1,097 research outputs found

    The interfacial contact of Cu/ZnO, and doped ZnO – different routes to modify the electronic, structural, and catalytic properties

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    In this thesis, Cu/ZnO catalysts active in the reduction of CO2 were investigated using operando conductivity measurements. These measurements made use of a contact-free microwave cavity perturbation technique (MCPT). For the CO2 reduction in methanol synthesis or the reverse water-gas shift reaction, the commonly used catalyst is Cu/ZnO/Al2O3 with high content of Cu. However, the exact electronic processes occurring between the ZnO support and the copper particles under reaction conditions are yet to be completely understood. Furthermore, the relevance and nature of the interface between the catalyst components Cu and ZnO are to be further studied. To contribute to this research, work regarding the structural, electronic, and catalytic properties of Cu/ZnO samples is presented, focusing on the interaction of Cu and ZnO. To reduce the system’s complexity as well as facilitate the use of additional characterisation techniques, often model catalysts are employed. To achieve the above-mentioned aims, binary Cu/ZnO samples were synthesised, where the loading of Cu was varied and kept low. Furthermore, different degrees of interaction were achieved by employing two synthetic approaches, namely impregnation and coprecipitation. Both the low Cu content as well as the chosen synthetic techniques are common strategies in the generation of Cu/ZnO model catalysts. The two synthesis methods were aimed at the generation of two very different precursors: while impregnation ideally leads to precursors with fully separated CuO and ZnO phases, coprecipitated samples were found to contain Cu incorporated into the ZnO lattice. Conversely, by activating the catalysts, a portion of the Cu contained in the samples generated by impregnation can migrate into the ZnO lattice, while some of the incorporated Cu in the coprecipitated samples can be extracted and form metallic Cu particles. A thorough characterisation of the samples enabled the investigation of their structural, electronic, and catalytic properties. By measuring the catalytic activity of these samples simultaneously with the MCPT conductivity, the electronic and catalytic properties can be related. A further aim of this investigation was to assess the suitability of the samples to function as models for the industrially applied catalytic system. By using MCPT, the conductivity of the samples was measured operando in the reverse water-gas shift reaction. Interestingly, this revealed a qualitatively different behaviour of the samples generated by the distinct synthetic methods. While the CO production rate increased for both types of sample upon increasing the proportion of hydrogen in the reaction feed, the conductivity of samples generated by impregnation increased simultaneously, but the conductivity of the coprecipitated samples was found to decrease instead. This striking difference points at very different interactions between Cu and ZnO in these two sorts of samples. Further characterisation revealed that the samples differ not only as a consequence of their synthetic history, but also depending on their Cu content. The catalytic performance, e.g., the apparent activation energies of the samples towards the rWGS reaction, was found to differ significantly from the values expected for binary Cu/ZnO catalysts with industrially relevant Cu content. This shows that these samples with low Cu loadings are not applicable as model catalysts for the industrial system and highlights the importance of ensuring the comparability of model and technical system before transferring conclusions from one to the other. The reversible incorporation of Cu into the ZnO lattice, even when the sample is synthesised by impregnation, was further studied. For this, a sample with a Cu content below the dissolution limit of Cu in ZnO was characterised in more detail. This highlighted the contribution of small clusters and the modification of the ZnO structure by Cu ions. It was revealed that in its oxidised state, the sample contained isolated Cu2+ species in the ZnO lattice. These Cu2+ ions get reduced when a hydrogen containing gas feed is applied, which was demonstrated using inert transfer EPR and in situ MCPT measurements. This effect was also shown to be reversible by reoxidation of the sample. Besides Cu, many other dopants are known to modify the properties of ZnO. Using fluorine as a modifier, the structural and electronic properties of ZnO as well as the way it interacts with applied gas phases were investigated. The fluorine-modification of polycrystalline ZnO was notably achieved by the application of gaseous fluorine and could be controlled by the variation of the treatment parameters such as the F2 partial pressure. Two fluorinated samples with differing F contents were compared to pristine ZnO. Of these, the sample with lower F content was found to consist of a homogeneous distribution of fluorine as a dopant in ZnO, while the sample treated at a higher F2 partial pressure contained ZnF2 as a by-phase. The conductivity of the samples measured using MCPT revealed that the sample with less F content had a stronger response to the application of a hydrogen containing gas phase compared to pure ZnO or the sample containing the ZnF2 by-phase, indicating that fluorine doping of ZnO positively affects the ability of the material to activate and chemisorb H2. This finding can have extensive implications for the use of fluorine-doped ZnO in catalytic applications such as CO2 reduction, which will be interesting to explore in the future

    Serotonin and Social Competency

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    Despite the fact that serotonergic drugs are called upon to treat a myriad of psychopathologies, the effect of serotonin on core behaviors and cognitive abilities are poorly understood. This is especially true for cognitive functions which underlie socially competent behavior. This dissertation aims to increase understanding of the role of serotonin in other monitoring and social competency throughout development. Species of primates, including humans, that live in complex social environments must allocate extensive cognitive resources to monitor conspecifics. However, they must balance the benefits of gathering social information with the need to monitor their non-social environments. Social monitoring strategies vary across species, populations of the same species, and even within populations. This variation seems to be dependent upon the amount of social monitoring that is required for an individual to avoid conflict and maintain its dominance rank. The serotonergic system has a history connecting it to socially competent behavior, like other monitoring, although its causal role is not understood. Therefore, better understanding how increasing concentrations of serotonin impact other monitoring behaviors will clarify serotonin’s role in psychopathology and may help clinicians predict how serotonergic interventions will influence pathologies. Furthermore, better understanding how the relationship between early life stress and serotonin impacts social competency will improve our understanding of psychiatric disorders and help develop novel interventions.In Chapter 2 of the present dissertation, the role of serotonin in the allocation of attention to social images, a core component of social monitoring, was studied by assaying rhesus macaques’ unconstrained looking to social and non-social stimuli using a free viewing paradigm (Dal Monte et al., 2014). We used a quantitative, repeated, within-subject, design to test how increasing central concentrations of serotonin would impact social looking behavior. Importantly, we found that increasing central concentrations of serotonin with its direct precursor, 5-Hydroxytrypotophan (5-HTP), modulated looking duration relative to individual differences in looking. 5-HTP decreased looking duration in animals with high baseline attention, but increased looking duration in low baseline attention animals. 5-HTP’s effects were also reflected in how engaged individuals were in the task and how they allocated attention to salient facial features—the eyes and mouth—of stimulus animals. Individual differences seem to be based in serotonergic function. Compared to low baseline animals, high baseline looking animals exhibited higher baseline concentrations of 5-HTP and serotonin and lower 5-HIAA to serotonin ratios indicating central serotonergic functioning may underlie and predict variation in serotonin’s effects on cognitive operation. The individual differences in 5-HTPs effects on looking increased our interest in serotonin’s role in balancing the costs and benefits of monitoring others (Weinberg‐Wolf and Chang, 2019). In Chapter 3, we tested the effect of 5-HTP on macaque’s abilities to flexibly switch between two actions: orienting to faces, or, at other times, inhibiting orientation towards faces. Critically, we found that 5-HTP also only impaired the ability to inhibit orientation to faces, but did not impact inhibition performance on trials with control images. It also seems that 5-HTP made animals less flexible, causing them to persevere in actions more. Furthermore, 5-HTP’s effects on performance are likely due to changes in arousal and motivation state as 5-HTP’s impairments were linked to increased reaction time, animals taking longer to initiate trials, and a constricted pupil. Serotonin is also implicated in the development of psychiatric disorders, especially Autism Spectrum Disorders. In Chapter 4, we examined the relationship between infant serotonergic function, assayed via CSF concentrations of 5-HIAA, and the acquisition of social status. We found that neonatal (11-32 days) 5-HIAA concentrations positively predict eventual, acquired, social rank. Furthermore, this relationship was strongest amongst macaques who had been reared by their mothers compared to those reared without mothers. In addition, mother reared infants exhibited higher concentrations of CSF 5-HIAA and attained higher social rank than their peers. These finds support the relationship between serotonin and early social experience in socially competent development. By considering the findings presented in Chapters 2, 3 and 4, we discuss, in Chapter 5, the role of serotonin in competent social monitoring and its development. We also discuss a plausible evolutionary explanation for variability in other monitoring behaviors and for variable effects of serotonin on cognition and behavior. Finally, we consider future directions researchers should explore as the field progresses

    Environmental Apocalypse in Richard Wagner’s Das Rheingold

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    48 pagesFears concerning the destruction of the natural world and the imminence of an environmental apocalypse came to fruition long before the realization of global climate change. In fact, as early as 1848, Richard Wagner pondered the end of nature when he wrote the first drafts of what became his four-part opera cycle, Der Ring des Nibelungen (The Ring). In this thesis, I will examine how the first music drama in this cycle, Das Rheingold, functions as a vision of environmental apocalypse

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    Gaps in Protoplanetary Disks as Signatures of Planets: I. Methodology and Validation

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    We examine the observational consequences of partial gaps being opened by planets in protoplanetary disks. We model the disk using a static alpha-disk model with detailed radiative transfer, parametrizing the shape and size of the partially cleared gaps based on the results of hydrodynamic simulations. Shadowing and illumination by stellar irradiation at the surface of the gap leads to increased contrast as the gap trough is deepened by shadowing and cooling and the far gap wall is puffed up by illumination and heating. In calculating observables, we find that multiple scattering is important and derive an approximation to include these effects. A gap produced by a 200 M_Earth (70 M_Earth) planet at 10 AU can lower/raise the midplane temperature of the disk by up to ~-25/+29% (~-11/+19%) by shadowing in the gap trough and illumination on the far shoulder of the gap. At the distance of Taurus, this gap would be resolvable with ~0.01" angular resolution. The gap contrast is most significant in scattered light and at thermal continuum wavelengths characteristic of the surface temperature, reducing or raising the surface brightness by up to order of magnitude. Since gaps sizes are correlated to planet mass, this is a promising way of finding and determining the masses of planets embedded in protoplanetary disks.Comment: 11 pages, 9 figures. Accepted to Ap

    Ziviles Krisenmanagement der EU: den Ambitionen mĂŒssen Taten folgen

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    Europas Sicherheitsumfeld verĂ€ndert sich drastisch. Damit steht auch das zivile Krisenmanagement der EU an einem Scheideweg. Die aktuellen Herausforderungen können weder von einzelnen Mitgliedstaaten noch mit ausschließlich militĂ€rischen Mitteln bewĂ€ltigt werden. Ein neuer Prozess auf EU-Ebene bietet den Mitgliedstaaten die Möglichkeit, das zivile Krisenmanagement zu verbessern und zentrale Fragen auf konzeptioneller und institutioneller Ebene zu beantworten

    IL-17C contributes to NTHi-induced inflammation and lung damage in experimental COPD and is present in sputum during acute exacerbations

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    Neutrophilic inflammation results in loss of lung function in chronic obstructive pulmonary disease (COPD). Gram-negative bacteria, such as nontypeable Haemophilus influenzae (NTHi), trigger acute exacerbations of COPD (AECOPD) and contribute to chronic lung inflammation. The pro-inflammatory cytokine interleukin-17C (IL-17C) is expressed by airway epithelial cells and regulates neutrophilic chemotaxis. Here, we explored the function of IL-17C in NTHi- and cigarette smoke (CS)-induced models of COPD. Neutrophilic inflammation and tissue destruction were decreased in lungs of IL-17C-deficient mice (Il-17c-/-) chronically exposed to NTHi. Numbers of pulmonary neutrophils were decreased in Il-17c-/- mice after acute exposure to the combination of NTHi and CS. However, Il-17c-/- mice were not protected from CS-induced lung inflammation. In a preliminary patient study, we show that IL-17C is present in sputum samples obtained during AECOPD and associates with disease severity. Concentrations of IL-17C were significantly increased during advanced COPD (GOLD III/IV) compared to moderate COPD (GOLD I/II). Concentrations of IL-17A and IL-17E did not associate with disease severity. Our data suggest that IL-17C promotes harmful pulmonary inflammation triggered by bacteria in COPD
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