Often synthetic graphene requires transfer onto an arbitrary substrate prior to use because the substrate it was originally synthesized on is inappropriate for either electrical measurement or characterization. While a variety of routes have been developed they are substrate dependant and often involve the use of harsh treatments. Here we present a facile and cheap route that can be applied to graphene over any substrate. This universal transfer route is based on a wet chemical reaction producing gaseous species which can intercalate between the substrate and the graphene and thus gently delaminate the two.

Here we propose, for the first time, a new and green ethanol-thermal reaction method to synthesize highquality and pure thiophene–sulfur doped reduced graphene oxide (rGO), which establishes an excellent platform for studying sulfur (S) doping effects on the physical/chemical properties of this material. We have quantitatively demonstrated that the conductivity enhancement of thiophene–S doped rGO is not only caused by the more effective reduction induced by S doping, but also by the doped S atoms, themselves. Furthermore, we demonstrate that the S doping is more effective in enhancing conductivity of rGO than nitrogen (N) doping due to its stronger electron donor ability. Finally, the dye-sensitized solar cell (DSCC) employing the S-doped rGO/TiO₂ photoanode exhibits much better performance than undoped rGO/TiO₂, N-doped rGO/TiO₂ and TiO₂ photoanodes. It therefore seems promising for thiophene–S doped rGO to be widely used in electronic and optoelectronic devices.

Die Untersuchung von Zuverlässigkeitsnetzwerken geht bis zum frühen 20. Jahrhundert zurück. Diese Arbeit beschäftigt sich hauptsächlich mit der Zweifach-Kantenzusammenhangswahrscheinlichkeit. Zuerst werden einfache Algorithmen, die aber für allgemeine Graphen nicht effizient sind, gezeigt, zusammen mit Reduktionen. Weiterhin werden Charakterisierungen von Kanten bezogen auf Wegemengen gezeigt. Neue strukturelle Bedingungen für diese werden vorgestellt. Neue Ergebnisse liegen ebenfalls für Graphen hoher Dichte und Symmetrie vor, genauer für vollständige und vollständig bipartite Graphen. Naturgemäß sind Graphen von geringer Dichte hier einfacher in der Untersuchung. Die Arbeit zeigt Ergebnisse für Kreise, Räder und Leiterstrukturen. Graphen mit beschränkter Weg- beziehungsweise Baumweite haben polynomiale Algorithmen und in Spezialfällen einfache Formeln, die ebenfalls vorgestellt werden. Der abschließende Teil beschäftigt sich mit Schranken und Approximationen.

The main objective of the present thesis is to deepen the understanding of the mechanisms involved in catalytic growth of carbon nanotubes (CNT) and related processes, such as the catalytic hydrogenation, and to use this knowledge to optimize the experimental approaches in order to gain better control in the synthesis and modification of carbon nanomaterials. Controlled growth of the CNT is achieved using gas-phase prepared catalyst particles (Fe, Co) which serve as individual catalytic nucleation sites in a chemical vapor deposition (CVD) process. These studies highlight that the controlled preparation of catalyst particles is a crucial step in order to control the CNT morphology. The resultant CNT diameter and the CNT density are found to increase with increasing nanoparticle diameter and density, respectively. The number of walls of the CNT also increases with increasing primary catalyst size. The experimentally derived correlations between the particle diameter on one hand and the CNT diameter and the CNT number of walls on the other hand are attributed to an increase of the catalyst's volume-to-surface area ratio with increasing particle size. While the availability of carbon dissolved within the catalyst at the point of nucleation is determined by the catalyst volume, the amount of carbon required to form a cap depends on the surface area of the catalyst particle. Electron microscopy studies of the catalyst/substrate/carbon interfaces of CNT grown from Fe nanoparticles reveal that the CNT walls are anchored to the oxide substrate which contests the general argument that the CNT walls stem from atomic steps at the catalyst. It is argued that after nucleation, the substrate itself provides a catalytic functionality towards the stimulation of ongoing CNT growth, whereas the catalytic activity of the metal particle is more restricted to the nucleation process. Selective hard-magnetic functionalization of CNT tips has been achieved in a plasma-enhanced CVD process. Hard-magnetically terminated CNT, i.e. CNT with a FePt nanoparticle at each tip, are directly grown using FePt catalysts. Fe/Pt thin films with a strongly over-stoichiometric Fe content in the starting catalyst composition yield CNT with a significant number of particles in the hard-magnetic phase. Anisotropic etching of graphite through Co catalyst particles in hydrogen atmosphere at elevated temperatures (i.e. catalytic hydrogenation) is reported. Catalytic hydrogenation is a potential key engineering route for the fabrication of graphene nanoribbons with atomic precision. While in previous studies the etching of zigzag channels was preferred, the present investigations reveal preferential etching of armchair channels, which provides a means to tailor graphene nanostructures with specific edge termination. Further, detailed morphological and structural characterization of the Co particles provide insight into the hydrogenation mechanism which is still a matter of controversy.

The thesis presents a contribution to the analysis and visualization of computational performance based on event traces with a particular focus on parallel programs and High Performance Computing (HPC). Event traces contain detailed information about specified incidents (events) during run-time of programs and allow minute investigation of dynamic program behavior, various performance metrics, and possible causes of performance flaws. Due to long running and highly parallel programs and very fine detail resolutions, event traces can accumulate huge amounts of data which become a challenge for interactive as well as automatic analysis and visualization tools. The thesis proposes a method of exploiting redundancy in the event traces in order to reduce the memory requirements and the computational complexity of event trace analysis. The sources of redundancy are repeated segments of the original program, either through iterative or recursive algorithms or through SPMD-style parallel programs, which produce equal or similar repeated event sequences. The data reduction technique is based on the novel Complete Call Graph (CCG) data structure which allows domain specific data compression for event traces in a combination of lossless and lossy methods. All deviations due to lossy data compression can be controlled by constant bounds. The compression of the CCG data structure is incorporated in the construction process, such that at no point substantial uncompressed parts have to be stored. Experiments with real-world example traces reveal the potential for very high data compression. The results range from factors of 3 to 15 for small scale compression with minimum deviation of the data to factors > 100 for large scale compression with moderate deviation. Based on the CCG data structure, new algorithms for the most common evaluation and analysis methods for event traces are presented, which require no explicit decompression. By avoiding repeated evaluation of formerly redundant event sequences, the computational effort of the new algorithms can be reduced in the same extent as memory consumption. The thesis includes a comprehensive discussion of the state-of-the-art and related work, a detailed presentation of the design of the CCG data structure, an elaborate description of algorithms for construction, compression, and analysis of CCGs, and an extensive experimental validation of all components. / Diese Dissertation stellt einen neuartigen Ansatz für die Analyse und Visualisierung der Berechnungs-Performance vor, der auf dem Ereignis-Tracing basiert und insbesondere auf parallele Programme und das Hochleistungsrechnen (High Performance Computing, HPC) zugeschnitten ist. Ereignis-Traces (Ereignis-Spuren) enthalten detaillierte Informationen über spezifizierte Ereignisse während der Laufzeit eines Programms und erlauben eine sehr genaue Untersuchung des dynamischen Verhaltens, verschiedener Performance-Metriken und potentieller Performance-Probleme. Aufgrund lang laufender und hoch paralleler Anwendungen und dem hohen Detailgrad kann das Ereignis-Tracing sehr große Datenmengen produzieren. Diese stellen ihrerseits eine Herausforderung für interaktive und automatische Analyse- und Visualisierungswerkzeuge dar. Die vorliegende Arbeit präsentiert eine Methode, die Redundanzen in den Ereignis-Traces ausnutzt, um sowohl die Speicheranforderungen als auch die Laufzeitkomplexität der Trace-Analyse zu reduzieren. Die Ursachen für Redundanzen sind wiederholt ausgeführte Programmabschnitte, entweder durch iterative oder rekursive Algorithmen oder durch SPMD-Parallelisierung, die gleiche oder ähnliche Ereignis-Sequenzen erzeugen. Die Datenreduktion basiert auf der neuartigen Datenstruktur der "Vollständigen Aufruf-Graphen" (Complete Call Graph, CCG) und erlaubt eine Kombination von verlustfreier und verlustbehafteter Datenkompression. Dabei können konstante Grenzen für alle Abweichungen durch verlustbehaftete Kompression vorgegeben werden. Die Datenkompression ist in den Aufbau der Datenstruktur integriert, so dass keine umfangreichen unkomprimierten Teile vor der Kompression im Hauptspeicher gehalten werden müssen. Das enorme Kompressionsvermögen des neuen Ansatzes wird anhand einer Reihe von Beispielen aus realen Anwendungsszenarien nachgewiesen. Die dabei erzielten Resultate reichen von Kompressionsfaktoren von 3 bis 5 mit nur minimalen Abweichungen aufgrund der verlustbehafteten Kompression bis zu Faktoren > 100 für hochgradige Kompression. Basierend auf der CCG_Datenstruktur werden außerdem neue Auswertungs- und Analyseverfahren für Ereignis-Traces vorgestellt, die ohne explizite Dekompression auskommen. Damit kann die Laufzeitkomplexität der Analyse im selben Maß gesenkt werden wie der Hauptspeicherbedarf, indem komprimierte Ereignis-Sequenzen nicht mehrmals analysiert werden. Die vorliegende Dissertation enthält eine ausführliche Vorstellung des Stands der Technik und verwandter Arbeiten in diesem Bereich, eine detaillierte Herleitung der neu eingeführten Daten-strukturen, der Konstruktions-, Kompressions- und Analysealgorithmen sowie eine umfangreiche experimentelle Auswertung und Validierung aller Bestandteile.

For a set of graphs H, we call a graph G H-free if G-S is non-isomorphic to H for each S⊆V(G) and each H∈H. Let f_H^* ∶N_(>0)↦N_(>0 )be the optimal χ-binding function of the class of H-free graphs, that is, f_H^* (ω)=max⁡{χ(G): ω(G)=ω,G is H-free} where χ(G),ω(G) denote the chromatic number and clique number of G, respectively. In this thesis, we mostly determine optimal χ-binding functions for subclasses of P_5-free graphs, where P_5 denotes the path on 5 vertices. For multiple subclasses we are able to determine them exactly and for others we prove the right order of magnitude. To achieve those results we prove structural results for the graph classes and determine colourings. We sometimes obtain those results by researching the prime graphs and combining the two decomposition methods by homogeneous sets and clique-separators. Additionally, we use the Strong Perfect Graph Theorem and analyse the neighbourhood of holes. For some of these subclasses we characterise all graphs G with χ(G)>χ(G-\{u\}), for each u∈V(G) and use those to determine the function.

A novel strategy for the intercalation of antimony (Sb) under the (6√3 × 6√3)R30° reconstruction, also known as buffer layer, on SiC(0001) is reported. Using X-ray photoelectron spectroscopy, low-energy electron diffraction, and angle-resolved photoelectron spectroscopy, it is demonstrated that, while the intercalation of the volatile Sb is not possible by annealing the Sb-coated buffer layer in ultrahigh vacuum, it can be achieved by annealing the sample in an atmosphere of Ar, which suppresses Sb desorption. The intercalation leads to a decoupling of the buffer layer from the SiC(0001) surface and the formation of quasi-freestanding graphene. The intercalation process paves the way for future studies of the formation of quasi-freestanding graphene by intercalation of high-vapor-pressure elements, which are not accessible by previously known intercalation techniques, and thus provides new avenues for the manipulation of epitaxial graphene on SiC.

Emerging contaminants represent newly identified organic chemical pollutants that are not yet covered by routine monitoring and regulatory programs. Current research on these contaminants is greatly hindered by the shortage of analytical methods due to the complex matrices, extremely low concentration and their “emerging” nature. In this study the innovative analytical and monitoring methods have been developed and validated for determination of emerging pollutants in water (including pharmaceutical and personal care products, pesticides and artificial sweeteners) based on graphene-silica composite as the solid-phase extraction (SPE) sorbent and as the receiving phase in passive sampler. Graphene, a new allotropic member in the carbon family, has been considered to be a promising candidate for sorption material with high loading capacity because of its ultra-high specific surface area and large delocalized π-electron-rich structure. The composite employed in this work was synthesized by using the cross-link agent to covalently combine carboxylic acid groups of graphene-oxide with the amino groups of the modified silica gel. Afterwards, graphene-silica composite was obtained after treated with hydrothermal reaction in the microwave autoclave, which was demonstrated by X-ray diffraction (XRD). The analytical procedure entails SPE followed by high performance liquid chromatography equipped with tandem mass spectrometers (HPLC-MS/MS). Several crucial parameters were optimized to improve recovery of the analytes, including the amount of sorbents, the ratio of graphene oxide/amino-silica and pH value of water samples. The best recovery results were achieved with 100 mg 10 % (w/w) graphene-silica composite, which were over 70 % except four artificial sweeteners, ranitidine and triclosan. Compared with its commercial counterpart Oasis HLB, pH value variation of water samples has less effect on the recoveries, making graphene composite to be a potential receiving phase of monitoring tool. The batch-to-batch reproducibility was verified on six independently SPE cartridges with graphene-silica composites from two repeatable synthetic batches, showing relative standard deviations (RSDs) in the range of 8.3 % to 19.1 %, except ibuprofen and saccharin. The cartridges proved to be reusable for at least 10 times consecutive extractions, with RSD < 14.9 %, except ibuprofen and diclofenac. The Chemcatcher® passive sampler is frequently used for monitoring polar organic chemicals in surface water. Uptake kinetics is necessary to be quantified to calculate time-weighted average (TWA) concentration. A series of calibration experiments were conducted in the beaker renewal experiments as well as in the flow-through system with styrenedivinylbenzene-cross connect (SDB-XC) disks and graphene-silica composite as the receiving phase. The results obtained from the beaker renewal experiments showed that the uptake kinetics of accumulated compounds with all Chemcatcher® configurations can keep linear within 2 weeks. The innovative configuration using graphene-silica composite powder placed between two PES membranes was able to accumulate eleven of the selected compounds with uptake rate (Rs) from 0.01 L/day (acesulfame K and sucralose) to 0.08 L/day (chlothianidin), while its commercial counterpart SDB-XC disks with polyethersulfone (PES) membranes can accumulate seven substances with Rs from 0.02 L/day (sucralose and chlothianidin) to 0.15 L/day (carbamazepine). In the flow-through system, when Chemcatchers® were equipped with SDB-XC disks without PES membranes, the linear uptake range for the majority of compounds was only in one week, except atrazine. The Rs of accumulated compounds were from 0.16 L/day (chloramphenicol) to 1.04 L/day (metoprolol) that are higher than the same substances in the beaker renewal experiments, in which the Rs of chloramphenicol and metoprolol were 0.09 L/day and 0.56 L/day respectively. However, if the PES membranes were employed, the uptake kinetics in both calibration experimental designs were comparable: the Rs of accumulated compounds from the configuration with SDB-XC disks covered by PES membranes were from 0.035 L/day (sucralose) to 0.17 L/day (carbamazepine) and from the configuration with graphene-silica composite were from 0.01 L/day (gemfibrozil) to 0.08 L/day (chlothianidin). Moreover, the uptake range can keep linear within two weeks. The developed Chemcatcher® method was successfully applied in real surface waters. 1-H benzontriazole, tolyltriazole and caffeine were the main contaminants in Elbe River and the Saidenbach drinking water reservoir. The investigated results between summer and autumn monitoring period were not significantly different.:Acknowledgement I Abstract III Zusammenfassung V Content IX List of Figures XIII List of Tables XVII Table of Abbreviations XIX 1. Motivation 1 2. Introduction 3 2.1 Emerging contaminants 3 2.1.1 Definition 3 2.1.2 Sources 3 2.1.3 Concern about the adverse impacts 5 2.2 Analysis of the emerging contaminants 7 2.2.1 General analytical process 7 2.2.2 Enrichment techniques 8 2.2.2.1 Liquid-liquid extraction (LLE) 8 2.2.2.2 Solid-phase extraction (SPE) 9 2.2.2.3 Innovative type of solid-phase extraction 13 2.2.3 Analytical methods 15 2.3 Graphene and its application in analytical chemistry 19 2.3.1 Introduction 19 2.3.2 Synthesis methods of graphene 20 2.3.3 Application in sample pre-treatment 21 2.3.3.1 Graphene-based material as SPE sorbent 21 2.3.3.2 Graphene-coated fibers as SPME sorbent 22 2.3.3.3 Magnetic graphene as MSPE sorbent 23 2.3.3.4 Graphene-based MIPs 24 2.4 Chemcatcher®—a passive sampling technique 25 2.4.1 Introduction 25 2.4.2 Theory 26 2.4.2.1 Equilibrium passive sampling 27 2.4.2.2 Kinetic passive sampling 28 2.4.3 Concept of Chemcatcher® 28 2.4.4 Calibration of Chemcatcher® 33 2.4.5 Performance and reference compounds 36 3. Study objectives and hypotheses 39 3.1 Study objectives 39 3.2 Hypotheses 41 4. Material and methods 43 4.1 Materials 43 4.1.1 Chemicals and solutions 43 4.1.2 Consumable materials and instruments 44 4.2 Synthesis of graphene-silica composite 46 4.3 SPE experiments 49 4.3.1 Packing method 49 4.3.2 SPE procedure 49 4.3.3 Optimization of SPE procedures 51 4.3.4 Repeatability and reusability test 52 4.4 Chemcatcher® experiments 53 4.4.1 Preparation and precondition 53 4.4.2 Calibration of Chemcatcher® 55 4.4.2.1 Preliminary test 55 4.4.2.2 Experimental design of the beaker batch tests 56 4.4.2.3 Experimental design of the flow-through system 57 4.4.3 Monitoring application of Chemcatcher® in surface water 59 4.4.4 Elution process 60 4.4.5 Statistic data evaluation 61 4.5 HPLC-MS/MS analysis 62 5. Results and discussion 63 5.1 Preparation and characterization of graphene-silica composite 63 5.2 SPE performance of the graphene-silica composite 67 5.2.1 Preliminary test of packing methods 67 5.2.2 Optimization of SPE procedures 68 5.2.2.1 The amount of sorbent 68 5.2.2.2 Graphene ratio in the composites 68 5.2.2.3 pH value of the water sample 69 5.2.3 Repeatability and reusability test 72 5.2.3.1 Performance of the off-line SPE 72 5.2.3.2 Repeatability and reusability test results 75 5.2.4 Summarized discussion of the SPE performance 76 5.3 Calibrating results of Chemcatcher® 86 5.3.1 Pre-test results 86 5.3.1.1 Feasibility test of commercial disks as receiving phase 86 5.3.1.2 Stability test 88 5.3.1.3 Elution optimization. 88 5.3.1.4 Recovery of the filters 92 5.3.2 Calibration results of renewal experiments 93 5.3.2.1 SDB-XC disks without and with membranes 93 5.3.2.2 Graphene-silica composite as receiving phase 97 5.3.3 Calibration results of the flow-through system experiments 101 5.3.3.1 Determination of experimental parameters 101 5.3.3.2 Concentration control 103 5.3.3.3 Calibration results 105 5.3.3.4 Preliminary evaluation of performance and reference compounds 112 5.4 Application of Chemcatcher® in surface water 114 5.5 Discussion about problems of commercial disks as receiving phase in Chemcatcher® 118 5.5.1 Deformation of commercial disks 118 5.5.2 The particles in the solution after elution 119 6. Conclusion and perspective 121 7. Annex 125 7.1 Material and methods 125 7.1.1 Chemicals 125 7.1.2 Silica gel and graphene oxide 144 7.1.3 Microwave reduction program 144 7.1.4 Working schedule of the calibration experiments in flow-through system 144 7.1.5 HPLC-MS/MS conditions 146 7.2 Experimental results 149 7.2.1 Stability of the colloid solution of graphene oxide 149 7.2.2 EDX analysis results 149 7.2.3 HPLC-MS/MS results 152 7.2.4 Calibrating results of the beaker renewal experiment 153 7.2.5 Calibrating results of the flow-through system experiments 157 7.2.6 Monitoring results in the Elbe River 161 Reference 163

Nach der Entwicklung des Nicht-Kontakt-Rasterkraftmikroskops (NC-AFM) konnten dessen Leistung, Empfindlichkeit und Anwendungsmöglichkeiten deutlich gesteigert und somit neue grundlegende physikalische Eigenschaften von Festkörperoberflächen mit hoher Auflösung und Präzision untersucht werden. Dabei gibt es jedoch immer wieder neue Errungenschaften, die die Technik noch weiter verbessern können – sei es auf dem Gebiet der Signalverarbeitung, der -detektion oder der prinzipiellen Funktionsweise des Mikroskops. So wird in der vorliegenden Arbeit das theoretische Verständnis der Regelkreise und des Rauschverhaltens des NC-AFMs im Messbetrieb verbessert. Die Regelkreise verhalten sich – anders als im freischwingenden System – in Wechselwirkungsnähe mit der Probe hochgradig dynamisch, sodass die ursprünglich gewählten Parameter der Regelkreise sich nicht eins zu eins auf den echten Messbetrieb übertragen lassen und suboptimale Einstellungen die Bildqualität dadurch beeinträchtigen können. Mithilfe der korrekten Modellierung der Regelkreise in Probennähe kann diese Störquelle nun minimalisiert werden, was durch experimentell bestimmte Spektren bestätigt wird. Bei der Exfoliation von Graphen auf CaF2 an der Raumluft werden Wassermoleküle eingeschlossen, die nicht durch Heizen entfernt werden können, ohne dass das Graphen Blasen schlägt und reißt. Unterschiedliche Mengen an Wasser zwischen den Graphenflocken und dem Substrat haben einen großen Einfluss auf das elektrische Kontaktpotenzial, das mithilfe der Kelvin-Sonden-Kraftmikroskopie vermessen werden kann. Ergebnisse der Kapitel sind die berechnete Adhäsionsenergie von Graphen auf CaF2, inwieweit das Wasser das Graphen dotieren kann und die Erklärung des großen Unterschieds des Kontaktpotenzials.

Spectral graph theory widely increases the interests in not only discovering new properties of well known graphs but also proving the well known properties for the new type of graphs. In fact all spectral properties of proverbial graphs are not acknowledged to us and in other hand due to the structure of nature, new classes of graphs are required to explain the phenomena around us and the spectral properties of these graphs can tell us more about the structure of them. These both themes are the body of our work here. We introduce here three models of random graphs and show that the eigenvalue counting function of Laplacians on these graphs has exponential decay bound. Since our methods heavily depend on the first nonzero eigenvalue of Laplacian, we study also this eigenvalue for the graph in both random and nonrandom cases.