This work describes several studies into the electroreduction of carbon dioxide (CO2RR), both regarding mechanistical aspects and catalyst stability considerations. Mechanistic insights into carbon... Show moreThis work describes several studies into the electroreduction of carbon dioxide (CO2RR), both regarding mechanistical aspects and catalyst stability considerations. Mechanistic insights into carbon-carbon bond formation on a silver catalyst are described in Ch 2, were we find an acetaldehyde-like surface adsorbate to be a key intermediate. Gold stability in alkaline environment under strongly reducing conditions and the effect of near-surface CO on said stability is reported on in Ch 3, showing catalyst degradation under reductive conditions which is furthermore exacerbated by CO adsorption. Chapter 4 details the voltammetric behavior of variously oriented copper surfaces when prepared via a non-standard methodology, showing good agreement with prior literature. The last chapter (Ch 5) contains investigations into the stability of copper under reductive conditions in near-neutral buffered electrolyte and in alkaline electrolyte, where it was observed that copper is morphologically stable under strongly alkaline conditions and neutral conditions in the presence of CO2 and buffer ions, so long as strictly reducing potentials are applied. Show less
Copper(I) hydridotrispyrazolylborate complexes were synthesized and analyzed as potential candidates for highly sensitive ethene detection. The best complexes were selected and used as sensitizers... Show moreCopper(I) hydridotrispyrazolylborate complexes were synthesized and analyzed as potential candidates for highly sensitive ethene detection. The best complexes were selected and used as sensitizers for extremely sensitive graphene-based ethene gas sensors. Show less
Nuclear magnetic resonance force microscopy (MRFM) is a technique which combines magnetic resonance imaging (MRI) with scanning probe microscopy (SPM). The final goal is to develop this technique... Show moreNuclear magnetic resonance force microscopy (MRFM) is a technique which combines magnetic resonance imaging (MRI) with scanning probe microscopy (SPM). The final goal is to develop this technique to such a level that the atomic structure of a virus or protein can be revealed by this microscope. This thesis shows nuclear magnetic resonance force measurements on copper in which the interaction of the magnetic moments of the nuclei of copper with a magnetic cantilever has delivered a detectable signal at a temperature of 50 millikelvin. Furthermore, we show measurements, which support a new theory where at low magnetic field and low temperature, non contact friction between the magnetic cantilever and paramagnetic electron spins is described. These measurements were enabled by technical improvements such as vibration reduction in a cryogen free dilution refrigerator. As a benchmark for the low vibration, we show atomic resolution scanning tunneling microscopy at 15 millikelvin temperature on graphite. We also show a method to create small magnets for MRFM from a thin magnet film. With these small magnets the field gradient and therefore the sensitivity may be significantly enhanced. Show less
The filamentous soil bacteria of the genus Streptomyces are commercially exploited for the production of a wide range of natural products such as antibiotics, anticancer agents and... Show moreThe filamentous soil bacteria of the genus Streptomyces are commercially exploited for the production of a wide range of natural products such as antibiotics, anticancer agents and immunosuppressants. Additionally, there is a strong interest in the use of these bacteria for the production of industrial proteins. Optimal production of these secondary metabolites and enzymes is tightly coupled to morphology. However, relatively little is known about the genetic determinants influencing the morphology of streptomycetes in liquid-grown cultures. The work presented in this thesis focuses on the formation of extracellular macromolecules and their influence on morphogenesis, with a special emphasis on the role of the cellulose synthase-like protein CslA and the radical copper oxidase GlxA in the production of a tip-localized glycan. This research is of fundamental importance for understanding the determinants of growth and development of this multicellular model organism, and at the same time may help us to further optimize their exploitation for the industrial production of secondary metabolites and enzymes. Show less
A study of the effect of chloride and sulfate anions, as well as of SPS molecules on Cu electrodeposition is presented in this thesis. The deposition process was analyzed by means of a home-built... Show moreA study of the effect of chloride and sulfate anions, as well as of SPS molecules on Cu electrodeposition is presented in this thesis. The deposition process was analyzed by means of a home-built fast electrochemical STM in situ after and during deposition. Show less
Clearly gold deposited as nanoparticles on a support is a very active catalyst in contrast to bulk gold which does not show any catalytic activity. The question arises if this particle size effect... Show moreClearly gold deposited as nanoparticles on a support is a very active catalyst in contrast to bulk gold which does not show any catalytic activity. The question arises if this particle size effect is exclusively valid for gold catalysis or can a similar effect be found in other metals? In the research described in this thesis we investigated copper and silver based catalysts for similar particle size effects as for gold based catalysts. In contrast to gold bulk silver and copper are known to be active in catalysis and both metals are used as catalysts. Silver is the metal of choice for the formation of ethylene oxide from ethylene but also for the formation of formaldehyde in the BASF process. A Cu/Zn-based catalyst is used for the synthesis of methanol from CO and \hydrogen, and copper-based catalysts are also active in oxidation reactions. As the interaction between the gold nanoparticles with the additives is very important for the catalytic activity, the effect of additions of lithiumoxide and ceria have also been investigated for the silver and copper based catalysts. These additives stabilize the nanoparticles and ceria which is known for its oxygen storage and oxidation capacities and is one of the best additives for gold based catalysts. Various oxidation and dehydrogenation reactions have been investigated over copper, silver and gold based catalysts, which are presented in this thesis. In chapter 2 the preferential oxidation of CO is discussed. Chapter 3 deals with the selective oxidation of \ammonia. Chapter 4 is devoted to the oxidation and dehydrogenation of methanol. Chapter 5 presents the results of formation of ethylene oxide in the oxidation and dehydrogenation of ethanol on silver and copper based catalysts. In chapter 6 more results of ethanol dehydrogenation and oxidation on gold based catalysts are presented. Chapter 7 gives insight into the activity of gold based catalysts in oxidation and dehydrogenation of 1-propanol and 2-propanol. Show less
The research described in this thesis deals with the synthesis of copper(II) complexes with phenol-based or macrocyclic ligands, which can be regarded as model compounds of the active site of... Show moreThe research described in this thesis deals with the synthesis of copper(II) complexes with phenol-based or macrocyclic ligands, which can be regarded as model compounds of the active site of catechol oxidase, and with the mechanism of the catalytic oxidation of catechol mediated by these compounds. Catechol oxidase is a type-3 copper enzyme usually encountered in plants and in some crustaceans, which catalyzes a conversion of a wide range of o-diphenols (catechols) to the respective o-benzoquinones. These highly reactive compounds subsequently auto-polymerize, resulting in the formation of a dark pigment melanin, which is thought to protect a damaged tissue from pathogens. In the thesis, the structural and physicochemical properties of the obtained copper complexes are discussed. The kinetic studies on the catalytic oxidation of model substrates, e.g. 3,5-ditert-butylcatechol and tetrachlorocatechol, by these complexes and the catalytic oxidation mechanism are further reported. Show less
