Summer Research Experience for Undergraduate Projects 2013
Here's a full list of the summer projects available to students interested in the Summer Research Experience for Undergraduate Students program. You can also download a full listing here.
- Mechanistic Chemistry of TG Oil Cracking
- Graphite Furnace Atomic Absorption Spectrometer (GFAAS) Modeling of Trace Elements (TE) Atomization in Coal Combustion Furnaces
- Photovoltaic Cell Manufacture to Explore Ru(II) and Re(I)-Terpyridines
- Particulate Emissions from Coal-Biomass Combustion
- Development and Testing of Membrane Electrode Assemblies (MEA) Using UND-Developed Silica-Based Nanocatalysts
- Atmospheric Aerosol Formation from Renewable Biofuels
- Computational Chemistry Research in Coal and Biomass Combustion
- Scanning Tunneling Microscopy Study on Self-Assembled Monolayers of Porphyrin Molecules on Highly Oriented Pyrolytic Graphite for Solar Cells
- Uncertainty Quantification and Optimization in Modeling Advanced Combustion Systems
- The Four-Electron Reduction of Carbon Dioxide (CO2)
- Functionalization of Aliphatic and Aromatic C-H Bonds Using Pd(II) for Renewable Chemical Production
- Pretreatment and Enzymatic Hydrolysis of Forage Sorghum as a Renewable Source for Biofuels and Green Chemicals
- Proteins Circular Dichroism
- Atmospheric Reactions of Polycyclic Aromatic Hydrocarbons
- Life Cycle Analysis of the SUNRISE Crop Oil Conversion Processes
- Renewable Chemical Reaction Optimization
- Renewable Pitch for Carbon Fibers
Mentors: E. Kozliak and A. Kubatova (Chem) and W. Seames (ChE)
The triacyl glycerides (TGs) in bio-oils produced by oil seed crops, algae, and microbes can be processed into fuels by a number of pathways. Thermal (i.e., non-catalyzed) cracking in an oxygen-free environment is attractive because it models the natural conversion of TGs to petroleum, only conducted on a much shorter timescale. Recently, thermal TG cracking was shown to be a unique and surprisingly specific pathway leading to a well-defined mixture consisting mostly of linear saturated hydrocarbons and fatty acids of a specific homology pattern, as well as aromatic and other cyclic hydrocarbons . This project is designed to gain insights into the chemistry of TG oil cracking, focusing on the mechanism of formation and structure of chemicals formed as by-products. Capitalizing on the use of analytical techniques developed in prior research [1, 2], reaction pathways will be evaluated using an on-line pyrolysis unit directly connected to a gas chromatograph with flame ionization and mass spectrometric detectors (GC-FID/MS). Evaluation will be based on quantification of the decay of initial compounds, e.g., pure individual TGs of varied chemical structure, combined with the identification and quantification of products. Insights into the specific mechanisms associated with TG cracking will be explored.
Graphite Furnace Atomic Absorption Spectrometer (GFAAS) Modeling of Trace Elements (TE) Atomization in Coal Combustion Furnaces
Mentors: E. Kozliak, D. Pierce (Chem) and W. Seames (ChE)
The physical property data necessary to model the vapor-melt partitioning of TEs (e.g. As, Se, Sb) in the presence of Si, Si-Al, and Fe matrices at localized combustion conditions at the micro-environmental conditions of the burning char particles are currently not available (temperatures >2400K, which creates insurmountable problems for accurate modeling). A robust and reliable method has been developed to determine the Arrhenius activation parameters for any target analyte, using a GFAAS as an extremely high-temperature in-situ burning char simulator/sample collector/analytical platform (all at the same time). This follow-on undergraduate project will focus on applying this method to TEs embedded in matrices, i.e., determining the activation parameters for TE atomization over Fe, Si, and Si-Al melts at 1900 to 2400 K. To model separately the matrix effects in the organic fraction of coal and inorganic inclusions, experiments will be conducted with and without carbon (using plain and W- and Ta-coated AA furnace).
Mentors: Sean E. Hightower (Chem) and Edward Kolodka (ChE)
Recent research in our laboratory has shown that the oxidation potential of Re(I)-terpyridines occurs at potentials near those of commonly used redox mediators such as the iodide/triiodide couple. Furthermore, these complexes absorb light throughout the entire visible spectrum. These data suggest higher efficiencies can be achieved using these systems. In this project, the REU student will prepare photovoltaic devices based on either Ru(II) or Re(I)- terpyridines - none of which have been previously prepared. Studies will also include the investigation of different redox mediators.
Mentors: Steve Benson (ChE), Frank Bowman (ChE)
Combustion of biomass together with coal has the potential to reduce the carbon footprint of coal-fired electricity generation. The chemical composition of biomass used can influence the composition and size distribution of fly ash particles produced during coal combustion, leading to changes in particulate and trace element emissions to the atmosphere. In this project, the REU student will help run experiments with a downflow combustor fed by a mixture of biomass and coal. Aerosol samples from the exhaust gas will be collected and analyzed to determine elemental composition and size distributions.
Development and Testing of Membrane Electrode Assemblies (MEA) Using UND-Developed Silica-Based Nanocatalysts
Mentors: Michael Mann (ChE), Julia Zhao (Chem)
The REU student will determine optimal fabrication conditions for MEAs using both carbon-based catalysts (baseline) and UND produced silica-based MEAs. Factors to be investigated include solvent type, hot pressing conditions, and cathode and anode catalyst loading. The student will also participate in testing generating data to quantify electrical performance as characterized by fuel cell losses, fuel crossover, and catalyst poisoning as a function of time.
Mentors: Frank Bowman (ChE) and Alena Kubatova (Chem)
Biofuels are a promising replacement for existing transportation fuels because they can significantly reduce net carbon emissions. However their other atmospheric emissions have not yet been fully characterized. A new laboratory aerosol chamber will be used to investigate particulate matter formation reactions arising from biofuel combustion emissions. The system consists of a 20 m3 Teflon reaction chamber within a temperature controlled enclosure surrounded by UV lights to mimic solar radiation. Gas and particle emissions from biofuel combustion are added into the chamber and gas reactions, particle growth, and dilution and depositional losses are monitored by a variety of gas and particulate instrumentation. In this project, the REU student will help with chamber characterization experiments to determine particle deposition rates, photochemical reaction rates, and instrument responses, followed by a series of experiments exploring the formation of secondary aerosol formation from different biofuels.
Mentor: Dr. Mark Hoffmann (Chem)
This project explores the quantum mechanical descriptions of the electronic structures of molecules and reactions of relevance to the understanding of combustion processes. Our primary focus is on chemical reactions that are difficult or impossible to measure accurately in the laboratory, so that the computational results are critical to developing a correct understanding of the chemical systems. We are able and interested in examining reactions that involve excited electronic surfaces, as a result of thermal or photochemical processes. We are particularly interested in reactions that involve O2, O3, and oxides of nitrogen with reactive molecules in the upper atmosphere and in coal combustors. Recent work has extended our capabilities in describing gas-phase reactions to reactions occurring on clusters that mimic surfaces. The student will develop familiarity with the use and theoretical underpinnings of well- established main techniques of modern quantum chemistry (e.g., Hartree-Fock (HF) method, hybrid density functional methods such as B3LYP, and second-order Møller-Plesset perturbation theory), as well as novel multireference perturbation theory approaches developed at UND, in the context of a combustion-relevant chemical problem. The results to be obtained will be matched with the experimental results obtained by chemists (Kozliak) and ChEs (Seames).
Scanning Tunneling Microscopy Study on Self-Assembled Monolayers of Porphyrin Molecules on Highly Oriented Pyrolytic Graphite for Solar Cells
Mentor: Nuri Oncel (Physics)
Thin films of molecules with certain physical and chemical properties have been implemented in various electronic and optoelectronic devices such as electroluminescent devices, sensors, diodes, and photovoltaic cells. High quality molecular films and interfaces can be realized with the help of self-assembly. Molecular self-assembly is due to the mutual interactions between the molecules ranging from weak and non-directional van der Waals bonds to strong and directional hydrogen bonds. Porphyrins have a nearly square core conformation, with a two-dimensional (2D) delocalized conjugated p-electron system. The REU student will study the physical properties of thin films of porphyrin molecules adsorbed on HOPG at solid liquid interfaces using a scanning tunneling microscope. We are particularly interested in controlling surface morphology of a porphyrin film by co-adsorbing them with chain-like molecules.
Mentor: Gautham Krishnamoorthy (ChE)
High fidelity computational models of the flows within emerging power generation system devices, such as gasifiers, carbon capture systems, and oxy-fuel combustors, can yield valuable insights into their design, operation and optimization. Modern computational power enables us to model these devices at resolutions and accuracies not possible previously. However, in any modeling exercise we need to achieve a useful trade-off between computational speed and accuracy. We also need to be able to predict the variations in output subject to uncertainties and variations in the fuel, flow rates, boundary conditions and material properties. The goal of this project is to examine a range of physical models for multi-phase flows encountered in oxy-fuel combustion and coal/biomass gasifiers that vary in their computational speeds and accuracies. Next, the inherent errors and uncertainties encountered when employing them will be quantified to enable us to undertake model refinements or select the "optimum" models among existing ones to accurately simulate gasifiers or oxy-combustors within a reasonable time.
Mentor: Sean E. Hightower (Chem)
Polypyridine complexes of d6 metals such as Ru(II), Os(II), and Re(I) have received a great deal of attention because they can act as electrocatalysts and photocatalysts for the reduction of carbon dioxide (CO2) to formate (O2CH–) and
carbon monoxide (CO). Although these reactions have been significant in determining the efficacy of these systems in the reduction of CO2, they only proceed by way of a two-electron reduction. This is a significant drawback when considering that the complete sequence for the reduction of CO2 to methanol (CH3OH), for example, requires an overall six-electron reduction. In this project, the REU student will design and prepare catalytic systems capable of proceeding past the two-electron stage.
Functionalization of Aliphatic and Aromatic C-H Bonds Using Pd(II) for Renewable Chemical Production
Mentor: Irina Smoliakova (Chem)
Catalytic functionalization of C-H bonds is the most atom- and energy-efficient method for preparation of fine chemicals. The ultimate goal of our studies is to use catalytic transformations for synthesis of novel types of compounds, which could be employed as catalysts in new catalytic processes, essential for sustainable production of chemicals from non-petroleum sources. Members of our group study regioselective functionalization of C-H bonds in aryl and alkyl groups using the two-step approach: C-H activation of appropriate heteroatom-containing substrates by stoichiometric or catalytic amounts of a Pd(II) species followed by reaction of the formed metalated species with metal phosphides or secondary phosphines. The products of the proposed reaction sequence are aminophosphines and related hemilabile ligands, which are highly efficient catalysts in a number of asymmetric transformations.
Pretreatment and Enzymatic Hydrolysis of Forage Sorghum as a Renewable Source for Biofuels and Green Chemicals
Mentor: Yun Ji (ChE)
The development and conversion of sustainably produced biomass as a feedstock for biorefineries, biofuels, bioproducts and bioenergy is a critical priority due to concerns in achieving energy security, environmental and human health, rural economic development, and the need to diversify products and markets for the forest and agricultural industries. The objective of the proposed project is to evaluate and optimize the biofuel production from forage sorghum as a non-food resource and thus improve the local economy and reduce the dependence of our nation on foreign sources of energy. This project is divided into two tasks (pretreatment and enzymatic hydrolysis) to evaluate the forage sorghum as a potential biofuel feedstock. This project is appropriate for an undergraduate student interested in bioenergy research. The student will obtain hands-on experience in using a steam-jacketed biomass pretreatment reactor, an incubator shaker for enzymatic hydrolysis and instruments such as High Performance Liquid Chromatography (HPLC) and UV for analytical measurements.
Mentor: Kathryn Thomasson (Chem)
There are a wide variety of proteins important for biofuel production. There are protein enzymes responsible for the metabolic pathways in the organisms producing the biofuels (e.g., ethanol). Other enzymes are capable of degrading the complex carbohydrates into materials that can become biofuels (e.g., cellobiose dehydrogenase degrades lignin and cellulose). To understand how any of these proteins work, a basic knowledge of dynamic protein is needed. Circular dichroism (CD) is a spectroscopic technique that follows the dynamics of proteins in solution. The physics of CD is poorly understood. The development and testing of theoretical methods to predict CD for proteins can assist in the interpretation of the dynamical structure of the proteins and how they function. Some protein structures are known in the solid state (X-ray crystal structures) and these can be used with molecular dynamics to create ensembles of solutions structures. The technique of homology modeling can be used to generate 3D protein structures when well-defined crystal structures are unavailable. The continued development of the dipole interaction model (DInaMo) to predict the far UV CD of proteins aids the understanding of the solution structures and their dynamic behavior. Undergraduate students will learn these computational methods and will contribute to a growing body of knowledge of protein dynamics, enzyme catalysis, and cellular energy generation and degradation, both fundamental processes for sustainable energy projects that depends on biological sources.
Mentor: A. Kubatova
Polycyclic aromatic hydrocarbons (PAHs) and more importantly their oxidation products are known to impose negative health effects on humans. While there is currently a vast understanding of how PAHs are oxidized in the gas phase, there is limited knowledge on the mechanisms behind their transformation in the gas-particle phase. Due to the increasing rate of anthropogenic release of particulate matter (PM) into the atmosphere, gas-particle phase oxidation of PAHs on the surface of PM has become a major source of these toxic PAH oxidation products. One important class of PAH oxidation products is nitrated PAHs (nitro-PAHs) due to their directly mutagenic character. In order to elucidate the mechanisms of PAH reactions and formation of nitro-, oxy- and hydroxy-PAHs, they must be studied under controlled atmospheric conditions. Therefore, this project will involve utilizing a large-scale indoor reaction chamber to study PAH transformation pathways on PM upon exposure to NO2 under various conditions.
Mentor: Wayne Seames
SUNRISE researchers have invented a suite of technologies that take fatty acid- or triacyl glycerol-based oils and convert them into renewable transportation fuels and by-product chemical products. The emerging interdisciplinary field of sustainability requires that any new technology be studied to assess its economic, environmental, and social impacts. To date, the true environmental impact of the new SUNRISE technology has yet to be assessed.
Life cycle analysis (LCA) is a recognized standard method for evaluating the environmental, ecological, and health impacts of any manufacturing process. To conduct an LCA, data from the entire life cycle chain (from earth to earth) must be identified and estimated. A top level LCA requires identification of all inputs and outputs from the life cycle chain. Factors associated with the impact of consuming inputs and discharging outputs are then determined following accepted methodologies. The results are then analyzed to draw conclusions about the technology’s impact.
The objective of project is to conduct an LCA for both the new SUNRISE technology and for petroleum analogs in order to assess the true technology impacts on the environment.
Student Role in Project: The student will work with their faculty mentor and graduate students to learn the life cycle chain for both the SUNRISE technology and petroleum-derived analogs and to identify the inputs and outputs. Literature data and data from in-house experimental work will be used to perform the quantitative portion of the LCA. Analysis of the results will be conducted and a paper documenting the findings will be written.
Mentor: Wayne Seames
The primary objective is to optimize conditions for the decomposition reaction of a mixture of sugars into lactic acid, quantify reaction yields and co-products. The development of new and efficient methods to make fuels and chemicals from lignocellulosic biomass is a promising technology that will not compete with our current food supply. Currently lactic acid is a promising compound for the production of biodegradable polymers as well as a reactant to build highly selective fuel compounds.
Student Role in Project: The student will work with their faculty mentor and graduate students to optimize current techniques for the production of lactic acid and its derivatives. Lab work will consist of catalyst doping, testing doped catalyst on cellulosic sugar solutions, and analyzing the end product. Outside the lab, the student will be exposed to chromatogram analysis, experimental optimization, and kinetic modeling.
Menor: Wayne Seames
This project will build upon previous UND research to optimize the conditions for the generation of a mesophase pitch product from crop oils. Previous research has shown that bio pitch, a tar-like byproduct of advanced biofuels refining, is a potential feedstock for carbon fiber formation. Continued research suggests that better carbon fibers can be produced if certain steps are taken to treat the bio pitch. These steps involve extended thermal treatment, high vacuum film evaporation, and hot filtering.
Student Role in Project: The student will work with their faculty mentor and graduate students to produce bio pitch and to test the pitch quality. Experiments will be conducted to optimize the pitching conditions. Laboratory tests such as FTIR, TGA, and optical microscopy will be used to test the pitch. Finally, the pitch will be shipped to a national laboratory for carbon fiber production.