibration des Kalorimeters ist. / The efficient use of the limited resources on earth is a critical factor to sustainable life. The development of better catalysts can make a significant contribution. Complete understanding of the catalytic activity would facilitate the design and control of specific catalytic processes. In this work, the correlation of the catalyst structure and the heats of adsorption of gas-phase particles were investigated. In particular, the heat of adsorption for CO on Pd particles was determined as a function of particle size, using a well-characterized model catalyst system, Pd particles supported on an iron oxide film, and UHV single crystal adsorption microcalorimetry. It was possible to resolve the longstanding controversy, how the heat of adsorption of CO on Pd particles changes with particle size. The heat of adsorption for CO on Pd particles was studied on supported Pd particles with a mean diameter of 1.8 to 8 nm and Pd(111). The initial heat of adsorption was found to decrease with decreasing particle size. The completed microcalorimeter experiment comprises a preparation chamber and a calorimetry chamber, providing all means to prepare and characterize oxide supported metal nanoparticles and to perform adsorption energy measurements. The calorimeter is based on the design of Campbell et al., using a pyroelectric ribbon as a detector. Improvements with respect to alignment, temperature stability, and vibration isolation were implemented. A pulsed molecular beam is used to expose the surface to a stable and homogeneous flux of gas-phase molecules. Further, a dedicated in situ reflectivity measurement setup allows optical characterization of the model catalyst surfaces, which is crucial for an accurate energy calibration of the calorimeter.

Um die Korrelation zwischen Partikelgröße und Reaktivität von Pd Nanopartikeln auf Eisenoxid zu untersuchen wurde die experimentelle Methode Einkristalladsorptionskalorimetrie mit der Präparation von Modellsystemen kombiniert. Da diese Systeme mit mikroskopischen Methoden untersucht wurden, liegen detaillierte strukturelle Informationen vor. Es konnte gezeigt werden, dass die Adsorptionsenergie auf 3.4 nm großen Pd Nanopartikeln um 69 kJ/mol höher ist als auf Pd(111). Dieser Effekt resultiert aus der Änderung des Adsorptionsplatzes von Facettenplätzen auf Pd(111) zu Kantenplätzen auf Pd Nanopartikeln. Die Änderung der Partikelgröße im Bereich 3.4 nm - 1.9 nm führt zu einer Verringerung der Adsorptionsenergie um 70 kJ/mol. Eine Reduktion der Adsorptionsenergie auf kleineren Nanopartikeln wurde auch für CO gemessen. Die Differenz in der Pd-O Bindungsenergie zwischen den verschiedenen Systemen verringert sich bei erhöhter Adsorbatbedeckung. Die Anzahl adsorbierter Sauerstoffatome auf frisch präparierten Pd Nanopartikeln bei 300 K ist um drei bis vier mal höher als die Anzahl an Sauerstoffatomen welche Pd Oberflächenplätze sättigen können. Diese Beobachtung kann mit Sauerstoffdiffusion in die Nanopartikel oder in den Träger erklärt werden. Die Wechselwirkung zwischen Sauerstoff und CO auf Pd(111) und Pd Nanopartikeln verschiedener Größen wurde als Funktion der Bedeckung studiert. Aufgrund der CO-O Wechselwirkung verringert sich die CO Adsorptionsenergie um ~40 kJ/mol auf sauerstoffvorbedeckten Pd(111) und Pd Nanopartikeln der Größen 2.9 nm und 3.4 nm. / To determine the correlation between the particle size and the reactivity of Pd nanoparticles, which are supported on iron oxide, the experimental method single crystal adsorption calorimetry has been combined with the preparation of model systems. Detailed structural information on the supported systems is available from previous structural studies. It was found that the oxygen adsorption energy is 69 kJ/mol higher on 3.4 nm sized Pd nanoparticles compared to Pd(111) due to a change of the local adsorption site from threefold hollow to low coordinated sites. A reduction of the particle size in the range 3.4 nm - 1.9 nm was found to lead to a decrease of the adsorption energy by 70 kJ/mol. A reduction of the adsorbate binding energy has also been found for CO. The difference in the Pd-O binding energy between the different systems decreases with increasing coverage. It was demonstrated that the number of adsorbed oxygen atoms on freshly prepared Pd nanoparticles at 300 K is three to four times higher than the amount of oxygen atoms which saturate the Pd surface sites. This observation can be explained with oxygen diffusion either into the nanoparticles or into the support. The interaction between oxygen and CO has been studied on Pd(111) and Pd nanoparticles of different sizes as a function of the coverage. Due to CO-O interaction, the CO adsorption energy is reduced by ~40 kJ/mol on oxygen precovered Pd(111) and Pd nanoparticles of 2.9 nm and 3.4 nm.