Physical Chemistry Commons^™

Density Functional Theory Study On The Structures Of Solvent-Ion In The Electrolyte Of Lithium Ion Battery, Li-Dan Xing, Ru Yang, Xian-Wen Tang, Wen-Na Huang, Qi-Feng Liu, Qi-Peng Yu, Wei-Shan Li

Journal of Electrochemistry

In this work, the possible structures of solvent-ion complex, resulting from the electrostatic interaction in the propylene carbonate (PC) base electrolyte of lithium ion battery, have been investigated using the density functional theory. The calculated results show that the structure of solvent-ion complex depends on the solvent number. In the PC base electrolyte, maximum number of PC solvents that coexist in the Li⁺-solvent sheath is four. Additionally, the salt anion exists in a complex with the positively charged alkyl group of PC rather than in a free state. The calculated results give a good explanation to the reported …

Incorporation Of Charge Transfer Into Classical Molecular Dynamics Force Fields With Applications In Physical Chemistry., Marielle Soniat

LSU New Orleans Theses and Dissertations

The presence of charge transfer (CT) interactions is clear in a variety of systems. In CT, some electron density is shifted from one molecule to another (non-bonded) molecule. The importance of this CT interaction is unclear. Previous attempts to look at the conse- quences of CT required the use of ab initio molecular dynamics (AIMD), a computationally intensive method. Herein, a method for including CT in force field (FF) simulations is described. It is efficient, produces charges in agreement with AIMD, and prevents long- ranged CT.

This CT MD method has been applied to monatomic ions in water. When solvated, …

The Effect Of Ph And Counterion On The Size Distribution And Luminescence Lifetime Of Terbium-Doped Lanthanum Nanocrystals, Sarah Baker

Undergraduate Honors Theses

In recent years, nanoparticles have been applied to and have gained prevalence in fields such as chemistry, biology, the medical sciences, and biotechnology,and have attracted the attention of medical researchers as potential microscopic drug delivery systems in the human body. In particular, nanoparticles made with the lanthanides have shown themselves to be useful to many biological applications due to their unique luminescent properties. It is crucial to determine optimum synthetic parameters so that nanoparticles are both small enough to pass through the kidneys and also have the ability to attach different functional groups so that they may be relevant to …

Comparison Of Upper Tropospheric Carbon Monoxide From Mopitt, Ace-Fts, And Hippo-Qcls, Sara Martínez-Alonzo, Merritt N. Deeter, Helen M. Worden, John C. Gille, Louisa K. Emmons, Laura L. Pan, Mijeong Park, Gloria L. Manney, Peter F. Bernath, Chris D. Boone

Chemistry & Biochemistry Faculty Publications

Products from the Measurements Of Pollution In The Troposphere (MOPITT) instrument are regularly validated using in situ airborne measurements. However, few of these measurements reach into the upper troposphere, thus hindering MOPITT validation in that region. Here we evaluate upper tropospheric (~500 hPa to the tropopause) MOPITT CO profiles by comparing them to satellite Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) retrievals and to measurements from the High-performance Instrumented Airborne Platform for Environmental Research Pole to Pole Observations (HIPPO) Quantum Cascade Laser Spectrometer (QCLS). Direct comparison of colocated v5 MOPITT thermal infrared-only retrievals, v3.0 ACE-FTS retrievals, and HIPPO-QCLS measurements shows …

Neutron Study Of Structure And Dynamics Of Rigid Polymers, Naresh Osti

All Dissertations

The structure and the dynamics in two different classes of rigid polymers; ionomers and rigid luminescent polymers, have been investigated predominantly by neutron techniques. Rigidity of the backbones of both polymers affects their properties. For ionomers, it affects transport pathways, therefore, their applications for energy and separation membranes. In luminescent polymers, it determines the conformations of the chains and their electro-optical response. One group of the polymers consists of rigid hydrophobic para-phenylene backbone decorated with pendant phenyl side chains functionalized with sulfonic acid (SPP). The other family of polymers consists of poly para-phenyleneethynylene (PPE) backbone that becomes conjugated upon conformational …

Development And Application Of Combined Quantum Mechanical And Molecular Mechanical Methods, Rui Lai

Department of Chemistry: Dissertations, Theses, and Student Research

Compromising of computational cost and accuracy, combined quantum mechanical and molecular mechanical (QM/MM) methods are practical methods for studying large molecular systems. The use of induced dipole polarizable force fields can significantly improve the accuracy of MM and QM/MM methods. However, induced dipole models tend to overestimate the polarization energy at short interaction distances. Damping functions can be applied to reduce the over polarization. MM-MM damping schemes have been developed to correct the overestimated polarization between MM atoms; QM-MM damping scheme has not been developed. In this thesis, a QM-MM damping scheme is developed for the damping of the MM …

Oxidative Damage To Dna 2´-Deoxyribose By Carbonate Radicals: Reaction Mechanisms And Products, Terence J. Moore

Electronic Theses and Dissertations

The carbonate radical anion (CO₃^•-, CR) is an important reactive oxygen species produced in vivo by one-electron oxidation of CO₂ or bicarbonate, constituents of the major physiological buffer. It was demonstrated for the first time by using an HPLC-based analysis of low-molecular products of DNA damage that CRs react with DNA 2΄-deoxyribose by the hydrogen abstraction mechanism. CRs exhibit a ~ 800-fold preference for one-electron oxidation of guanine over hydrogen abstraction from DNA sugar, in sharp contrast with •OH. CRs also have, as compared to •OH, an increased preference for the H1΄ abstraction, which is the …

Magnetic Nickel Nanoparticles: Synthesis, Environmental Lmplications And Potential Role As Drug Carriers, Setare Tahmasebi Nick

Dissertations

The design and synthesis of well-defined magnetic particles with nanoscale dimensions is opening new avenues in understanding their fundamental chemical and physical properties. Our work describes a novel facile procedure for the synthesis of homogenous isotropic and anisotropic magnetic nickel nanoparticles. These nanoparticles were produced using a wet-chemical process and characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), powder x-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and thermogravimetric analysis (TGA). Magnetic measurements were acquired using a superconducting quantum interference device (SQUID) magnetometer. While there is significant interest in using magnetic nanoparticles for biological …

Spectroscopic Investigation Of The Chemical And Electronic Properties Of Chalcogenide Materials For Thin-Film Optoelectronic Devices, Kimberly Horsley

UNLV Theses, Dissertations, Professional Papers, and Capstones

Chalcogen-based materials are at the forefront of technologies for sustainable energy production. This progress has come only from decades of research, and further investigation is needed to continue improvement of these materials.

For this dissertation, a number of chalcogenide systems were studied, which have applications in optoelectronic devices, such as LEDs and Photovoltaics. The systems studied include Cu(In,Ga)Se2 (CIGSe) and CuInSe2 (CISe) thin-film absorbers, CdTe-based photovoltaic structures, and CdTe-ZnO nanocomposite materials. For each project, a sample set was prepared through collaboration with outside institutions, and a suite of spectroscopy techniques was employed to answer specific questions about the system. These …

Catechol Oxidation By Ozone And Hydroxyl Radicals At The Air-Water Interface, Elizabeth A. Pillar, Robert C. Camm, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air–water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon …

Influence Of Pt:Ru Ratio In Nanotubes Array Structures On The Electrocatalytic Activity Of Methanol Oxidation, Jin-Hua Yuan, Feng-Bin Wang, Xing-Hua Xia

Journal of Electrochemistry

Bimetallic PtRu nanotubes array electrodes (NTAEs) with varied Pt to Ru atomic ratios have been prepared by electrochemical codeposition in 3-aminopropyltri-methoxysilane modified porous anodic alumina (PAA) membranes. The structure and morphology of the catalysts were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electrochemical results showed that the NTAEs with varied atomic ratios could be achieved by controlling the precursor concentration for deposition. The prepared nanoarrays composed of Pt or PtRu alloy promoted the mass-normalized activity toward the sluggish electrooxidation reaction of methanol due to the increased catalytic activity and real surface area, as well as the …

Electrochemistry Of Glucose Oxidase Modified On Porin-Phospholipid Biomimic Membrane, Kun-Qi Wang, Zuo-Ming Zhang, Wei Xing, Chang-Peng Liu, Xing Zhou

Journal of Electrochemistry

Biomimic membrane with nano-channels, which is made up of porin MspA and 1,2-Dimyristoyl-sn-glycero-3-phosphocholine (DMPC) is constructed on glassy carbon substrate, and glucose oxidase (GOD) is modified on it. The direct electrochemical reaction and electrocatalytic behavior to oxygen and glucose of GOD on the GOD/MspA-DMPC/GC electreode are expounded by the cyclic voltammetric method. The study shows that GOD immobilized on porin MspA and DMPC biomimic membrane displays direct and surface-controlled electrochemical reaction nearby formal potential (E0′) of the flavoprotein active centre (FAD/FADH), and the electrochemical reaction contains two electrons and two protons exchange in 0.1 mmol·L^-1 phosphate buffer solution (PBS) …

Effect Of Imidazole Ionic Liquids On The Electro-Oxidation Of P-Methoxy Toluene, Qiong Chen, Ying-Hong Zhu, Ying Zhu, Yan-Fang Li, Chun-An Ma

Journal of Electrochemistry

The interactions between four Imidazole ionic liquids (EMIMBF₄, BMIMBF₄, BMIMHSO₄, BMIMAc) and p-methoxy toluene were investigated by ultraviolet spectroscopy. The red shifts of absorption peak were obviously observed, and the fine structures of the spectroscopy were disappeared on the long wave district. p-MT producing stable excited state was benefit from the interaction with solvent molecules. The electro-oxidation behavious of p-MT were studied in the four ILs on platinum electrode by cyclic voltammetry (CV) and chronoamperometry (CP), and the diffusion coefficients (D) and activation energies (ED) were calculated. The results indicated that the electro-oxidation process …

Review Of Carbon Materials Energy Storage Mechanism In Lead-Carbon Battery, Le-Ying Wang, Hao Zhang, Chen Hu, Shu-Kai Zhang, Hai-Lei Zhao, Gao-Ping Cao, Wen-Feng Zhang, Yu-Sheng Yang, Xiao-Kang Lai

Journal of Electrochemistry

The traditional lead-acid batteries are mainly used for automobile and various internal combustion engine starting, wireless communication base stations and renewable energy storage; however, their negative plates are easily sulfated under partial-state-of-charge duty, then their charging capacity and cycle life are greatly reduced. Lead-carbon battery is a new type of lead-acid battery, in which a carbon material with high specific surface area and conductivity is added into a negative plate, and has excellent rate discharge performance and higher PSoC cycle life. Lead-carbon battery has a good application prospect in energy storage and hybrid electric vehicle, so these years the study …

Determination Of Folic Acid By Composite Film Electrode Modified With Poly-Alizarin Red And Multi-Walled Carbon Nanotubes, Xue-Ping Du, Tong-Fang Lou, Ying Dong, Jian-Ying Qu

Journal of Electrochemistry

The novel modified electrode was fabricated by electropolymerizing alizarin red onto the surface of multi-walled carbon nanotubes on glassy carbon electrode surface, which exhibited good electrocatalytic activity for folic acid. The experimental results showed that the reduction peak current of folic acid at -0.63 V was linear to its concentration over the range of 1.25×10^-6 ~ 4.00×10^-5 mol·L^-1 in the optimized experimental conditions (R = 0.9985). Test for recovery was carried out by standard addition method, and the recovery ratios were in the range of 92.0% ~ 102.0%. The modified electrode was prepared simply with excellent stability, …

Electro-Catalytic Properties Of Β-Pbo2/Sb-Sno2/Ti Electrode On Phenol Oxidation, Peng Li, Yue-Min Zhao, Li-Zhang Wang, Yan-Le Zhang, Zhao-Qing Lu

Journal of Electrochemistry

The combination technology of brush pyrolysis and electroplating was employed in the preparation of β-PbO₂/Sb-SnO₂/Ti electrode. X-ray Diffraction (XRD) and Scanning Electron Microscope (SEM) results showed that the Sb-SnO₂ as an interlayer would restrain the formation of lead fluoride and the crystallization degree on the electrode surface could be as high as 100%. The grain size was calculated by Scherrer formula to be 25.2 nm and the agglomeration of lead dioxide was effectively eliminated. The potential span of diffusion control phase, oxygen evolution potential, Tafel slope for the β-PbO₂/Sb-SnO₂/Ti electrode during …

On The Origin Of The Errors Of IK As Estimated From K-L Equation In Rotating Disk Electrode System, Wei Chen, Ling-Wen Liao, Zheng-Da He, Yan-Xia Chen

Journal of Electrochemistry

Rotating disk electrode system is mainly used to study the kinetics of reactions whose reactants have very low solubility in the electrolyte. For an irreversible reaction, Koutecky-Levich equation (K-L Eq.) is frequently used to deduce the kinetic current i_k). Since K-L Eq. is derived based on the assumption that a system should conform the steady-state diffusion conditions, the data recoded from the actual system which deviates from such a condition, great error may be induced for the i_k estimated. In this work, polarization curves for oxygen reduction reaction at polycrystalline Pt electrode recorded in solutions with various …

Electrochemical And Spectroscopic Studies Of Ethanol Oxidation On Nano-Cubic Pt Modified By Tin Adatoms, Lu Rao, Bin-Wei Zhang, Yan-Yan Li, Yan-Xia Jiang, Shi-Gang Sun

Journal of Electrochemistry

The nano-cubic Pt modified by tin (Sn) was synthesized and used to investigate the role of this adatom played in the ethanol oxidation. The onset potential of ethanol oxidation was significantly shifted negatively which can be forward about 300 mV when the coverage of Sn (θSn)was 0.9. The electrtochemical in situ FTIR result demonstrated that the amount of CO₂ increased first, and then decreased with θSn increased, and reached the maximun when θSn was 0.38. Furthermore, the formation of acetic acid could be observed at very low potential (-0.05 V) after modifying Sn adatom, and the amount of acetic …

Preparation Of Pt/Dna-Mwcnts/Gc Electrode And Its Electrocatalytic Activity Toward H2O2 Reduction, Li-Li Fan, Li-Na Wu, Zhi-Yu Qu, Dan-Feng Liu, Jun-Ming Zhang, Si-Ming Fan, You-Jun Fan

Journal of Electrochemistry

The DNA-multi-walled carbon nanotubes (MWCNTs)/glassy carbon (GC) electrode was prepared by modifying the DNA functionalized MWCNTs composite on a GC electrode. A novel non-enzymatic H₂O₂ sensing electrode was fabricated by electrodepositing Pt nanoparticles on the DNA-MWCNTs/GC electrode. The modified electrodes were characterized by scanning electron microscope (SEM). The response properties of the sensing electrode to H₂O₂ were investigated by cyclic voltammetry and chronoamperometry. The results indicated that the sensing electrode exhibited a good linear relationship between response current and H₂O₂ concentration in the range of 0.04 ~ 18.07 mmol·L^-1 with …

Boosting Electrocatalytic Activity Of Nitrogen-Doped Graphene/Carbon Nanotube Composite For Oxygen Reduction Reaction, Yu Zhang, Jin-Song Hu, Wen-Jie Jiang, Lin Guo, Zi-Dong Wei, Li-Jun Wan

Journal of Electrochemistry

Developing low-cost catalysts with high electrocatalytic activity for oxygen reduction reaction (ORR) has recently attracted much attention because the sluggish ORR currently limits the performance and commercialization of fuel cells and metal-air batteries as well. Nitrogen doped carbon materials have been considered as a promising candidate for the replacement of high-cost and scarce Pt-based catalysts although their electrocatalytic activity still needs to be much improved. In this work, an improved nitrogen-doped graphene/carbon nanotubes composite (N-rGO/CNT) was developed as an efficient ORR electrocatalyst. It was found that the ORR activity of N-rGO/CNT composite could be significantly enhanced by introducing iron in …

Electrochemical Deposition Of Copt Alloy Thin Film And Its Abnormal Infrared Effects, Qing-Song Chen, Guo-Cong Guo, Shi-Gang Sun

Journal of Electrochemistry

Nanostructured CoPt alloy thin film was deposited on glassy carbon substrate (denoted as CoPt/GC) under cyclic voltammetric conditions. SEM studies demonstrated that the CoPt/GC was composed of nonuniform nanoparticles with an average size of 139 nm. The composition of the CoPt/GC was analyzed by energy dispersive X-ray spectroscopy (EDS), which depicts a Co:Pt ratio of ca. 3:5. In situ FTIR spectroscopy employing CO adsorption as a probe reaction revealed that the CoPt/GC exhibits abnormal infrared effects (AIREs). The unique anomalous IR features of CO adsorbed (CO_ad) on CoPt/GC consist in the complete inversion of the CO_ad IR …

Recent Progress In Heteroatoms Doped Carbon Materials As A Catalyst For Oxygen Reduction Reaction, Wei Ding, Xue Zhang, Li Li, Zi-Dong Wei

Journal of Electrochemistry

Developing catalytic materials for oxygen reduction reactions (ORR) with high performance and low cost has been one of the major challenges for large-scale applications of fuel cells. In this review, we summarize the recent progress in the heteroatoms doped carbon materials as a catalyst for the catalysis of ORR, with an emphasis on the universal origin of their catalytic mechanisms. The future prospects of the metal-free catalyst were to find precisely controlled doping methods, to explore the role of heteroatoms in the catalysis, and to generate more active catalysts with suitable nanostructure.

Fabrication Of Pattern Of Graphene Oxide And Au Nanoparticles By Microcontanct Printing Technique, Wen-Hui Pang, Xiao-Jian Xiao, Meng-Wei Ye, Kai-Chao Deng, Jing Tang

Journal of Electrochemistry

Graphene oxide (GO) was prepared by modified Hummers method. Using the GO solution as "ink", Au nanoparticles (AuNPs) and GO were transferred to the surface of ITO substrate modified with (3-aminopropyl) triethoxysilane (APTES/ITO) in a sequence. The transferred AuNPs and GO could form a uniform and dense composite pattern which was characterized by FE-SEM and AFM. Moreover, using the APTES/ITO substrate surface potential as zero, the sequences of the surface potential were APTES>GO>Au.

Fabrication And Characterization Of The Ni-Scsz Composite Anodes With A Cu-Lscm-Ceo2 Catalyst Layer In The Thin Film Sofc, Yao Lv, Bo Huang, Xi-Zhi Gu, Chun-Yi Hou, Yi-Xing Hu, Xiao-Yin Wang, Xin-Jian Zhu

Journal of Electrochemistry

Solid oxide fuel cell (SOFC) directly operating on hydrocarbon without external reforming has the potential of greatly speeding up the application of SOFCs for transportation. In this paper, a three-layer structure anode was fabricated by tape casting and screen printing method. The addition of Cu-LSCM-CeO₂ to the supported anode surface presented better performance running on H₂ and ethanol. The maximum power densities were 511 and 390 mW?cm^-2, respectively, running on H₂ and ethanol at 750 °C. No significant degradation was observed on the anode. Consequently, the Cu-LSCM-CeO₂ catalyst layer on the surface of the …

Preparation And Electrochemical Behavior Of Pbo/Gn/Ac, Yun-Fang Gao, Yan-Ping Wang, Qiu-Shi Yao, Fu-Hua Wang, Dong-Lei Ren, Xin Xu

Journal of Electrochemistry

The lead oxide/graphene/activated carbon (PbO/GN/AC) composite materials were prepared by impregnating commercial activated carbon and graphene in saturated lead nitrate solution followed by calcination. The structures and morphologies of the composite were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The results show that PbO crystals (about 200 nm) were dispersed uniformly on the surface of activated carbon and graphene. Electrochemical data indicate that the composite exhibited good electrochemical performances. The PbO/GN/AC composite possessed the higher over-potential of hydrogen evolution and the high specific capacitance of 312.6 F·g^-1, while the internal resistance …

Determination Of Disulfide Bond Connecting Patterns Via Tandem Mass Spectrometry (Msn) And Biomolecular Ion/Radical Reactions, Kirt Lenroy Durand

Open Access Dissertations

Disulfide bond formation is one of the most common post translational modifications to occur in proteins and naturally occurring peptides. Disulfide bond formation plays a critical role in stabilizing their three-dimensional structure; therefore, it is very important to pinpoint the correct disulfide bond connecting pattern in order to fully understand the biological functions of these proteins and peptides. To fully characterize an analyte containing disulfide bonds, the sequence must first be known followed by the disulfide bond connecting pattern. This presents an analytical challenge as there are very few methodologies that can produce those essential pieces of information. The gold …

Excited States Of Chromophores And Vibronic Interactions, Benjamin T. Nebgen

Open Access Dissertations

The main focus of my Ph.D. work has been on building a vibronic coupling model for multichromophores and extending that model to more general systems. This Dissertation serves as both a summary of this work as well as a manual for the two vibronic coupling programs I have written. It is my hope that the instructions written here are complete enough for any who would like to replicate my work on vibronic coupling on other systems. ^ Additionally, I have also worked on a few purely computational projects not directly related to the vibronic coupling work. The status of these …

Supersonic Jet Spectroscopy Of Synthetic Foldamers, Multichromophores, And Their Water Containing Clusters, Evan Gardner Buchanan

Open Access Dissertations

A central theme specific to this dissertation concerns the conformation-specific spectroscopy of flexible molecules in an effort to bridge the complexity gap. Generally, molecules in the complexity gap have several flexible coordinates yet conformational isomerization still occurs along a simple reaction coordinate on the potential energy surface. Molecules in this regime benefit greatly from experiments probing the potential energy surfaces and provide a means to develop and test new theories in an effort to explain more complex system. These measurements are possible through the utilization of a supersonic jet expansion to collisionally cool molecules into their vibrational zero-point levels, collapsing …

Line Lists For The A2Π-X 2Σ+ (Red) And B2Σ+-X 2Σ+ (Violet) Systems Of Cn, 13c14n, And 12c15n, And Application To Astronomicalspectra, Christopher Sneden, Sara Lucatello, Ram S. Ram, James S. A. Brooke, Peter Bernath

Chemistry & Biochemistry Faculty Publications

New red and violet system line lists for the CN isotopologues ¹³C¹⁴N and ¹²C¹⁵N have been generated. These new transition data are combined with those previously derived for ¹²C¹⁴N, and applied to the determination of CNO abundances in the solar photosphere and in four red giant stars: Arcturus, the bright, very low-metallicity star HD 122563, and the carbon-enhanced metal-poor stars HD 196944 and HD 201626. When both red and violet system lines are detectable in a star, their derived N abundances are in good agreement. The mean N abundances determined in …

Resonant Two-Photon Ionization Studies Of Non Covalent Interactions In Halo Aromatic Clusters And Spin-Orbit Coupling Modeling In Mono-Halocarbenes, Silver Nyambo

Dissertations (1934 -)

Non-covalent interactions in halobenzenes (PhX) (X=F, Cl, Br) and phenylamine (C₆ H₅ NH₂ ) have been studied here using resonance two-photon ionization (R2PI) spectroscopy combined with a linear TOF-mass spectrometer. Their interaction with polar molecules in form of ammonia (NH ₃ ) and trifluorohalomethanes (CF₃ X) has also been studied. DFT and TD-DFT calculations using M06-2X functionals were carried out on different cluster conformations to compliment experimental results. A general trend of broadness in homogenous dimers (PhX)₂ , has been attributed to mainly the presence of multiple cluster isomers and Frank-Condon activity in the low …