Materials Chemistry Commons^™

Α-Eleostearic Acid Extraction By Saponification Of Tung Oil And Its Subsequent Polymerization, Amanda Murawski

Electronic Theses and Dissertations

The goal of environmentally sound research is to provide alternatives that are more sustainable and renewable, such as vegetable oil-based polymers, than the current petroleum-based products. Vegetable oil-based polymers have received a lot of attention recently due their multifaceted properties, which are simply achieved by adjusting the monomer or resin composition. The carbon-carbon double bonds in unsaturated oils are ideal reactive sites for the free radical or cationic polymerizations. Most vegetable oils must be modified before polymerization due to the low reactivity of their non-conjugated fatty acid chains. Tung oil (TO) contains ~83% of a triply conjugated fatty acid ( …

Asymmetric Membranes For High Capacity Lithium-Ion Battery Electrodes, Ian Byrd

Electronic Theses and Dissertations

Lithium-Ion Batteries (LIBs) have broad applications such as portable electronic devices, electric vehicles, and for green energy storage from intermittent sources. Current LIBs are limited by their low capacity materials at both the anode and cathode. At the anode, graphite suffers from a low capacity of only 372 mAh g^-1. The most commonly used cathode material is LiCoO₂ which has a meager capacity of 140 mAh g^-1. Thereby the broader applications of LIBs are limited due to these low capacities. It is imperative to develop higher capacity materials to further improve the performance of LIBs. …

Synthesis Of Multifunctional Polyacrylates And A Binding Group To Hemoglobin For The Treatment Of Traumatic Brain Injuries, Marina Michaud

Honors College Theses

Hemoglobin based oxygen carriers (HBOCs) hold promise as an effective emergency treatment of severe traumatic brain injuries (TBI). In the latest generation of HBOCs, polynitroxyl-pegylated hemoglobin (PNPH), cell-free hemoglobin is modified with TEMPO and PEG which reduce the toxicities associated with earlier generations of HBOCs. In our efforts to optimize the economic and therapeutic impacts of PNPH’s we have synthesized polydimethylaminoethyl methacrylate (poly-DMAEMA) under controlled living conditions via reverse addition-fragmentation chain transfer (RAFT) polymerization. The poly-DMAEMA was then successfully functionalized via quaternization of its NMe₂ groups using chloroacetate derivatives of the TEMPO and PEG. This process was quantitative and …

Size And Shape Control In Metal Nanoparticles And Nanocomposites, Tomendro Subedi

Theses and Dissertations (Comprehensive)

This thesis describes major findings on the shape transformation of the precursor silver decahedral nanoparticles (AgDeNPs) with pentagonal symmetry and twin defects into silver pentagonal prism nanoparticles (AgPPNPs) using Br¯ as a shape selective reagent. Silica-encapsulation of the gold-plated AgDeNPs was also carried out forming ordered arrays of silica encapsulated gold-plated AgDeNPs (SiO₂@Au@AgDeNPs) of different sizes. At first, synthetic procedures for AgDeNPs (pentagonal bipyramids), silver pentagonal rod nanoparticles (AgPRNPs) and gold-plating of AgDeNPs (Au@AgDeNPs) were optimized. Gold plating enhances the chemical stability of AgDeNPs and preserves the superior plasmonic properties of silver. This thesis deals with the transformation …

A Density Functional Theory Study Of Intrinsically Chiral Semiconductor Nanocrystals, Richard Edwards

Theses and Dissertations (Comprehensive)

A plethora of work has been done in the area of nanoparticles of late due to the fact that chemists (and physicists) have discovered that the properties of nanoparticles differ from both those of the bulk material and the atoms themselves. Nanoparticles have become of high interest for the use as catalysts while materials like graphene, being only one atom thick, have been shown to be great electrical conductors in comparison with the 3D structure of diamond. Among these peculiar nanoscale properties is the phenomenon of nanochirality, where a nanoparticle can exhibit chirality that does not extend to the macroscale …

Lithium-Sulfur (Selenium) Batteries: Interface Issues And Solving Strategies, Nian-Wu Li, Ya-Xia Yin, Yu-Guo Guo

Journal of Electrochemistry

The stable interface is still a challenge for lithium-sulfur (selenium) batteries because of the low conductivity of sulfur (selenium), dissolution of polysulfide (polyselenide), volume expansion of sulfur (selenium), and lithium dendrite growth. This review describers some recent developments in lithium-sulfur (selenium) batteries and highlights our efforts in this field. The possible strategies for building stable interface in the lithium-sulfur (selenium) batteries including nano-restriction effect, chemical bonding, interface adsorption, surface coating, electrolyte optimization, and Lithium anode treatment have been discussed.

Syntheses Of Ag@Pd@Pt Nanoparticles With Tunable Shell Thickness For Electrochemical Oxidation Of Formic Acid, Xiao-Dong Lin, Du-Hong Chen, Zhong-Qun Tian

Journal of Electrochemistry

In an effort to lower cost of a catalyst, the silver (Ag) core with palladium (Pd) layer then platinum (Pt) island (Ag@Pd@Pt) nanoparticles were synthesized and the electrocatalytic activity of Ag@Pd@Pt nanoparticles on formic acid was compared with that of Au@Pd@Pt nanoparticles reported previously. The results showed that the existence of a small amount of Pt could significantly improve the activity of the catalyst. When the surface coverage of Pt approached 0.5 monolayers, the activity of Ag@Pd@Pt nanoparticles reached the maximum. Though the onset potential of the electro-oxidation was slightly more positive (about 50 mV), the overall electrocatalytic activity of …

Intrinsic Interfacial Property Between High-Voltage Lini0.5Mn1.5O4 Cathode And Electrolyte, Li Li, Jing-Jing Xu, Shao-Jie Han, Wei Lu, Li-Wei Chen

Journal of Electrochemistry

To obtain high energy density, developing high-voltage cathode materials is an effective approach. The cathode/electrolyte interface stability is the key factor for the cycle performance and safety performance of high-voltage lithium ion batteries. It is, therefore, of significant importance to study the stability of cathode/electrolyte interface. However, many reports have shown that at the cathode/electrolyte interface the cathodes were prepared by coating the mixture of active materials with a conductive additive and a binder on an Al current collector. The introduction of additives will interfere the surface morphology and component analyses, resulting in difficulty to acquire the intrinsic information at …

Lithium Plating Identification From Degradation Behaviors Of Lithium-Ion Cells, Jian-Bo Zhang, Lai-Suo Su, Xin-Yu Li, Hao Ge, Ya-Kun Zhang, Zhe Li

Journal of Electrochemistry

Lithium plating has huge impact on the lifetime and safety of lithium-ion cells. It is, therefore, necessary to identify lithium plating. In this study, the accelerated stress tests of lithium-ion cells were conducted under different conditions with multi-stress loads. Based on the different effects of the two major aging mechanisms, namely, SEI (Solid Electrolyte Interface) layer growth and lithium plating, on the degradation behaviors, two lithium plating identification methods of resistance-capacity plot and Arrhenius plot were employed. The experimental results revealed that the two identification methods are highly consistent with each other. Furthermore, the origins of capacity loss were distinguished …

Stm Investigation Of Oxygen Reduction Reaction On Solid Interface In Fuel Cell, Zhen-Feng Cai, Bing Sun, Wen-Jie Jiang, Ting Chen, Dong Wang, Li-Jun Wan

Journal of Electrochemistry

An electrocatalyst for oxygen reduction reaction (ORR) is an important component for fuel cells. An investigation at interfacial electrochemical reactions toward ORR at a molecular scale benefits mechanistic understanding as well as rational design of catalysts. Scanning tunneling microscopy (STM) has been proven to be a powerful tool to monitor chemical reactions and to provide in-situ information about the interfacial electrochemical reactions at a molecular level. This review summarizes the recent STM studies in monitoring the interface processes such as morphological changes, molecular changes, reaction intermediates, and oxidation products. The prospects of future development in this field are outlined.

A Study On The Oxidation Of Hydrogen Peroxide At Au(111) And Au(100) Electrodes, Yong-Li Zheng, Jie Wei, Yan-Xia Chen

Journal of Electrochemistry

The oxidation reactions of hydrogen peroxide (H₂O₂) at Au(111) and Au(100) electrodes in 0.1 mol·L^-1 HClO₄ were investigated by using rotating disk electrode system. It was found that H₂O₂ could be readily oxidized to O₂ at both Au(100) and Au(111) surfaces with the onset potential close to its equilibrium potential. In contrast, the onset overpotential for H₂O₂ reduction was above 0.4 V, while the onset overpotential for H₂O₂ oxidation at Au(100) was ca. 0.1 V more negative than that at Au(111), this is probably …

Electrochemical Behaviors And Determinations Of Terbutaline Sulfate At Poly Eriochrome Black T Modified Electrode, Yan-Jie Zheng, Hong Yao, Shao-Huang Weng, Hua-Ping Peng, Shi-Wen Gong, Li Huang, Qiang Dai, Xin-Hua Lin

Journal of Electrochemistry

The poly eriochrome black T modified electrode was prepared by electropolymerization. This modified electrode was characterized by scanning electron microscopy(SEM), electrochemical impedance spectroscopy(EIS) and cyclic voltammetry (CV). The electrochemical behaviors of terbutaline sulfate were studied by CV, while the recoveries were measured by differential pulse voltammetry (DPV). The modified electrode shows excellent electrocatalytic characteristics for terbutaline sulfate. In pH 7.0 phosphate buffer solution, the oxidation peak currents obtained by DPV were linear to the terbutaline sulfate concentrations over the range of 1.2x10^-7~2.0x10^-6 mol•L^-1. The detection limit was estimated to be 1.5x10^-8 mol•L^-1 and …

Chitosan/Nonahydrate Gel Derived Fe-N-Doped Porous Carbon Sheet As High-Efficient Orr Electrocatalyst, Fan-Lu Meng, Xin-Bo Zhang, Jun-Min Yan

Journal of Electrochemistry

The chitosan/nonahydrate gel was used as a precursor to realize the uniform mixture of N-polymer and metal salt. After lyophilization treatment, the gel went through heat treatment and acid etch. Accordingly, the Fe-N-doped porous carbon sheet with homogenous composition and microstructure was prepared. Compared with the commercial Pt/C catalyst, the Fe-N-doped porous carbon sheet exhibited more positive onset potential and half-wave potential, higher current density, and especially, excellent durability. The power density of 318 mW·cm^-2 was obtained in alkaline fuel cell with the Fe-N-doped porous carbon sheet as a cathode catalyst, which is higher than 267 mW·cm^-2 with …

Synthesis Of Ultrathin Co3O4 Nanoflakes Film Material For Electrochemical Sensing, Hui-Juan Wang

Journal of Electrochemistry

Ultrathin cobalt oxide (Co₃O₄ ) nanoflakes film material was synthesized by using an electro-deposited cobalt layer as a raw material through a simple oxidation method and followed by a heat treatment at 350 ^oC. The physical characterizations of the Co₃O₄ nanoflakes film were performed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) technologies, and the electrochemical activity was measured by cyclic voltammetry (CV). As a promising material for electrochemical sensing, the as-synthesized ultrathin Co₃O₄ nanoflakes film material exhibited excellent electrochemical activity for H₂O …

An Stm Study On The Structure Of Pt(100)/Ionic Liquid Omipf6 Interface, Jin Peng, Mian-Gang Li, Li-Qiang Xie, Jia-Wei Yan, Bing-Wei Mao

Journal of Electrochemistry

Potential-dependent structures of Pt(100)/ionic liquid 1-methyl-3-octylimidazolium hexafluorophosphate (OMIPF₆) interface have been studied by electrochemical scanning tunneling microscopy (ECSTM). The cation OMI⁺ forms ordered structure on Pt(100) surface, which exists in a potential region of about 1.2 V. When the potential is more negative than -0.6 V, it can be seen that the ordered structure transforms to disordered structure. When the potential shifts positively to +0.6 V, the desorption of cations OMI⁺ occurs, which indicates that strong electrostatic repulsion is needed to overcome chemical interaction between OMIPF6 and Pt(100) surface, leading to the desorption. The above results …

Investigation On Laser Induced Deposition Of Cu-Based Materials At [Bmim]Bf4/Pt Electrode Interface, Min-Min Xu, Jin-Hua Mei, Jian-Lin Yao, Ren-Ao Gu

Journal of Electrochemistry

By controlling the negative potential, Cu-based materials were deposited at the [BMIm]BF₄/Pt electrode interface under the laser irradiation. The effects of laser power and irradiation time on the yield of deposition products were studied by using different laser powers and different irradiation time. The product yield could be directly determined by the size of deposition point through the observation from the optical microscope. Further mechanism study combined with the formula deduced that the thermal effect of the laser could make the electrode surface temperature rise 110 degrees, which can promote the occurrence of electrodeposition. By SEM characterization, the …

Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree

Electronic Thesis and Dissertation Repository

This thesis describes the investigation of a novel strategy for the synthesis of metal-containing small molecules, polymers, and nanomaterials. In this context, a new family of air-stable, homo- and heterometallic primary, secondary, and tertiary phosphines were prepared via the radical-initiated hydrophosphination reaction of PH₃ with vinylferrocene and/or vinylruthenocene. The full characterization of the phosphines confirmed their targeted structures and proved that the properties of the starting metallocenes are reflected in those of the resulting phosphines.

To study the coordination behavior of this family of phosphines, primary, secondary, and tertiary ethylferrocene phosphines were reacted with Group 6 metal carbonyl adducts …

Creating Functional Materials With Phosphorus, Tyler John Cuthbert

Electronic Thesis and Dissertation Repository

Understanding the relationship between small molecules or polymers and how they affect the properties of materials they compose is the basis of materials science. Using unique and versatile components can impart useful and interesting properties to materials. Here, we aimed to extend this understanding to phosphorus, and the known properties it possesses. This included the production of photopolymerizable coatings containing phosphonium molecules and polymers for antifouling and antibacterial applications. The synthesis and characterization of these phosphonium components was completed and materials were produced utilizing UV curing technology. Addition of these components produced coatings that could resist bacteria attachment and efficiently …

X-Ray Absorption And Emission Studies Of Anodic Titania Nanostructures, Jun Li

Electronic Thesis and Dissertation Repository

One-dimensional (1D) TiO₂ nanomaterials with ordered structure have been extensively applied in various fields, such as photocatalysts, solar cells, supercapacitors and rechargeable batteries, due to the unique structural and functional properties compared to the disordered nanoparticulate forms. Nevertheless, intrinsic disadvantages of TiO₂, such as its large band gap (~3 eV), fast recombination rate of photoexcited electron–hole pairs and insufficient ionic conductivity, severely limit the development of 1D TiO₂ nanomaterials for practical applications. To address the above issues, the scope of this thesis focus on the fundamental understandings of the electronic structure of highly ordered TiO_{2 …}

Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, Joseph A. Paquette

Electronic Thesis and Dissertation Repository

The work presented in this thesis details the synthesis and characterization of two different families of multifunctional polymers. The first family involved the incorporation of stable 6-oxoverdazyl radicals into polymer scaffolds. This was originally achieved by the polymerization of the radical precursors, phenyl- and isopropyl-6-oxotetrazanes, followed by post-polymerization oxidation to afford the phenyl- and isopropyl-6-oxoverdazyl polymers. A second methodology involved the direct polymerization of isopropyl-6-oxoverdazyl radicals using ring-opening metathesis polymerization (ROMP) to afford polymers with controlled molecular weights and narrow molecular weight distributions. The polymers were characterized by the close comparison of the physical and spectroscopic properties …