Synthesis and Characterization of Ordered Mesoporous Silica Films on Oxidized Silicon Substrates

Synthesis and Characterization of Ordered Mesoporous Silica Films on Oxidized Silicon Substrates
Author: David Jacques Picciotto
Publisher:
Total Pages: 236
Release: 2000
Genre:
ISBN:

The fabrication of advanced electronic devices that operate on quantum effects requires the patterning of semiconductors on the scale of 50 A, which cannot be achieved by any of the currently available patterning technologies. This project pursued a novel approach: the fabrication of a self-assembling template which would allow the deposition of ordered arrays of germanium dots on silicon substrates, on length scales permitting the operation of quantum devices at room temperature. The template is the mesoporous silicate MCM-41, discovered by researchers at Mobil Chemical Corp. This material consists of highly ordered, two-dimensional, hexagonal arrays of very uniform pores in silicon dioxide, with diameters tunable from 20 A to over 100 A. If pore arrays of this material can be grown as thin films on silicon substrates, with the pores oriented normal to the substrate surface, the resulting structure will provide a template for the deposition of germanium dots. Germanium can then be deposited through the pores in the film and onto the silicon substrates by chemical or physical vapor deposition. The template film can then be etched away, leaving a hexagonally ordered array of germanium dots on the silicon substrate. Mesoporous silica films were grown on oxidized silicon substrates by acidic synthesis. The substrates were first patterned by optical lithography to produce vertical features with dimensions of the order of microns. The substrates were then coated with hydrophobic polymer monolayers to alter their surface energy. This monolayer was selectively removed from the horizontal surfaces of some of the substrates, leaving it only on the vertical surfaces of the patterned features. It was thought that the difference in surface energy between horizontal and vertical surfaces would induce the pores to align along the vertical surfaces.

Ordered mesoporous silica COK-12: mesoscale tailoring, upscaling, continuous synthesis and application in the oxidative coupling of methane

Ordered mesoporous silica COK-12: mesoscale tailoring, upscaling, continuous synthesis and application in the oxidative coupling of methane
Author: Colmenares, Maria
Publisher: Universitätsverlag der TU Berlin
Total Pages: 203
Release: 2018-07-19
Genre: Technology & Engineering
ISBN: 3798329885

Ordered mesoporous silica (OMS) materials are a family of silica nanomaterials with pores ranging in size from 2 to 50 nm which are arranged periodically within the silica matrix. They have expanding applications in various fields of research, such as drug delivery, adsorption, separation and catalysis. COK-12 is an OMS produced by the soft-templating method, using the block copolymer P123 as a structure-directing agent. The synthesis takes place at room temperature under mild reaction conditions. In comparison with the most widely known OMS, the synthesis of COK-12 is more time efficient, inexpensive and environmentally friendly, yielding a material analogous to the well-known SBA-15. This thesis encompasses investigations regarding the production of the ordered mesoporous silica material (OMS) known as COK-12, in terms of upscaling of the synthesis and tailoring of the size and shape of its characteristic hexagonal pore structure. Batch upscaling of the synthesis yielded a material with nearly identical properties to that of the original COK-12. Upscaling of the COK-12 synthesis was also studied in continuous mode. The installation and operation of a continuous COK-12 production unit was carried out with the aim to determine the possibility of large-scale production of COK-12 with consistent material properties. COK-12 was produced in continuous mode by varying the time of aging of the COK-12 slurry and the flow rate of the feed streams, yielding materials with properties nearly identical to those of the original COK-12. COK-12 was used as a support for the Na2WO4-Mn/SiO2 catalyst for the oxidative coupling of methane reaction in various forms (powder, granular produced by pressing and monolithic), showing promising results comparable to the enhanced activity of the catalyst supported on the SBA-15. The advantage of using COK-12 over other OMS materials is that the facile nature of COK-12 synthesis makes it a viable candidate for industrial production of the Na2WO4-Mn/SiO2 catalyst, if paired with appropriate pelletizing and preparation method. The introduction of hexane and polypropylene glycol (PPG) as micellar swelling agents into the original COK-12 synthesis was studied in order to tailor the mesoporous structure of the system. Hexane was used as a micelle expander and as an agent to produce silica mesocellular foams, with “ink-bottle” shaped pores with a larger diameter than that of the original COK-12. By adding PPG into the synthesis, the shift of the mesostructure of COK-12 from 2D hexagonal to a multilamellar vesicular configuration was studied, resulting in the progressive formation of this type of material with increasing concentration of PPG. The flexibility of the COK-12 synthesis in terms of upscaling and tailoring of the mesostructure was examined throughout this work, with an aim to contribute to the existing and expanding knowledge regarding more versatile, sustainable and possibly industrial OMS production. Ordered Mesoporous Silica (OMS) gehört zu der Familie der Silica-Nanomaterialien mit periodisch angeordneten Mesoporen im Größenbereich zwischen 2 und 50 nm. Diese werden zunehmend in unterschiedlichen Forschungsfeldern wie Medikamentenfreisetzung, Adsorption, Separation und Katalyse eingesetzt. COK-12 ist ein OMS, das über eine Soft-Templating-Methode unter Nutzung des Blockcopolymers P123 als strukturbestimmenden Zusatz erzeugt wird. Die Synthese erfolgt bei Raumtemperatur unter milden Reaktionsbedingungen. Im Vergleich zu den am weitesten bekannten OMS-Materialien ist die Synthese von COK-12 zeiteffizient, günstig und umweltfreundlich. Dabei wird ein OMS-Material analog zu dem bereits etablierten SBA-15 erzeugt. Die vorliegende Dissertation umfasst die Synthese eines als COK-12 bekannten OMS-Materials, dem Scale-Up der Synthese sowie die Anpassung und Modifizierung der ursprünglich hexagonal-angeordneten Mesoporen bezüglich Porengrößen und Porenform. Das diskontinuierliche Scale-Up im Batchprozess führt zu nahezu identischen Materialeigenschaften im Vergleich zu dem ursprünglichen COK-12. Ein Scale-Up der COK-12-Synthese wurde zusätzlich im kontinuierlichen Prozess erprobt. Dessen Installation und Operation wurde mit dem Ziel durchgeführt, um die Möglichkeit einer Produktion von großen Mengen an COK-12 mit einheitlichen Materialeigenschaften zu validieren. Durch eine Variation der Alterungszeit als auch der Fließrate der Lösungen konnte COK-12 im kontinuierlichen Prozess mit nahezu identischen Eigenschaften wie das ursprüngliche COK-12 erzeugt werden. COK-12 wurde erfolgreich in verschiedenen Formen (Pulver, Pressgranulate und Monolithe) als Trägermaterial für Na2WO4-Mn/SiO2-Katalysatoren für die Oxidative Kopplung von Methan eingesetzt. Die resultierenden Aktivitäten ist sind vergleichbar mit denen des auf SBA-15-geträgerten Katalysators Der Vorteil der Nutzung von COK-12 im Vergleich zu anderen OMS-Materialien liegt in der vergleichsweise simplen COK-12-Synthese, weshalb es ein interessanter Kandidat für eine mögliche industrielle Produktion des Na2WO4-Mn/SiO2-Katalysators ist, wenn wenn geeignete Pelletierungs- und Herstellungsmethoden angewendet werden. Die Zugabe von Hexan und Polypropylenglykol (PPG) zur Aufweitung der Mizellen in der ursprünglichen COK-12-Synthese wurde untersucht, um die mesoporöse Struktur des Systems zu variieren. Hexan wurde eingesetzt zur Aufweitung der Mizellen und als Hilfsmittel zur Produktion mesozellulärer Silica-Schäume mit „ink-bottle“-förmigen Poren sowie vergrößertem Porendurchmesser im Vergleich zu denen des ursprünglichen COK-12. Durch die Zugabe von PPG in die Synthese verändert sich die Mesoporenstruktur der ursprünglichen hexagonalen 2D-Struktur zu einer multilamellaren vesikulären Anordnung, die mit zunehmender PPG-Konzentration verstärkt wird. Die Flexibilität der COK-12-Synthese wurde in dieser Arbeit in Bezug auf ein Scale-Up und eine Porenmodifikation weitreichend untersucht, mit dem Ziel das existierende Wissen in Bezug auf eine vielseitige, nachhaltige sowie eine potentielle Industrieproduktion der COK-12-Synthese zu entwickeln.

Mesoporous Ordered Silica Films

Mesoporous Ordered Silica Films
Author: Plinio Innocenzi
Publisher: Springer Nature
Total Pages: 122
Release: 2021-12-16
Genre: Technology & Engineering
ISBN: 303089536X

This book introduces the fascinating world of self-assembly in mesoporous ordered silica films. Beginning from a single droplet, it guides the reader, in a step-by-step learning process, how to obtain and control ordered porous mesophases in thin films by varying only the precursor chemistry and the process. It explains, in great detail, how order control is achieved through chemical design and post-deposition processing, the latter of which is a unique property in materials science. The book places a special focus on silica, whose particularly complex chemistry enables order control over a range of different length scales. This book is suitable for students and researchers in the fields of sol-gel or colloidal chemistry and interested in the topics of self-assembly and mesoporous phases.

Synthesis, Characterization and Structure Control of Ordered Mesoporous Silica Nanoparticles

Synthesis, Characterization and Structure Control of Ordered Mesoporous Silica Nanoparticles
Author: Teeraporn Suteewong
Publisher:
Total Pages: 156
Release: 2011
Genre:
ISBN:

Ordered mesoporous silica materials are characterized by uniform and tunable pore size, high surface area and large pore volume. In particular, nano-sized ordered mesoporous silica particles have drawn interest from several fields, including biorelated areas, because silica is benign, possesses chemical stability and can be integrated with other materials. Structural aspects, such as pore connectivity, geometry and pore size are known to govern materials performance. Extensive efforts have been devoted to synthesize mesoporous silica particles with different structures, functionalities and sizes. In contrast, only a small number of studies so far have concentrated on the formation mechanism of these particles. This is hence the focus of the present dissertation. The first part reports on the synthesis and characterization of ordered mesoporous silica nanoparticles with and without embedded magnetic nanoparticles. The formation mechanism of silica nanocomposites is investigated by capturing particle formation at different time points during the synthesis. A combination of transmission electron microscopy (TEM) and small angle x-ray scattering (SAXS) is used to characterize the structure evolution of resulting materials. Incorporating organic moieties into the silica matrix provides additional functionalities to ordered mesoporous silica nanoparticles. However, it often leads to disordered pore structure or pore blockage. The second part demonstrates the preparation of aminated and ordered mesoporous silica nanoparticles using a cocondensation method. Increasing the amount of aminosilane in the synthesis feed causes a structural transition of organically modified particles from hexagonal to cubic. Pore size of ordered mesoporous silica and aminated ordered mesoporous silica nanoparticles can be tailored by the addition of a swelling agent during the synthesis. The structural transformation from hexagonal to cubic is also observed in the latter case, albeit at different amino silane concentrations. The final part reports on the internalization of nanoparticles into cells. Fluorescent aminated mesoporous silica nanoparticles are first prepared and then coated with poly(ethylene glycol) to improve particle stability and lower protein adsorption. Dye-labeled aminated mesoporous silica nanoparticles are spontaneously internalized by cells.

Synthesis and Characterization of Mesoporous Semiconductors

Synthesis and Characterization of Mesoporous Semiconductors
Author: Chris Byung-hwa Kang
Publisher:
Total Pages: 61
Release: 2012
Genre:
ISBN:

Widely studied mesoporous oxide materials have a range of potential applications, such as catalysis, absorption and separation. However, they are not generally considered for their optical and electronic properties. Elemental semiconductors with nano-sized pores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms. This thesis describes two different routes to synthesize thin film mesoporous silicon and powder mesoporous germanium. Thin film of mesoporous silicon was produced from thin film of mesoporous silica at low temperature (

Nanocasting

Nanocasting
Author: An-Hui Lu
Publisher: Royal Society of Chemistry
Total Pages: 279
Release: 2010
Genre: Science
ISBN: 0854041885

Nanostructured materials with tailored properties are regarded as a fundamental element in the development of future science and technology. Research is still ongoing into the nanosized construction elements required to create functional solids. The recently developed technique, nanocasting, has great advantage over others in terms of the synthesis of special nanostructured materials by the careful choice of suitable elements and nanoengineering steps. This new book summarizes the recent developments in nanocasting, including the principles of nanocasting, syntheses of novel nanostructured materials, characterization methods, detailed synthetic recipes and further possible development in this area. The book focuses on the synthesis of porous solids from the viewpoint of methodology and introduces the science of nanocasting from fundamental principles to their use in synthesis of various materials. It starts by outlining the principles of nanocasting, requirements to the templates and precursors and the tools needed to probe matter at the nanoscale level. It describes how to synthesize nano structured porous solids with defined characteristics and finally discusses the functionalization and application of porous solids. Special attention is given to new developments in this field and future perspectives. A useful appendix covering the detailed synthetic recipes of various templates including porous silica, porous carbon and colloidal spheres is included which will be invaluable to researchers wanting to follow and reproduce nanocast materials. Topics covered in the book include: * inorganic chemistry * organic chemistry * solution chemistry * sol-gel and interface science * acid-base equilibria * electrochemistry * biochemistry * confined synthesis The book gives readers not only an overview of nanocasting technology, but also sufficient information and knowledge for those wanting to prepare various nanostructured materials without needing to search the available literature.