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Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes
(2017)
Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures.
In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges.
These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure.
Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1.
In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.
Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.
Gamification als Motivator in der Sprachtherapie bei Menschen mit intellektueller Beeinträchtigung
(2021)
Gen 32,23-32
(2022)
Generated-X LMS (GXLMS)
(2021)
The quality of the reference signal is essential for the adaptation process of an LMS or one of its derivatives. The reference signal affects the stability, the convergence rate and the maximum achievable attenuation. Since the error signal and the control signal are available as numerical values in the algorithm for the LMS, the reference signal can be calculated from both signals. The error signal is the interference between the control signal and the reference signal. This interference of the control signal and the reference signal can be noted mathematically as a simple addition. It is therefore possible to deduce the reference signal from a known error signal and control signal. This approach is the basis of the generated-x LMS (GxLMS) developed by us. It calculates the reference signal itself without having to rely on an externally supplied reference signal. The advantages of the GxLMS are primarily in fields where the reference signal is difficult or impossible to detect. For example, the detection of the reference signal can be problematic due to design reasons or measurement technology. For example, flow noise could have a negative effect on an acoustic detection of the reference signal. However, the calculation of the reference signal in the GxLMS represents a further feedback signal path, which affects the stability of the algorithm as a whole. Based on the theoretical principles mathematically sufficient convergence conditions can be formulated taking into account the delays existing in the signal paths. The experimental testing took place on an acoustic duct with monofrequency disturb signals. Since the use of an efficient design of experiments (DoE) could be excluded, the measurement was designed as parameter variation (one factor at time) and therefore very time-consuming. The theoretical background of the GxLMS as well as the results from the experiments are presented.
Digitalisation in industry – also called “Industry 4.0” – is seen by numerous actors as an opportunity to reduce the environmental impact of the industrial sector. The scientific assessments of the effects of digitalisation in industry on environmental sustainability, however, are ambivalent. This cumulative dissertation uses three empirical studies to examine the expected and observed effects of digitalisation in industry on environmental sustainability. The aim of this dissertation is to identify opportunities and risks of digitalisation at different system levels and to derive options for action in politics and industry for a more sustainable design of digitalisation in industry. I use an interdisciplinary, socio-technical approach and look at selected countries of the Global South (Study 1) and the example of China (all studies). In the first study (section 2, joint work with Marcel Matthess), I use qualitative content analysis to examine digital and industrial policies from seven different countries in Africa and Asia for expectations regarding the impact of digitalisation on sustainability and compare these with the potentials of digitalisation for sustainability in the respective country contexts. The analysis reveals that the documents express a wide range of vague expectations that relate more to positive indirect impacts of information and communication technology (ICT) use, such as improved energy efficiency and resource management, and less to negative direct impacts of ICT, such as electricity consumption through ICT. In the second study (section 3, joint work with Marcel Matthess, Grischa Beier and Bing Xue), I conduct and analyse interviews with 18 industry representatives of the electronics industry from Europe, Japan and China on digitalisation measures in supply chains using qualitative content analysis. I find that while there are positive expectations regarding the effects of digital technologies on supply chain sustainability, their actual use and observable effects are still limited. Interview partners can only provide few examples from their own companies which show that sustainability goals have already been pursued through digitalisation of the supply chain or where sustainability effects, such as resource savings, have been demonstrably achieved. In the third study (section 4, joint work with Peter Neuhäusler, Melissa Dachrodt and Marcel Matthess), I conduct an econometric panel data analysis. I examine the relationship between the degree of Industry 4.0, energy consumption and energy intensity in ten manufacturing sectors in China between 2006 and 2019. The results suggest that overall, there is no significant relationship between the degree of Industry 4.0 and energy consumption or energy intensity in manufacturing sectors in China. However, differences can be found in subgroups of sectors. I find a negative correlation of Industry 4.0 and energy intensity in highly digitalised sectors, indicating an efficiency-enhancing effect of Industry 4.0 in these sectors. On the other hand, there is a positive correlation of Industry 4.0 and energy consumption for sectors with low energy consumption, which could be explained by the fact that digitalisation, such as the automation of previously mainly labour-intensive sectors, requires energy and also induces growth effects. In the discussion section (section 6) of this dissertation, I use the classification scheme of the three levels macro, meso and micro, as well as of direct and indirect environmental effects to classify the empirical observations into opportunities and risks, for example, with regard to the probability of rebound effects of digitalisation at the three levels. I link the investigated actor perspectives (policy makers, industry representatives), statistical data and additional literature across the system levels and consider political economy aspects to suggest fields of action for more sustainable (digitalised) industries. The dissertation thus makes two overarching contributions to the academic and societal discourse. First, my three empirical studies expand the limited state of research at the interface between digitalisation in industry and sustainability, especially by considering selected countries in the Global South and the example of China. Secondly, exploring the topic through data and methods from different disciplinary contexts and taking a socio-technical point of view, enables an analysis of (path) dependencies, uncertainties, and interactions in the socio-technical system across different system levels, which have often not been sufficiently considered in previous studies. The dissertation thus aims to create a scientifically and practically relevant knowledge basis for a value-guided, sustainability-oriented design of digitalisation in industry.
Gruppierung von Daten
(2022)
Dieser Beitrag beinhaltet einen Vergleich zwischen den Methoden der Topologischen Datenanalyse (TDA) und statistischen Clusterverfahren bei der Gruppierung von Daten. Es werden Gemeinsamkeiten und Unterschiede bei der Bildung der Cluster und Zuordnung der statistischen Einheiten identifiziert. Hierzu werden zwei empirische Datensätze aus der Biologie und Medizin herangezogen.
Zusammengefasst haben sich die Verfahren der TDA als ein praktikables Werkzeug bei der Gruppierung von Objekten erwiesen. Vor allem mit dem Mapper-Algorithmus konnten adäquate Cluster erkannt werden. Beim Iris Flower-Datensatz hat die TDA ähnliche Ergebnisse wie die Clusteranalyse erzielt. Der Heart Disease-Datensatz war schwieriger zu behandeln. Die genutzten clusteranalytischen Verfahren waren nicht geeignet, die beiden Gruppen von Patienten korrekt zu identifizieren. Im Vergleich zu den Standardverfahren der Clusteranalyse zeigte sich eine leichte Überlegenheit der topologischen Verfahren.
The concept of hydrologic connectivity summarizes all flow processes that link separate regions of a landscape. As such, it is a central theme in the field of catchment hydrology, with influence on neighboring disciplines such as ecology and geomorphology. It is widely acknowledged to be an important key in understanding the response behavior of a catchment and has at the same time inspired research on internal processes over a broad range of scales. From this process-hydrological point of view, hydrological connectivity is the conceptual framework to link local observations across space and scales.
This is the context in which the four studies this thesis comprises of were conducted. The focus was on structures and their spatial organization as important control on preferential subsurface flow. Each experiment covered a part of the conceptualized flow path from hillslopes to the stream: soil profile, hillslope, riparian zone, and stream.
For each study site, the most characteristic structures of the investigated domain and scale, such as slope deposits and peat layers were identified based on preliminary or previous investigations or literature reviews. Additionally, further structural data was collected and topographical analyses were carried out. Flow processes were observed either based on response observations (soil moisture changes or discharge patterns) or direct measurement (advective heat transport). Based on these data, the flow-relevance of the characteristic structures was evaluated, especially with regard to hillslope to stream connectivity.
Results of the four studies revealed a clear relationship between characteristic spatial structures and the hydrological behavior of the catchment. Especially the spatial distribution of structures throughout the study domain and their interconnectedness were crucial for the establishment of preferential flow paths and their relevance for large-scale processes. Plot and hillslope-scale irrigation experiments showed that the macropores of a heterogeneous, skeletal soil enabled preferential flow paths at the scale of centimeters through the otherwise unsaturated soil. These flow paths connected throughout the soil column and across the hillslope and facilitated substantial amounts of vertical and lateral flow through periglacial slope deposits.
In the riparian zone of the same headwater catchment, the connectivity between hillslopes and stream was controlled by topography and the dualism between characteristic subsurface structures and the geomorphological heterogeneity of the stream channel. At the small scale (1 m to 10 m) highest gains always occurred at steps along the longitudinal streambed profile, which also controlled discharge patterns at the large scale (100 m) during base flow conditions (number of steps per section). During medium and high flow conditions, however, the impact of topography and parafluvial flow through riparian zone structures prevailed and dominated the large-scale response patterns.
In the streambed of a lowland river, low permeability peat layers affected the connectivity between surface water and groundwater, but also between surface water and the hyporheic zone. The crucial factor was not the permeability of the streambed itself, but rather the spatial arrangement of flow-impeding peat layers, causing increased vertical flow through narrow “windows” in contrast to predominantly lateral flow in extended areas of high hydraulic conductivity sediments.
These results show that the spatial organization of structures was an important control for hydrological processes at all scales and study areas. In a final step, the observations from different scales and catchment elements were put in relation and compared. The main focus was on the theoretical analysis of the scale hierarchies of structures and processes and the direction of causal dependencies in this context. Based on the resulting hierarchical structure, a conceptual framework was developed which is capable of representing the system’s complexity while allowing for adequate simplifications.
The resulting concept of the parabolic scale series is based on the insight that flow processes in the terrestrial part of the catchment (soil and hillslopes) converge. This means that small-scale processes assemble and form large-scale processes and responses. Processes in the riparian zone and the streambed, however, are not well represented by the idea of convergence. Here, the large-scale catchment signal arrives and is modified by structures in the riparian zone, stream morphology, and the small-scale interactions between surface water and groundwater. Flow paths diverge and processes can better be represented by proceeding from large scales to smaller ones. The catchment-scale representation of processes and structures is thus the conceptual link between terrestrial hillslope processes and processes in the riparian corridor.
Die Fachtagungen HDI (Hochschuldidaktik Informatik) beschäftigen sich mit den unterschiedlichen Aspekten informatischer Bildung im Hochschulbereich. Neben den allgemeinen Themen wie verschiedenen Lehr- und Lernformen, dem Einsatz von Informatiksystemen in der Hochschullehre oder Fragen der Gewinnung von geeigneten Studierenden, deren Kompetenzerwerb oder auch der Betreuung der Studierenden widmet sich die HDI immer auch einem Schwerpunktthema.
Im Jahr 2021 war dies die Berücksichtigung von Diversität in der Lehre. Diskutiert wurden beispielsweise die Einbeziehung von besonderen fachlichen und überfachlichen Kompetenzen Studierender, der Unterstützung von Durchlässigkeit aus nichtakademischen Berufen, aber auch die Gestaltung inklusiver Lehr- und Lernszenarios, Aspekte des Lebenslangen Lernens oder sich an die Diversität von Studierenden adaptierte oder adaptierende Lehrsysteme.
Dieser Band enthält ausgewählte Beiträge der 9. Fachtagung 2021, die in besonderer Weise die Konferenz und die dort diskutierten Themen repräsentieren.