As an important chemical raw material, alcohols can be used as fuels, solvents and chemical feedstocks to produce a variety of downstream products. With limited fossil fuel resources, alcohol synthesis from syngas reactions can be a potential alternative to the traditional petroleum based alcohol synthesis. Among many catalysts active for syngas to alcohol processes, alkali promoted Mo2C has shown promising performance. More interestingly, the alkali promoter was found to play an important role in shifting the reaction selectivity from hydrocarbons to alcohols. However, limited understanding of the mechanism of this alkali promoter effect is available due to the complexity of syngas reaction mechanism and low content of alkali added to the catalysts. In this thesis, we performed a comprehensive investigation of the alkali promoter effect with density functional theory (DFT) calculations as our primary tool. We first examine various Mo2C surfaces to determine a representative surface structure active to alkali adsorption. On this particular surface, we develop a syngas reaction network including relevant reaction mechanisms proposed in previous literature. With energetics derived from DFT calculations and a BEP relation, we predict the syngas reaction selectivity and find it to be in excellent agreement with experimental results. The dominant reaction mechanism and selectivity determining steps are determined from sensitivity analysis. We also propose a formation mechanism of alkali promoters on Mo2C catalysts that shows consistency between experimental IR and DFT computed vibrational frequencies. Finally, the effect of alkali promoters on the selectivity determining steps for syngas reactions are investigated from DFT calculations and charge analysis. We are able to rationalize the role of alkali promoters in shifting the reaction selectivity from hydrocarbons to alcohols on Mo2C catalysts.

Gold nanoparticles are excellent candidates for all the biomedical applications due to their size and shape dependent optical and physiological properties. In this study, gold nanoparticles were synthesized chemically for bio-application. It was observed that the size and shape of gold nanoparticles depend strongly on the concentration of chemical solution, type of reducing agent used in the reaction, temperature of the solution and stabilizing agent for reaction. Transmission electron microscopy (TEM) has been used extensively to determine the size and shape of the gold nanoparticles. Optical properties of the size and shape selected nanoparticles were studied using UV-vis spectrophotometer in absorption mode. The chemically synthesized gold nanoparticles were observed to show excellent absorption property which is reflected by the presence of the characteristic surface plasmon resonance (SPR) band peak. The SPR peak was found to be predominantly dependent on the size of nanoparticles. We have observed a strong red shift with increasing the size of gold nanoparticles. The position of the SPR peak was also observed to change with shape of gold nanostructures. Synthesis and characterization of the composites of gold nanoparticles and Poly (Oanisidine) (POAS) have been carried out in this thesis. Gold-POAS materials system was characterized using UV-vis spectroscopy, TEM, Fourier Transform Infrared Spectroscopy. The chemically synthesized gold nanoparticles were successfully utilized for the study of Respiratory Syncycial Virus (RSV) interaction. Gold nanoparticles were found to inhibit the RSV infection. The electrochemical behavior of gold nanoparticles was studied and their potentials for biosensing applications were tested. Cyclic voltaammetry was performed for the detection of dopamine and ascorbic acid using gold nanoparticles of different sizes. Interaction of gold nanoparticles with Bovine Serum Albumin (BSA) has been studied via absorption spectroscopy and TEM measurements. The absorption spectra of the GNP-BSA show remarkable shift in SPR band peak towards high wavelength. Catalytic properties of the gold nanoparticles were studied by using them as a catalytic activator for the gas sensing applications.

CO hydrogenation and CO oxidation are two important processes addressing the energy and environmental issues of great interest. Both processes are carried out using metallic catalysts. The objective of this dissertation is to study the catalytic processes that govern these two reactions from a molecular perspective using quantum mechanical calculations. Density Functional Theory (DFT) has proven to be a valuable tool to study adsorption, dissociation, chain growth, reaction pathways etc., on well-defined surfaces. DFT was used to study the CO reduction reactions on promoted cobalt catalyst surfaces and CO oxidation mechanisms on cobalt surfaces. CO hydrogenation via Fischer-Tropsch Synthesis (FTS) is a process used to produce liquid fuels from synthesis gas. The economics of the Fischer-Tropsch process strongly depends on the performance of the catalyst used. The desired properties of a catalyst include selectivity towards middle distillate products such as diesel and jet fuel, higher activity and longer catalyst life. Catalysts are often modified by adding promoters to obtain these desirable properties. Promoters can influence the reaction pathways, reducibility, dispersion, activity and selectivity. In FTS, understanding the effect of promoters in the molecular scale would help in tailoring catalysts with higher activity and desired selectivity. Preventing deactivation of catalyst is important in FTS to increase the catalyst life. Deactivation of Co catalyst can occur by reoxidation, C deposition, sintering, formation of cobalt-support compounds etc. Designing catalyst with resistance to deactivation by the use of promoters is explored in this dissertation. The influence of promoters on the initiation pathways of CO hydrogenation is also explored as a first step towards determining the selectivity of promoted catalyst. The influence of Pt promoter on O removal from the surface of Co catalyst showed that Pt promoter reduced the activation barrier for the removal of O on both flat and stepped Co surfaces. An approximate kinetic model was developed and a volcano plot was established. The turn-over frequency (TOF) calculated based on the activation barriers showed that Pt promoted Co surface had a higher rate than unpromoted Co surface. The effect of Pt and Ru promoters on various pathways of C deposition on Co catalyst was studied to gain a mechanistic understanding. The promoters did not affect the subsurface C formation but they increased the barriers for C-C and C-C-C formation and also decreased the barriers for C-H formation. The promoters also influence the stabilities of C compounds on the Co surface suggesting that Pt and Ru promoters would decrease C deposition on Co catalysts. The effect of Pt promoter on unassisted and H-assisted CO activation pathways on Co catalyst was studied. Pt promoted Co surface followed H-assisted CO activation. Pt promoter decreased the activation barriers for CO activation pathways on Co catalyst thereby increasing the activity of Co catalyst. CO oxidation is a process used to prevent poisoning of fuel cell catalysts and reduce pollution of the atmosphere through exhaust gases containing CO. Expensive catalysts like Pt are widely used for CO oxidation which significantly increases the cost of the process and hence it is necessary to search for alternative lower cost catalysts. Understanding the mechanism of a reaction is the first step towards designing better and efficient catalyst. DFT is helpful in determining the basic mechanism and intermediates of reactions. The mechanism of CO oxidation on CoO catalyst was explored. Four possible mechanisms for CO oxidation on CoO catalyst were studied to determine the most likely mechanism. The mechanism was found to be a two-step process with activation barrier for formation of CO2 larger than the barrier for formation of the intermediate species.

Solid oxide fuel cells (SOFCs) are electrochemical energy conversion devices that directly transform the chemical energy of fuel into electrical energy. They generate electricity far more efficiently and with fewer emissions per megawatt-hour compared to any combustion-based power generation system. More remarkably, SOFCs can directly use hydrocarbon fuels without requiring external fuel reforming, employing low-cost Ni catalyst instead of noble-metal catalysts used for low-temperature fuel cells. However, the conventional SOFCs using Ni-based anodes fed with carbon-containing fuels have one pitfall; the carbon produced by hydrocarbon cracking is deposited on the Ni surface, thereby precluding the surface of the Ni-based anodes from being available for further fuel oxidation and consequently impeding SOFC operation. This dissertation focuses on overcoming this critical drawback to allow for the simultaneous use of Ni-based anodes and hydrocarbon fuels. Further work focuses on improving SOFC performance to provide the highest efficiencies possible. To boost the power densities of SOFCs, a novel, facile approach to modify the surface structure of anode powders and thereby enlarge the three-phase boundary (TPB) regions of anodes is presented. One such powder preparation method based on the electric charge variation of oxides depending upon the pH of the solution results in significantly extended TPB regions and thus a remarkable increase in power densities of SOFCs. Another method involves the formation of Ce₁₋[subscript x]Gd₁₋[subscript y]Ni[subscript x+y]VO₄₋[subscript delta] at the phase boundaries between NiO and Ce₀.₈Gd₀.₂O₁.₉ (GDC) by V⁵⁺-incorporation onto NiO surface; this method improves the microstructure of Ni-GDC-based anodes and considerably lowers GDC electrolyte sintering temperature, thereby enhancing the SOFC performance. With these high performance anodes, natural gas-fueled SOFCs are studied through two strategies to alleviate coking: incorporation of catalytic materials onto the Ni surface and the introduction of catalytic functional layers (CFLs) to the outer surface of an anode-supported single cell. Hydrogen tungsten bronze and hydroxylated Sn formed on the Ni surface provide hydroxyls for the deposited solid carbon, removing it from the anodes as CO₂. Moreover, the use of hydrophilic Sn or Sb-incorporated Ni-GDC CFLs prevents the anode from being exposed directly to hydrocarbon fuels and controls the solid carbon accumulation similarly to the former strategy. / text

Proton exchange membrane fuel cells (PEMFCs) have attracted great attention due to their high power density, low-temperature operation and high energy conversion efficiency. However, the high cost of Pt catalysts and durability problems hinder their commercialization. So their cost must be lowered drastically and their durability must be extended. In an effort to overcome these problems, there have been intensive efforts to enhance the activity, durability and to lower the price of catalysts by alloying with other less expensive metals. In particular, the sluggish kinetics of ORR caused by Pt oxide at cathode and Pt catalyst degradation by electrochemical surface area (ECSA) loss have been a huge research area where a lot of researchers have paid lots of attention to solve. In this regard, the objective of this dissertation is to evaluate a series of Pt catalyst electrode surface electrochemical reactions on PEMFC electrode in order to help searching new catalysts and enhancing system design, assist in the search for new catalysts and improved system design by suggesting the developed mechanism of electrocatalyst activity and stability (durability). We have been focused on understanding the oxide-mediated dissolution of Pt by using electrochemical experiment methods such as RRDE, EQCN, SECM with a combination of ICP-MS and computational simulation with COMSOL Multiphysics. Firstly, in chapter 3, we showed the oxide-mediated Pt dissolution rate and the influence of hydrogen and cation underpotential deposition on Pt dissolution. In chapter 4, we revealed oxygen reduction reaction (ORR) plays a significant role in Pt oxide formation and reduction that influences the Pt catalyst dissolution, resulting in accelerated Pt dissolution rate at specific potential range. Finally, we found out the nature of mobile species generated during PtO₂ reduction process which have been disputed as Pt ion or other mobile species and fulfilled computational simulation for evaluation of SECM experiment in chapter 5. Based on these experiments and simulation, we were able to explain some mechanism of literature results that already were reported but have not been clearly explained so far. In terms of the purpose of this dissertation, the mechanism of oxide-mediated Pt dissolution, influence of ORR to Pt oxide formation/reduction and Pt dissolution, the nature of mobile species generated during PtO₂ reduction process, are sure to be very helpful in developing new catalysts and enhancing system design and suggested operating conditions. / text

When an electronic system is confined in one or more dimensions to a length scale comparable to the de Broglie wavelength, quantum confinement occurs. In metallic quantum thin films grown on semiconductor substrates, such confinement occurs between the vacuum-solid and the solid-solid interfaces, which results in the formation of distinctive quantum well states (QWS). Due to this confinement, many physical phenomena occurring in the thin metal system are totally different from the bulk system, which makes the study of quantum thin films interesting and important. In this thesis, quantum thin film studies, mainly based on the Pb/Si(111) system, were performed utilizing low-temperature scanning tunneling microscopy/spectroscopy (STM/STS) with a focus on three main aspects: phase relationship, surface reactivity, and coherent coupling. The Pb/Si(111) system is chosen due to its unique phase matching between the Fermi wavelength and the lattice spacing along [111], leading to a bi-layer quantum oscillation in many physical properties, including the surface energy and the work function. Surprisingly, STM/STS measurement revealed that quantum oscillations of work function and surface energy have identical phase, in contrast to a theoretically predicted 1/4 wavelength phase shift in the phase relationship. Here, a new solution to this puzzle is provided. Furthermore, it is found out that the oxidation rate of Pb/Si(111) system is greatly enhanced in the presence of atomic scale catalyst -- Cs substitutional atoms, while the reactivity to CO is saturated after the initial enhanced nucleation. Finally, by inserting thin Ag layers in between Pb/Si(111) system, the coherent coupling of double quantum wells (a Pb quantum well and a Ag quantum well) are probed, where combined QWS features are observed by STS measurement. The growth mechanism of these heterostructures -- Pb/Ag/Si(111) -- is also investigated. / text

Recently, because of the increase of environmental concerns in process design, the need to enhance conversion to product and prevent generation of wasteful byproducts in the reactor network has become urgent. This prevents high cost treatment and separation costs downstream in the process. Therefore, in this thesis I focus on making production of vinyl chloride monomer (VCM) more efficient and on possible ways of industrial organochlorine waste (OCW) recycling. In particular, in the first experiment, we investigate how catalyst and its structure can affect product output. Infrared spectroscopy and X-ray diffraction analysis were utilized to investigate the structure of the γ-Al2O3 carrier with CuCl2 catalyst on its surface. Structure of the two catalysts, HarshowX1 and MEDC-B, and their effect on the mechanism of ethylene oxidative chlorination reaction into 1,2-dichlorethane were studied. Differential thermal analysis and mass spectroscopy were applied to study the structure and the mechanism differences between the deposited and permeated CuCl2 catalysts. The second experiment deals with ecological processing and recycling methods of wasteful byproduct that can be called chlororganic wastes. Typical waste products are 1,2-dichloroethane, 1,1,2-trichloroethane, vinylidene, and vinyl chloride monomer. Polymerization and copolymerization of typical waste products with their C5-C9 fraction resulted in non-toxic polymer products that can be used in construction and road-building industries. The possibility of joint chlorine and sulfide-containing chemical wastes recycling into polysulfide oligomeric products is discussed. This comprehensive recycling allows utilizing 80-90% of all wastes generated during synthesis of chlorinated products in the chemical industry. The results of the studies aim to improve the conversion of ethylene to vinyl chloride and minimize the formation of byproducts.

The objective of this work is to develop mathematical models to predict molecular weight distributions (MWDs) of ethylene copolymers produced in an industrial gas-phase reactor using a Ziegler-Natta (Z-N) catalyst. Because of the multi-site nature of Z-N catalysts, models of Z-N catalyzed copolymerization tend to be very large and have many parameters that need to be estimated. It is important that the data that are available for parameter estimation be used effectively, and that a suitable balance is achieved between modeling rigour and simplification. In the thesis, deconvolution analysis is used to gain an understanding of how the polymer produced by various types of active sites on the Z-N catalyst responds to changes in the reactor operating conditions. This analysis reveals which reactions are important in determining the MWD and also shows that some types of active sites share similar behavior and can therefore share some kinetic parameters. With this knowledge, a simplified model is developed to predict MWDs of ethylene/hexene copolymers produced at 90 °C. Estimates of the parameters in this isothermal model provide good initial guesses for parameter estimation in a subsequent more complex model. The isothermal model is extended to account for the effects of butene and temperature. Estimability analysis and cross-validation are used to determine which parameters should be estimated from the available industrial data set. Twenty model parameters are estimated so that the model provides good predictions of MWD and comonomer incorporation. Finally, D-, A-,and V-optimal experimental designs for improving the quality of the model predictions are determined. Difficulties with local minima are addressed and a comparison of the optimality criteria is presented. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2009-05-28 20:43:58.37

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