<p dir="ltr">Catalyzing a green hydrogen economy can accelerate progress towards achieving the goal of a sustainable energy map with net-zero carbon emissions by rapid strides. An environmentally benign electrochemical energy conversion system is the Polymer Electrolyte Fuel Cell (PEFC) which uses hydrogen as a fuel to produce electricity and is notably used in a variety of markets such as industries, commercial setups, and across the transportation sector, and is gaining prominence for use in heavy-duty vehicles such as buses and trucks. Despite its potential, the commercialization of PEFCs needs to address several challenges which are manifested in the form of mass transport limitations and deleterious mechanisms at the interfacial scale under severe operating conditions. Achieving a robust electrochemical performance in this context is predicated on desired interactions at the triple-phase boundary of the electrochemical engine of the PEFC – the porous cathode catalyst layer (CCL) where the principal oxygen reduction reaction (ORR) takes place. The liquid water produced as a byproduct of the ORR helps minimize membrane dehydration; however, excess water renders the reaction sites inactive causing reactant starvation. In addition, the oxidation of the carbonaceous support in the electrode and loss of valuable electrochemically active surface area (ECSA) pose major barriers that need to be overcome to ameliorate the life expectancy of the PEFC.</p><p dir="ltr">In this thesis, the multimodal physicochemical interactions occurring inside the catalyst layer are investigated through a synergistic blend of visualization and computational techniques. The spatiotemporal dynamics of capillary force-driven liquid transport that ensues concentration polarization thereby affecting the desired response will be probed in detail. The drop in efficacy of the ORR due to competing catalyst aging mechanisms and the impact of degradation stressors on chemical potential-induced instability will be examined. The reaction-transport-mechanics interplay in core-shell nanoparticles, a robust class of electrocatalysts that promises better mass activity compared to the single metal counterparts is further highlighted. Finally, the influence of electrode microstructural attributes on the electrochemical performance of the reverse mode of fuel cell operation, i.e., Proton Exchange Membrane Water Electrolyzers (PEMWEs) is investigated through a mesoscale lens.</p>

Obwohl wir sie oft nicht bewusst wahrnehmen, sind Nanopartikel heutzutage in den meisten Bereichen unseres Alltags präsent, unter anderem in Lebensmitteln und ihren Verpackungen, Medizin, Medikamenten, Kosmetik, Pigmenten und in elektronischen Geräten wie Computermonitoren. Ein Großteil dieser Partikel weist, beabsichtigt oder unbeabsichtigt, eine Kern-Schale Morphologie auf. Einfachheitshalber wird diese Morphologie eines Kern-Schale-Nanopartikels (CSNP) oft als ideal angenommen, d.h. als ein sphärischer Kern, der komplett von einer Schale homogener Dicke bedeckt ist, mit einer scharfen Grenzfläche zwischen Kern- und Schalenmaterial. Außerdem wird vielfach auch davon ausgegangen, alle Partikel der Probe hätten gleiche Schalendicken. Tatsächlich weichen die meisten realen CSNPs in verschiedenster Weise von diesem Idealmodell ab, mit oft drastischen Auswirkungen darauf, wie gut sie ihre Aufgabe in einer bestimmten Anwendung erfüllen. Das Thema dieser kumulativen Doktorarbeit ist die exakte Charakterisierung der wirklichen Morphologie von CSNPs mit modernen Röntgen-basierten Methoden, konkret Röntgen-Photoelektronen-Spektroskopie (XPS) und Raster-Transmissions-Röntgen-Mikroskopie (STXM). Der Fokus liegt insbesondere auf CSNPs, die von einer idealen Kern-Schale-Morphologie abweichen. Aufgrund der enormen Vielfalt an CSNPs, die sich in Material, Zusammensetzung und Form unterscheiden, kann eine Messmethode nicht völlig unverändert von einer Probe auf eine andere übertragen werden. Nichtsdestotrotz, da die als Teil dieser Doktorarbeit präsentierten Artikel eine deutlich ausführlichere Beschreibung der Experimente enthalten als vergleichbare Publikationen, stellen sie eine wichtige Anleitung für andere Wissenschaftler dafür dar, wie aussagekräftige Informationen über CSNPs durch Oberflächenanalytik erhalten werden können. / Even though we often do not knowingly recognize them, nanoparticles are present these days in most areas of our daily life, including food and its packaging, medicine, pharmaceuticals, cosmetics, pigments as well as electronic products, such as computer screens. The majority of these particles exhibits a core-shell morphology either intendedly or unintendedly. For the purpose of practicability, this core-shell nanoparticle (CSNP) morphology is often assumed to be ideal, namely a spherical core fully encapsulated by a shell of homogeneous thickness with a sharp interface between core and shell material. It is furthermore widely presumed that all nanoparticles in the sample possess the same shell thickness. As a matter of fact, most real CSNPs deviate in several ways from this ideal model with quite often severe impact on how efficiently they perform in a specific application. The topic of this cumulative PhD thesis is the accurate characterization of the actual morphology of CSNPs by advanced X-ray analytical techniques, namely X-ray photoelectron spectroscopy (XPS) and scanning transmission X-ray microscopy (STXM). A special focus is on CSNPs which deviate from an ideal core-shell morphology. Due to the vast diversity of nanoparticles differing in material, composition and shape, a measurement procedure cannot unalteredly be transferred from one sample to another. Nevertheless, because the articles in this thesis present a greater depth of reporting on the experiments than comparable publications, they constitute an important guidance for other scientists on how to obtain meaningful information about CSNPs from surface analysis.

Im Folgenden werden Transferprozesse in Nanohybridsystemen theoretisch untersucht. Diese Hybridsysteme sind vielversprechende Kandidaten für neue optoelektronische Anwendungen und erfahren daher ein erhebliches Forschungsinteresse. Jedoch beschränken sich Arbeiten darüber hauptsächlich auf experimentelle Untersuchungen und kaum auf die dazugehörige theoretische Beschreibung. Bei den theoretischen Betrachtungen treten entscheidende Limitierungen auf. Es werden entweder Details auf der atomaren Ebene vernachlässigt oder Systemgrößen betrachtet, die wesentlich kleiner als im Experiment sind. Diese Thesis zeigt, wie die bestehenden Theorien verbessert werden können und erweitert die bisherigen Untersuchungen durch die Betrachtung von vier neuen hoch relevanten Nanohybridsystemen. Das erste System ist eine Nanostruktur, die aus einem Au-Kern und einer CdS-Schale besteht. Beim zweiten System wurde eine ZnO/Para-Sexiphenyl Nanogrenzfläche untersucht. Die zwei anderen Systeme beinhalten jeweils einen CdSe-Nanokristall, der entweder mit einem Pheophorbide-a-Molekül oder mit einem röhrenförmigen Farbstoffaggregat wechselwirkt. In allen Systemen ist der Anregungsenergie-Transfer ein entscheidender Transfermechanismus und steht im Fokus dieser Arbeit. Die betrachteten Hybridsysteme bestehen aus zehntausenden Atomen und machen daher eine individuelle Berechnung der einzelnen Subsysteme sowie deren gegenseitiger Wechselwirkung notwendig. Die Halbleiter-Nanostrukturen werden mit der Tight-Binding-Methode und der Methode der Konfigurationswechselwirkung beschrieben. Für das molekulare System wird die Dichtefunktionaltheorie verwendet. Die dazugehörigen Rechnungen wurden von T. Plehn ausgeführt. Das metallische Nanoteilchen wird durch quantisierte Plasmon-Moden beschrieben. Die verwendeten Theorien ermöglichen eine Berechnung von Anregungsenergietransfer in Nanohybridsystemen von bisher nicht gekannter Systemgröße und Detailgrad. / In the following, transfer phenomena in nanohybrid systems are investigated theoretically. Such hybrid systems are promising candidates for novel optoelectronic devices and have attracted considerable interest. Despite a vast amount of experimental studies, only a small number of theoretical investigations exist so far. Furthermore, most of the theoretical work shows substantial limitations by either neglecting the atomistic details of the structure or drastically reducing the system size far below the typical device extension. The present thesis shows how existing theories can be improved. This thesis also expands previous theoretical investigations by developing models for four new and highly relevant nanohybrid systems. The first system is a spherical nanostructure consisting of an Au core and a CdS shell. By contrast, the second system resembles a finite nanointerface built up by a ZnO nanocrystal and a para-sexiphenyl aggregate. For the last two systems, a CdSe nanocrystal couples either to a pheophorbide-a molecule or to a tubular dye aggregate. In all of these systems, excitation energy transfer is an essential transfer mechanism and is, therefore, in the focus of this work. The considered hybrid systems consist of tens of thousands of atoms and, consequently, require an individual modeling of the constituents and their mutual coupling. For each material class, suitable methods are applied. The modeling of semiconductor nanocrystals is done by the tight-binding method, combined with a configuration interaction scheme. For the simulation of the molecular systems, the density functional theory is applied. T. Plehn performed the corresponding calculations. For the metal nanoparticle, a model based on quantized plasmon modes is utilized. As a consequence of these theories, excitation energy transfer calculations in hybrid systems are possible with unprecedented system size and complexity.

No description available.

No / Microcarrier cell culture systems provide an attractive alternative to the conventional monolayer cell culture for cell amplification, due to their high surface area-to-volume ratio. Unlike enzymatic methods for removing cells from microcarriers after cell culture, which can lead to irreversible damage of the cells, microcarriers which release cells by temperature adjustment have been developed. This was achieved by grafting a temperature-responsive polymer, poly(N-isopropylacrylamide) (PNIPAAm), on the microcarrier surface. This review comprehensively presents various methods to prepare such thermo-responsive microcarriers based on PNIPAAm. These methods include the grafting-to technique, grafting-from technique, grafting-through technique, along with methods leading to PNIPAAm hydrogel beads, seeded polymerization, and non-covalent adsorption. The methods for controlling PNIPAAm grafting density, molecular weight and molecular architecture are also outlined. Further, the efficiency of cell attachment, proliferation and thermally-induced detachment of such thermo-responsive microcarriers is introduced and compared. (C) 2015 Elsevier Ltd. All rights reserved.

Nanostructured ZnO films were obtained via thermal oxidation of thin films formed with metallic Zn-nanoparticle dispersions. Commercial zinc nanoparticles used for this work were characterized by microscopic and thermal analysis methods to analyze the Zn-ZnO core shell structure, surface morphology and oxidation characteristics. These dispersions were spin-coated on SiO₂/Si substrates and then annealed in air between 100 and 600 °C. Significant nanostructural changes were observed for the resulting films, particularly those from larger Zn nanoparticles. These nanostructures, including nanoneedles and nanorods, were likely formed due to fracturing of ZnO outer shell due to differential thermal expansion between the Zn core and the ZnO shell. At temperatures above 227 °C, the metallic Zn has a high vapor pressure leading to high mass transport through these defects. Ultimately the Zn vapor rapidly oxidizes in air to form the ZnO nanostructures. We have found that the resulting films annealed above 400 °C had high electrical resistivity. The zinc nanoparticles were incorporated into zinc indium oxide solution and spin-coated to form thin film transistor (TFT) test structures to evaluate the potential of forming nanostructured field effect sensors using simple solution processing. The functionalization of zinc tin oxide (ZTO) films with self-assembled monolayers (SAMs) of n-hexylphosphonic acid (n-HPA) was investigated. The n-HPA modified ZTO surfaces were characterized using contact angle measurement, x-ray photoelectron spectroscopy (XPS) and electrical measurements. High contact angles were obtained suggesting high surface coverage of n-HPA on the ZTO films, which was also confirmed using XPS. The impact of n-HPA functionalization on the stability of ZTO TFTs was investigated. The n-HPA functionalized ZTO TFTs were either measured directly after drying or after post-annealing at 140 °C for 48 hours in flowing nitrogen. Their electrical characteristics were compared with that of non-functionalized ZTO reference TFTs fabricated using identical conditions. We found that the non-functionalized devices had a significant turn-on voltage (V[subscript ON]) shift of ~0.9 V and ~1.5 V for the non-annealed and the post-annealed conditions under positive gate bias stress for 10,000 seconds. The n-HPA modified devices showed very minimal shift in V[subscript ON] (0.1 V), regardless of post-thermal treatment. The VON instabilities were attributed to the interaction of species from the ambient atmosphere with the exposed ZTO back channel during gate voltage stress. These species can either accept or donate electrons resulting in changes in the channel conductance with respect to the applied stress. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Jan. 6, 2012 - Jan. 6, 2013

Neste trabalho, a estrutura local e média de nanopartículas foi estudada utilizando-se métodos de espalhamento e difração de raios X. Os métodos utilizados foram: Análise da Função de Distribuição de Pares Atômicos (Atomic Pair Distribution Function Analysis, em inglês) para o estudo do ordenamento estrutural de curto alcance, Refinamento de Rietveld e Modelamento Total do Perfil de Difração de Pó para o estudo do ordenamento médio. Os materiais estudados foram: nanopartículas de KY3F10 dopadas com Tb, nanocubos núcleo-camada (core-shell, em inglês) de FeO-Fe3O4 e nanopartículas de ferritas de Mn-Zn. O trabalho teve como objetivo demonstrar como os métodos mencionados podem ser utilizados de forma complementar para fornecer informações de curto, médio e longo alcance usando-se dados de espalhamento e difração de raios X. Neste trabalho, ressalta-se a importância de cada método no estudo da estrutura cristalina e demonstra avanço e desenvolvimento de metodologias para a sua aplicação. / In this work, local and average structure of nanoparticles were studied using X-ray scattering and diffraction methods. The methods used were: Atomic Pair Distribution Function Analysis to study the short-range ordering, Rietveld refinement and Whole Powder Pattern Modelling to study the long-range ordering. The studied materials were: Tb-doped KY3F10 nanoparticles, core-shell FeO-Fe3O4 nanocubes and Mn-Zn ferrite nanoparticles. The objective of this work was to demonstrate how the methods mentioned can be used in a complementary way to provide short, average and long range information about the structure using X-ray scattering and diffraction data. The importance of each method to study the crystalline structure is highlighted demonstrating progress and development of methodologies for its application.

Das Thema dieser Arbeit ist die Synthese von Ferromagnet-Halbleiter-Nanodraht-Strukturen in einer Kern-Hülle-Geometrie. Diese wird mittels Molekularstrahlepitaxie unter der Verwendung von GaAs und Fe3Si ausgeführt. Im Zentrum der Arbeit steht die Frage, ob sich mit derartigen Strukturen Magnetisierungen senkrecht zum Substrat realisieren lassen. Eine solche Konfiguration der Magnetisierung innerhalb bestimmter Strukturen ist wünschenswert, denn sie bildet die Grundlage einiger zukunftsweisender spintronischer Bauteilkonzepte. Aufgrund der Formanisotropie dünner Schichten ist diese Konfiguration der Magnetisierung in planaren Strukturen nur mit erheblichem Aufwand zu bewerkstelligen. Bildet sich hingegen in den Nanodraht-Hüllen eine Stabmagnetisierung aus, so führt dies direkt zur gewünschten senkrechten Magnetisierung. Im ersten Teil dieser Arbeit wird der Epitaxie-Prozess vorgestellt. Abhängig von den Wachstumsparametern können Hüllen mit glatten Seitenflachen, einer hohen Kristallordnung, ebenen Grenzflachen zum GaAs-Kern und epitaktischer Ausrichtung realisiert werden. Der zweite Teil behandelt die magnetischen Eigenschaften der Nanodrahte. Ensemble-Charakterisierungen sind hierbei in diesem Fall nicht geeignet. Einzeldraht-Messungen hingegen zeigen, dass sich in den Nanodraht-Hüllen wie erhofft eine Stabmagnetisierung ausbildet. Der dritte und letzte Teil dieser Dissertation umfasst die Einführung mehrerer zukunftsweisender Bauteilkonzepte, basierend auf den speziellen magnetischen Eigenschaften der hier vorgestellten Nanodrahte. Dazu gehören dreidimensionale Speicherarchitekturen mit bislang unerreichten Speicherkapazitäten und zirkular polarisiertes Licht emittierende Leuchtdioden für einen enorm schnellen Spininformations-Transfer zur Intrachip-Kommunikation. / The subject of the present work is the synthesis of ferromagnet-semiconductor coreshell nanowires. To realize such structures molecular beam epitaxy has been employed. For the investigation the well-suited materials systems GaAs and Fe3Si are used. Within the framework of this thesis the open question whether a magnetization in the nanowires that is perpendicular to the nanowire’s substrate can be realized is of special interest. Such a configuration of the magnetization is desirable, because some spintronic device concepts rely on magnetizations perpendicular to the substrate. In general, with the exception of very limited and highly specific materials, the shape anisotropy of thin magnetic layers causes the magnetic moments to orient along an in-plane direction and therefore, perpendicular configurations of the magnetization do not occur at equilibrium conditions. In contrast, magnetic nanowires with moments pointing along the wire axis directly provide the desired out-of plane magnetization. In the first part, the epitaxial procedure to realize the core-shell nanowires is described. Nanowires with smooth side walls, smooth interface to the GaAs core, a fairly high structural ordering and an epitaxial orientation relationship are produced. In the second part, the magnetic properties of the core-shell nanowires are analyzed. It is shown that characterizations of an ensemble of wires cannot resolve magnetic properties of the shells. Investigations on single nanowires however revealed that the magnetization in the shells is indeed as desired oriented along the wires. Several innovative device concepts based on the specific magnetic properties of these core-shell nanowires are finally introduced in the third part of this work. Within these concepts three-dimensional magnetic recording devices with unsurpassed data storage capacities and circular polarized light emitting diodes for tremendously fast spin information transfer for intrachip communication can be realized.

Neste trabalho, a estrutura local e média de nanopartículas foi estudada utilizando-se métodos de espalhamento e difração de raios X. Os métodos utilizados foram: Análise da Função de Distribuição de Pares Atômicos (Atomic Pair Distribution Function Analysis, em inglês) para o estudo do ordenamento estrutural de curto alcance, Refinamento de Rietveld e Modelamento Total do Perfil de Difração de Pó para o estudo do ordenamento médio. Os materiais estudados foram: nanopartículas de KY3F10 dopadas com Tb, nanocubos núcleo-camada (core-shell, em inglês) de FeO-Fe3O4 e nanopartículas de ferritas de Mn-Zn. O trabalho teve como objetivo demonstrar como os métodos mencionados podem ser utilizados de forma complementar para fornecer informações de curto, médio e longo alcance usando-se dados de espalhamento e difração de raios X. Neste trabalho, ressalta-se a importância de cada método no estudo da estrutura cristalina e demonstra avanço e desenvolvimento de metodologias para a sua aplicação. / In this work, local and average structure of nanoparticles were studied using X-ray scattering and diffraction methods. The methods used were: Atomic Pair Distribution Function Analysis to study the short-range ordering, Rietveld refinement and Whole Powder Pattern Modelling to study the long-range ordering. The studied materials were: Tb-doped KY3F10 nanoparticles, core-shell FeO-Fe3O4 nanocubes and Mn-Zn ferrite nanoparticles. The objective of this work was to demonstrate how the methods mentioned can be used in a complementary way to provide short, average and long range information about the structure using X-ray scattering and diffraction data. The importance of each method to study the crystalline structure is highlighted demonstrating progress and development of methodologies for its application.

L’agencement relatif de systèmes cristallins moléculaires, par une méthode d’organisation avancée est une stratégie de premier plan. Le développement de tels systèmes permet la conception de dispositifs innovants dans le domaine des matériaux poreux, magnétiques ou optiques.Les travaux menés dans le cadre de cette étude ont pour objectif l’élaboration d’architectures macroscopiques hiérarchisées concernant l’état cristallin, de type « réseaux de cristaux ». Dans un premier temps, le développement et la caractérisation de réseaux iso-structuraux ont été réalisés. Ces séries, formées par liaisons hydrogènes, servent à l’étude de la croissance cristalline épitaxiale, développée par la suite. À partir de ces résultats, la préparation d’architectures monocristallines de type cristal cœur-coquille ainsi que la soudure cristalline sont entreprises.Enfin, la généralisation de cette mise en forme de l’état cristallin à des systèmes formés par liaisons de coordination est présentée. / The relative disposition of applicative molecular systems by an advanced organization method is a well-defined strategy (core-shell type crystals). It is aimed at developing innovative materials.The presented study deals with the elaboration of a new organization method concerning the crystalline matter to obtain “network of crystals”. This strategy of materials processing occurs at a macroscopic scale and in a hierarchical way.Firstly, series of isostructural crystalline molecular networks have been designed with a molecular tectonics approach. These series, formed by hydrogen bonds, are then used for the study of the epitaxial growth of crystal. The preparation of a single crystalline architecture with a defined sequenced area of different compositions is demonstrated: core-shell crystals and welded crystals.Finally, the developed strategy is applied to coordination networks exhibiting luminescent properties in order to generalize the described process.