Chemistry Commons^™

Structural Evolution Of Gold-Doped Bismuth Clusters AubiN– (N = 4−8), Seema Pande, Tian Jian, Navneet S. Khetrapal, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The structures of gold-doped bismuth clusters, AuBi_n⁻ (n = 4−8), are investigated through a joint photoelectron spectroscopy and density functional theory (DFT) study. Well-resolved photoelectron spectra are obtained at several photon energies. Global minimum searches coupled with DFT calculations yield low-lying structures, whose relative energies are further evaluated by single-point energy calculations at the CCSD(T) level of theory. Vertical detachment energies are calculated with the inclusion of spin−orbit effects to compare with the experimental data. Three-dimensional structures are found to be dominant in this size range, while a planar low-lying isomer is observed only for AuBi_{4 …}

Probing The Surface Of Nanodiamonds At Stanford Synchrotron Radiation Lightsource And San Jose State University, Jocelyn Valenzuela, Jackson Earl, Cynthia Melendrez, Grace Jeanpierre, Dennis Nordlund, Abraham Wolcott

STAR Program Research Presentations

The nitrogen-vacancy center in diamond is a promising tool in oncology, electric field sensing, and quantum cryptography. High-pressure high-temperature (HPHT) nanodiamonds (NDs) are prime contenders for these fields because they host nitrogen-vacancy centers (NVCs) which are applicable towards cancer detection and electric and magnetic field sensing. However, to apply HPHT NDs to these fields, the surface must first be functionalized—a difficult process because of the inert nature of the surface. The project at hand focuses on surface modification of HPHT NDs with amines to allow for further bioconjugation of small molecules and plasmonic shells. This is done via liquid-phase chemistry …

Radical Chemistry In A Femtosecond Laser Plasma: Photochemical Reduction Of Ag+ In Liquid Ammonia Solution, Victoria K. Meader, Mallory G. John, Laysa M. Frias Batista, Syeda Ahsan, Katharine M. Tibbetts

Chemistry Publications

Plasmas with dense concentrations of reactive species such as hydrated electrons and hydroxyl radicals are generated from focusing intense femtosecond laser pulses into aqueous media. These radical species can reduce metal ions such as Au3+ to form metal nanoparticles (NPs). However, the formation of H2O2 by the recombination of hydroxyl radicals inhibits the reduction of Ag+ through back-oxidation. This work has explored the control of hydroxyl radical chemistry in a femtosecond laser-generated plasma through the addition of liquid ammonia. The irradiation of liquid ammonia solutions resulted in a reaction between NH3 and OH·, forming peroxynitrite and ONOO−, and significantly reducing …

Surfactant Driven Assembly Of Freeze-Casted, Polymer-Derived Ceramic Nanoparticles On Grapehene Oxide Sheets For Lithium-Ion Battery Anodes, Ali Zein Khater

Honors Undergraduate Theses

Traditional Lithium-Ion Batteries (LIBs) are a reliable and cost-efficient choice for energy storage. LIBs offer high energy density and low self-discharge. Recent developments in electric-based technologies push for replacing historically used Lead-Acid batteries with LIBs. However, LIBs do not yet meet the demands of modern technology. Silicon and graphene oxide (GO) have been identified as promising replacements to improve anode materials. Graphene oxide has a unique sheet-like structure that provides a mechanically stable, light weight material for LIB anodes. Due to its structure, reduced graphene oxide (rGO) is efficiently conductive and resistive to environmental changes. On the other hand, silicon-based …

Biosensing And Catalysis Applications Of Nanoporous Gold (Npg) And Platinum-Speckled Nanoporous Gold (Npg-Pt) Electrodes, Christopher J. Freeman

Theses and Dissertations

The importance of porous materials has risen substantially in the last few decades due to their ability to reduce the size and cost of bioanalytical devices and fuel cells. First, this work aims to describe the fabrication of nanoporous gold (NPG) electrodes that are resistant to electrode passivation due to fibrinogen biofouling in redox solutions. The effect on potentiometric and voltammetric experiments was seen as a deviation from ideal behavior on planar gold electrodes, whereas NPG electrodes were consistently behaving in a Nernstian fashion at low concentrations of ferri-ferrocyanide (£100 mM). An improvement in electrode behavior on NPG electrodes versus …

Synthesis And Characterization Of Magnetic Cabides And Oxides Nanomaterials, Hei Man Tsui

Theses and Dissertations

The design and development of nanoparticles is of great interest in the current energy and electronic industry. However, based on the current materials available the production cost can be high with insignificant magnetic and mechanical properties. Specifically, rare-earth magnetic materials composed of neodymium and samarium are known for their high magnetic performance, however, due to the cost of development there is a need to develop a versatile and cost effective material. Alternatively, cobalt carbide nanomaterials have shown to be a promising alternative for rare-earth free magnets as they exhibit comparable properties as hexaferrite magnetic materials. The primary goal of this …

New And Optimized Green Synthesis Of Silver Nanoparticles Using Mullein, Marisa Thompson, Cuong Nguyen, Anna Holmes

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Richard Smalley And The Materials Of Tomorrow: The Discovery, Properties, And Science Of Fullerenes, Creighton A. Jackson

Natural Sciences Student Research Presentations

These are slides accompanying a presentation given at the Natural Sciences Poster Session at Parkland College outlining the properties of and ongoing research pertaining to fullerenes in materials science.

Lignin Depolymerization: Mechanistic Analysis, Optimization And Application, Eric Michael Nagel

Electronic Theses and Dissertations

Lignin is the most abundant aromatic biopolymer and is a potential source for phenolic chemical feedstocks. Lignin is composed of phenolic units connected by more than eight different linkages, the most common being β-O-4 which constitutes 50-60%. The hydrothermal decomposition of a guaiacol based β-O-4 lignin dimer was studied under neutral and basic conditions to elucidate the mechanism of β-O-4 bond cleavage and the formation of downstream products. Phenol-carbonyl condensation and vinyl-ether formation were shown to be the primary causes for low monomer yields under the tested conditions. Three Ni catalyst systems, Ni/C + H₂, Ni/C-Zn, and Ni/Zn, …

Crystallographically Defined Silicon Macropore Membranes, Shannon C. Knight, Bret A. Unger, Kurt W. Kolasinski

Chemistry Faculty Publications

Laser ablation with nanosecond-pulsed Nd:YAG laser irradiation combined with anisotropic alkaline etching of Si wafers creates 4–20 µm macropores that extend all the way through the wafer. The walls of these macropores are crystallographically defined by the interaction of the anisotropy of the etchant with the orientation of the single-crystal silicon substrate: rectangular/octagonal on Si(001), parallelepiped on Si(110), triangular/hexagonal on Si(111). Laser ablation can create pillars with peak-tovalley heights of over 100 µm. However, with nanosecondpulsed irradiation at 532 nm, the majority of this height is created by growth above the original plane of the substrate whereas for 355 nm …

Plume And Nanoparticle Formation During Laser Ablation, Kurt W. Kolasinski, Mool C. Gupta, Leonid V. Zhigilei

Chemistry Faculty Publications

The processes that lead to material ejection when a solid sample is irradiated near and above the pulsed laser ablation threshold are discussed. Emphasis is placed on the thermal and mechanical mechanisms that occur during pulsed laser irradiation of metals and semiconductors. Distinctions are drawn between ultrafast-pulsed irradiation, which occurs under stress confinement, and shortpulsed irradiation, in which stress is released during the laser pulse. Similarly, the distinctions between the spallation and phase explosion regimes are discussed. Spallation is only possible when the time of the laser heating is shorter than the time needed for mechanical equilibration of the heated …

Hierarchical Porous Silicon And Porous Silicon Nanowires Produced With Regenerative Electroless Etching (Reetching) And Metal Assisted Catalytic Etching (Mace), Kurt W. Kolasinski, Bret A. Unger, Haibo Yu, Alexis T. Ernst, Mark Aindow, Ermei Mäkilä, Jarno Salonen

Chemistry Faculty Publications

ReEtching produces nanostructured silicon when a catalytic agent, e.g. dissolved V2O5, is used to facilitate etching between Si and H2O2. H2O2 regenerates dissolved V in a 5+ oxidation state, which initiates etching by injecting holes into the Si valence band. Independent control over the extent of reaction (controlled by the amount of H2O2 added) and the rate of reaction (controlled by the rate at which H2O2 is pumped into the etchant solution) allows us to porosify Si substrates of arbitrary size, shape and doping, including wafers, single-crystal powders, polycrystalline powders, metallurgical grade powder, Si nanowires, Si pillars and Si powders …

Silicon Surface Photochemistry, Kurt W. Kolasinski

Chemistry Faculty Publications

General concepts of photochemistry on metal and semiconductor surfaces are elucidated. These concepts are then applied more specifically to describe photochemical transformation of molecules on and with silicon surfaces. The mechanisms by which light can induce chemical reactions following electronic excitation are described. Processes reviewed include photodissociation of adsorbed molecules, photo-induced attachment of organic molecules and photo-induced corrosion.

Cascade Annulation And Ring-Opening Reactions Of Castagnoli-Cushman-Derived Allylic And Benzylic Thiomorpholinonates, Abdikani Omar Farah

All Master's Theses

Sulfur-containing compounds are prevalent in antibiotics, essential amino acids, bacterial RNA, food flavors, and enzymes. The divalent sulfur atom introduces a metabolic liability from a drug discovery standpoint. Indeed, it is quite telling that all the top ten best-selling drugs in 2012 contained sulfur. In this context, there is a growing need for the synthesis of sulfur-containing compounds in ways that are practical and cost-effective. One approach taken to achieve this goal is to employ diversity-oriented synthesis (DOS), which produces diverse complex molecules with similar core structures from a common precursor. When a DOS features a cascade or domino reaction …

Characterization Of Coacervate Systems Using Redox Sensitive Dyes, Caleb Kaiser

All Master's Theses

Coacervates are systems that spontaneously form when two oppositely charged polyelectrolytes are mixed in a concentrated salt solution. When coacervates form, a biphasic equilibrium occurs in the sample with two phases present in the solution. The two phases are described as the dense phase and the lean phase, named after the amount of polyelectrolyte material in each phase. Coacervates have been topics of interest to researchers in a variety of fields including biomedical applications, drug delivery devices, and more. This thesis worked towards the characterization of coacervate systems on the molecular level by investigating the interaction of the polyelectrolytes and …

Interfacial Corrosion Of Copper And The Formation Of Copper Hydroxychloride, Mary Teague, Shengxi Li, Hongbo Cong

Williams Honors College, Honors Research Projects

Electrical circuitry is an industry, among many others, heavily using the element of copper. Ensuring the mechanical integrity of Cu is crucial, especially in salt environments, for the multifaceted composition of circuits. 4N NaCl solution (equilibrium concentration in ~84% RH) simulated this three-phase system. Rectangular Cu samples were partially immersed in both ambient and continuous lab air sparging atmospheres to understand waterline corrosion of the metal. Open circuit potentials (OCP) were continuously taken during the immersion testing for a maximum of 5 days. A scanning electron microscopy (SEM) equipped with an energy dispersive X-ray spectrometer (EDS), Raman spectroscopy, and 3-D …

Modification Of Wheat Gluten For Improvement Of Binding Capacity With Keratin In Hair, Shukun Wang, Danyang Meng, Sisi Wang, Zhong Zhang, Ruijin Yang, Wei Zhao

Department of Food Science and Technology: Faculty Publications

In this study, enzymatic hydrolysis and cationization with epoxypropyldodecyldimethylammonium chloride of wheat protein, an economic protein complex containing great amount of disulfide bonds, were conducted to improve properties such as solubility and disassociation behaviour for recovery of damaged hair when used in shampoo. The optimal conditions for enzymatic hydrolysis were pH 8.2, 55°C with Alcalase for 60min. After the selected hydrolysis, the degree of hydrolysis, nitrogen solubility index, foaming capacity index, foam stability index, emulsifying activity index and emulsion stability index of hydrolysate with 58.71% of shortchain peptides (less than 1000 Da) were 8.81%, 39.07%, 225%, 56.67%, 9.62m² g …

Abnormal Phase Transition Between Two-Dimensional High-Density Liquid Crystal And Low-Density Crystalline Solid Phases, Wenbin Li, Longjuan Kong, Baojie Feng, Huixia Fu, Hui Li, Xiao Cheng Zeng, Kehui Wu, Lan Chen

Xiao Cheng Zeng Publications

Some two-dimensional liquid systems are theoretically predicted to have an anomalous phase transition due to unique intermolecular interactions, for example the first-order transition between two-dimensional high-density water and low-density amorphous ice. However, it has never been experimentally observed, to the best of our knowledge. Here we report an entropy-driven phase transition between a high-density liquid crystal and low-density crystalline solid, directly observed by scanning tunneling microscope in carbon monoxide adsorbed on Cu(111). Combined with first principle calculations, we find that repulsive dipole–dipole interactions between carbon monoxide molecules lead to unconventional thermodynamics. This finding of unconventional thermodynamics in two-dimensional carbon monoxide …

Fabrication Of Mnox/Mwcnts-Gc Nanocatalyst For Oxygen Evolution Reaction, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Amr M. Arafa Eng.

Chemical Engineering

Manganese oxide (MnOx) and multiwalled carbon nanotubes (MWCNTs) are intended to modify the GC electrode for oxygen evolution reaction (OER). Optimization of MnOx loading is carried out and the deposition of 55 cycles was sufficient to obtain the highest activity toward OER. The stability of the catalyst is enhanced by the addition of MWCNTs. As a result, an amount of 22 kWh/Kg of O2 of energy is saved. Several techniques including cyclic voltammetry, linear sweep voltammetry, chronoamperometry, chronopotentiometry, field-emission scanning electron microscopy, and energy dispersive X-ray spectroscopy will be combined to track the catalyst activity and to determine its morphology …

Assembling Of Niox/Mwcnts-Gc Anodic Nanocatalyst For Water Electrolysis Applications, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Saher D. Khamis Eng

Chemical Engineering

Glassy carbon (GC) electrode is intended to be modified with nickel oxide (NiOx) and multiwalled carbon nanotubes (MWCNTs) in the anodic reaction of water electrolysis. NiOx deposition time is optimized and a 5 min was enough to attain the maximum activity. A further modification of the catalyst with MWCNTs could greatly enhance its stability during continuous electrolysis. As an outcome, an energy amount of 21.7 kWh/KgO2 is minimized. Several electrochemical and materials characterization setups will be utilized to test the catalyst activity and to know its geometry and structure.

Fabrication Of Cuox-Pd Nanocatalyst Supported On A Glassy Carbon Electrode For Enhanced Formic Acid Electro-Oxidation, Islam M. Al-Akraa Dr., Ahmad M. Mohammad Prof, Mohamed S. El-Deab Prof, Bahgat E. El-Anadouli Prof

Chemical Engineering

Formic acid (FA) electro-oxidation (FAO) was investigated at a binary catalyst composed of palladium nanoparticles (PdNPs) and copper oxide nanowires (CuOxNWs) and assembled onto a glassy carbon (GC) electrode. /e deposition sequence of PdNPs and CuOxNWs was properly adjusted in such a way that could improve the electrocatalytic activity and stability of the electrode toward FAO. Several techniques including cyclic voltammetry, chronoamperometry, field-emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction were all combined to report the catalyst’s activity and to evaluate its morphology, composition, and structure. /e highest catalytic activity and stability were obtained at the CuOx/Pd/GC …

Characterization Of Tetraethyl Orthosilicate-Based Dynamic Hydrogels For Use As Reversible 3-D Cell Culture Matrices, Krisitan Stipe

Graduate Student Theses, Dissertations, & Professional Papers

No abstract provided.

Synthesis, And Structural, Electrochemical, And Magnetic Property Characterization Of Promising Electrode Materials For Lithium-Ion Batteries And Sodium-Ion Batteries, Ruixin Han

Theses and Dissertations--Chemistry

Iron oxides, have been widely studied as promising anode materials in lithium-ion batteries (LIBs) for their high capacity (≈ 1000 mA h g^-1 for Fe₂O₃ and Fe₃O_4,), non-toxicity, and low cost. In this work, β-FeOOH has been evaluated within a LIB half-cell showing an excellent capacity of ≈ 1500 mA h g^-1 , superior to Fe₂O₃ or Fe₃O_4. Reaction mechanism has been proposed with the assistance of X-ray photoelectron spectroscopy (XPS). Various magnetic properties have been suggested for β-FeOOH such as superparamagnetism, antiferromagnetism and complex …

Carbon Quantum Dots: Bridging The Gap Between Chemical Structure And Material Properties, Timothy J. Pillar-Little Jr.

Theses and Dissertations--Chemistry

Carbon quantum dots (CQDs) are the latest generation of carbon nanomaterials in applications where fullerenes, carbon nanotubes, and graphene are abundantly used. With several attractive properties such as tunable optical property, edge-functionalization, and defect-rich chemical structure, CQDs have the potential to revolutionize optoelectronics, electro- and photocatalysis, and biomedical applications. Chemical modifications through the addition of heteroatoms, chemical reduction, and surface passivation are found to alter the band gap, spectral position, and emission pathways of CQDs. Despite extensive studies, fundamental understanding of structure-property relationship remains unclear due to the inhomogeneity in chemical structure and a complex emission mechanism for CQDs.

This …

Study Of The Effect Of Steric Bulk Of Side Chains On The Properties Of Conjugated Polymers, Bei Zhang

Theses and Dissertations--Chemistry

Donor-acceptor conjugated polymers opened a new era for conjugated polymer research due to the abundant selection and combination of different conjugated units. This class of polymers function as semiconductor materials with potential application in plastic consumer electronics. The frontier molecular orbital energies of the polymers are generally determined by the selection of donor and acceptor units in the backbone structure, and their substituents. The side chains attached to the backbone not only affect the solubility of the materials, but also their self-assembly and morphological characteristics, which indirectly govern optoelectronic properties. It is important therefore to consider backbone architectures and the …

Design And Synthesis Of Functional Organic Materials, Anthony Joseph Petty Ii

Theses and Dissertations--Chemistry

Control of solid state ordering in conjugated small molecules is paramount to the continued development and implementation of organic materials in electronic devices. However, there exists no reliable method on which to predicatively determine how a change to the molecular structure will impact the solid-state packing. As such, the molecule must be synthesized before its solid-state packing can be definitively evaluated. However, once the packing structure of a material is known there exist both qualitative structure- function relationships derived from the literature, as well as quantitative computational methods that can be employed to suggest if a material will perform well …

Effects Of -No2 And -Nh2 Functional Groups In Mixed-Linker Zr-Based Mofs On Gas Adsorption Of Co2 And Ch4, Zana Hassan Rada, Hongqi Sun, Jin Shang, Jiaye Li, Yingdian He, Shaomin Liu, Shaobin Wang

Research outputs 2014 to 2021

This study was undertaken to evaluate the effects of mixing BDC-NO₂ and BDC-NH₂ linkers in the synthesis of Zr-based metal organic frameworks (Zr-MOFs) on their adsorption and separation of CO₂ and CH₄. UiO-66 with single or binary -NO₂ and -NH₂ samples were synthesized under solvothermal conditions and activated by solvent exchanging using methanol. Structural analyses of the materials were conducted using FTIR, XRD, TGA, SEM, ¹HNMR and N₂ adsorption/desorption techniques and adsorption of CO₂ and CH₄ at high pressures and different temperatures (273 and 298 K) was investigated. It …

Ferromagnetic Shape Memory Heusler Materials: Synthesis, Microstructure Characterization And Magnetostructural Properties, Riaz Ahamed Ahamed Khan, Reza Ghomashchi, Zonghan Xie, Lei Chen

Research outputs 2014 to 2021

An overview of the processing, characterization and magnetostructural properties of ferromagnetic NiMnX (X = group IIIA-VA elements) Heusler alloys is presented. This type of alloy is multiferroic-exhibits more than one ferroic property-and is hence multifunctional. Examples of how different synthesis procedures influence the magnetostructural characteristics of these alloys are shown. Significant microstructural factors, such as the crystal structure, atomic ordering, volume of unit cell, grain size and others, which have a bearing on the properties, have been reviewed. An overriding factor is the composition which, through its tuning, affects the martensitic and magnetic transitions, the transformation temperatures, microstructures and, consequently, …

Use Of Surface Enhanced Raman Spectroscopy For The Detection Of Bioactive Lipids, Christopher M. Ohlhaver

Theses and Dissertations

The detection and analysis of lipids in biological matrices for clinical applications poses many challenges, but rapid and reliable detection will prove invaluable for clinical diagnosis. Herein, we report the application of drop-casted Ag nanoplatelets as surface enhanced Raman scattering (SERS) substrates for qualitative detection of 20-hydroxyeicosatetraenoic acid (20-HETE), which is a potential biomarker for diagnosis of hypertensive disorders. Biomarker peaks of 20-HETE can be reliably detected and differentiated from those of the structurally similar lipids (arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid) commonly found in human blood, even 1 pM concentrations. Additionally, one study mixed 20-HETE with three structurally …

Colloidal Synthesis And Photophysical Characterization Of Group Iv Alloy And Group Iv-V Semiconductors: Ge1-Xsnx And Sn-P Quantum Dots, Venkatesham Tallapally

Theses and Dissertations

Nanomaterials, typically less than 100 nm size in any direction have gained noteworthy interest from scientific community owing to their significantly different and often improved physical properties compared to their bulk counterparts. Semiconductor nanoparticles (NPs) are of great interest to study their tunable optical properties, primarily as a function of size and shape. Accordingly, there has been a lot of attention paid to synthesize discrete semiconducting nanoparticles, of where Group III-V and II-VI materials have been studied extensively. In contrast, Group IV and Group IV-V based nanocrystals as earth abundant and less-non-toxic semiconductors have not been studied thoroughly. From the …