Chemistry Commons^™

High Temperature Rare Earth Compounds: Synthesis, Characterization And Applications In Device Fabrication, Joseph R. Brewer

Department of Chemistry: Dissertations, Theses, and Student Research

As the area of nanotechnology continues to grow, the development of new nanomaterials with interesting physical and electronic properties and improved characterization techniques are several areas of research that will be remain vital for continued improvement of devices and the understanding in nanoscale phenomenon. In this dissertation, the chemical vapor deposition synthesis of rare earth (RE) compounds is described in detail. In general, the procedure involves the vaporization of a REClx (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho) in the presence of hydride phase precursors such as decaborane and ammonia at high temperatures and low …

A Systematic Study Of The Effect Of Silver On The Chelation Of Formic Acid To A Titanium Precursor And The Resulting Effect On The Anatase To Rutile Transformation Of Tio2, Nicholas Nolan, Michael Seery, Steve Hinder, Linda Healy, Suresh Pillai

Articles

Anatase to rutile transition in an unmodified synthetic titania usually occurs at a temperature range of 600 – 700 °C. Various methods such as addition of metallic and non-metallic dopants and modifying the precursor have previously been reported to influence the anatase to rutile transition temperature. In the current study, the effect of addition of increasing amounts of silver to the extent of chelation of a formate group to a titanium precursor and the resulting effects on the transformation of anatase to rutile has been studied. The addition of silver (0, 1, 3 and 5 mol %) on the anatase …

Tobacco Mosaic Virus Based Thin Film Sensor For Detection Of Volatile Organic Compounds, Michael A. Bruckman, Jie Liu, Goutam Koley, Yu Li, Brian C. Benicewicz, Zhongwei Niu, Qian Wang

Faculty Publications

A thin film sensor for the detection of volatile organic compounds (VOC) was fabricated by deposition of oligo-aniline grafted tobacco mosaic virus (TMV) onto a glass substrate. The oligo-aniline motifs were conjugated onto the TMV surface by a traditional diazonium coupling reaction to tyrosine residues followed by Cu(I) catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The modified TMV was easily fabricated into a thin film by directly drop coating onto a glass substrate. Upon integration of the glass substrate into a prototypical device, the virus-based thin film exhibited good sensitivity and selectivity toward ethanol and methanol vapour.

A High Performance Sulfur/Carbon Xerogel Composite In Lithium Sulfur Battery Application, Chong Wang, Jia-Jia Chen, Qiu-Jie She, Qian Zhang, Yi-Ning Shi, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

Sulfur/carbon composite was synthesized by the thermal method with the carbon xerogel as the conductive framework. The property of composite was characterd by XRD and SEM. It shown that the composite with the particle size below 10 μm had the same morphology as the carbon xerogel and the sulfur was absorbed in the pores in non-crystalline. The discharge capacity of the composites were 1311 mAh/g and 1107. 1 mAh/g at 0. 1C and 0. 2 C rates,respetively. And a retention capacity was about 800 mAh/g after 30 cylcyes.

Nano/Micro-Structured Electrode Materials For Lithium-Ion Batteries, Yu-Guo Guo, Zhong-Li Wang, Xing-Long Wu, Wei-Ming Zhang, Li-Jun Wan

Journal of Electrochemistry

Nanostructured materials are currently of interest as high performance anodes and cathodes for rechargeable lithium-ion batteries because of their novel nano-size effects and significantly enhanced kinetics. This review paper describes some recent developments in this field,addressing the size effects,morphology effects,as well as the functions of carbon coating layers toward lithium storage. Several"kinetically stabilized"nano/microstructured electrode materials and high-rate electrode materials with mixed-conducting networks based on the work of the authors are highlighted for illustration.

Electrocatalytic Oxidation Of Hcooh At Au(Core)-Pd(Shell)-Pt(Cluster) Nanocubes, Qing-Ning Jiang, Huan Li, Ning Yang, Ping-Ping Fang, Feng-Ru Fan, Zhong-Qun Tian

Journal of Electrochemistry

Gold nanocubes were synthesized by a two-step seed-mediated growth method. The Aucore-Pdshell and Au_core-Pd_shell-Pt_cluster nanocubes with controllable shell thickness of Pd and cluster coverage of Pt were synthesized by simply changing the amount ratio of H₂PdCl₄ or H₂PtCl₆. The samples were characterized by scanning electron microscope (SEM) , transmission electron microscopc (TEM) and cyclic voltammetry (CV). CV was then used to make a systematic study on the dependence of the electrocatalytic properties on the shell thickness of Au_core-Pd_shell and Pt coverage of Au_core-Pd …

Prerapation And Supercapacitor Property Of Mesoporous Carbon Nanofibers, Yong-Wen Wang, Ming-Bo Zheng, Jian Cao, Jie-Ming Cao, Guang-Bin Ji, Jie Tao

Journal of Electrochemistry

Two different mesoporous carbon nanofibers with large mesopore or core-shell structure were prepared by using the resol/F127 mixture to fill the AAO template. The morphology and structural parameters of the samples were characterized by SEM,TEM,and N₂ adsorption-desorption analysis. The supercapacitive behaviors of the electrodes were tested by cyclic voltammetry and galvanostatic charge-discharge. The results show that the specific capacitances of mesoporous carbon nanofibers increased obviously and the fine supercapacitive performances were achieved at high scan rate or large current density.

Blocking Method In Enzyme-Amplified Amperometric Dna Biosensor, Miao He, Wei Chen, Xiong-Wei Xu, Ai-Lin Liu, Xin-Hua Lin

Journal of Electrochemistry

Non-specific absorption of enzyme and nucleotide is a main source leading to the background staining in enzyme-amplified amperometric detection of DNA. To eliminate the background staining in this system, the blocking procedure by mercapto-hexanol (MCH) and bovine serum albumin (BSA) was studied systematically. The results show that the anti-fouling effect of BSA is better than that of MCH. A simple and efficient blocking strategy employing BSA as the sole blocking reagent was established and applied in the detection of PMLRARα fusion gene in acute promyelocytic leukemia. It can effectively eliminate the background staining,shorten the pre-processing time,and achieve strong signal amplification.

Optimization Of Membrane Electrode Assembly In Air-Breathing Direct Methanol Fuel Cell, Liang Ma, Wei-Wei Cai, Jing Zhang, Liang Liang, Jian-Hui Liao, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

The structure and performance of MEA were optimized by tailoring the catalyst layer,cathodic microporous layer (MPL) ,anodic MPL and membrane,with the considerations of unique characteristics of airbreathing direct methanol fuel cell (DMFC) such as methanol crossover and cathode flooding. It was found that high catalyst loading could suppress the methanol crossover effectively,but too high catalyst loading can lead to high mass transport resistance. Hydrophobic anodic MPL with 30% (by mass) PTFE could facilitate the CO₂ bubble detachment,which decreased the methanol concentration gradient and suppressed the methanol crossover accordingly. When Nafion 115 was used as membrane,methanol crossover was severe,while Nafion …

Preparation And Electrochemical Performance Of Three-Dimensional Porous Snco Alloy Electrode, Lian-Jie Xue, Ling Huang, Fu-Sheng Ke, Guo-Zhen Wei, Xiao-Mei Zheng, Jun-Tao Li, Xiao-Yong Fan, Shi-Gang Sun

Journal of Electrochemistry

Three-dimensional porous Cu film was prepared by electroless plating,and used as a current collector for preparation of three-dimensional structured SnCo alloy electrode,which was mainly prepared by an electrodeposition method,and composed of pure Sn and CoSn₂ phases. Electrochemical experimental results show that three-dimensional structured SnCo alloy electrode exhibits much better cycleability than planar SnCo alloy electrode,with first discharge capacity and charge capacity of 636. 3 and 528. 7 mAh·g^-1,respectively. After 70^th cycling,capacity retention is 83. 1% with 529. 5 mAh·g^-1. The lithiation process during first discharge was investigated by electrochemical impedance spectroscopy.

Measurement And Wavelet Analysis Of The Electrochemical Noise Of Rebar Steel In Simulated Concrete Pore Solution, Rong-Gang Hu, Chen-Qing Ye, Shi-Gang Dong, Chang-Jian Lin

Journal of Electrochemistry

Electrochemical noise (ECN) measurement can provide information about both corrosion rate and corrosion type while inflicting no perturbation on the studied system. The ECN data of steel rebar in SPS with different amount of Cl-were collected and treated by discrete wavelet transformation to evaluate the contribution from transients in different frequency in the overall signals. Energy distribution plot (EDP) indicated in SPS with 0.0001 mol/L NaCl, the transients with time constant between 16 ～ 32 s were found to be predominant over other processes; while in SPS with higher Cl-concentration, the trend toward active corrosion became the main process. It …

High-Rate Cyclic Properties Of Hollow Carbon Hemisphere As Anode Materials For Lithium Ion Batteries, Guang-Hui Zhang, Zao-Xue Yan, Hong-Li Zou, Pei-Kang Shen

Journal of Electrochemistry

High surface area hollow carbon hemispheres (HCHs) covered with hard carbon layers have been synthesized by using polystyrene spheres (PSs) as templates under hydrothermal method combined with the intermittent microwave heating (IMH) method. The morphologies of the materials are characterized by SEM and TEM. The electrochemical properties of the HCHs are tested. Comparing with graphite and mesocarbon microbeads (MCMB) ,the HCHs show higher capacity and excellent cyclic life performance.

Research On Electrochemical Performance Of Lithium-Ion Battery Cathode Material Lini(1/3)Co(1/3)Mn(1/3)O2 In Aqueous Lino3 Solution, Jun Zheng, Xin Jia, Chong Wang, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

The cathode material of LiNi_1/3Co_1/3Mn_1/3O₂ synthesized by sol-gel method shows excellent high rate performance, and high output power density during discharge process. A well-ordered layered α-NaFeO₂ structure was confirmed by XRD and a primary particle size of about 500 nm was indicated by SEM. Galvanostatic charge-discharge test indicates that LiNi_1/3Co_1/3Mn_1/3O₂ in 2 mol·L^-1 LiNO₃ aqueous solution with pH 12 reached a ca-pacity of 147 mAh/g while charged and discharged at 2C. The capacities were 64, 33, 16 mAh/g with 80C (14.4 A/g), 150C …

Fabrication Of Electrochemically Activated Glassy Carbon/Bismuth Film Electrodes For Sensitive Analysis Of Pb(2+) And Cd(2+), Kang Shi, Wen-Jing Wang, Kun Hu

Journal of Electrochemistry

The application of electrochemically activated glassy carbon (GC) in the in-situ preparing of bismuth film electrodes (BiFEs) to analyze Pb^{2 +} and Cd^{2 +} was investigated. The glassy carbon electrodes were electrochemically activated by either potentiostic or cyclic polarization in 1 mol·L^-1 NaOH solution. Experimental results show that employment of HCl solution as the analytical solution not only can reproducibly renew the electrochemically activated GC electrode surface with an electrochemical clear procedure, but also can greatly enhance the sensitivity of BiFes method for analysis of Pb^{2 +} and Cd^{2 +}. The test range thus …

Preparation And Application Of Ti/Ceo2-F-Pbo2 Electrode In Electrochemical Degradation Of Organics, Xun-Hua Wang, Tie-Ming Zhang, Shao-Ping Tong, Chun-An Ma

Journal of Electrochemistry

The CeO₂-modified PbO₂ on Ti plate (Ti/CeO₂-F-PbO₂) was prepared by electrodeposition. The SEM and XRD analyses indicated that the CeO₂ particle could be beuniformly co-deposited in the film of PbO₂. The results of electrochemical test showed that the Ti/CeO₂-F-PbO₂ anode had higher potential (1.83 V. vs. SCE) for oxygen evolution (OE) than the Ti/F-PbO₂ anode (1.78 V,vs. SCE). The degradation of 4-chlorophenol was carried out to test electrocatalytic performance of this novel electrode, which indicated that Ti/CeO₂-F-PbO₂ anode had high COD removal rate …

Synthesis Of Cosalen Composite In Apo-5 And Its Electrocatalytic Behaviour For Reaction Of Dioxygen Reduction, Rong Zhang, Li-Hua Tang, Bin-Bin Fan, Jing-Hong Ma, Rui-Feng Li

Journal of Electrochemistry

CoAPO-5 molecular sieve was hydrothermally synthesized. The Cobalt ions in CoAPO-5 were coordinated with the SALEN ligend diffusing into the channels of the molecular sieve to form CoSALEN complexes. The electrochemical behaviors and electrocatalysis for dioxygen reduction of the CoSALEN complex immobilized in APO-5 modified glassy carbon electrodes (GCEs) have been investigated by cyclic voltammetry (CV) and chronoamperometry (CA) in differrent pH aqueous solutions. The results showed that the PS/CoSALEN/APO-5 /GC modified electrode is of the high electrocatalytic activity towards dioxygen reduction in pH 6. 86 buffer solution with a reduced overpotential of 447 mV lower than bare GC electrode. …

Failure Reaction Mechanism Of Internal Short-Circuit For Lithium-Ion Batteries, He Li, Shen-Jun Yu, Zhi-Kui Chen, Guang-Chuan Liang

Journal of Electrochemistry

In this work, the battery impact testing machine has been used to study the failure progress of internal short-circuit (ISC) for lithium ion batteries. The reaction mechanisms between cathode/anode and electrolyte in the battery at different temperatures were characterized by differential scanning calorimetry (DSC), gas chromatography/mass spectrometry (GC/MS) and X-ray diffraction (XRD). The experimental results show that the ISC failure of the battery was mainly due to the reaction between cathode Li_0.5CoO₂ and electrolyte. The decomposition and oxygen evolution reactions of cathode occurred when the temperature reached a certain value. At the same time a fierce oxidation …

Influence Of Ions Dimension On The Electric Field Activation Of Micro-Crystallite Carbon, Gang-Wei Sun, Wen-Hua Song, Guo Cheng, Wen-Ming Qiao, Li-Cheng Ling

Journal of Electrochemistry

Micro-crystallite carbon (CC) was synthesized by KOH activation of carbonized petroleum coke precursors. The porous properties structure and crystallite structure were characterized by N₂ adsorption-desorption, X-ray diffraction (XRD) measurements. The capacitive behavior of CC was investigated in the electrolyte of Et₄NBF₄/PC, Et₄NBF₄/AN, Bu₄NBF₄/PC and Bu₄NBF₄/AN, respectively. Results showed that the lower potential of electric field activation (EFA) was obtained in the solvent of AN than in PC, which was ascribed to the fact that smaller solvated ions dimension in AN facilitating the intercalation …

Electrochemical Behaviors Of Hydrazine In Bmimpf6 Solution At Ag Electrode, Jie Sun, Yan Li, Yi-Ling Feng, Rong Wang, Xia-Qin Wu

Journal of Electrochemistry

In this work, the electrochemical behaviors of hydrazine at Ag electrode in the room temperature ionic liquid, BmimPF₆, were studied by cyclic voltammetry. Results suggested that Ag electrode showed a good catalytic activity towards hydrazine oxidation. The catalytic peak current showed a good linear relationship with the hydrazine concentration in the range of 0 ～ 3.4 mmol/L. The rate-determining step of the electrocatalytic reaction involved one electron transfer form hydrazine molecule to Ag⁺ ion.

Hydrogen Evolution Reaction Activtity Of Ni-Ru-Ir Oxide Cathode Coating, Yin-Hui Fu, Xue-Ming Li, Wu-Lin Li, Jun Zhang

Journal of Electrochemistry

The Ni-Ru-Ir electrode coating was fabricated by thermal decomposition and oxidation. Electrochemical properties of Ni-Ru-Ir electrode coating and pure nickel cathode in the 30% NaOH solutions at 90 ℃(conditions of the industrial electrolysis) ,have been investigated by cyclic voltammetry,Tafel curves and chronoamperometry. The results show that the Ni-Ru-Ir oxide electrode coating exhibited high catalytic activity. At the current density of 0. 3 A·cm^-2,the lowest hydrogen evolution overpotential of Ni-Ru-Ir oxide electrode coating was about 300 mV lower than Ni. The roughness and excharge current density of Ni-Ru-Ir electrode coating were 32 and 4 times,respectively,larger than those of pure …

Study On Electrocatalytic Properties For Oxygen Evolution Of Ti/Iro2-Ta2O5 Anodes With Different Ir Contents, Yong-Lei Xin, Li-Kun Xu, Jun-Tao Wang

Journal of Electrochemistry

The anodes of Ti/IrO₂-Ta₂O₅ were prepared by Pechini method. The effects of coating loading on the surface morphology and electrochemical properties of the anodes were characterized by scanning electron microscope (SEM) ,energy dispersive X-ray detector (EDX), potentiodynamic polarization,cyclic voltammetry and accelerated life test. The results indicate that with the increase of the coating loading,the oxide anode presents evident IrO₂ crystallite segregation,and cracks become narrow and shallow. Moreover,it has larger electrochemically active surface area,better electrocatalytic activity for oxygen evolution and higher stability. It was observed that for an iridium content of 1.98 ～ 9. 08 …

Synthesis And Electrochemical Properties Of Li3V2(Po4)3/C Cathode Materials For Lithium Ion Battery, Li-Ying Liu, Hai-Yan Zhang, Lian Chen, Yu-Chun Zhai

Journal of Electrochemistry

Cathode material Li₃V₂(PO₄) ₃ /C for Lithium-ion battery was synthesized by combination of ball milling and baking. Physical and electrochemical performances of as-prepared materials were characterized through XRD,EIS and galvanostatic cell cycling. The results show that the products were monoclinic Li₃ V₂ (PO₄) ₃ with well-developed crystal structure. At 0. 1C,0. 25C and 0. 5C,the initial discharge capacities were 150. 6,134. 1 and 107. 1 mAh·g^-1 ,respectively. Capacity retention rates were 87. 3% after 130 cycles at 0. 25C and 87. 2% after 105 cycles at 0. 5C. Charge-discharge …

Nano-Sized Au On Nickel Foam As Cathode Of Alkaline Al-H2O2 Semi Fuel Cell, Shu-Li Chen, Bang-An Lu, Yao Liu, Gui-Ling Wang, Dian-Xue Cao

Journal of Electrochemistry

Nano-sized Au particles were deposited on a nickel foam substrate by a fast spontaneous deposition method using AuCl₃ as the source of Au. The effects of AuCl₃ concentration and deposition time on the size and distribution of Au particles,and the performance of the obtained Au/Ni electrode as the cathode of Al-H₂O₂ semi fuel cell were investigated. It was found that after the nickel foam was immersed in a 2 mmol·L^-1 AuCl₃ solution for 60 s,Au particles with diameters smaller than 100 nm were deposited on its surfaces and cover the surface completely. The …

Tuning Quantum Dots Optical Properties By Temperature And Concentration Modulation, Amber Sexton

Renée Crown University Honors Thesis Projects - All

Quantum dots have recently been awarded attention due to their tunable optical and spectroscopic properties. The optical and spectroscopic behavior of quantum dots was investigated as a function of mean particle size. Manipulation of the reaction conditions and constituents impact the controllability of size and surface conditions. Therefore, synthesis of CdSe and CdS semiconductor nanoparticles with tunable particle size were created using temperature, time, and composition as variables. Analytical techniques used to characterize the nanoparticles included fluorescence and electronic absorption. The effect of temperature, aside from changing the size of the particle, also eliminated defects on the surface and caused …

Rational Design Of Self-Assembled Nanostructures Based On Polymers Synthesized Via Aqueous Reversible Addition-Fragmentation Chain Transfer Polymerization, Stacey Kirkland York

Dissertations

Recent advances in reversible addition-fragmentation chain transfer (RAFT) polymerization have allowed the rational, bottom-up design of biorelevant assemblies. Utilizing foresight, polymers can be tailored to self-assemble into nano-, micro-, and macroscopic structures. Given the size scale on which rationally-designed polymers can be tailored, they hold significant promise in the biomedical field. For example, nanoscale materials can be designed to carry small-molecule and gene therapeutics while macroscopic structures can be tailored for cell growth scaffolds. The design process begins by selecting monomers, chain transfer agents, and reaction conditions which will yield the desired polymer architecture and composition.

The work herein builds …

Investigation Of Novel Quasiliving Polyisobutylene Chain-End Functionalization (Quenching) Methods, David Lee Morgan

Dissertations

This volume recounts efforts toward the development and understanding of chain functionalization techniques involving the direct addition of nucleophiles to quasiliving polyisobutylene (PIB). Nucleophiles included in the study were sterically hindered organic bases, (di)sulfides, N-substituted pyrroles, and alkoxybenzenes. A kinetic investigation of the end-quenching of TiCl4-catalyzed quasiliving PIB with sterically hindered amines was used to determine the mode of interaction with TiCl4 and the active species responsible for -proton abstraction. 2,5-disubstituted-N-hydropyrroles formed pyrrole-TiCl3 adducts that were active in formation of exo-olefin chain ends; whereas, with other sterically hindered amines, only an equilibrium fraction of the amine that did not complex …

Nanomaterials From Biologically Active Molecules: Self-Assembly And Molecular Recognition, Min Yu

Dissertations

This dissertation describes the development of molecular assemblies and molecular recognition of phospholipids (PLs) that exhibit potential applications in emerging nanotechnologies. It consists of two parts: (1) structural features of PLs responsible for recognition of synthetic copolymers, and (2) design, synthesis and analysis of magnetic nanotubes obtained from PLs with a common theme of colloidal synthesis served as a platform for film formation and nano-assemblies of nanotubes. Poly(methyl methacrylate/n-butyl acrylate) (p-MMA/nBA) colloidal particles that were stabilized by 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) PLs were synthesized, and upon the particle coalescence, PL stratification resulted in the formation of surface localized ionic clusters (SLICs). These …

Aqueous Raft Synthesis Of Stimuli-Responsive, Amphiphilic Block Copolymers And Self-Assembly Behavior In Solution And Incorporation Into Lbl Films, Matthew Grady Kellum

Dissertations

Of all the living radical polymerization techniques, reversible addition– fragmentation chain transfer (RAFT) polymerization is arguably the most versatile in terms of the reaction conditions (e.g. temperature and solvent selection), monomer selection (e.g. neutral, anionic, cationic, and zwitterionic), and purification. Since the introduction of RAFT in 1998, the McCormick research group and others including the Lowe, Sumerlin, and Davis research groups have synthesized a wide range of (co)polymers with predetermined molecular weights, low polydispersities, and advanced architectures utilizing aqueous RAFT (ARAFT) polymerization. These research groups have also studied how various block copolymers exhibit stimuli-responsive behavior due to a change in …

Multi Stimuli-Responsive Copolymers Obtained From Colloidal Dispersions, Fang Liu

Dissertations

This dissertation describes the design, synthesis, and development of multi stimuli-responsive random copolymers that exhibit collective responsiveness to temperature, pH or electromagnetic radiation. New colloidal particles of poly(N-(DL)-(1- Hydroxyymethyl) propylmethacrylamide/n-butyl acrylate) (p(DL-HMPMA/nBA) and poly(2-(N,N′-dimethylamino)ethyl methacrylate/n-butyl acrylate) (p(DMAEMA/nBA)) were synthesized, which upon coalesce to form solid continuous films. The presence of lower glass transition (Tg) nBA components not only facilitate film formation, but also provide sufficient free volume for polymer chain rearrangements. These studies showed that coalesced films exhibit 3D dimensional changes upon external stimuli, which are attributed to the collapse and conformational changes of stimuli-responsive components as well as buckling …

Synthesis, Characterization, And Deuterium Labeling Of Polyamides Studied By Nuclear Magnetic Resonance Spectroscopy, Christopher Allen Lange

Dissertations

The synthesis, characterization, and deuterium labeling of polyamides have been investigated. In Chapter II, selective deuterium labeling of various polyamides was demonstrated via a facile method which does not require organic solvent or catalyst. Quantitative solution-state NMR analysis showed deuterium incorporation at the carbon alpha to the carbonyl ranged from 20-75%. Incorporation in ε-caprolactam increased with repeated treatments. Isotopic shift effects for the deuterated materials were additive for all sites within experimental error.

In Chapter III, the effect of stoichiometric imbalances on the polymerization of poly(dodecamethylene terephthalamide)was investigated. Molecular weight was varied by polymerizing the monomer salt with excess diaminododecane, …