There has been growing demands towards the efficient production of enantiopure compounds through either asymmetric synthesis or separation from racemic mixtures. Recent studies have examined numerous different methods that may address this challenge. One of these methods involved the interaction of chiral molecules on achiral metal surfaces such as copper to create chiral templates while another method utilizes the interaction of chiral molecules on intrinsically chiral surfaces. Earlier studies using nonhybrid Density Functional Theory (DFT) functional has provided some insights into the geometric structures and relative energies of some of these interactions, but it failed to achieve quantitative agreement with experimental studies. Using dispersion corrected DFT functionals, this thesis present a study of chemisorbed dense adlayers of glycine and alanine on Cu(110) and Cu(3,1,17), physisorbed R-3-methycyclohexanone (R-3MCHO) on Cu(100), Cu(110), Cu(111), Cu(221), and Cu(643)R, and the hydrogenation of formaldehyde and methoxide on Zn or Zr heteroatoms promoted Cu surfaces. In the dense glycine and alanine adlayer study, we have resolved a disagreement between experimental observation made on LEED, STM, and XPD, and we showed that heterochiral and homochiral glycine adlayer coexist on Cu(110). Our model failed to show the minute enantiospecificity for dense alanine adlayer on Cu(3,1,17) which indicated a numeric limitation for computational modeling of surface adsorption. In the physisorbed system, the dispersion corrected methods calculated adsorption energies were in better quantitative agreement with the experimentally observed values than the nonhybrid functionals, but it also created a significant overestimation of total adsorption energies. On the other hand, our model had indicated a previously unexpected adsorbate-induced surface reconstruction on Cu(110). This is promising news in term of computational modeling's capability in examining surface-adsorbate interaction on an atomic scale. As for the hydrogenation of formaldehyde and methoxide on copper surfaces, the model showed that the increased binding strength between the reaction intermediates and the heteroatom promoted copper surfaces to be the primary contributor of the increased reaction rates. Furthermore, our model had also indicated that while clustered heteroatoms are relatively rare, a significant portion of reaction takes place near these clustered structures. It is our hope that the results and techniques presented in this thesis can be used to better understand and predict the interaction of more complex surface-adsorbate interactions.

University, Diss., 2004--Freiburg (Breisgau).

Die vorliegende Arbeit stellt Ergebnisse von Monte-Carlo-Simulationen zur Adsorption und Selbstorganisation amphiphiler Moleküle an Feststoffoberflächen vor. Ziel der Arbeit ist die Untersuchung des Zusammenhanges zwischen Moleküleigenschaften und thermodynamischen Bedingungen für die Bildung von adsorbierten Aggregaten. Im Rahmen eines coarse grainined-Gittermodells wird die Adsorption von Modelltensiden auf ebenen Oberflächen beschrieben. Es werden hydrophile, hydrophobe und chemisch heterogene Modelloberflächen berücksichtigt. Die Resultate der Simulationen stehen im Einklang mit experimentellen Untersuchungen und liefern Interpretationshilfen für die beobachteten Strukturen. Für den Einsatz von Tensidmischungen bei der Kalziumfluorit-Flotation konnte gezeigt werden, dass die Wirkung des Co-Sammler-Tensids auf einer Adsolubilisation im Adsorptionsfilm beruht.

Porous solids are a class of materials of high scientific and technological significance. Indeed, they have the ability to interact with atoms, ions or molecules not only at their surface but also throughout the bulk of the solid. This ability places these materials as a major class involved in many applications such as gas storage and separation, catalysis, drug delivery and sensor technology. Metal-Organic Materials (MOMs) or coordination polymers (CPs) are crystalline compounds constructed from metal ions or clusters and organic components that are linked via coordination bonds to form zero-, one-, two or three-periodic structures. Porous Metal-Organic Materials (MOMs) or Metal-Organic Frameworks (MOFs) are a relatively new class of nanoporous materials that typically possess regular micropores stable upon removal of guests. An extraordinary academic and industrial interests was witnessed over the past two decades and is evidenced by a fantastic grow of these new materials. Indeed, due to a self-assembly process and readily available metals and organic linkers, an almost infinite number of materials can, in principle, be synthesized. However, a rational design is very challenging but not impossible. In theory, MOMs could be designed and synthesized with tuned functionalities toward specific properties that will determine their potential applications. The present research involves the design and synthesis of functional porous Metal-Organic Materials that can be used as platforms for specific studies related to many applications such as for example gas storage and particularly hydrogen storage. In this manuscript, I will discuss the studies performed on existing major Metal-Organic Frameworks, namely Zeolite-like Metal-Organic Frameworks (ZMOFs) that were designed and synthesized in my research group. My research was also focused on the design and the synthesis of new highly porous isoreticular materials based on Metal-Organic Polyhedra (MOP) where desirable functionality and unique features can be introduced in the final material prior and/or after the assembly process. The use of hetero-functional ligands for a rational design toward binary or ternary net will also be discussed in this dissertation.

Physisorption of CO and N2O on surfaces of ceria (CeO2) was investigated by means of high-level quantum-mechanical embedded cluster calculations. Both systems have high relevance in the field of environmental chemistry and heterogeneous catalysis. The CO/CeO2 system, has been investigated in a couple of both experimental and theoretical studies, but for the N2O/CeO2 system, this is the first study in the literature, experimental or theoretical. In physisorption, the interaction relies entirely on classical electrostatic interactions and electron dispersion forces. No covalent bond is formed between the molecule and the surface. A proper description of the dispersion requires some of the most accurate quantum-mechanical methods available, such as MP2 or CCSD(T). Moreover, even the most sophisticated methods cannot heal errors anywhere else in the theoretical treatment. Standard periodic models cannot be used with methods such as CCSD(T), but embedded cluster models can, and have been thoroughly explored in this thesis. In this thesis, embedded cluster models were constructed for the CeO2(110) and (111) surfaces. Using a range of assessment tests, it was verified that the electronic structure of the central region of a large and fully embedded surface cluster agrees well with the corresponding region in a periodic system. CO physisorption was investigated at the CCSD(T) level. Due to the prohibitively large expenses (in computer time) for standard CCSD(T) calculations, the method of increments, previously used in the literature for bulk systems, was extended to adsorption problems. It was found that, electron correlation contributes by 30 - 80% to the molecule-surface interaction and that the contribution depends on the topology of the surface. The calculated CO-ceria interaction energy is 20 kJ/mol for the (111) surface and 27 kJ/mol for the (110) surface. In low temperature TPD experiments for the N2O/CeO2(111) system, one surface species was found with an adsorption energy of about 29 kJ/mol. IR measurements showed stretching frequencies that are typically assigned to N2O adsorption with the O-end directed towards surface cations. However, theoretical calculations up to the MP2 level predicted two equally favorable adsorption species. Improvements in the structural model (larger clusters, consideration of molecule-induced relaxation) or the computational method (larger basis sets) did not affect this result. Only at the CCSD(T) level was one dominating surface species found, namely N2O adsorbed over a Ce ion, with the O-end of the molecule directed towards the surface. The calculated stretching vibrational frequency shifts (with respect to the gas phase) for this adsorbed species agree well with the measured IR spectra.

It is of great interest to develop and utilize a high surface area material with optimized hydrogen sorption properties. The need for a renewable energy source to replace automobile gasoline has become more critical in the past decade. Hydrogen is a viable fuel source for automobile usage; however, the question of how hydrogen will be safely and efficiently stored still remains. Critical factors for optimum hydrogen storage include ambient conditions and low activation temperature for adsorption and desorption phenomena. In order for optimum hydrogen adsorption to be achieved, the properties of (1) high surface area, (2) optimum hydrogen adsorption energy, and (3) Kubas interactions between metals and hydrogen molecules need to be considered. Fullerenes have recently become more popular with the discovery and mass production of graphene sheets derived from graphite. Graphene is a modified form of graphite that takes the form of sheets with less agglomeration than its respective graphitic form. This form has the potential for high surface area and storage capabilities. Storage of hydrogen at room temperature must be optimized by increasing the surface area and having an adsorption enthalpy between 15 - 20 KJ/mol. Graphene (G) sheets and graphene oxide (GO) sheets have been utilized as a matrix for hydrogen storage. These materials can also be cross-linked with organic spacers in order to form a porous framework of higher surface area. Metal decorating by calcium and platinum of the G/GO matrix has been used to enhance Kubas interactions, adsorption enthalpies, and spillover phenomenon. The use of a polymer matrix has also been implemented. Polyaniline is a novel superconducting polymer with unique electronic properties. Complexes of Polyaniline with graphene and graphene oxide have been investigated for hydrogen storage properties. Graphene and graphene oxide surface modification via metal decoration have been investigated in order to determine the most efficient synthesis and particle size on the G/GO matrix. Characterization by XRD, BET, adsorption enthalpy, PCT, TGA, FT-IR, and TEM/SEM (when applicable) were employed to optimize and compare the materials in the effort to develop a suitable storage material.

Les interactions gaz-grains jouent un rôle important dans la chimie des milieux interstellaires et protoplanétaires. Le paramètre-clé qui gouverne les échanges entre la surface des grains et la phase gazeuse est l’énergie d’adsorption Ea. Ce travail a pour but de développer une approche jointe expérimentale et théorique afin de déterminer les énergies d’adsorption pour des atomes et molécules d’intérêt astrophysique sur des substrats-modèles des surfaces des grains de poussière interstellaires. Expérimentalement, la méthode employée est la désorption programmée en température (TPD). Le travail a contribué en l’établissement d’une méthode de traitement des courbes de désorption, basée sur une distribution d’énergie d’adsorption et utilisant un set limité de données à plusieurs rampes de chauffage, pour déterminer le couple de paramètres de l’équation de Polanyi-Wigner que sont l’énergie d’adsorption et le préfacteur. D’un point de vue de la chimie théorique, les énergies d’adsorption sont déterminées en utilisant la théorie de la fonctionnelle de la densité (DFT) implémentée dans le module Vienna Ab initio Simulation Package (VASP). Cette méthode permet également d’accéder aux géométries d’adsorption, ainsi qu’aux différents sites sur la surface. La méthode expérimentale a été validée par une comparaison avec un système connu : l’adsorption du méthanol CH3OH sur le graphite. L’adsorption des gaz rares Ar/Kr/Xe sur les glaces d’eau a été étudiée comme un cas d’intérêt pour la planétologie. L’adsorption de l’acétonitrile (CH3CN) et de son isomère l’isoacétonitrile (CH3NC) sur les surfaces de graphite, de quartz et de glaces d’eau a également été étudiée, puisque ces deux molécules sont détectées dans le milieu interstellaire. Les énergies d'adsorption trouvées dans le cadre de ce travail seront intégrées dans la base des données KIDA. / Gas-grain interaction plays an important role in the chemistry of the cold interstellar medium and protoplanetary disks. A key parameter for modeling the exchange between grain surfaces and gas phase is adsorption energy, Ea. This work aims to develop a reliable and systematic experimental/theoretical approach to determine the adsorption energies of relevant atoms and molecules on models of interstellar grain surfaces. Employed experimental technique is the Temperature Programmed Desorption. Developed experimental protocol and data treatment technique based on distribution of adsorption energies and use of a set of heating rates enable to determine the coupled parameters of Polanyi-Wigner equation: adsorption energy Ea and prefactor N. Computational chemistry approach, Density Functional Theory (DFT) as implemented in Vienna Ab initio Simulation Package (VASP) is used to get the insight on the behaviour of the surface-adsorbate systems at the atomic level. This approach allows as well to determine adsorption energies. A presence of multiple adsorption sites with different adsorption energies is predicted. Methanol CH3OH adsorption on graphite is used as a known example to validate the technique. Ar/Kr/Xe adsorption on water ice is studied as a case relevant for planetology. Acetonitrile (CH_3CN) and methyl isocyanide (CH_3NC) adsorption on water ice, quartz and graphite is investigated since those two molecules are both detected in the interstellar medium. Adsorption energies determined in this work will be included in KIDA database.

No description available.

Im Fokus dieser Arbeit stand die Methode Zwillingspolymerisation zur Synthese organisch-anorganischer Hybridmaterialien. Die simultane Zwillingspolymerisation wird als neues Konzept zur gezielten Herstellung homogener, nanostrukturierter Hybridmaterialien unterschiedlicher Zusammensetzung vorgestellt. Hierfür wurden die Zwillingsmonomere 2,2’-Spirobi[4H-1,3,2-benzodioxasilin] und 2,2 Dimethyl-4H-1,3,2-benzodioxasilin in einem Arbeitsschritt gemeinsam polymerisiert. Die erhaltenen Phenolharz-Siliciumdioxid/Dimethylsiloxan-Hybridmaterialien weisen aufgrund einstellbarer Syntheseparameter unterschiedliche Eigenschaftsprofile auf, die systematisch analysiert wurden. Die Charakterisierung der Produkte erfolgte mit Hilfe der Festkörper-NMR-Spektroskopie, Elektronenmikroskopie, DSC, TGA-MS, sowie durch Extraktionsversuche und die Erzeugung und Analyse poröser Materialien. Neben der simultanen Zwillingspolymerisation wird die Synthese, Charakterisierung und thermisch induzierte Polymerisation literaturunbekannter Silicium-Spiroverbindungen mit einfach- oder zweifach substituierter Salicylalkohol-Einheit beschrieben. Hierbei wurden nanostrukturierte Hybridmaterialien mit teils hohem löslichen Anteil erhalten. Die Produktbildung wird in Abhängigkeit von der Entstehung und Weiterreaktion gefundener Chinonmethid-Strukturen diskutiert.

Im Fokus dieser Arbeit stand die Methode Zwillingspolymerisation zur Synthese organisch-anorganischer Hybridmaterialien. Die simultane Zwillingspolymerisation wird als neues Konzept zur gezielten Herstellung homogener, nanostrukturierter Hybridmaterialien unterschiedlicher Zusammensetzung vorgestellt. Hierfür wurden die Zwillingsmonomere 2,2’-Spirobi[4H-1,3,2-benzodioxasilin] und 2,2 Dimethyl-4H-1,3,2-benzodioxasilin in einem Arbeitsschritt gemeinsam polymerisiert. Die erhaltenen Phenolharz-Siliciumdioxid/Dimethylsiloxan-Hybridmaterialien weisen aufgrund einstellbarer Syntheseparameter unterschiedliche Eigenschaftsprofile auf, die systematisch analysiert wurden. Die Charakterisierung der Produkte erfolgte mit Hilfe der Festkörper-NMR-Spektroskopie, Elektronenmikroskopie, DSC, TGA-MS, sowie durch Extraktionsversuche und die Erzeugung und Analyse poröser Materialien. Neben der simultanen Zwillingspolymerisation wird die Synthese, Charakterisierung und thermisch induzierte Polymerisation literaturunbekannter Silicium-Spiroverbindungen mit einfach- oder zweifach substituierter Salicylalkohol-Einheit beschrieben. Hierbei wurden nanostrukturierte Hybridmaterialien mit teils hohem löslichen Anteil erhalten. Die Produktbildung wird in Abhängigkeit von der Entstehung und Weiterreaktion gefundener Chinonmethid-Strukturen diskutiert.