Chemistry Commons^™

Fabrication And Characterization Of Gel-Type Solar Cells Sensitized By Green-Synthesized Zinc Sulfide Quantum Dots, Adam Alman

Undergraduate Honors Theses

Three different types of fully integrated ZnS quantum dot-TiO₂ nanoparticle gels were used to create films for usage in photovoltaic cells. The films were annealed onto TEC-8 F:SnO₂ conductive glass electrode and the cell was completed by adding a polyolsolvated I/I₃ redox couple to the film and capping the cell with a counter electrode constructed of graphite-coated TEC-8 glass. Electrical output of the cells under a 360 W halogen light source and a natural or simulated (1000 W xenon arc lamp) sunlight source were estimated by multi-meter. The highest absolute energy conversion efficiency seen was from an …

Effects Of Silver Nanoparticles On Photochemical Processes Focusing On Luminol Chemiluminescence, Scott Milam

Master's Theses and Doctoral Dissertations

Silver nanoparticles of varying sizes were synthesized. Their effects on enhancing or quenching the photochemical processes of tryptophan fluorescence, a ruthenium complex decay constant and chemiluminescence of luminol and ferricyanide, were studied. The tryptophan fluorescence was slightly enhanced by smaller nanoparticles and showed slight quenching in the presence of larger nanoparticles. The tris (2,2’-bipyridyl ruthenium (II) chloride) complex was excited using a 532 nm laser, and the decay constant was measured. Neither gold nor silver nanoparticles showed an impact on this process. The luminol chemiluminescence was studied with an emphasis on holding the concentration of nanoparticles, surface area, and silver …

Corrosion Protection Of Aa 2024-T3 Aluminium Alloys Using 3, 4-Diaminobenzoic Acid Chelated Zirconium-Silane Hybrid Sol-Gels, P.C. Rajath Varma, John Colreavy, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, Brendan Duffy

Articles

Organic-inorganic polymers formed by hydrolysis/condensation reactions of alkoxide precursors, such as organically modified silanes (Ormosils) have found applications as electronic, optical and protective coatings. Such coatings possess important characteristics such as chemical stability, physical strength and scratch resistance. Further performance improvement is achieved through the incorporation of zirconium and titanium based nanoparticles, also formed through the sol-gel process. However due to the inherent difference in the reactivity of the precursors, the hydrolysis of each precursor must be carried out separately before being combined for final condensation. Zirconium precursors are commonly chelated using acetic acid or acetyl acetonate prior to hydrolysis, …

Synthesis And Characterization Of Metallic, Core-Shell And Composite Nanoparticles, Amar Kumbhar

All Dissertations

ABSTRACT
Silver nanoparticles exhibit size, shape and the surrounding dielectric medium dependent optical properties (scattering and absorption) in the visible spectral region. These optical properties can be explained in terms of the collective oscillation of the 'free conduction band electrons' or 'surface plasmons' induced by an external electromagnetic field. Dipole and Quadrupole Plasmon resonances have been observed for silver particles less than 100nm in diameter prepared using various synthetic techniques. However higher order resonances have been elusive due to lack of experimental techniques to prepare colloidal solutions of large silver nanoparticles in the size range above 100nm. Controlled hydrogen reduction …

Adsorption Of Co On Supported Gold Nanoparticle Catalysts: A Comparative Study, Heather Hartshorn, Christopher J. Pursell, Bert D. Chandler

Chemistry Faculty Research

The adsorption of CO on three different gold nanoparticle catalysts supported on high surface area TiO₂ was studied using infrared transmission spectroscopy at room temperature and CO pressures typically used in CO oxidation reactions. The three, real-world catalysts were Au catalysts synthesized in our laboratory from thiol monolayer protected clusters (MPCs) and two commercial catalysts from the World Gold Council (WGC and AuTEK). Within experimental reproducibility, the adsorption data for the three catalysts are indistinguishable. While showing approximately Langmuir behavior, the adsorption data also show coverage dependence, as others have observed for many catalyst systems. Two approaches were used …

Optical Properties Of Multilayer-Polyelectrolyte Films With Incorporated Gold Nanomaterials (Solid Nanoparticles And Hollow Nanoshells), Robert Watson Day

Honors Theses

The growth of various multilayer‐polymer multilayer‐nanoparticle films was successfully achieved. Multilayer‐polymer multilayer‐nanoparticle films with 1, 3, and 5 polymer layers between nanoparticle layers exhibit significantly different optical properties due to the differences in magnitude of particle plasmon coupling. These film systems were also successfully extended to hollow gold nanoshells, which have significantly enhanced optical properties in comparison to solid gold nanoparticles of similar sizes. A proposal for utilizing this increased sensitivity of the gold nanoshells to explore the ‘microenvironments’ for optimizing potential sensing applications is also presented.

Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Multi-layer films of nanoparticles and nanoshells featuring various polymeric linkage molecules have been assembled and their optical properties characterized. The growth dynamics, including molecular weight effects, and stability of the various nanoparticle film constructions, using both single polymer as well as combinations of alternating charge polyelectrolytes as linking mechanisms, are presented. The polymeric linkers studied include poly-L-lysine, poly-L-arginine, poly(allylamine hydrochloride), and polyamidoamine dendrimers. Significantly air stable films were achieved with the use of multi-layered polymeric bridges between the nanoparticles and nanoshells. Optical sensitivity normally observed with these nanomaterials in solution was observed for their corresponding film geometries, with the nanoshell …

Photoelectrochemical Properties Of Tio2 Nanoparticles, Jie Qu, Ying Li, Qi-Wei Jiang, Xue-Ping Gao

Journal of Electrochemistry

The protonated titanate nanoparticles were obtained at room temperature and subsequently calcined at different temperatures(300 ℃,400 ℃,500 ℃,600 ℃ and 700 ℃) in air.The obtained products were characterized by XRD,TEM and UV-Vis.It is found that the grain sizes of TiO₂ nanoparticles calcined at 300 ℃ were about 20 nm,and increased gradually with the temperature rise.Photoelectric performance was measured with I～V curve and electrochemical impedance spectroscopy(EIS).The TiO₂ nanoparticles obtained at 500 ℃ showed the best photoelectrochemical properties with a photovoltaic conversion efficiency of 6.39%,which is much higher than those at other temperatures.In addition,it is also demonstrated that the charge …

Quantitative Measurement Of Surface Trapping In Europium Iii Doped Ytrium Oxide (Y20₃: Eu 3+), Rusty Mann

Undergraduate Honors Theses

This study is the beginning of a project that is aimed at quantitatively modeling energy losses due to crystalline surface defects of nanometer sized particles of Yttrium oxide doped with europium (Y₂O₃:Eu³⁺). Information gained from this study will be useful to lighting and displaying industries as well as to the nano-tech community as we are investigating the behavior of matter at the interface between bulk and molecular properties. Five different particles diameters, ranging from 112 nm to 37 nm, of Y₂O₃:Eu³⁺ were synthesized at both 5% and 10% concentrations …

Synthesis And Characterization Of Zinc-Based Quantum Dot Materials With Blue To Green Fluorescence From An Aqueous-Based Synthetic Method, Heather Durkee

Undergraduate Honors Theses

Blue to green fluorescence is exhibited by zinc-based quantum dot (QD) materials capped with sodium polyphosphate and L-cysteine. The factors governing this final fluorescence and intensity were explored using kinetic studies. Fluorescence and absorption spectroscopy were used to monitor relative size of QDs and fluorescence intensity as a function of time. Fluorescence data shows gradual formation of an emission peak at 520 nm, and shows shifting of this emission peak to 480 nm over a 24 hr time period. Fluorescence results suggest that zinc oxide is forming on the surface of the ZnS nanocrystals and during early heating stages may …

A Facile Method For The Preparation Of Poly(4-Vinylpyridine) Nanoparticles And Their Characterization, Nurettin Sahiner

Turkish Journal of Chemistry

Submicron size particles were synthesized from 4-vinylpyridine (4-VP) using an oil-in-water emulsion system. Divinyl benzene (DVB) and ethylene glycol dimethacrylate (EGDMA) were utilized as crosslinkers for the synthesis of p(4-VP) hydrogel nanoparticles in sodium dodecyl sulfate (SDS) surfactant systems. Characterization of the particles was made by transmission electron microscopy (TEM) and dynamic light scattering (DLS) methods. To render a positive charge, p(4-VP) particles were reacted with 1-bromo butane (1-BB).

Effect Of Organic Chelates On The Performance Of Hybrid Sol–Gel Coated Aa2024-T3 Aluminium Alloys, Rajath Varma, John Colreavy, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, Brendan Duffy

Articles

Sol–gels are organic–inorganic polymers formed by hydrolysis/condensation reactions of alkoxide precursors, primarily silanes, which have found applications as electronic, optical and protective coatings. These coatings possess important characteristics such as chemical stability, physical strength and scratch resistance. Further performance improvement is achieved through the incorporation of zirconium and titanium based nanoparticles, also formed through the sol–gel process. However due to the inherent difference in the reactivity of the precursors, the hydrolysis of each precursor must be carried out separately before being combined for final condensation. Zirconium precursors are commonly chelated using acetic acids, prior to hydrolysis, to lower the hydrolysis …

Task Specific Ionic Liquids For Enantiomeric Recognition And Nanomaterials For Biomedical Imaging, David Kipkogei Bwambok

LSU Doctoral Dissertations

Ionic liquids (ILs) are organic salts that melt at or below 100°C. Interest in ILs continues to grow due to their unique properties such as lack of measurable vapor pressure, high thermal stability, tunability and recyclability. The first part of this dissertation explores the use of chiral ionic liquids (CILs) for enantiomeric recognition of chiral analytes using fluorescence spectroscopy. Chiral analyses continue to be a subject of considerable interest primarily as a result of legislation introduced by the Food and Drug Administration. This has led to an increased need for suitable chiral selectors and methods to verify the enantiomeric forms …

Imaging And Spectroscopy Of Conducting Polymer-Fullerene Composite Materials, Daeri Tenery

Electronic Theses and Dissertations

Since the development and optical study of conjugated (conducting) polymers it has become apparent that chain conformation and aggregation at the molecular scale result in complex heterogeneous nanostructured bulk materials for which a detailed insight into morphological, spectroscopic as well as optoelectronic properties and mechanisms is overwhelmingly difficult to obtain. Nanoparticles composed of the conjugated polymer poly (MEH-PPV) and nanocomposite nanoparticles consisting of MEH-PPV doped with 1-(3-methoxycarbonylpropyl)-1-phenyl-C61 (PCBM) were prepared as model systems to study these materials at the length scale of one to a few domains. The MEH-PPV and PCBM doped nanoparticles were analyzed by single imaging/particle spectroscopy (SPS) …

Observed Superspin-Glass Behavior In Ni0.5zn0.5fe2o4 Nanoparticles, Antony Adair

Open Access Theses & Dissertations

In this investigation we seek to identify the magnetic behavior of Ni0.5Zn0.5Fe2O4 nanoparticles though AC-susceptibility and DC-magnetization measurements. Powder x-ray diffraction was performed to determine the purity and average diameter ( ~ 9nm) of the particles. Aditionally, structure was confirmed by comparison through the International Centre for Diffraction Data's Powder Diffraction File [52] (PDF # 08-0234).

Zero-field cooled and field cooled DC magnetization measurements (bifurcation and blocking temperature), as well as M(H) hysteresis (below and above the blocking temperature) lead us to initially suggest that the material may in fact be superparamagnetic. However, further investigation of the real AC susceptibility …

Spectroscopic Investigation Of Palladium-Copper Bimetallic Systems For Pem Fuel Cell Catalysts, Timo Hofmann

UNLV Theses, Dissertations, Professional Papers, and Capstones

One of the main barriers to commercialization of polymer electrolyte membrane fuel cells systems is cost, which is largely due to the need of platinum (Pt)-containing catalysts. In this thesis we investigate bimetallic systems consisting of a base metal (copper) and a noble metal (palladium) that, as an alloy on the nanoscale, mimic the electronic properties that make Pt desirable as a catalyst.

We present a detailed investigation of the electronic structure of carbon-supported Pd/Cu nanoparticle catalysts, model bilayer thin film systems, alloys, and various metal reference samples. We have investigated the valence band structure of the catalysts using a …

Fabrication And Optical Properties Of Noble Metal Nanostructures, Mark Kinnan

All Dissertations

Experimental and theoretical results are presented in Chapters 2, 3, and 4 on the effects of dielectric medium, particle size, and interparticle distance, respectively, on plasmon coupling in two-dimensional arrays of silver nanoparticles. The arrays were fabricated via the self-assembly of single crystal particles from c.a. 46 nm to 287 nm on PVP-modified glass substrates. Spin-coated poly(methylmethacrylate) layers were used to immobilize the particles and prevent their surface aggregation. Varying the thickness of the PMMA layer made it possible to change the average dielectric medium between the particles. UV-Visible spectra of different arrays were compared to the corresponding electron microscope …

Working Report On The Status Quo Of Nanomaterials Impact On Health And Environment, Harald Krug, Margarita Apostolova, Marite Arija Bake, Gordon Chambers, Horia Chiriac, Eva Herzog, Victoria Hand, Jürgen Höck, Peter Hoet, Nicoleta Lupu, Declan Mccormack, Maja Remskar, George Robillard, Jamila Smisterova, Jan Stetkiewicz, Speranta Tanasescu, Aris Tsatsakis, David Vaughn, Peter Wick, Jörg Wörle-Knirsch

Articles

Nanotechnology is regarded as one of the key technologies of the future and associated with high expectations by politics, science and economy. Artificially produced nanosized particles and nanoscale system components have new properties which are of importance for the development of new products and applications. Such new properties of materials and substances result from the special properties of surfaces and interfaces and in part, from the geometric shape of the material. In theory nanoparticles (NPs) can be produced from nearly any chemical; however, most NPs that are currently in use today have been made from transition metals, silicon, carbon (single-walled …

Preparation And Characterization Of 3 Nm Magnetic Niau Nanoparticles, Bethany J. Auten, B. P. Hahn, G. Vijayaraghavan, K. J. Stevenson, Bert D. Chandler

Chemistry Faculty Research

Using PAMAM dendrimers as nanoparticle templates, a synthetic route to prepare 3 nm magnetic NiAu nanoparticles was developed. Aqueous solutions of hydroxyl-terminated generation 5 PAMAM dendrimers in 25 mM NaClO₄ were shown to bind aqueous Ni^II. Coreduction of Ni^II and Au^III salts yielded bimetallic dendrimer stabilized nanoparticles, which were extracted into toluene with decanethiol. Characterization of the resulting monolayer protected clusters (MPCs) with transmission electron microscopy and UV–visible, atomic absorption, and X-ray photoelectron spectroscopies suggested that the MPCs had substantial surface enrichment in Au. Superconducting quantum interference device (SQUID) measurements at 5 K show the …

Monolayer-Protected Nanoparticle Film Assemblies As Platforms For Controlling Interfacial And Adsorption Properties In Protein Monolayer Electrochemistry, Andrew F. Loftus, Katelyn P. Reighard, Susanna A. Kapourales, Michael C. Leopold

Chemistry Faculty Publications

Assembled films of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), are investigated as adsorption platforms in protein monolayer electrochemistry (PME), a strategy for studying the electron transfer (ET) of redox proteins. Modified electrodes featuring MPC films assembled with various linking methods, including both electrostatic and covalent mechanisms, are employed to immobilize cytochrome c (cyt c) for electrochemical analysis. The background signal (non-Faradaic current) of these systems is directly related to the structure and composition of the MPC films, including nanoparticle core size, protecting ligand properties, as well as the linking mechanism utilized during assembly. Dithiol-linked films of Au225(C6)75 are …

Stable Aqueous Nanoparticle Film Assemblies With Covalent And Charged Polymer Linking Networks, Lesley E. Russell, Anne A. Galyean, Sherilyn M. Notte, Michael C. Leopold

Chemistry Faculty Publications

The construction of highly stable and efficiently assembled multilayer films of purely water soluble gold nanoparticles is reported. Citrate-stabilized nanoparticles (CS-NPs) of average core diameter of 10 nm are used as templates for stabilization-based exchange reactions with thioctic acid to form more robust aqueous NPs that can be assembled into multilayer films. The thioctic acid stabilized nanoparticles (TAS-NPs) are networked via covalent and electrostatic linking systems, employing dithiols and the cationic polymer poly(l-lysine), respectively. Multilayer films of up to 150 nm in thickness are successfully grown at biological pH with no observable degradation of the NPs within the film. The …

Dna-Templated Nanomaterials, Hector Alejandro Becerril-Garcia

Theses and Dissertations

Nanomaterials display interesting physical and chemical properties depending on their shape, size and composition. Self assembly is an intriguing route to producing nanomaterials with controllable compositions and morphologies. DNA has been used to guide the self assembly of materials, resulting in: (1) metal nanowires; (2) metal or semiconductor nanorods; (3) carbon nanotubes; and (4) semiconductor, metal or biological nanoparticles. My work expands the range of DNA templated nanomaterials and develops novel ways of using DNA to pattern nanostructures on surfaces. I have performed the first synthesis of silver nanorods on single stranded DNA, an attractive material for localizing DNA coupled …

Air And Water Free Solid-Phase Synthesis Of Thiol Stabilized Au Nanoparticles With Anchored, Recyclable Dendrimer Templates, John D. Gilbertson, G. Vijayaraghavan, K. J. Stevenson, Bert D. Chandler

Chemistry Faculty Research

Solid-phase synthetic templates for Au nanoparticles were developed using Merrifield resins and polyamidoamine (PAMAM) dendrimers. This synthetic scheme affords the opportunity to prepare metal nanoparticles in the absence of air and water, and it does not necessitate phase transfer agents that can be difficult to remove in subsequent steps. Amine-terminated generation 5 PAMAM (G5NH2) dendrimers were grafted to anhydride functionalized polystyrene resin beads and alkylated with 1,2-epoxydodecane to produce G5C12anch. The anchored dendrimers bound both CoII and AuIII salts from toluene solutions at ratios comparable to those of solution phase alkyl-terminated PAMAM dendrimers. The encapsulated AuIII salts could be reduced …

A Novel Processing Route For The Production Of Nanoparticulate Zinc Oxide Using An Isophthalate Precursor, Grainne Duffy, Declan Mccormack, Suresh Pillai

Articles

Zinc oxide nanoparticles have been processed from a novel isophthalate precursor. In contrast to those processed from an oxalate precursor, this material exhibits three-dimensional, non-directional aggregation behaviour.

Such non-directional aggregation of uniaxial crystallites may allow for the production of structures with a higher proportion of catalytically active surfaces than can be prepared through conventional sol–gel methods. XRD,

FTIR, TEM and SEM were used to characterize the synthesized materials.

Zinc oxide particles synthesized by using isophthalic acid (C6H4-1,3-(COOH)2) are found to be slightly smaller than the previously reported materials prepared through chelation with oxalic acid (H2C2O2・2H2O).

Phase-Transfer Technique For Polymer-Protected Noble Metal Nanoparticles, Xing-Li Feng, Ming-Hui Huang, Xiao-Kai Zhang, Shao-Xin Huang, Wei Pan, Hou-Yi Ma

Journal of Electrochemistry

A novel phase-transfer method was developed based on the decrease of PVP's solubility in water with increasing temperature,by means of which PVP-protected gold,silver and platinum nanoparticles can be conveniently transferred from aqueous phase to 1-butanol phase.Monodispersed metal nanoparticles were electrochemically synthesized at first in the aqueous,and then 1-butanol of appropriate volume was added to the aqueous phase.Heating the oil-water mixture to 80 ℃ under vigorous stirring would make metal nanoparticles leave the aqueous phase and enter into the 1-butanol phase,with high phasetransfer efficiency and without aggregation between nanoparticles.An electrochemical method to synthesize metal nanoparticles in the oil-water mixtures was further …

Electrodeposition Of Nano-Sb-Zn Alloy In Acetamide-Urea-Nabr-Kbr Melt, Peng Liu, Xin-Ai Guo, Ye-Xiang Tong, Qi-Qin Yang

Journal of Electrochemistry

The electroreduction of Zn(II) and Sb(III) in acetamide-urea-NaBr-KBr(343 K) were studied by cyclic volatmmetry.The reduction of Zn(II) or Sb(III) to the metals is an irreversible process.The transfer coefficient of Zn(II)+2e→Zn and Sb(III) +3e→Sb were calculated to be 0.231 and 0.319,the diffusion coefficient of Zn(II) and Sb(III) in the melt were determined as 1.70*10^-6 and 3.21*10^-6 cm²· s^-1 respectively.The Zn-Sb films with different Zn content from 29.67 at% to 97.34 at% were electrodeposited in acetamide-urea-NaBr-KBr melt at 343 K by controlling the deposition potential and the Zn(II)/Sb(III) molar ratio.The morphology of Zn-Sb film was observed by …

Crown Ether-Metal ‘Sandwiches’ As Linking Mechanisms In Assembled Nanoparticle Films, Rebecca R. Pompano, Phillip G. Wortley, Leslie M. Moatz, D. J. Tognarelli, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Crown ether ligands attached to monolayer-protected clusters (MPCs) were assembled as films and the linking mechanism between the crown ether–metal ion–crown ether bridges between nanoparticles was examined. Thicker films exhibited a red shift in the absorbance maximum for the surface plasmon band which was attributed to the increasing aggregation and cross linking within the film. Quantized double layer charging peaks suggest that film growth is selective toward a specific core size or exchange rate, either of which affect the number of potential linking ligands in the periphery of the MPCs. Multi-layer growth of films was only achieved with metal ions …

Tuning Supported Catalyst Reactivity With Dendrimer-Templated Pt-Cu Nanoparticles, Natalie N. Hoover, Bethany J. Auten, Bert D. Chandler

Chemistry Faculty Research

The effects of particle composition on heterogeneous catalysis were studied using dendrimer-encapsulated nanoparticles (DENs) as precursors to supported Pt-Cu catalysts. Bimetallic Pt-Cu DENs with varying Pt/Cu ratios were prepared in an anaerobic aqueous solution and deposited onto a high-purity commercial alumina support. The dendrimer template was then thermally removed to yield supported nanoparticle catalysts, which were studied with toluene hydrogenation and CO oxidation catalysis as well as infrared spectroscopy of adsorbed CO. Incorporating Cu into Pt nanoparticles had opposite effects on the two test reactions. Cu acted as a mild promoter for CO oxidation catalysis, and the promoting effect was …

Nanometal Containing Nanocomposites And Photolithographic Polyaniline Nanofibers, Frank D. Blum, Sunil K. Pillalamarri, Lalani K. Werake, J. Greg Story, Massimo F. Bertino, Akira Tokuhiro

Chemistry Faculty Research & Creative Works

A report on recent progress from our laboratories on the nanostructures produced from novel synthesis techniques will be discussed. Using high-energy radiation (γ-rays) we have been able to produce conducting polymer nanofibers and nanorods of polyaniline and polypyrrole without the use of a separate template or capping agent. This technique has been extended, with the addition of metal ions, to a "one pot" synthesis, producing conducting nanocomposites. These nanocomposites contain metal nanoparticles which decorate the conducting nanofibers. We have also recently shown that these systems can be photopatterned to produce novel structures. We believe that these systems will be useful …

Analysis Of Nanoparticle Transmission Electron Microscopy Data Using A Public- Domain Image-Processing Program, Image, Gerd H. Woehrle, James E. Hutchison, Sai̇m Özkar, Richad G. Finke

Turkish Journal of Chemistry

The need to easily and quickly count larger numbers of nanoparticles, in order to obtain statistically useful size and size-distribution data, is addressed via the use of a readily available, free, public-domain program for particle counting, NIH-Image (and 2 others derived from it, Scion Image and Image J), collectively referred to herein as Image. The best protocols that we have found useful for the use of Image are reported; both appropriate as well as problematic applications of Image are then illustrated with a series of TEM images of Ir(0), Pd(0) and Au(0) nanoclusters. Methods to detect and image nanoclusters with …