Physical Chemistry Commons^™

Modeling Vitexin And Isovitexin Flavones As Corrosion Inhibitors For Aluminium Metal, Abdullahi Muhammad Ayuba, Umaru Umar

Karbala International Journal of Modern Science

Theoretically, the aluminium corrosion inhibitive performance of vitexin (VTX) and isovitexin (SVT) were evaluated with a view of establishing the mechanism of the inhibition process. Calculations which include the consideration of several global descriptors were studied to describe and correlate the reactivity of the molecules with the computed descriptors. First and second-order condensed Fukui functions were employed to analyze local reactivity parameters, while simulations involving the adsorbed molecules on Al (1 1 0) surface were conducted through quench dynamic simulations and the mechanism of physical adsorption was established with SVT relatively been a better inhibitor on Al surface than VTX.

Investigation On The Dissociative Photoionization Mechanism Of Furfural, Investigation Of The Absolute Photoionization Cross Sections Of Three Potential Propargylic Fuels, And Ab Initio Analysis On Potential Superbases Of Several Hyperlithiated Species: Li3f2o And Li3f2(Oh)N (N = 1, 2, 3), Matthew Winfough

Master's Theses

This thesis presents the study photoionization cross sections of three different propargylic biofuels; dipropargyl ether, propargyl alcohol, and propargylamine, in chlorine radical-initiated combustion experiments at the Chemical Dynamics Beamline (9.0.2) at the Advanced Light Source of the Ernest Orlando Berkeley National Laboratory in Berkeley, California. Additionally, the unimolecular dissociative photoionization mechanism of furfural was studied using photoelectron photoionization coincidence (PEPICO) spectroscopy at the vacuum ultraviolet beamline at the Swiss Light Source of the Paul Scherrer Institut in Villigen, Switzerland. Dissociation products and mechanisms for furfural were identified over a photon energy range of 10.9 to 14.5 eV. Lastly, a study …

Photoelectrochemical Studies On Non-Noble Metal Based Catalysts Towards Tandem Solar Water Splitting, Arun Siddarth Sridhar

Dissertations

Photoelectrochemical (PEC) water splitting makes direct use of solar energy incident on semiconductor photoelectrodes, and it is a convenient, economic option to produce high purity hydrogen at low temperatures. The use of multiple light absorbers can increase overall solar energy utilization and provide a solution to the trade-off between overall band gap and band edge positioning of photoelectrodes specific to solar water oxidation and water reduction. The study of non-noble metal based catalysts for hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) are essential for economic practical commercialization of photo-electrolyzers. This dissertation focuses on the use of a variety …

Systematic Postsynthetic Modification Of Nanoporous Organic Frameworks And Their Performance Evaluation For Selective Co2 Capture, Timur Islamoglu

Theses and Dissertations

Porous organic polymers (POPs) with high physicochemical stability have attracted significant attention from the scientific community as promising platforms for small gas separation adsorbents. Although POPs have amorphous morphology in general, with the help of organic chemistry toolbox, ultrahigh surface area materials can be synthesized. In particular, nitrogen-rich POPs have been studied intensively due to their enhanced framework-CO₂ interactions. Postsynthetic modification (PSM) of POPs has been instrumental for incorporating different functional groups into the pores of POPs which would increase the CO₂ capture properties. We have shown that functionalizing the surface of POPs with nitro and amine groups …

Photooxidation Reactions Of Small-Chain Methyl Esters, Aerosol Photoelectron Spectroscopy, And The Photodissociation Of Ethylenediamine, Giel Muller

Master's Theses

Research conducted at the University of San Francisco is presented within this masters thesis, including the Cl-initiated photooxidation reactions of methyl propanoate, methyl butanoate, and methyl valerate (pentanoate), the aerosol photoelectron spectroscopy of isoprene and gamma-valerolactone, and the TPEPICO investigation of ethylenediamine. Experiments were conducted at the Lawrence Berkeley National Lab Advanced Light Source (ALS), the National Synchrotron Radiation Research Center in Hsinchu City (NSRRC), and the University of Stockton in California, respectively.

Spectroscopic Investigation Of The Chemical And Electronic Properties Of Chalcogenide Materials For Thin-Film Optoelectronic Devices, Kimberly Horsley

UNLV Theses, Dissertations, Professional Papers, and Capstones

Chalcogen-based materials are at the forefront of technologies for sustainable energy production. This progress has come only from decades of research, and further investigation is needed to continue improvement of these materials.

For this dissertation, a number of chalcogenide systems were studied, which have applications in optoelectronic devices, such as LEDs and Photovoltaics. The systems studied include Cu(In,Ga)Se2 (CIGSe) and CuInSe2 (CISe) thin-film absorbers, CdTe-based photovoltaic structures, and CdTe-ZnO nanocomposite materials. For each project, a sample set was prepared through collaboration with outside institutions, and a suite of spectroscopy techniques was employed to answer specific questions about the system. These …

The Impact Of Driving Conditions On Phev Battery Performance, Nathan Christensen, John Patten, Steven Srivastava, Gary P. Nola

Green Manufacturing Research Journal

The battery performance of a modified Prius with a 5 kWh plug-in battery was documented for a year to determine the impact of environmental conditions and user attributes on vehicle performance.  Both fuel economy and pure electrical efficiency were compared to ambient temperature.  The fuel economy has a positive relationship with ambient temperature until approximately 70˚F where the efficiency begins to drop.  Electrical performance has a positive linear relationship with ambient temperature.  With the emergence of electric vehicles (EVs) and PHEVs from a variety of automotive manufacturers, information on EV and PHEV performance for consumers will become more important.

Investigation Of Titanium Nitride As Catalyst Support Material And Development Of Durable Electrocatalysts For Proton Exchange Membrane Fuel Cells, Bharat Avasarala

Legacy Theses & Dissertations (2009 - 2024)

The impending energy and climatic crisis makes it imperative for human society to seek non-fossil based alternative sources for our energy needs. Although many alternative energy technologies are currently being developed, fuel cell technology provides energy solutions, which satisfy a wide range of applications. But the current fuel cell technology is far from its target of large scale commercialization mainly because of its high cost and poor durability. Considerable work has been done in reducing the cost but its durability still needs significant improvement. Of the various materials in a PEM fuel cell, the degradation of electrocatalyst affects its durability …

Site-Specific Photocatalytic Splitting Of Methanol On Tio2(110), Chuanyao Zhou, Zefeng Ren, Shijing Tan, Zhibo Ma, Xinchun Mao, Dongxu Dai, Hongjun Fan, Xueming Yang, Jerry L. Larue, Russell Cooper, Alec M. Wodtke, Zhou Wang, Zhenyu Li, Bing Wang, Jinlong Yang, Jianguo Hou

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Clean hydrogen production is highly desirable for future energy needs, making the understanding of molecular-level phenomena underlying photocatalytic hydrogen production both fundamentally and practically important. Water splitting on pure TiO₂ is inefficient, however, adding sacrificial methanol could significantly enhance the photocatalyzed H₂ production. Therefore, understanding the photochemistry of methanol on TiO₂ at the molecular level could provide important insights to its photocatalytic activity. Here, we report the first clear evidence of photocatalyzed splitting of methanol on TiO₂ derived from time-dependent two-photon photoemission (TD-2PPE) results in combination with scanning tunneling microscopy (STM). STM tip induced molecular manipulation …

Characterization Of Iron Oxide Thin Films For Photoelectrochemical Hydrogen Production, Kyle Eustace Nelson George

UNLV Theses, Dissertations, Professional Papers, and Capstones

Solar energy is the most sustainable source of energy available. However, solar applications such as photovoltaic cells represent only a partial solution to weaning our dependence upon fossil fuels. Several methods of storing solar energy are currently being pursued, and chemical storage stands out as a promising option - combining design simplicity with high energy density, with hydrogen being particularly attractive because of its abundance and inherently clean nature. A monolithic Photoelectrochemical (PEC) device that produces hydrogen by electrolyzing water directly from sunlight has the benefit of utilizing "free" solar energy to drive the reaction.

Although α-Fe 2 O 3 …

Solar Thermochemical Hydrogen Production Project – Progress Toward Industrial Scale Water Splitting, Roger Rennels

UNLV Renewable Energy Symposium

The 2008 UNLV Renewable Energy Symposium was presented by the Office of Strategic Energy Programs and co-sponsored by the Division of Research and Graduate Studies on August 20, 2008 on the UNLV campus.

The event focused on renewable energy production in Nevada, the US Southwest, and renewable research projects nationwide. It was a great opportunity for anyone working on renewable projects to collaborate with others in this field and exchange information. Over 230 individuals attended the event this year.

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

Observations related to the oxidation of iodide to iodine (I₂) or hypoiodic acid (HIO) by MnO₂ were continued. The formation of triiodide presumable involves the adsorption of iodide onto the MnO₂ surface (perhaps displacing a surface hydroxyl group). The iodide should be subsequently oxidized and released back into solution as IOH or I₂, which rapidly forms I₃ ^-. The kinetic data has been modeled as a first order process. First order rate constants have been obtained for the formation of iodine in the presence of MnO₂. The increase in iodide …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process (FLEX). The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the actinides …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective was to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solutions, and use this data to effectively separate species with very similar chemical properties.

In consultation with a DOE collaborator, electrochemical methods and materials were evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project, in its third year, successfully completed phases 1, 2. Phase 3 was partially completed. The project expanded to include phase 4.

The following were specific goals for 2007-2008:

• To …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU; includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership (GNEP). In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in …

F-Element Electrochemistry In Rtil Solutions: Electrochemical Separation Of Lanthanides And Actinides, David W. Hatchett

Separations Campaign (TRP)

Electrochemical methods can be used to effectively separate actinide and lanthanide species from complex mixtures. This is based on the unique electrochemical properties of each specific target species. In studies it has been found that, with the exception of Ce, aqueous solutions provide unsuitable electrochemical windows to effectively evaluate the thermodynamic properties that are useful for chemical separations. Therefore, a more novel approach was examined which eliminated the aqueous solution with a room temperature ionic liquid (RTIL) solution. RTIL solutions do not suffer from the side reactions that are prominent in aqueous environments. In addition, the potential window is much …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic and microscopic methods, intermediate chemical phases at the interface, intermixing/diffusion behavior, and the electronic interface structure for different coating materials and metals are examined.

In detail, the project studies the interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon. Using SiC single crystals and highly-ordered pyrolytic carbon (HOPG) as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied …

Solution-Based Synthesis Of Nitride Fuels, Kenneth Czerwinski, Tyler A. Sullens

Fuels Campaign (TRP)

One of the original synthetic routes devised for the synthesis of U (III)N involved the entire reaction taking place in liquid ammonia. Several experimental reactions were conducted in an attempt to synthesize the UI₃(NH₃)_x and U(NH₂)₃(NH₃)_x precursors of U(III) N. Each attempt involved cleaning of the uranium metal to remove the oxide coating of the metal reagent with 3 washes of concentrated nitric acid, each followed by a rinse with liquid ammonia. Success of this cleaning procedure was varied, with a majority of cleaned metal oxidizing rapidly once …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process, or FLEX. The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic methods, intermediate chemical phases at the interface, intermixing/ diffusion behavior, and the electronic interface structure as a function of material (metal and coating materials) and temperature are examined.

In the past year, emphasis was placed on a detailed analysis and description of the Cs/SiC interface formation process.

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU–includes Np, Pu, Am, and Cm) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership. In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in this new …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

The stability of the association of iodine with FCC and NOM products were studied. Product distributions for the various matrices under various reaction conditions were examined in order to maximize the binding of iodine. The recovery of the iodine from the sequestration matrices was also examined, along with the conversion of the iodine to matrices more suitable for geological storage and/or use as transmutation targets.

The following are the specific research objectives and goals:

• Develop bench-scale experimental set-up and procedures for simulating plutonium extraction process (PUREX) head-end vapor phase.
• Develop experimental procedures for evaluating iodine sequestering methods using bench-scale procedures. …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objectives of this project are to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solution, and to use this data to effectively separate species with very similar chemical properties. In consultation with a national laboratory collaborator, electrochemical methods and materials will be evaluated and used to exploit the thermodynamic differences between similar chemical species, enhancing the ability to selectively target and sequester individual species from mixtures. This project is in its third year and has successfully completed phases 1 and 2. Phase 3 has been partially completed. The tasks have been expanded …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are …

F-Element Electrochemistry In Room Temperature Ionic Liquids, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

This proposal focuses on f-element electrochemistry in room temperature ionic liquids (RTILs). The ultimate goal is to fully characterize the oxidation/reduction of elements in RTILs to establish the baseline thermodynamic and kinetic data for these systems. The data will be used to critically evaluate the ability to use electrochemical methods for controlled, potential mediated, separation off-elements by electroplating on electrodes surfaces. Factors that will influence the ability to measure the redox processes in f-elements in RTIL solutions and electroplating on electrode surfaces include the structure, solubility, and stability of the target species in these solutions. These factors will be addressed …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the UREX separation scheme, providing data useful to modeling. The areas to be examined include the speciation of U and Pu with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK system. The complexation constants of U and Pu with tributylphosphate will be evaluated. In the TALSPEAK system, …

Criticality Studies Of Dilute Plutonium Mixtures For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of higher actinides (HA, includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel has been identified as a requirement to construct prototype plants such as the Engineering-Scale Demonstration (ESD) and the Advanced Fuel Cycle Facility (AFCF) for the Global Nuclear Energy Partnership (GNEP). GNEP is a program to develop a worldwide consensus to enable the expanded use of economical, environmental nuclear energy to meet growing electricity demand. In this program and the Advanced Fuel Cycle R&D program (AFC) that supports it, we are developing economic …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Organic Matrix: Quaterly Report January-March 2006, Spencer M. Steinberg

Separations Campaign (TRP)

Project Highlights:

• Established that iodide can be oxidized by MnO₂ to I₂ at pHs of 4-8 and moderate temperature.

• Demonstrated that p-hydroxybenzoic acid can be iodinated by MnO₂ and KI at pHs of 2-8.

• Established that humic acids can be iodinated by MnO₂ and iodide at room temperature in pH range of 4-8.