Ce travail développe une nouvelle approche de la catalyse biphasique aqueuse qui repose sur la construction de micelles réticulées à partir de polymères de type cœur-coquille. Le catalyseur (Rh) doit être incorporé sur les ligands du polymère dans la couche interne lipophile et la coquille hydrophile externe permettra de le séparer aisément du milieu réactionnel organique (oct-1-ène, nonanal, pour la réaction modèle d'hydroformylation choisie). La première partie du projet a donc consisté à préparer ces polymères à couche périphérique hydrophile assurant leur confinement en phase aqueuse et une partie interne lipophile contenant les sites actifs pour la réaction. Deux stratégies ont été explorées avec succès pour aboutir à ces structures en s'appuyant sur la polymérisation radicalaire par transfert d'atome. La première, dite « convergente », met en jeu la réticulation des copolymères linéaires fonctionnalisés préformés en présence de monomères divinyliques. La préparation des macroamorceurs linéaires fonctionnalisés a permis d'effectuer en parallèle une optimisation des conditions d'introduction d'un monomère fonctionnalisé par une phosphine qui servira par la suite de ligand pour le métal. Cette voie d'assemblage s'est avérée inefficace car un résidu des chaines linéaires non-incorporées accompagnait les produit de réticulation. Sa contrepartie, l'approche dite « divergente », a été abordée à partir de l'extension de chaines provenant d'un cœur réticulé. Les structures cœur-coquille fonctionnalisées ainsi obtenues ont des distributions de taille très homogènes. Dans le but d'évaluer leur potentiel catalytique, les copolymères fonctionnalisés, linéaires et réticulés, ont été utilisés comme ligands pour l'hydroformylation de l'oct-1-ène catalysée par le rhodium en phase homogène. Le confinement du complexe au sein des polymères a entraîné une amélioration de la régiosélectivité ainsi qu'une diminution de l'activité avec les deux types de polymères utilisés par rapport au ligand PPh3. Grace au caractère vivant de la polymérisation qui permet l'association des étapes synthétiques en séquence, il a été possible d'introduire des blocs de type PtB(M)A comme précurseurs pour l'obtention d'un bloc externe hydrophile de type P(M)AA. Les résultats préliminaires d'hydrosolubilisation des nanoréacteurs sont aussi présentés. / The current project is focused on the development of a new tool for the rhodium-catalyzed aqueous biphasic hydroformylation based on the construction of crosslinked micelles from core-shell polymers. The first goal of the project was the preparation of polymers having an hydrophilic shell that insures solubility and total confinement in the aqueous phase and a lipophilic inner shell acting as a support of active catalytic sites. Two strategies were explored to achieve such structures based on atom transfer radical polymerization. The first one, known as “arm-first”, involved the crosslinking of preformed functionalized linear copolymers in the presence of divinyl monomers. The preparation of functionalized linear macroinitiators allowed at the same time the optimization of the conditions for the introduction of a functionalized phosphine monomer that will ultimately serve as a ligand for the metal. This assembly pathway was ineffective because some residual dead chains accompanied the crosslinking product of the reaction. Its counterpart, the approach called "core-first", is based on the extension of chains from a crosslinked core. From this second approach, functionalized core-shell structures with very uniform size distributions were obtained. Both linear and cross-linked copolymers were used as ligands for the rhodium catalyzed hydroformylation of 1-octene under homogeneous conditions in order to test their catalytic performance. Because of the confinement of the ligand inside the polymer coils, a selectivity improvement as well as the slowdown of the reaction rate was observed relative to PPh3 ligand. The living character of the synthesis technique allowed the introduction of external PtB(M)A blocks: precursors to obtain a hydrophilic outer shell P(M)AA. Preliminary hydrosolubilization results of the nanoreactors will be presented in the last part of the manuscript.

Master of Science / Department of Chemistry / Emily McLaurin / Cu-doped ZnSe/CdSe core/shell nanocrystals were synthesized using the growth doping method. Upon shell growth, the nanocrystals exhibit dual emission. The green luminescence peak is assigned as band edge emission and the broad, lower energy red peak is due to Cu dopant. Although, the oxidation state of Cu in the nanocrystals is debated, the emission is explained as recombination of a hole related to Cu²⁺ with an electron from the conduction band. The emission changed in the presence of dodecanethiol. Generally, the band edge emission intensity decreases and the Cu emission intensity increases. One explanation is the thiol acts as a hole trap, preventing hole transfer to the conduction band. Samples were obtained with varying amounts of Cd²⁺. In the presence of larger amounts of Cd²⁺, the nanocrystals had “thicker shells”, and both the band edge and Cu emission were less sensitive to thiol. The sensitivity likely decreased because the shelled, larger nanocrystals have fewer surface defects resulting in more available electrons.

Doctor of Philosophy / Department of Chemistry / Jun Li / Solar energy as a sustainable resource is a promising alternative to fossil fuels to solve the tremendous global energy crisis. Development of three generation of solar cells has promoted the best sunlight to electricity conversion efficiency above 40%. However, the most efficient solar cells rely on expensive nonsustainable raw materials in device fabrication. There is a trend to develop cost-effective biophotovoltaics that combines natural photosynthetic systems into artificial energy conversion devices such as dye sensitized solar cells (DSSCs). In this research, a model system employs natural extract light-harvesting complex II (LHCII) as a light-absorbing sensitizer to interface with semiconductive TiO₂ and plasmonic nanoparticles in DSSCs. The goal of this research is to understand the fundamental photon capture, energy transfer and charge separation processes of photosynthetic pigment-protein complexes along with improving biophotovoltaic performance based on this model system through tailoring engineering of TiO₂ nanostructures, attaching of the complexes, and incorporating plasmonic enhancement. The first study reports a novel approach to linking the spectroscopic properties of nanostructured LHCII with the photovoltaic performance of LHCII-sensitized solar cells (LSSCs). The aggregation allowed reorganization between individual trimers which dramatically increased the photocurrent, correlating well with the formation of charge-transfer (CT) states observed by absorption and fluorescence spectroscopy. The assembled solar cells demonstrated remarkable stability in both aqueous buffer and acetonitrile electrolytes over 30 days after LHCII being electrostatically immobilized on amine-functionalized TiO₂ surface. The motivation of the second study is to get insights into the plasmonic effects on the nature of energy/charge transfer processes at the interface of photosynthetic protein complexes and artificial photovoltaic materials. Three types of core-shell (metal@TiO₂) plasmonic nanoparticles (PNPs) were conjugated with LHCII trimers to form hybrid systems and incorporated into a DSSC platform built on a unique open three-dimensional (3D) photoanode consisting of TiO₂ nanotrees. Enhanced photon harvesting capability, more efficient energy transfer and charge separation at the LHCII/TiO₂ interface were confirmed in the LHCII-PNP hybrids, as revealed by spectroscopic and photovoltaic measurements, demonstrating that interfacing photosynthesis systems with specific artificial materials is a promising approach for high-performance biosolar cells. Furthermore, the final study reveals the mechanism of hot electron injection by employing a mesoporous core-shell (Au@TiO₂) network as a bridge material on a micro-gap electrode to conduct electricity under illumination and comparing the photoconductance to the photovolatic properties of the same material as photoanodes in DSSCs. Based on the correlation of the enhancements in photoconductance and photovoltaics, the contribution of hot electrons was deconvoluted from the plasmonic near-field effects.

The objective of this Ph.D. study is to explore an important and fertile research topic on the methods for synthesis of nanomaterials by homogeneous nonaqueous solution phase reaction. Research in this work focuses on synthesizing several kinds of nanomaterials in different environments and structure, including spherical nanoparticles, nanowires and core-shell structure composites We first synthesized metallic nanomaterials in this system, such as ~10 nm Fe nanoparticles, ~6 nm Au nanoparticles, and ~100 nm Bi nanoparticles, this system are the preparation for the following studies. Secondly, we synthesized bimetallic nanomaterials in this system, such as Fe50Co50 alloy and Bi doped with Mn. For FeCo alloy, after annealing at 500 °C, a pure phase of Fe50Co50 was obtained. And we first synthesized the nanowires of bismuth doped with manganese. By studying intermediates at different temperatures during the growth process of nanowires, the evolution of the crystallization of metallic products and the mechanism of the formation of the nanowires are investigated. Thirdly, we synthesized core-shell structure nanocomposites, including either gold as the shell or polymer as the shell. Au-coated magnetic Fe nanoparticles have been successfully synthesized by partial replacement reaction in a polar aprotic solvent with about 11 nm core of Fe and about 2.5 nm shell of Au. HRTEM images show clear core-shell structure with different crystal lattices from Fe and Au. SQUID magnetometry reveals that particle magnetic properties are not significantly affected by the overlayer of a moderately thick Au shell. The Aucoated particles exhibit a surface plasmon resonance peak that red-shifts from 520 to 680 nm. And Poly (Vinyl Pyrolidone) (PVP) coated iron nanoparticles also have been successfully synthesized in a polar aprotic solvent, which shows the welldefined core-shell structures. In this approach, Poly (Vinyl Pyrolidone) (PVP) was employed as the coating polymer directly coated on metallic core (iron) nanoparticles. In this work, a combination of TEM (transmission electron microscopy), EDS (Energy disperse X-ray spectroscopy), XRD (X-ray powder diffractometry), ICP (inductively-coupled plasma spectrometer), TGA (Thermogravimetric analysis), UV-visible absorption spectroscopy, IR (infrared) spectroscopy and SQUID magnetometry (Superconducting Quantum Interference Device) were employed to characterize the morphology, structure, composition and magnetic properties of the products. In summary, this Ph.D. study successfully and systematically synthesized several kinds of nanocomposites in a system. The synthetic procedure is simple, economic and easily scaled-up for further applications. And many techniques were employed to characterize the products.

La manipulation des propriétés physiques des nanostructures, telles que leur forme ou leur composition, suscite de plus en plus l’intérêt des recherches à cause des propriétés exceptionnelles des matériaux à cette échelle. L’ingénierie des contraintes a pour objet d’utiliser la déformation pour contrôler les propriétés. Cela est particulièrement intéressant dans les nano-objets car ils peuvent supporter des déformations élastiques élevées. Dans ce travail, nous étudions la déformation et l’influence de la température dans des nanofils uniques de type coeur/coquille. Ceci est possible en utilisant la diffraction cohérente des rayons X (CDI) en condition de Bragg, une technique d’imagerie qui remplace les lentilles optiques par des algorithmes d’inversion capables de reconstruire l’amplitude (densité électronique) et la phase (projection du champ de déplacement atomique) de l’échantillon à partir des clichés de diffraction. Cette méthode a également été appliquée à des particules facettées de platine qui ont des propriétés catalytiques exceptionnelles. Des expériences CDI in situ ont permis d’étudier l’évolution du champ de déformation dans les particules pendant des réactions chimiques et donc de progresser vers le découplage entre leur déformation intrinsèque et leur activité chimique. / Manipulating the physical and chemical properties of nanostructures by changing their characteristics (such as shape, strain or composition) is a vivid field of research spurred by the numerous applications that may take advantage of the unique properties that materials offer at this scale.Strain engineering aims to tune the strain in order to control the properties of materials. This is particularly interesting in nano-objects because they can sustain much higher elastic strains before the occurrence of defects. In this work, we study the strain and the influence of temperature in single core/shell nanowires. This is possible thanks to X-ray coherent diffraction (CDI) in Bragg condition, an imaging technique that replaces the optical lenses by inversion algorithms that are able to reconstruct the amplitude (electronic density) and the phase (projection of the atomic displacement field) of the sample from the experimental diffraction patterns. In addition to nanowires, the method is applied to metallic particles of platinum with exceptional catalyticproperties. In situ CDI experiments allowed to study the strain evolution within particles during chemical reactions, thereby moving forward in the understanding of important relationships such as the intrinsic strain and chemical activity of the nanoparticles.

Les problématiques liées à la diminution de la taille des dispositifs actuels amènent l’industrie à réfléchir à des techniques de gravure ayant des résolutions à l’échelle de l’atome. Dans ce contexte, les techniques de nanostructuration directes sont très bien adaptées et représentent un potentiel important pour un futur proche dans les laboratoires de recherches. Le projet sur lequel j’ai travaillé avait pour but de coupler dans un environnement Ultra-Vide (UHV), un Dual-Beam, composé d’un FIB (Faisceau d’Ions Focalisé) et d’un MEB (Microscope électronique à balayage) et un bâti d’épitaxie par jet moléculaire (MBE), technique ultime en termes de dépôt. Cet environnement UHV répond à la nécessité de propreté absolue des substrats et constitue un moyen pertinent de rendre fonctionnels les dispositifs ainsi élaborés dans des domaines aussi variés que la micro-nanoélectronique, l’optoélectronique, le photovoltaïque, la spintronique, la plasmonique, etc. La connexion sous UHV de la nanofabrication FIB à la croissance MBE représente une voie unique pour fabriquer des structures 3D en alternant des étapes gravure/dépôt. Parmi les différentes applications, nous avons choisi de nous focaliser sur nanostructures de silicium. Le principal challenge pour l’industrie microélectronique et pour les chercheurs est d’être capable de réaliser une optoélectronique entièrement intégrée à base de Si. Cela nécessite de convertir les matériaux à base de Si en absorbeur/émetteur efficaces de lumière. Une des pistes les plus prometteuses pour obtenir une bande interdite directe est de combiner les effets de la fonctionnalisation chimique et du confinement quantique dans les nano-objets. / The reduction of device sizes represents a major issue in microelectronic industry which motivates several teams of researchers to develop nanopatterning with atomic resolution. In this context, maskless nanostructuration techniques are well-adapted and have an important potential for the nearest future in labs and industry. The aim of the project I worked on is the connection in a Ultra-High-Vacuum (UHV) environment between a Dual-Beam, equipped with a FIB (Focused Ion Beam) and a SEM (Scanning Electron Microscopy) and a MBE (Molecular Beam Epitaxy) cluster, which is the highest-controlled deposition technique. The UHV environment is the solution for an absolute cleanliness and represents a relevant way to fabricate functionalized devices for micro-nanoelectronics, optoelectronics, photovoltaic, spintronic, plasmonic, etc… This UHV connection combining FIB nanostructuration and epitaxy growth technique provides a unique platform to elaborate tridimensional structures with milling/deposition steps. Among different applications, we decided to focus on silicon based nanostructures. Regarding silicon nanostructures. The main challenge for microelectronics industry and for the researchers in this field is the realization of optoelectronics devices fully integrated in silicon systems. This requires to convert silicon based materials into absorber/emitter of light. One of the most promising way to change the electronic structure and to get a direct bandgap is the combination of chemical functionalization and quantum confinement into silicon based nano-objects.

No presente trabalho propõe-se o uso de substratos de Au poli e monocristalinos modificados superficialmente com Pt para o estudo da reação de oxidação de etanol. Serão apresentados os resultados obtidos no estudo da influência da concentração superficial de Pt depositada na distribuição dos produtos da eletrooxidação de etanol. Os resultados mostram que no caso do sistema Pt/Au-poli, a superfície de Au que possui o menor teor superficial de Pt depositada tem uma habilidade maior para quebrar a ligação C-C. Porém quanto menor a quantidade de Pt depositada na superfície de Au, maior o efeito de desativação. Estes comportamentos são explicados pelas estruturas superficiais formadas pelos depósitos. Adicionalmente, são apresentados os resultados obtidos no estudo sistemático da influência de defeitos superficiais nos substratos de Au na atividade catalítica de camadas de Pt. Os resultados sugerem que, mesmo que os substratos de Au não estejam em contato com a solução eletrolítica devido ao grau de cobertura utilizado, a presença de defeitos nos substratos de Au induzem variações na distribuição de produtos resultantes da eletrooxidação de etanol. Mais especificamente, quanto maior é a densidade de defeitos nos substratos de Au a via de produção de ácido acético é favorecida, com a consequênte inibição na produção de CO2. / In this work we propose the use of poly and single crystalline Au surfaces modified with Pt as a model system of core-shell nanoparticles to study the ethanol oxidation reaction (EOR). Results regarding the study of the influence of Pt coverage on the product yields of EOR are presented. The results show that the in the case of the Pt/Au-poly system, the Au surface modified with lower amounts of Pt has a higher ability to break the C-C bond present in the ethanol molecule. On the other hand, deposits having small amounts of Pt suffer a faster deactivation due to CO poisoning. This behavior is explained by the structure adopted by the catalytic layer. Additionally, results regarding the study of the influence of defects on the Au surfaces on the catalytic behavior of Pt layer will be shown. The results suggest that, even though Au active site are not in contact with electrolityc solution, the defects lying under the Pt layer influence the catalytic response of the layer. Specifically, as the step density in the Au substrate increases, the acetic acid path is privileged over the CO2 production path.

The presented project explores the optical properties of magnetoplasmonic Au/Ni core-shell structures. The work aims at controlling dimensions and parameters in order to influence and analyze the optical properties of the nanostructures. The softwares utilized for the simulations were COMSOL Multiphysics 5.1 and MATLAB. Experimental results were acquired from labs done at Ångströms laboratory. From the research based study where the gold to nickel ratio was influenced, it was observed that the transmissions for the nanostructures at the differing wavelengths produced transmissions of similar bearings. Modes for certain wavelengths were found in correspondence with the transmissions and could potentially render explanations for influence on the optical properties of the nanostructures. Conclusively, it can be stated that the optical properties of the nanostructures could be influenced and controlled by varying the dimensions and properties of the said structure. Differing dimensions corresponded to noteworthy changes in the cross sections, the transmissions as well as the mode formations.

Thesis advisor: Chia-kuang Frank Tsung / Pt-based alloy and core-shell nanoparticles have been intensively studied to regulate its size and shape. It has known that these nanoparticles show enhanced catalytic activity in various important fields such as heterogeneous catalysis, and electrochemical energy storage including fuel cells and metal-air batteries. Here, we report a facile hydrothermal synthesis of sub-10 nm PdPt alloy and sub-20 nm Au@PdPt core-shell structures. By using a mild reducing agent in aqueous solution, metal precursors are co-reduced. Specific gases are introduced during the synthesis to optimize the reaction conditions. The PdPt alloy and Au@PdPt core-shell nanostructures were characterized and confirmed by TEM, HRTEM, EDS, ICP-OES and XRD. The resulting PdPt and Au@PdPt particles are monodispersed single crystalline and octahedral shape enclosed by (111) facets. The electrocatalytic activity for the oxidation of formic acid was tested. It was found that the catalytic activity toward the formic acid oxidation of Au@PdPt core-shell particles were much higher than those of PdPt alloy particles. In addition, Pt-rich compositions were the most active in both PdPt alloy and Au@PdPt core-shell nanoparticles. Further studies on thinner alloy-shell core-shell nanoparticles reveal that there is a volcano-curve relationship between the lattice strain strength related to alloy-shell thickness and the catalytic performance. It is proposed that there are three key parameters that can determine the catalytic activity: the alloy composition, the presence of the gold core, and the thickness of alloy-shell. / Thesis (MS) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The self-assembling properties of a core-shell system are considered to be the most desirable characteristics that allow using this class of polymers in different applications. New hairy nanoparticles (HNPs) with hydrophobic polystyrene cores (PS Cores) and hydrophilic poly(2-hydroxyethylmethacrylate) (PHEMA) shells were synthesized by coupling polymerization methods. Living anionic polymerization in one-pot step was used to synthesize cross-linked polystyrene cores functionalized with hydroxyl groups and atom transfer radical polymerization (ATRP) was then carried out to prepare PHEMA hairs following the grafting form technique. The structural characterizations were carried out by FT-IR and NMR spectroscopy (1H NMR, 13C NMR, APT 13C NMR and 1H 13C HMQC). Dynamic light scattering measurements of obtained HNPs show small increase in the order of nanometers of their hydrodynamic radii after the grafting. Thermal properties were studied by TGA and DSC. The thermal stability of PS cores was affected by functionalization with the hydroxyl group. However, the stability of the PS core was not affected by grafting of PHEMA on their surfaces. DSC thermograms of the HNPs shows two distinct transition temperatures corresponding to glass transition temperatures (Tg) of a PS phase and of a PHEMA phase indicating the formation of a hydrophobic-hydrophilic phase separated system. SEM and AFM were utilized to study the morphologies and self-assembly of nanoparticles. The self-assembled HNPs morphologies were dependent on the solvents used. Complexes of the synthesized HNPs and R- or S-mandelic acid were prepared and characterized by circular dichroism (CD) and AFM. CD was used to study the induced chiral properties of the complexes. The CD spectra indicated the formation of enantiomeric chiral structures and the AFM images show toroidal self-assembled structures. Polymer blends of polystyrene functionalized with hydroxyl groups and PHEMA show different morphology and different thermal properties than the core-shell HNP system.