Title: Morfology and surface chemical composition of porous silicon prepared at various conditions Author: Bc. Martin KONEČNÝ Author's e-mail: konecmar@seznam.cz Department: Department of Chemical Physics and Optics Supervisor: Doc. RNDr. Juraj Dian, CSc. Supervisor's e-mail: Juraj.Dian@mff.cuni.cz Abstract: Porous silicon is a silicon-based material prepared mainly by anodic etching of crystalline silicon in hydrofluoric acid. Physical and chemical properties of porous silicon are governed by structures with sizes of the order of ones to tens of nanometers. Properties of nanostructure material are affected - as compared to macroscopic counterparts - by quantum confinement effect and enormous internal surface. According to type of silicon substrate (type of dopant, conductivity, crystallographic orientation) and technological conditions a material with different mean size of pores (macro-, meso- and nanoporous silicon) and surface chemical composition (different ratio of Si-O and Si-H bond) can be prepared. Morphology and surface chemical composition predestinated application potential of porous silicon for sensors of chemical species by taking advantage of strong sensitivity of physical properties of silicon nanocrystals - especially of photoluminescence - on the chemical state of a surface. Detection of...

Master of Science / Department of Biological and Agricultural Engineering / Donghai Wang / Acid catalysts have been successfully used for pretreatment of cellulosic biomass to improve sugar recovery and its later conversion to ethanol. However, use of acid requires a considerable equipment investment as well as disposal of residues. Acid-functionalized nanoparticles were synthesized for pretreatment and hydrolysis of lignocellulosic biomass to increase conversion efficiency at mild conditions. Advantages of using acid-functionalized metal nanoparticles are not only the acidic properties to catalyze hydrolysis and being small enough to penetrate into the lignocellulosic structure, but also being easily separable from hydrolysis residues by using a strong magnetic field. Cobalt spinel ferrite magnetic nanoparticles were synthesized using a microemulsion method and then covered with a layer of silica to protect them from oxidation. The silanol groups of the silica serve as the support of the sulfonic acid groups that were later attached to the surface of the nanoparticles. TEM images and FTIR methods were used to characterize the properties of acid-functionalized nanoparticles in terms of nanoparticle size, presence of sulfonic acid functional groups, and pH as an indicator of acid sites present. Citric acid-functionalized magnetite nanoparticles were also synthesized and evaluated. Wheat straw and wood fiber samples were treated with the acid supported nanoparticles at 80°C for 24 h to hydrolyze their hemicellulose fraction to sugars. Further hydrolysis of the liquid fraction was carried out to account for the amount of total solubilized sugars. HPLC was used to determine the total amount of sugars obtained in the aqueous solution. The perfluroalkyl-sulfonic acid functional groups from the magnetic nanoparticles yielded significantly higher amounts of oligosaccharides from wood and wheat straw samples than the alkyl-sulfonic acid functional groups did. More stable fluorosulfonic acid functionalized nanoparticles can potentially work as an effective heterogeneous catalyst for pretreatment of lignocellulosic materials.

As nanomaterials continue to garner interest in a wide range of industries and scientific fields, commercial suppliers have met growing consumer demand by readily offering custom particles with size, shape and surface functionality made-to-order. By circumventing the challenging and complex synthesis of functionalized nanoparticles, these businesses seek to provide greater access for the experimentation and application of these nanoscale platforms. In many cases, amine functional groups are covalently attached as a surface coating on a nanoparticle to provide a starting point for chemical derivatization and commonly, conjugation of biomolecules in medical science applications. Successful conjugation can improve the compatibility, interfacing and activity of therapeutic and diagnostic nanomedicines. Amines are amongst the most popular reactive groups used in bioconjugation pathways owing to the many high-yield alkylation and acylation reaction are involved in. For the design of functionalized nanomaterials with precisely tuned surface chemical properties, it is important to develop techniques and methods which can accurately and reproducibly characterize these materials. Quantification of surface functional groups is crucial, as these groups not only allow for conjugation of chemical species, but they also influence the surface charge and therefore aggregation behavior of nanomaterials. The loss of colloidal stability of functionalized nanomaterials can often correspond to a significant if not complete loss of functionality. Thus, we sought to develop multiple characterization approaches for the quantification of surface amine groups. Silica nanoparticles were selected as a model nanomaterial as they are widely used, commercially available, and their surface chemistry has been investigated and studied for decades. Various commercial batches of silica nanoparticles were procured with sizes ranging from 20 – 120 nm. Two colorimetric assays were developed and adapted for their ease-of-use, sensitivity, and convenience. In addition, a fluorine labelling technique was developed which enabled analysis by quantitative solid-state 19F NMR and X-ray photoelectron spectroscopy (XPS). XPS provided data on surface chemical composition at a depth of ≈ 10 nm, which allowed us to determine coupling efficiencies of the fluorine labelling technique and evaluate the reactivity of the two assays. The ensemble of surface-specific quantification techniques was used to evaluate multiple commercial batches of aminated silica and investigate batch-to-batch variability and the influence of particle size with degree of functionalization. In addition, resulting measurements of surface amine content were compared and validated by an independent method based on quantitative solution 1H NMR, which was developed for total functional group content determination. This allowed for us to assess the role of accessibility and reactivity of the amine groups present in our silica particles. Overall, the objective of this study was to develop a multi-method approach for the quantification of amine functional groups on silica nanoparticles. At the same time, we hoped to set a precedent for the development and application of multiple characterization techniques with an emphasis of comparing them on the basis of reproducibility, sensitivity, and mutual validation.

Esta dissertação de mestrado aborda dois estudos que foram desenvolvidos utilizando a técnica de microscopia FTIR (micro-FTIR): a reatividade do grafeno funcionalizado e a eletroquímica in-situ com micro-FTIR para avaliação de reações redox. A reatividade e a distribuição de cargas em materiais 2D, mais especificamente em folhas individuais de grafeno, têm sido alvo de muita investigação na última década. No entanto, ainda não é conhecido como elas se apresentam em grafeno com grandes áreas, uma vez que a maioria dos estudos utilizam áreas muito pequenas (~μm2). Neste estudo, investigou-se experimentalmente como um eletrodo formado por uma única folha de grafeno se comporta quando sua estrutura é alterada por funcionalização covalente. Utilizando microespectroscopia na região do infravermelho, avaliou-se a funcionalização de grafeno com unidades de ácido benzoico no grafeno ancorados eletroquimicamente. O mapeamento químico mostrou que a distribuição espacial dessas unidades não ocorre uniformemente, ao invés disso, existem pontos específicos de ancoramento. Por fim, observou-se que a funcionalização ocorre mais intensamente na borda da folha de grafeno, alterando as propriedades óticas e eletroquímicas deste material, reduzindo o ganho ótico proporcionado pelos plásmons e aumentando a resistência de transferência heterogênea de elétrons. Para o segundo capítulo dessa dissertação, aplicou-se a microespectroscopia FTIR multiplex ao estudo da mudança química de um eletrodo de ouro modificado com azul da prússia (AP). Para isso, observou-se que uma etapa limitante era a confecção de um porta-amostra que reduzisse a camada de eletrólito ao mínimo de forma que a água não mais absorvesse a radiação de forma majoritária. Logo, foi possível o estudo vibracional de vários pontos da superfície do eletrodo, observando-se a influência do potencial aplicado, onde tem-se uma grande dependência dos sinais referentes ao estiramento C≡N do AP com a condição de potencial imprimida no eletrodo. / This Masters dissertation approaches two studies developed using the FTIR microspectroscopy technique (micro-FTIR): the activity of graphene functionalized and the in-situ electrochemistry with micro-FTIR for the evaluation of redox reactions. Reactivity and charge distribution in 2D materials, especially in single graphene sheets, have been the focus of extensive investigation during the last decade. However, there is still no knowledge on how large-area graphene behaves, since most of the studies utilize too small areas (~μm2). In this study, we aim to investigate experimentally how an electrode composed of only one single sheet of graphene behaves when its structure is changed by covalent functionalization. Using infrared microspectroscopy, the electrochemically induced covalent functionalization of graphene with benzoic acid unities was evaluated. The chemical mapping showed that the spatial distribution of these unities does not occur uniformly, instead, there are specific anchoring points. Lastly, it was observed that the functionalization occurs more intensely on the edges of the graphene sheet and that the covalent, affecting its optical and electrochemical properties, reducing the optical gain provided by the plasmons and increasing the resistance of heterogeneous electron transfer. In the second chapter of this dissertation, multiplex FTIR microspectroscopy was applied to the study of the chemical changes of a gold electrode modified with Prussian blue (PB). It was observed that the limiting step for this type of analysis was the building of a sample holder that reduces the electrolyte layer to the minimum in a way that water did not absorb the radiation in majority. Therefore, a vibrational study of several points of the electrode surface was possible evaluating the influence of the applied potential, where there is a dependence of the signals related to the C≡N stretching mode from PB on the potential condition applied to the electrode.

Este trabalho trata do estudo teórico atomístico das conformações da molécula de estireno sobre a superfície de Si(100)(2xl):H. Estudamos a molécula fisissorvida e quimissorvida sobre esta superfície. Os cálculos foram realizados através de Dinâmica Molecular Clássica. Nós reparametrizamos o Universal Force Field (UFF) com base em cálculos ab initio para sistemas modelo, e comparação a dados experimentais. Nossos resultados indicam que no processo de fississorção a região de vale da superfície é preferencial, e ocorre formação de agregados de moléculas antes do contato com a superfície. Quando passamos à análise da quimissorção de uma molécula, a região de vale permanece sendo o sítio preferencial para a posição do grupo vinil. Para as conformações de linhas de estireno, a estrutura mais estável tem todas as moléculas dispostas sobre a região de vale (ordenamento tipo \"pilha-1r\"); identificamos também outra estrutura, quase degenerada em energia, na qual o grupo vinileno se dispõe em conformação tipo \"espinha de peixe\", alternando entre a região de vale e sobre o dímero. / In this work we present a theoretical study of ,the conformation of styrene molecules on the Si(100)(2xl):H surface. We studied the conformations for styrene molecules physisorbed and chemisorbed on this surface. The study was conducted by Classical Molecular Dynamics. We performed a re-parametrization of the Universal Force Field (UFF), based on ab initio calculations for model structures, and comparison to experimental data. Our results show that for the physisorbed situations, the styrene molecules preferentially interact with the surface valley. We also identified that the molecules aggregate in clusters before reaching the surface. The valley is again the region of lowest energy for the vinylene position, for chemisorption of a single styrene molecule on the monohydride surface. For systems where we have a styrene layer chemisorbed on the dimer row, the most stable structure has ali the molecules arranged on the valley region o f the surface ( 1r -stack); we find another structure, almost degenerate in energy, in which molecules arrange in a herringbone- like configuration, with the vinylene group alternating between the valley and dimer regions.

Providing access to clean drinking water will continue to be a challenge for civil engineers for generations to come. Since many communities around the world rely on groundwater as a source of drinking water, remediation technologies must be implemented at sites where groundwater contamination exists due to years of mismanagement of hazardous waste. Using nanosized zero-valent metals such as iron and zinc embedded within and on the surface of functionalized (PAA) membrane filters has shown to be an effective dechlorination technique for contaminated groundwater. Introducing a noble metal such as Pd or Ni increases reaction rates by acting a catalyst for the dechlorination reaction. This study focuses on the treatment of contaminated groundwater at a hazardous waste site in Louisville, Kentucky. Once a chlorinated organic chemical manufacturing plant, the site now operates a treatment system for the contaminated groundwater to prevent migration into the nearby Ohio River. A portable membrane treatment system, built at the University of Kentucky, incorporates this functionalized bimetallic membrane technology for treatment of the groundwater found at the former manufacturing plant. Three bench scale tests were performed with membrane treatment system using DI water spiked with the chemical trichloroethylene (TCE). Results showed that using the functionalized Fe/Pd membranes significant decreased TCE concentrations over time. While further tests should be conducted to verify the results of the preliminary bench-scale tests, the membrane treatment system shows potential for use at the hazardous waste site in Kentucky.

The structuring of porous silica materials at the nanometer scale and their surface functionalization are important issues of current materials research. Many innovations in chromatography, catalysis and electronic devices benefit from this knowledge. The work at hand is dedicated to the targeted design of functional organosilica materials. In this context a new precursor concept based on boron-silanes is presented. These precursors combine the properties of a structure directing group and a silica source by covalent borane linkage. Formation of the precursor is easily realized by a sequential two-step hydroboration, firstly on bis(triethoxysilyl)ethene, and secondly on an unsaturated structure directing moiety such as alkenes or polymers. The so prepared precursors self-organize when hydrolysis of their inorganic moiety takes place via an aggregation of their organic side chains into hydrophobic domains. In this way, the additional use of a surfactant as a template is not necessary. Chemical cleavage of these moieties (e.g. by ammonolysis or oxidative saponification) yields an organosilica where all functionalities are exclusively located at the pore wall and therefore accessible. The accessibility of the functionalities is a vital point for applications and is not necessarily granted for common silica functionalization approaches. Further advantages of the boron-silane concept are the possibility to introduce a variety of surface functionalities by heterolytic cleavage of the boron linker and the control of the pore morphology. For that purpose the covalent linkage of different alkyl groups and polymers was studied. Another aspect is the access to chiral boron silane precursors yielding functionalized mesoporous organosilica with chiral functionalities exclusively located at the pore walls after condensation and removal of the structure directing moiety. These materials possess great potential for applications documented by preliminary investigations on chiral resolution of a racemic mixture by HPLC and asymmetric catalysis. In the course of this work valuable insights into the targeted structuring and surface functionalization of organosilicas were gained. A promising outlook for further investigations is the extension of this concept by altering the structure directing moieties of the precursor. That way the morphology of the final organosilica might be controlled by for example mesogens. Furthermore, the use of the boron linker enables the introduction of multiple functionalities into organosilicas, making the obtained material unique in its performance. / Die Nanostrukturierung von funktionalisierten porösen Materialien auf Silikatbasis steht im Brennpunkt der aktuellen Forschung. Anwendungen wie Chromatographie, Katalyse oder die Herstellung elektronischer Bauteile profitieren von den Erkenntnissen, die auf diesem Gebiet gewonnen werden. Die vorliegende Arbeit soll einen Beitrag zur gezielten Herstellung dieser Funktions-materialien leisten. Hierfür wurde ein neues Precursor-Konzept auf der Basis von Borsilanen vorgestellt. Diese Precursoren werden über eine sequentielle zweistufige Hydroborierung an Bis(triethoxysilyl)ethene und ein Alken oder ein ungesättigtes Polymer erhalten. Über den zweiten Schritt wird hierbei die so genannte strukturgebende Gruppe eingeführt und damit das Template kovalent gebunden. Dadurch entfällt im Vergleich zum bekannten Nanocasting-Mechanismus zum einen die Verwendung des herkömmlichen Templates für die Bildung der Porenstruktur und zusätzlich führt die Mikrophasenseparation während der Kondensation zu einer Anordnung der strukturgebenden Gruppen des Precursors an der Silikatphasengrenze. Nach der chemischen Abspaltung dieser Gruppen, die gleichzeitig zur Einführung funktioneller Gruppen führt, werden somit hochporöse Organosilikate erhalten, in denen sich die funktionellen Gruppen ausschließlich an der Porenoberfläche befinden. Ein Vorteil der Verwendung der Hydroborieung wird in der Vielfalt der funktionellen Gruppen deutlich, die eingeführt werden können. Die Zugänglichkeit der funktionellen Gruppen ist entscheidend für potentielle Anwendungen und bei herkömmlichen Organosilikaten nicht zwangsläufig gegeben. Ein herausragender Aspekt dieses Konzepts besteht in der Möglichkeit, sehr einfach chirale Precursoren und damit Organosilikate mit hoch funktionalisierten, chiralen Oberflächen herzustellen. Es konnte gezeigt werden, dass sich diese Materialien sowohl für die chromatographische Trennung von Racematen mittels HPLC als auch für die asymmetrische Katalyse eignen. Durch die in dieser Arbeit erhaltenen Ergebnisse konnten wertvolle Erkenntnisse zur Ober-flächenfunktionalisierung und Strukturierung von mesoporösen Silikaten gewonnen werden. Die Möglichkeit, das vorgestellte Konzept auf andere strukturgebende Gruppen wie zum Beispiel Mesogene zu übertragen und damit die Porenmorphologie gezielt zu steuern, eröffnet viele weitere interessante Materialeigenschaften.

Zeolites are a well-known class of crystalline oxide materials with tunable compositions and nanoporous structures, and have been used extensively in catalysis, adsorption, and ion exchange. The zeolite MFI is one of the well-studied zeolites because it has a pore size and structure suitable for separation or chemical conversion of many industrially important molecules. Modification of zeolite structures with organic groups offers a potential new way to change their properties of zeolites, beyond the manipulation of the zeolite framework structure and composition. The main goals of this thesis research are to study the organic-modification of the MFI pore structure, and to assess the effects of such modification on the adsorption and transport properties of zeolite MFI sorbents and membranes. In this work, the internal pore structure of MFI zeolite particles and membranes has been modified by direct covalent condensation or chemical complexation of different organic molecules with the silanol defect sites existing in the MFI structure. The organic molecules used for pore modification are 1-butanol, 1-hexanol, 3-amino-1-propanol, 1-propaneamine, 1,3-diaminopropane, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. TGA/DSC and 13C/29Si NMR characterizations indicated that the functional groups were chemically bound to the zeolite framework, and that the loading was commensurate with the concentration of internal silanol defects. Gas adsorption isotherms of CO2, CH4, and N2 on the modified zeolite materials show a range of properties different from that of the bare MFI zeolite. The MFI/3-amino-1-propanol, MFI/2-[(2-aminoethyl)amino]ethanol, and MFI/benzenemethanol materials showed the largest differences from bare MFI. These properties were qualitatively explained by the known affinity of amino- and hydroxyl groups for CO2, and of the phenyl group for CH4. The combined influence of adsorption and diffusion changes due to modification can be studied by measuring permeation of different gases on modified MFI membranes. To study these effects, I synthesized MFI membranes with [h0h] out-of-plane orientation on α-alumina supports. The membranes were modified by the same procedures as used for MFI particles and with 1-butanol, 3-amino-1-propanol, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. The existence of functional groups in the pores of the zeolite was confirmed by PA-FTIR measurements. Permeation measurements of H2, N2, CO2, CH4, and SF6, were performed at room temperature before and after modification. Permeation of n-butane, and i-butane were measured before and after modification with 1-butanol. For all of the studied gases, gas permeances decreased by 1-2 orders of magnitude compared to bare MFI membranes for modified membranes. This is a strong indication that the organic species in the MFI framework are interacting with or blocking the gas molecule transport through the MFI pores. A detailed fundamental study of the CO2 adsorption mechanism in modified zeolites is necessary to gain a better understating of the adsorption and permeation behavior of such materials. Towards this end, an in situ FTIR study was performe.For the organic molecules with only one functional group (1-butanol, benzenemethanol, and 1-propaneamine), physical adsorption was found - as intuitively expected - to be the only observed mode of attachment of CO2 to the modified zeolite material. Even in the case of MFI modified with 1,3-diaminopropane, only physical adsorption is seen. This is explained by the isolated nature of the amine groups in the material, due to which only a single amine group can interact with a CO2 molecule. On the other hand, chemisorbed CO2 species are clearly observed on bare MFI, and on MFI modified with 3-amino-1-propanol or 2-[(2-aminoethyl)amino]ethanol. Specifically, these are carbonate-like species that arise from the chemisorption of CO2 to the silanol group in bare MFI and the alcohol groups of the modifying molecule. The possibility of significant contributions from external surface silanol groups in adsorbing CO2 chemisorbed species was ruled out by a comparative examination of the FTIR spectra of 10 μm and 900 nm MFI particles modified with 2-[(2-aminoethyl)amino]ethanol.

Metal-organic frameworks (MOFs) are crystalline hybrid materials with interesting chemical and physical properties. This thesis is focused on the synthesis and characterization of different MOFs and their use in heterogeneous catalysis. Zeolitic imidazolate frameworks (ZIFs), including ZIF-4, ZIF -7 and ZIF -62, Ln(btc)(H2O) (Ln: Nd, Sm, Eu, Gd, Tb, Ho, Er and Yb), Ln2(bpydc)3(H2O)3, (Ln: Sm, Gd, Nd, Eu, Tb, Ho and Er), MOF-253-Ru and Zn(Co-salophen) MOFs were synthesized. Various characterization techniques were applied to study the properties of these MOFs. X-ray powder diffraction (XRPD), single crystal X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) were extensively used. The effect of synthesis parameters, such as batch composition and temperature, on the formation and morphology of ZIF-7 and ZIF-62 was studied. Structural transformation and flexibility of two series of lanthanide-based MOFs, Ln(btc)(H2O) (Ln: Nd, Ho and Er) and Ln2(bpydc)3(H2O)3, (Ln: Sm and Gd) upon drying and heating were characterized. Relations between metal coordination, structure flexibility and thermal stability among the Sm2(bpydc)3(H2O)3, Nd(btc)(H2O) and MOF-253 were investigated. Salophen- and phenanthroline-based organic linkers were designed, synthesized and characterized. Metal complexes were coordinated to these linkers to be used as catalytic sites within the MOFs. Catalytic studies using two MOF materials, Ln(btc) and MOF-253-Ru, as heterogeneous catalysts in organic transformation reactions were performed. The heterogeneous nature and recyclability of these MOFs were investigated and described. / <p>At the time of doctoral defence the following papers were unpublished and had a status as follows: Paper nr 4: Submitted; Paper nr 5: Submitted</p>

The overall goal of the present research is to provide a computationally based methodology to realize the projected extraordinary properties of Carbon Nanotube (CNT)- reinforced composites and polymeric nanofibers for engineering applications. The discovery of carbon nanotubes (CNT) and its derivatives has led to considerable study both experimentally and computationally as carbon based materials are ideally suited for molecular level building blocks for nanoscale systems. Research in nanomechanics is currently focused on the utilization of CNTs as reinforcements in polymer matrices as CNTs have a very high modulus and are extremely light weight. The nanometer dimension of a CNT and its interaction with a polymer chain requires a study involving the coupling of the length scales. This length scale coupling requires analysis in the molecular and higher order levels. The atomistic interactions of the nanotube are studied using molecular dynamic simulations. The elastic properties of neat nanotube as well as doped nanotube are estimated first. The stability of the nanotube under various conditions is also dealt with in this dissertation. The changes in the elastic stiffness of a nanotube when it is embedded in a composite system are also considered. This type of a study is very unique as it gives information on the effect of surrounding materials on the core nanotube. Various configurations of nanotubes and nanocomposites are analyzed in this dissertation. Polymeric nanofibers are an important component in tissue engineering; however, these nanofibers are found to have a complex internal structure. A computational strategy is developed for the first time in this work, where a combined multiscale approach for the estimation of the elastic properties of nanofibers was carried out. This was achieved by using information from the molecular simulations, micromechanical analysis, and subsequently the continuum chain model, which was developed for rope systems. The continuum chain model is modified using properties of the constituent materials in the mesoscale. The results are found to show excellent correlation with experimental measurements. Finally, the entire atomistic to mesoscale analysis was coupled into the macroscale by mathematical homogenization techniques. Two-scale mathematical homogenization, called asymptotic expansion homogenization (AEH), was used for the estimation of the overall effective properties of the systems being analyzed. This work is unique for the formulation of spectral/hp based higher-order finite element methods with AEH. Various nanocomposite and nanofibrous structures are analyzed using this formulation. In summary, in this dissertation the mechanical characteristics of nanotube based composite systems and polymeric nanofibrous systems are analyzed by a seamless integration of processes at different scales.