Thesis (Ph.D.) - University of St Andrews, March 2008. / Restricted until 14th March 2009.

The design of nanoparticles in mesoporous supports is explored through synthetic strategies of electrophoretic deposition and electroless deposition with application towards energy storage. Electrophoretic deposition of nanoparticles into a mesoporous thin film is examined using charged nanocrystals in a low-permittivity solvent. To provide a basis for the deposition, the mechanism of particle charging in a low-permittivity solvent was studied. Dispersions of carbon black particles in toluene with an anionic surfactant were characterized using differential-phase optical coherence tomography with close electrode spacing to measure the electrophoretic mobility. The particle charge in concentrated dispersions was found to decrease as a function of increasing surfactant concentration. Partitioning of cations between the surfactant-laden particle surface and micelle cores in the double-layer was found to govern the dynamics of particle charging. Subsequently, charged Au nanocrystals were deposited by electrophoresis within perpendicular mesochannels of a TiO2 support. High loadings of 21 wt% Au with good dispersion were achieved within the mesoporous TiO2 support using electrophoretic deposition, which would otherwise be inhibited by the weak nanocrystal-support interaction. According to a modified Fokker-Planck equation, the mean penetration depth of a single nanocrystal inside of the perpendicular pores was found to be dependent on the electric field strength, electrophoretic mobility, pore diameter, nanocrystal size, and local deposition rate constant. Nanocomposites for electrochemical capacitors were designed via electroless deposition of redox-active MnO2 in a high surface area mesoporous carbon support. Disordered mesoporous carbon supports with a pore size of ~8 nm were used both in amorphous (AMC) and graphitic (GMC) form, with a ~1000-fold larger conductivity for GMC. High loadings of 30 wt% MnO2 were achieved in the AMC in the form of ~1 nm thick domains, which were highly dispersed throughout the support. Oxidation of the GMC was necessary to facilitate wetting and deposition of the MnO2 precursor in order to achieve high loadings of 35 wt% MnO2 with ~1 nm thickness. High gravimetric MnO2 pseudocapacitances of >500 F/gMnO2 were achieved at low loadings and low scan rate of 2 mV/s for both carbon supports. However, at high scan rates ≥100 mV/s, the MnO2 pseudocapacitance is twofold larger for MnO2/GMC, relative to MnO2/AMC. Sodium ion diffusion throughout both MnO2/AMC and MnO2/GMC was shown to be facile. For the GMC versus AMC support, the higher MnO2 pseudocapacitance is attributed to the higher electronic conductivity, which facilitates electron transport to the MnO2 domains. / text

No description available.

M.Sc. (Chemistry) / According to the International Union of Applied Chemistry (IUPAC) mesoporous silica materials are a class of materials which contain pore size with diameters ranging from 2 to 50 nm. Due to their attractive features such as large surface area along with tunable pore size, accessible silano groups and easy functionalization make them with special properties to be employed as stationary phases for different chromatographic applications such as clean up, preconcentration, purification and separation of analytical samples. Organic–inorganic mesoporous hybrid materials are a new class of materials obtained when an inorganic material, such as mesoporous silicas are surface modified using an organic material via silylation. The main advantage of these hybrid materials is that they are formed by combining dissimilar properties of inorganic and organic materials into one material. Whereas the inorganic materials provide rigidity and thermal stability, the organic components provide flexibility, dielectric, ductility, and processability. Therefore the advantages of these hybrid materials lead them to be used over a wide range of applications. The main objective of this study was to synthesize organic-inorganic hybrid mesoporous silica materials for use as stationary phases for solid phase extraction and high performance liquid chromatography columns. The materials were prepared under basic conditions using silica gel and tetraethyl orthosilicate used as a source of silica and modified by either surface polymerization or grafting methods using octadecyltrimethoxysilane followed endcapping with hexamethyldisilazane. The materials were characterized before and after surface modification using different analytical methods. Scanning electron microscopy (SEM) pictures showed that the morphology of the materials remained unchanged after surface modification.

The development of mesoporous titania (meso-TiO2) films is a considerable research goal in the field of mesoporous material development due to their proven applicability in solar cells and phtocatalysts. In this work, the meso-TiO2 films were fabricated through different methods and these home-made titania structures were applied in DSSCs and photocatalysts. Meso-TiO2 powders were first prepared from ethanol/water or ethanol solvent. The meso-TiO2 made from the ethanol/water solvent did not have an ordered mesostructure, but that made from ethanol solvent had 2D-hexagonal mesostructure. Films were prepared by adding ordered meso-TiO2 particles into paste formulations of P25 nanoparticles with weight proportion ranging from 0 to 100%. These were used to form films by doctor blading, and the influence of paste composition on film structure, morphology, porosity, optical properties and cell performance were investigated. Secondly, ordered meso-TiO2 films were fabricated by dip coating from aqueous or ethanol solvent. Both films had cubic mesostructures, but the film coated from aqueous solvent was not uniform. The film formed from ethanol solvent was doped with sulphur. The effects of doping on the mesostructure, morphology, structure, optical properties and photocatalytic activity were studied. The thickness of films was increased by repeated coating. The number of layers had an influence on the mesostructure, morphology, optical properties and cell performance when these films were applied in DSSCs Finally, a novel method was adopted to prepared meso-TiO2 films. Molecular titania precursors or titania colloidal seeds were used as the titania source. Both of them can be used to prepare free-standing hybrid films at air-water interface by a self-assembly method, however the one synthesised from the molecular titania precursor did not contain very much titania and became a powder after calcination. In contrast, after calcination, the films formed from the colloidal titania solution remained intact, and were composed of mixtures of TiO2 nanoparticles and nanowires with mesopores arising from interparticle porosity. These films were applied in DSSCs. This interfacial method was also successfully extended to prepare free-standing ZnO films from a molecular precursor. After calcination, the free-standing ZnO films were found to be composed of rough spheres formed by flocculation of smaller nanoparticles.

Thesis (Ph.D.)--Kent State University, 2008. / Title from PDF t.p. (viewed Dec. 17, 2009). Advisor: Mietek Jaroniec. Keywords: mesoporous, FDU-1, SBA-16, organosilicas, pendant groups, bridging groups, adsorption, isocyanurate, template removal, cage-like structures. Includes bibliographical references (p. 219-238).

Amine functionalized silicas are promising chemisorbent materials for post-combustion CO₂ capture due to the high density of active sites per unit mass of adsorbent that can be obtained by tuning the synthesis protocol, thus resulting in high equilibrium CO₂ adsorption capacities. However, when compared to physisorbents, they have a few disadvantages. Firstly, oxidative degradation of the amine groups reduces the lifetime of these adsorbent materials. Furthermore, rapid heat release following the reaction between amines and CO₂ results in large local temperature spikes which may adversely affect adsorption equilibria and kinetics. Thirdly, there is a lack of fundamental understanding of CO₂-amine adsorption thermodynamics, which is key to scaling up these materials to an industrial-scale adsorption process. In this dissertation the qualitative and quantitative understanding of these three critical aspects of aminosilica adsorbents have been furthered so these materials can be better evaluated and further tuned as adsorbents for post-combustion CO₂ capture applications.

The recently discovered mesoporous molecular sieve MCM-41 was synthesized, modified, and characterized and proposed as an alternative adsorbent for VOC control. The synthesis conditions for pure-silica and aluminosilicate MCM-41 were optimized as follows: 4.5Na2O:30SiO2:5.2C16H33(CH3)3N + :2500H2O and 7.5Na2O:30SiO2:xAl2O3:7.2C16H33(CH3)3N + :3500H2O (x < 1), respectively, and at 373 K for 4 days. Our studies showed that MCM-41 is not stable in the presence of water vapor. For example, a hydrothermal treatment of MCM-41 at 723 K for 2 hour resulted in 50 % of structure collapses. Again, when a template-free MCM-41 sample was exposed to air with a relative humidity of 60 % for three months, almost total pore structure collapses were observed. Adsorption equilibrium results showed that MCM-41 has a narrow pore size distribution and exhibits extraordinary pore volume compared to the classical microporous adsorbents, such as molecular sieves and activated carbons. Despite the impressive adsorption capacities of this material, the Type IV isotherm behavior requires the VOCs, in the gas phase, to be at high partial pressure. This is not the case with most industrial VOC streams. A real VOC stream requires an adsorbent with not only a high adsorption capacity but also a high adsorption affinity at a low VOC concentration. To overcome the above mentioned two problems, both the surface chemistry and the pore-opening sizes of MCM-41 were modified. To modify the surface chemistry, one has to better understand the surface chemistry. Our pioneering study of the surface chemistry of MCM-41 using FTIR, 29 Si CP/MAS NMR, pyridine-TPD, and TGA demonstrated that three types of silanol groups, i.e. single, (SiO)3Si-OH, hydrogen-bonded, (SiO)3Si-OH---OH-Si(SiO)3 and geminal, (SiO)2Si(OH)2 are distributed over the surface of MCM-41. The number of silanol groups per unit nm 2 , aOH, varies between 2.5 and 3.0 depending on the template-removal method. To improve the hydrothermal stability and enhance the hydrophobicity, the surface chemistry of MCM-41 was modified by silylation. Though both the free and hydrogen-bonded SiOH groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol -1 , respectively, only the free SiOH groups are highly accessible to the silylating agent, chlorotrimethylsilane. The surface coverage of the modifying agent was found to has a linear relationship with the surface free silanol groups which can be controlled by different heating temperatures. Modification by silyaltion can significantly improve hydrophobicity and stability. Rehydration/dehydration experiments demonstrate that the surface-silylated MCM-41 is highly tolerable to water vapor due to the complete replacement of surface-hydrophilic silanols. A novel modification method, namely selective tailoring (ST), was developed to tailor the pore-opening sizes of MCM-41 (rather than the entire pores). The novelty is that only the pore mouths at both ends of a cylindrical pore of MCM-41 was modified by deposition of some alkoxides. By doing so, the types of adsorption isotherms of VOCs can be changed from Type IV to Type I while the pore volume can be significantly preserved. This is of course significance in VOC removal since the adsorption affinity has been drastically enhanced. Adsorption equilibria and kinetics for VOCs in the pore-opening-modified MCM-41 materials were measured, modeled and compared to that of activated carbons and hydrophobic molecular sieves. The pore-modified MCM-41 has a much higher adsorption capacity than that of the traditional microporous adsorbents such as activated carbons and molecular sieves. The adsorption equilibrium data fit the Langmuir-Uniform distribution (Unilan) models very well. Upon the equilibrium parameters being obtained and considering the pore structure of our pore-modified MCM-41 adsorbents, the kinetic data were further modeled using the literature-existed models recently developed by Do and coworkers, i.e. the constant surface diffusivity macropore, surface and micropore diffusion (CMSMD) model and the macropore and surface diffusion (MSD) model. Results demonstrated that the CMSMD model can predict our kinetic uptake curves reasonably fine. Some key kinetic parameters including pore and surface diffusivities, apparent diffusivity, activation energy for adsorption, and pore tortuosity factor can be readily obtained. The porosity of the MCM-41 materials were primarily evaluated using the traditional methods based on nitrogen adsorption/desorption data. Results indicated that the BJH method always underestimates the true pore diameter of MCM-41. An comparison plot (t-plot or as-plot) method was suggested and improved. Plotting of nitrogen adsorption data at 77 K versus the statistical film thickness reveals three distinct stages, with a characteristic of two points of inflection. The steep intermediate stage is caused by capillary condensation occurred in the highly uniform mesopores. From the slope of the section after condensation, the external surface area can be obtained. Therefore, the true surface area of the mesopores is readily calculated. The linear portion of the last section is extrapolated to the adsorption axis of the comparison plot, and this intercept is used to obtain the volume of the mesopores. From the surface area and pore volume, average mesopore diameter is calculated, and the value thus obtained is in good agreement with the pore dimension obtained from powder X-ray diffraction measurements. The principle of pore size calculation, the thickness of adsorbed nitrogen film, and the problems associated with the BJH method were discussed in detail. It has been found that at a given relative pressure, the smaller the pore radius, the thicker the adsorbed film. Thermodynamics analysis established that the stability of the adsorbed film is determined by interface curvature and the potential of interaction between adsorbate and adsorbent. A semi-empirical equation is proposed to describe the state of stable adsorbed films in cylindrical mesopores. It is also shown to be useful in calculations of pore size distributions of mesoporous solids. The desorption of four representative volatile organic compounds (VOCs), i.e. n-hexane, cyclohexane, benzene, and methanol from MCM-41 were also investigated and compared with the hydrophobic zeolite, silicalite-1, using the technique of temperature programmed desorption (TPD). The desorption energies of these organics to MCM-41 were evaluated and compared with the adsorption isosteric heats. The affinity of organics to MCM-41 and silicalite-1, which represents surface hydrophobicity/hydrophilicity were studied and discussed. Results showed that only one desorption peak can be found for all organics from MCM-41, different from that from the microporous adsorbents (activated carbons and hydrophobic molecular sieves). The activation energies for desorption of non-polar molecules are slightly higher than their latent heats of evaporation, whereas the activation energy for desorption of methanol is well above its latent heat of evaporation. These results are consistent with those derived from the adsorption isotherm measurements. The very high activation energy for the desorption of methanol is due to the hydrogen bonds between methanol molecules and silanol groups over MCM-41 surfaces. The affinity of volatile organics to MCM-41 are in the order of methanol > n-hexane > benzene > cyclohexane.

Thesis (M.S.)--University of Missouri-Columbia, 2006. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on May 7, 2009) Includes bibliographical references.

Thesis (Ph. D., Materials Science and Engineering)--University of Idaho, July 2008. / Major professor: Francis H. Froes. Includes bibliographical references. Also available online (PDF file) by subscription or by purchasing the individual file.