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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Synthesis and characterization of transition metal nitrides and carbides for catalysis and electrochemistry application

Metzke, Sarah January 2013 (has links)
It was the goal of this work to explore two different synthesis pathways using green chemistry. The first part of this thesis is focusing on the use of the urea-glass route towards single phase manganese nitride and manganese nitride/oxide nano-composites embedded in carbon, while the second part of the thesis is focusing on the use of the “saccharide route” (namely cellulose, sucrose, glucose and lignin) towards metal (Ni0), metal alloy (Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5, Cu0.5Ni0.5 and W0.15Ni0.85) and ternary carbide (Mn0.75Fe2.25C) nanoparticles embedded in carbon. In the interest of battery application, MnN0.43 nanoparticles surrounded by a graphitic shell and embedded in carbon with a high surface area (79 m^2/g) were synthesized, following a previously set route.The comparison of the material characteristics before and after the discharge showed no remarkable difference in terms of composition and just slight differences in the morphological point of view, meaning the particles are stable but agglomerate. The graphitic shell is contributing to the resistance of the material and leads to a fine cyclic stability over 140 cycles of 230 mAh/g after the first charge/discharge and coulombic efficiencies close to 100%. Due to the low voltage towards Li/Li+ and the low polarization, it might be an attractive anode material for lithium ion batteries. However, the capacity is still noticeably lower than the theoretical value for MnN0.43. A mixture of MnN0.43 and MnO nanoparticles embedded in carbon (surface area 93 m^2/g) was able to improve the cyclic stability to over 160 cycles giving a capacity of 811 mAh/g, which is considerably higher than the capacity of the conventional material graphite (372 mAh/g). This nano-composite seems to agglomerate less during the process of discharge. Interestingly, although the capacity is much higher than of the single phase manganese nitride, the nano-composite seems to only contain MnN0.43 nanoparticles after the process of discharge with no oxide phase to be found. Concerning catalysis application, different metal, metal alloy, and metal carbide nanoparticles were synthesized using the saccharide route. At first, systems that were already investigated before, being Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5 and Mn0.75Fe2.25C using cellulose as the carbon source were prepared and tested in an alkylation reaction of toluene with benzylchloride. Unexpectedly, the metal alloys did not show any catalytic activity, but the ternary carbide Mn0.75Fe2.25C showed fine catalytic activity of 98% conversion after 9 hour reaction time (110 °C). In a second step, the saccharide route was modified towards other carbon sources and carbon to metal ratios in order to improve the homogeneity of the samples and accessibility of the particle surfaces. The used carbon sources sucrose and glucose are similar in their basic structure of carbohydrates, but reducing the (polymeric) chain length. Indeed, the cellulose could be successfully replaced by sucrose and glucose. A lower carbon to metal ratio was found to influence the size, homogeneity and accessibility (as evidenced by TEM) of the samples. Since sucrose is an aliment, glucose is the better choice as a carbon source. Using glucose, the synthesis of Cu0.5Ni0.5 and W0.15Ni0.85 nano-composites was also possible, although the later was never obtained as pure phase. These alloy nano-composites were tested, along with nickel0 nanoparticles also prepared with glucose and on their catalytic activity towards the reduction of phenylacetylene. The results obtained let believe that any (poly) saccharide, including lignin, could be used as carbon source. The nickel0 nano-composites prepared with lignin as a carbon source were tested along with those prepared with cellulose and sucrose for their catalytic activity in the transfer hydrogenation of nitrobenzene (results compared with exposed nickel nanoparticles and nickel supported on carbon) leading to very promising results. Based on the urea-glass route and the saccharide route, simple equipment and transition metals, it was possible to have a one-pot synthesize with scale-up possibilities towards new material that can be applied in catalysis and battery systems. / Im Rahmen dieser Arbeit wird sowohl die Synthese von Mangannitrid- und -oxid-Nanopartikeln, als auch die Synthese verschiedener Metall- und Legierungsnanopartikel untersucht. Einen Schwerpunkt stellt dabei die Optimierung der Synthese unter den Gesichtspunkten der Nachhaltigkeit dar, was sich insbesondere in der Verwendung diverser nachwachsender Rohstoffe als Kohlenstoffquelle äußert. Für eine mögliche Anwendung in Akkumulatoren werden mit Graphit ummantelte MnN0.43-Nanopartikel mit einer großen Oberfläche (79 m^2/g) synthetisiert. Diese werden exemplarischen Ladezyklen unterzogen, wobei eine strukturelle und auch elektrochemische Stabilität festgestellt werden kann. Eine Mischung der Mangannitride mit Manganoxiden führt zu einer weiteren Verbesserung der Ladekapazität und einer weiteren Oberflächenvergrößerung (93 m^2/g). Die Langlebigkeit der Strukturen wird durch die Einbettung der Nanopartikel in Kohlenstoff unterstützt und kann zu einer Anwendung als Anodenmaterial in den heutzutage vielfach verwendeten Lithiumionen-Akkus führen. Im Sinne der Nachhaltigkeit ist auch die Entwicklung von Katalysatoren. Dabei soll insbesondere die Verwendung von Lignin, was als Bestandteil vieler Pflanzen zwar leicht verfügbar, aber unglücklicherweise bisher chemisch unverwertbar ist, fokussiert werden. Um sich diesem Ziel zu nähern und entsprechende Mechanismen zur Reduktion des Lignins zu entwickeln, werden in dieser Arbeit zunächst verschiedene Kohlenstoffquellen (wie Cellulose, Sucrose und Glucose) zur Synthese von reduktiven Katalysatoren untersucht. Der Kohlenstoff dient dabei sowohl als preiswertes Reduktionsmittel für Metallsalze zur Gewinnung von Metallnanopartikel als auch zur Stabilisierung ebendieser. Es werden vielfältige Legierungen mit Nickel (z.B. Pd0.9Ni0.1, Pd0.5.Ni0.5, Fe0.5.Ni0.5, und Cu0.5.Ni0.5) aber auch ternäre Carbide (z.B. Mn0.75Fe2.25C) erhalten, die schon in ersten Alkylierungs- und Hydrierungsreaktionen ein großes Potential als Katalysatoren zeigen. Um die erhaltenen Nanopartikel in zukünftigen Anwendungen nutzbar zu machen, ist eine ausführliche Charakterisierung unabdingbar. Auch die Ergebnisse der zahlreichen durchgeführten Analysen werden in dieser Arbeit zusammengestellt und bilden gemeinsam mit den optimierten Syntheserouten einen tiefgreifenden Überblick über dieses Forschungsfeld.
2

Kreuzung von Chlamydomonas-reinhardtii-Stämmen zur Steigerung der Glykolatexkretion

Schad, Antonia Christiane 10 July 2020 (has links)
No description available.
3

Sustainable biomass-derived hydrothermal carbons for energy applications

Falco, Camillo January 2012 (has links)
The need to reduce humankind reliance on fossil fuels by exploiting sustainably the planet renewable resources is a major driving force determining the focus of modern material research. For this reason great interest is nowadays focused on finding alternatives to fossil fuels derived products/materials. For the short term the most promising substitute is undoubtedly biomass, since it is the only renewable and sustainable alternative to fossil fuels as carbon source. As a consequence efforts, aimed at finding new synthetic approaches to convert biomass and its derivatives into carbon-based materials, are constantly increasing. In this regard, hydrothermal carbonisation (HTC) has shown to be an effective means of conversion of biomass-derived precursors into functional carbon materials. However the attempts to convert raw biomass, in particular lignocellulosic one, directly into such products have certainly been rarer. Unlocking the direct use of these raw materials as carbon precursors would definitely be beneficial in terms of HTC sustainability. For this reason, in this thesis the HTC of carbohydrate and protein-rich biomass was systematically investigated, in order to obtain more insights on the potentials of this thermochemical processing technique in relation to the production of functional carbon materials from crude biomass. First a detailed investigation on the HTC conversion mechanism of lignocellulosic biomass and its single components (i.e. cellulose, lignin) was developed based on a comparison with glucose HTC, which was adopted as a reference model. In the glucose case it was demonstrated that varying the HTC temperature allowed tuning the chemical structure of the synthesised carbon materials from a highly cross-linked furan-based structure (T = 180oC) to a carbon framework composed of polyaromatic arene-like domains. When cellulose or lignocellulosic biomass was used as carbon precursor, the furan rich structure could not be isolated at any of the investigated processing conditions. These evidences were indicative of a different HTC conversion mechanism for cellulose, involving reactions that are commonly observed during pyrolytic processes. The evolution of glucose-derived HTC carbon chemical structure upon pyrolysis was also investigated. These studies revealed that upon heat treatment (Investigated temperatures 350 – 900 oC) the furan-based structure was progressively converted into highly curved aromatic pre-graphenic domains. This thermal degradation process was observed to produce an increasingly more hydrophobic surface and considerable microporosity within the HTC carbon structure. In order to introduce porosity in the HTC carbons derived from lignocellulosic biomass, KOH chemical activation was investigated as an HTC post-synthesis functionalisation step. These studies demonstrated that HTC carbons are excellent precursors for the production of highly microporous activated carbons (ACs) and that the porosity development upon KOH chemical activation is dependent on the chemical structure of the HTC carbon, tuned by employing different HTC temperatures. Preliminary testing of the ACs for CO2 capture or high pressure CH4 storage yielded very promising results, since the measured uptakes of both adsorbates (i.e. CO2 and CH4) were comparable to top-performing and commercially available adsorbents, usually employed for these end-applications. The combined use of HTC and KOH chemical activation was also employed to produce highly microporous N-doped ACs from microalgae. The hydrothermal treatment of the microalgae substrate was observed to cause the depletion of the protein and carbohydrate fractions and the near complete loss (i.e. 90%) of the microalgae N-content, as liquid hydrolysis/degradation products. The obtained carbonaceous product showed a predominantly aliphatic character indicating the presence of alkyl chains presumably derived from the lipid fractions. Addition of glucose to the initial reaction mixture was found out to be extremely beneficial, because it allowed the fixation of a higher N amount, in the algae derived HTC carbons (i.e.  60%), and the attainment of higher product yields (50%). Both positive effects were attributed to Maillard type cascade reactions taking place between the monosaccharides and the microalgae derived liquid hydrolysis/degradation products, which were in this way recovered from the liquid phase. KOH chemical activation of the microalgae/glucose mixture derived HTC carbons produced highly microporous N-doped carbons. Although the activation process led to a major reduction of the N-content, the retained N-amount in the ACs was still considerable. These features render these materials ideal candidates for supercapacitors electrodes, since they provide extremely high surface areas, for the formation of electric double-layer, coupled to abundant heteroatom doping (i.e. N and O) necessary to obtain a pseudocapacitance contribution. / Die Notwendigkeit, die Abhängigkeit der Menschheit von fossilen Brennstoffen zu reduzieren ist die treibende Kraft hinter aktuellen Forschungsanstrengungen in den Materialwissenschaften. Folglich besteht heutzutage ein erhebliches Interesse daran Alternativen zu Materialien, die aus fossilen Resourcen gewonnen werden, zu finden. Kurzfristig ist zweifellos Biomasse die vielversprechendste Alternative, da sie aus heutiger Sicht die einzige nicht-fossile, nachhaltige und nachwachsende Kohlenstoffquelle ist. Konsequenterweise werden die Antrengungen neue Syntheseansätze zur Konvertierung von Biomasse und ihren Derivaten in kohlenstoffbasierten Materialien forwährend erhöht. In diesem Zusammenhang hat sich die Hydrothermalkarbonisierung (HTC) als sehr vielseitiges Werkzeug zur Konvertierung von Biomasse-basierten Ausgangsstoffen in funktionale Kohlenstoffmaterialien herausgestellt. Dennoch gibt es bisher wenige Ansätze um rohe Biomasse, genauer gesagt Lignicellulose, direkt in funktionale Materialien umzusetzen. Könnte der direkte Einsatz von roher Biomasse Verfahren wie der HTC zugänglich gemacht werden, würde dies die Nachhaltigkeit des Verfahrens immens steigern. Daher wurde in dieser Dissertation die Hydrothermalkarbonisierung von kohlenhydratreicher (d. h. Lignicelluse) und proteinreicher (d. h. Microalgae) Biomasse systematisch analysiert. Diese Untersuchung galt dem Ziel einen besseren Einblick in das Potential dieser thermochemischen Verarbeitungsmethode funktionale Kohlenstoffmaterialien aus unverarbeiteter Biomasse hervorzubringen zu gewinnen. Die hergestellten Materialien wurden mittels chemischer Aktivierung nachträglich weiter behandelt. Dieser zusätzliche Verarbeitungsschritt ermöglichte die Herstellung hochporöser aktiverter Kohlenstoffe (AC). Die aus Lignicellulose gewonnenen ACs zeigten exzellente Eigenschaften bei der Aufnahme von CO2 und der Hochdruckspeicherung von CH4 währen die aus Microalgae gewonnen Eigenschaften an den Tag legten (z. B. hohe Oberfläche und N-Dotierung), welche sie zu vielversprechenden Materialien für Superkondensatoren machen. Die in dieser Dissertation präsentierte Arbeit zeigte außergewöhnliche Fortschritte in Richtung der Anwendung von unbehandelter Biomasse als Ausgangsmaterial für die Produktion von funktionalen Kohlenstoffen.

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