Chemistry Commons^™

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

Legacy Theses & Dissertations (2009 - 2024)

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

Cetyltrimethylammonium Halide-Coated Electrodes For The Detection Of Dopamine In The Presence Of Interferents, Amber J. Yeary

Browse all Theses and Dissertations

Specially constructed carbon paste electrodes were coated with 10 mM cetyltrimethylammonium halide (CTAX) solutions, bromide and chloride being the counter anions. These surfactant modified electrodes were used to detect the catecholamine neurotransmitter dopamine using cyclic voltammetry. The coated electrodes gave reproducible quasi-reversible behavior for the analyte dopamine over a range of concentrations from 1 mM to 200 mM. When combined in solution with common interferents ascorbic acid (1 mM) and uric acid (300 μM), all cathodic and anodic current peaks maintained resolution at the biological pH of 7.4. When the coating solutions were below the critical micelle concentration (0.5 mM), …

Diffuse-Charge Dynamics Of Ionic Liquids In Electrochemical Systems, Hui Zhao

Mechanical Engineering Faculty Research

We employ a continuum theory of solvent-free ionic liquids accounting for both short-range electrostatic correlations and steric effects (finite ion size) [Bazant et al., Phys. Rev. Lett. 106, 046102 (2011)] to study the response of a model microelectrochemical cell to a step voltage. The model problem consists of a 1-1 symmetric ionic liquid between two parallel blocking electrodes, neglecting any transverse transport phenomena. Matched asymptotic expansions in the limit of thin double layers are applied to analyze the resulting one-dimensional equations and study the overall charge-time relation in the weakly nonlinear regime. One important conclusion is that our …

Synthesis, Assembly, And Characterization Of Monolayer-Protected Gold Nanoparticle Films For Protein Monolayer Electrochemistry,, Tran T. Doan, Michael H. Freeman, Adrienne R. Schmidt, Natalie T. Nguyen, Michael C. Leopold

Chemistry Faculty Publications

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified …

Investigation Of Nanoceria-Modified Platinum-Gold Composite Electrodes For The Electrochemical Reduction Of Oxygen In Alkaline Media, Rahul Hegishte

Electronic Theses and Dissertations

Platinum-gold and nanoceria-modified platinum-gold electrodes were prepared on a platinum surface via electrochemical reduction of solutions of platinum and gold salts in the dispersion of nanoceria. The molar ratios of Pt and Au were varied in both PtAu and PtAu/CeO₂ electrodes while the total concentration of the metals was maintained at 2 x 10⁻³M and the concentration of nanoceria was maintained constant at 5 x 10⁻³M. The electrodes were characterized by their cyclic voltammetry curves in 0.5M sulfuric acid solution. The electrochemically active area of the electrodes was determined using the copper underpotential deposition method. The linear sweep voltammograms of …

Electrochemical Performance Of Zinc Tetra (Trifluoroethoxy) Phthalocyaninate In Aqueous And Nonaqueous Solvents, Xiao-Shan Wu, Li-Ying Huang, Jin-Que Zhang, Shan-Lan Zhu

Journal of Electrochemistry

The cyclic voltammetric performance of ZnPcF in N,N-dimethylformaide(DMF),dimethyl sulfoxide(DMSO) solution and phosphate buffer solutions(PBS) has been examined.The results showed that four pairs of redox peaks appeared in nonaqueous solvents,and the values of half-wave redox potential were 0.558 V,-0.761 V,-1.034 V,-1.417 V,respectively,exhibiting four quasi-reversible phthalocyanine ligand based one-electron transfers.In PBS only two redox peaks were observed and the values of half-wave redox potential were-0.885 V,-1.104 V,exhibiting irreversible behavior characteristics.Comparing to the zinc phthalocyanine(unsubstitute ZnPc),introducing electron-withdrawing groups-trifluoroethoxyl to the peripheral sites of the phthalocyanines shifts the redox processes of the complex toward positive potentials.

Enhanced Electrochemistry Of Nanoparticle-Embedded Polyelectrolyte Films: Interfacial Electronic Coupling And Distance Dependence, Callie E. Dowdy, Michael C. Leopold

Chemistry Faculty Publications

Factors affecting the electronic communication believed to be responsible for the enhanced solution electrochemistry observed at electrodes modified with hybrid polyelectrolyte–nanoparticle (PE–NP) film assemblies were systematically investigated. Specifically, the faradaic current and voltammetric peak splitting recorded for cyclic voltammetry of ferricyanide redox species (Fe(CN)63−/4−) at films constructed with various architectures of citrate-stabilized gold NPs embedded in polyelectrolyte films composed of poly-l-lysine and poly-S-styrene were used to establish the relative importance of both distance and electronic coupling. Layer-by-layer construction of PE–NP films allowed for the position and density of NPs to be varied within the film to assess electronic coupling between …

Electrochemical Surface-Enhanced Raman Spectroscopy—Current Status And Perspective, Bin Ren, Jian-Feng Li, Yi-Fan Huang, Zhi-Cong Zeng, Zhong-Qun Tian

Journal of Electrochemistry

Electrochemical interface is a very important interface closely related to various energy and life processes. Surface-enhanced Raman scattering was widely used in electrochemistry soon after its discovery to understand the surface bonding,configuration,and orientation of the surface species. In recent 10 years,the fast development of nanoscience and nanotechnology has offered SERS with abundant substrates and characterization methods,which has allowed impressive development of electrochemical SERS. This articles will follow the time line to make systematically overview of SERS on Au and Ag,thin-layer transition-metal SERS,pure transition metal SERS,core-shell SERS and those methods for studying single crystal surfaces,including gap-mode SERS, TERS and SHINERS. Emphasis …

In-Situ Surface Enhanced Raman Scattering Electrochemical Investigation Of 4-Aminoantipyrine On Silver Electrode, Li-Jun Zhang, Wei Song, Ling Chen, Zong-Rang Zhang, Hai-Feng Yang

Journal of Electrochemistry

In this paper, 4-AAP was self-assembled on silver surface to form monolayers. Surface-enhanced Raman Spectroscopy (SERS) was used to in-situ investigate the adsorption mechanism of the 4-aminoantipyrine(4-AAP) on silver surface dependent on shifting potentials and the effect of solution pH. Based on density functional theory(DFT) calculation of vibration modes,approximate assignment of 4-AAP SERS spectrum was conducted. In situ SERS spectral electrochemical experiments indicated that the 4-AAP monolayers experience a dynamic adsorption process from a tilted fashion to a more vertical mode for benzene ring and more parallel for pyrine ring with the potential applied toward more negative voltages. The complete …

Mechanistic Studies On The Electrochemistry Of Proton Coupled Electron Transfer And The Influence Of Hydrogen Bonding, Timothy Alligrant

Theses and Dissertations

This research has investigated proton-coupled electron transfer (PCET) of quinone/hydroquinone and other simple organic PCET species for the purpose of furthering the knowledge of the thermodynamic and kinetic effects due to reduction and oxidation of such systems. Each of these systems were studied involving the addition of various acid/base chemistries to influence the thermodynamics and kinetics upon electron transfer. It is the expectation that the advancement of the knowledge of acid/base catalysis in electrochemistry gleaned from these studies might be applied in fuel cell research, chemical synthesis, the study of enzymes within biological systems or to simply advance the knowledge …

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 …

Adsorption Efficiency And Partitioning Capabilty Of Surfactant Monolayers On Gold, Carrie Jo M. Pruitt

Mahurin Honors College Capstone Experience/Thesis Projects

We are investigating adsorption efficiencies of sodium dodecyl sulfate (SDS) from pH 7 phosphate buffer onto polycrystalline gold substrates using electrostatics as the primary driving force via electrochemical control of the gold surface potential. It is shown through surface capacitance measurements by electrochemical impedance spectroscopy that the adsorption occurs readily. Measurement of the adsorption isotherms of SDS onto the substrate via the change in surface capacitance as a function of the bulk concentration of SDS has allowed us to determine that the minimum concentration of SDS required for efficient adsorption is below 0.011 mM. The investigation of the influence of …

A New Dinuclear Lead(Ii) Complex Of 2,3-Diphenyl-Tetrazole-5-Thione: Synthesis And Characterization, Ruirui Zhuang, Fangfang Jian, Kefei Wang

Turkish Journal of Chemistry

The present work reports on the synthesis, crystal structure, fluorescence, electrochemical behavior, and thermogravimetric analysis of a new dinuclear lead(II) complex of 2,3-diphenyl-tetrazole-5-thione. Its structure was characterized by X-ray crystallography, IR spectroscopy, and elemental analysis. Each lead atom adopts a distorted octahedral geometry by coordinating to 2 sulfur atoms from 2 2,3-diphenyl-tetrazole-5-thione ligands and 4 oxygen atoms from 3 nitrates. The fluorescence spectrum shows that the title complex has 2 fluorescence emission peaks, at 412 nm and 433 nm. Cyclic voltammetry studies show that the title complex has only one reduction peak, at 0.309 V. The thermogravimetric analysis indicates that …

Tricarbonylrhenium(I) And Manganese(I) Complexes Of 2-(Pyrazolyl)-4-Toluidine, Brendan J Liddle, Sarath Wanniarachchi, Sergey V. Lindeman, James R. Gardinier

Chemistry Faculty Research and Publications

A series of tricarbonyl rhenium(I) and manganese(I) complexes of the electroactive 2-(pyrazolyl)-4-toluidine ligand, H(pzAn^Me), has been prepared and characterized including by single crystal X-ray diffraction studies. The reactions between H(pzAn^Me) and M(CO)₅Br afford fac-MBr(CO)₃[H(pzAn^Me)] (M = Mn, 1a; Re, 1b) complexes. The ionic species {fac-M(CH₃CN)(CO)₃[H(pzAn^Me)]}(PF₆) (M = Mn, 2a; Re, 2b) were prepared by metathesis of 1a or 1b with TlPF₆ in acetonitrile. Complexes 1a and 1b partly ionize to {M(CH₃CN)(CO)₃[H(pzAn^Me)]^{+ …}

Synthesis And Development Of Novel Fullerene-Based Structures For Photovoltaics, Electronic Applications And Mri Contrast Agents, Manuel Chaur

All Dissertations

Metallic nitride endohedral metallofullerenes (EMFs) are one of the most interesting types of metallofullerenes due to their high yields and interesting electronic properties. The synthesis of these compounds allows the encapsulation of different metals inside fullerenes making it possible to combine the properties of the metal with those of the fullerene. Their interesting electrochemical and optical features make them potential candidates for several applications such as molecular electronics, biomedical imaging, non-linear optical devices, and magnetic resonance imaging (MRI) agents. This thesis reports the synthesis of novel metallic nitride EMFs based on Gd, Nd, Pr, Ce and La. These families of …

Electrochemical Characteristics Of Vitaminb6 At Polybromocresol Green Modified Electrode, Jun Yao, Jiang-Yuan Li, Yang Luo

Journal of Electrochemistry

Electrochemical characteristics of VB₆ were investigated at PBG modified electrode by Cyclic voltammetry and linear sweep voltammetry.The VB₆ produced an irreversible oxidation peak at 0.978 V(Vs.SCE) in HAc-NaAc(pH=4.0) buffer solution over the potential range of 0.7 to 1.2 V.The electron number,the proton number,the transfer coefficient were determined to be 1,1 and 0.37,respectively.The oxidation peak currents of VB₆ versus its concentration showed a linear relationship in the concentration range of 1×10^-3~2×10^-5mol/L with the correlation coefficient of 0.9967 and the detection limit of 2×10^-6mol/L.The recovery was 100.06%.

Hemeproteins Bathed In Ionic Liquids;Examining The Role Of Water And Protons In Redox Behavior And Catalytic Function, John Joseph Moran

ETD Archive

We investigate the changing behaviors of myoglobin and nitric oxide synthase (NOS) in the near-absence of bulk water and/or protons by using ionic liquid butyl methyl imidazolium tetrafluoroborate as a non-aqueous milieu. Through direct charge transfer and metalloprotein-mediated catalytic reduction of oxygen and nitric oxide, we shed light on diverging aspects on how the two hemeproteins face the scarcity of water and/or protons in bulk. Isotopic effect investigations using D2O further elucidates kinetic aspects of proton transfer. Finally, in the case of NOS oxygenase, pterin cofactor binding and NOS-mediated catalytic oxidation of L-arginine in ionic liquids interrogates proton and water …

A Lab To Stemulate Undergraduate Students Into Science, Technology, Engineering And Mathematics Majors, Nicole Lynn Speelman

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The central focus is the development and implementation of a research/lab module for first year chemistry courses. Electrochemical techniques are utilized to study oxidation and reduction reactions of neurotransmitters with a poly(2,2'-Bithiophene) modified electrode. The goal is to excite students about chemistry and encourage them to continue studies in Science, Technology, Engineering, and Mathematics (STEM) during their undergraduate education. The lab module was created for Project REEL (Research Experiences to Enhance Learning) and will be illustrated with results typically obtained by students. The experiment is inquiry-based, which includes challenging questions students have to do collaboration and research to answer, as …

The Endpoint Determination In Hydrochloric Pickling By Electrochemistry Method, Shu-Jie Chen, Chun-Jie Ye, Hong-Liang Pan

Journal of Electrochemistry

Pickling is an effective way to remove the oxide scale covered on steel materials.It is vital to determine the endpoint in the course of pickling process investigation.According to the reaction process of the oxide scale covered on hot-rolling strips with the hydrochloric acid,a method for determining the endpoint of pickling based on electrochemical principle was suggested.In the pickling experimentation of hot-rolling strips,an accurate precision can be obtained using this method.

Performance Of Magnetic Field Coupled With Electrochemical Process For Preparing Polyaluminum Chloride, Ke-Wu Pi, Wen-Qi Gong, Zheng-Qing Huang

Journal of Electrochemistry

Polyaluminum chloride(PAC) was prepared by electrochemical process coupled with magnetic field paralleling to the gravitation direction.The electrolyte of 0.1 M AlCl3 solution was used,with the iron plates as cathode and aluminum sheets as anode.PAC of 0.6 M total aluminum(AlT),83.2% Alb to AlT and basicity(Ba)=2.4 was synthesized when magnetic flux density was 0.4T,the distance of electrodes was 15 mm,the voltage of electrolysis cell was 2.4 V and current density was 300 A/m2.Under above experimental conditions,the voltage efficiency,energy efficiency and electrodes surface area to reduction cells of electrochemical reactor were 85.2%,81.5% and 140.1m2/m3,respectively.The polarization curves determined by constant-current method showed that the …

Β-Diketonate, Β-Ketoiminate, And Β-Diiminate Complexes Of Difluoroboron, Felipe P. Macedo, Chengeto Gwengo, Sergey V. Lindeman, Mark D. Smith, James R. Gardinier

Chemistry Faculty Research and Publications

A series of β-diketonate, keto(aryl)iminato, and β-bis(aryl)iminato complexes of difluoroboron, twenty in total, have been prepared to assess the impact of chelate ring and aniline substitution on the structural, electrochemical, and photophysical properties of these ubiquitous chelates. DFT (B3LYP/6-31G*) calculations supplemented the experimental results and both demonstrated that replacing oxygen with the more electron-donating aniline groups serves to only fine-tune the electronic properties because both the HOMO and LUMO energies are affected by such substitution. The electronic properties of all compounds are most greatly influenced by the nature of the substituents bound to the carbon portion of the chelate ring. …

Preparation Of Zn-Ni Alloy Whisker By Electrochemical Method, Zhen-Hai Liang, Xi-Hua Xia

Journal of Electrochemistry

The Zn-Ni alloy whiskers were prepared by electrochemical method and were characterized by XRD, SEM and EDS methods. The results showed that Ni₅Zn₂₁ and Ni₃Zn₂₂ whiskers were obtained with the length of 2~4 μm and the diameter of 250 nm, thereby the rations of length/diameter fell between 8 and 16. The electrochemical behavior was investigated by cyclic voltammetry method simultaneously. A new method was provided on whisker preparation based on this work.

Synthesis And Electrochemical Studies In Microstructured Media, Jamie Norton

All Dissertations

In-situ electrochemical methods involving both oxidative and reductive mediators were employed to modify the oxidation state (doping level) of PEDOT polymers in colloidal PEDOT-coated silica core-shell particles that were prepared as a dispersion encapsulated in a hydrogel matrix. The modifications of the redox states of the PEDOT coating induced a change in the absorbance characteristics. A mediated electron transfer system was employed to ferry charge from the electrodes of the cell to the isolated particles. The mediator diffuses between the electrode surface and the PEDOT-coated particles to accomplish (de)doping. The developed system was a fully self-contained and electrically driven device. …

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 …

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

Separations Campaign (TRP)

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

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

The following were specific goals for 2007-2008:

• To …

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

Separations Campaign (TRP)

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

Investigation On The Electrochemical And Spectra Properties Of Myricetin, Dong-Mei Wu, Shuang Liu, Hong-Fu Gao, Jin-Lian Li, Hai-Yan Liu, Qi-Chao Liang

Journal of Electrochemistry

The electrochemical mechanism of redox and stability of myricetin were investigated using cyclic voltammetry and electronic absorption spectra.Two oxidation reactions and two reduction reactions were achieved in B-R buffer solution.The oxidation reactions were both due to oxidation of 4′-OH on ring B and 3-OH on ring C within a one electron one proton process.The reduction reactions both correspond to the transformation of 4-carbonyl group on ring C to intermediate radical,and intermediate radical to hydroxyl group within a one electron one proton process,respectively.The redox of myricetin is pH dependent because of deprotonation,resulting in an increase of the antioxidant ability upon formation …

Template Synthesis And Electrochemical Studies Of Ag(Core)Au(Shell) Nanowires, Li Ling, Ya-Xian Yuan, Min-Min Xu, Jian-Lin Yao, Ren-Ao Gu

Journal of Electrochemistry

Agcore Aushell nanowires with different thicknesses were prepared by combining template synthesis and chemical reduction method,and characterized by SEM and cyclic voltammetry(CV).The CV results revealed that the AgcoreAushell nanowires with pinhole were transferred to pinhole free structure after several potential scans.By using thiophenol(TP)and p-aminothiophenol(PATP)as probe,the surface enhanced Raman scattering(SERS)effect was investigated on the core-shell nanowires.The results indicated that AgcoreAushell nanowires could be served as a potential SERS substrate,and the difference in the spectral feature of PATP adsorbed onto Au and Ag nanowires enable us to diagnose the pinhole effect of core-shell nanowires by SERS.

Study On The Electrochemical Extraction Of Oxygen And Influence Factors Of Oxygen Purity, Xiao-Ke Zhi, Guang-Chuan Liang, Xiu-Qin Ou, Shu-Guang Liu, Bin Han

Journal of Electrochemistry

A method for the electrochemical extraction of oxygen is prasented.The concentration of HO₂^-ions and the purity of oxygen were measured by KMnO₄ standard method,and by cuprammonium absorb method respectively.Effect of the membrane and the spacing between cathode and anode on the purity of oxygen were also tested.The experiment results were showed that the system could work continuously above 500h and the purity of oxygen was above 99.8% when using proper membrane at 80 mA·cm^-2 current density,Electrochemical reaction included 4e reacting course and 2e reacting course,the ratio of 2e reaction is about 38%~44% of the whole …

An Electrochemical Dna Biosensor For The Detection Of Dna Damage Caused By Radioactive Iodine And Technetium, Pinar Kara, Kağan Dağdevi̇ren, Mehmet Özsöz

Turkish Journal of Chemistry

A DNA damage process by radioactive iodine (I-131) and technetium (Tc-99m) is described. The procedure relies on a label-free electrochemical DNA biosensor. Fish sperm double stranded DNA was immobilized onto a carbon paste electrode (CPE) by electro deposition and the changes to the guanine oxidation signal were observed upon exposure to radioactive I-131 and Tc-99m by differential pulse voltammetry (DPV). The changes to the signal of guanine after exposure to therapeutic doses of Tc-99m and I-131 showed conformational changes in DNA molecules.