Physical Sciences and Mathematics Commons^™

Fast And Accurate Evaluation Of Lifepo4 Cathode Materials By Single Particle Microelectrode, Fu-Qing Wang, Yi-Min Wei, Yu-Zhuan Su, Bing-Wei Mao, Kai Wu, Feng-Gang Zhao, Chun-Lei Chen, Xing-Lu Li, Jin Chong

Journal of Electrochemistry

Single particle microelectrode enables to evaluate the electrochemical responses for single particle of active material without binder and conductive agent. Thus, the influences of additive and electrode structure on the electrochemical performance of active materials can be ignored. Furthermore, this technology can be used to evaluate active materials fast. Therefore, single particle microelectrode allows fast and accurate determination of the intrinsic performance of active material. Cyclic voltammogram (CV), cycle performance, and kinetic behavior of LiFePO4 cathode materials were evaluated by the single particle microelectrode. CV curve of LiFePO4 particle with a pair of oxidation and reduction peaks was obtained with …

Electrodeposition Of Lanthanum In Deep Eutectic Solvents, Li Wang, You-Jun Fan, Lu Wei, Hai-Xia Liu, Shi-Gang Sun

Journal of Electrochemistry

With the choline chloride/urea deep eutectic solvents (DESs) as the medium, the olive-like lanthanum particles with uniform shape and size were successfully prepared through a potentiostatic deposition method. The prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS). At the same time, the effect of deposition potential, temperature and time on the size and morphology of samples was investigated. The results demonstrated that the optimum conditions for the preparation of olive-like lanthanum particles were as follows: deposition potential of -1.7 V, temperature of 80 ^oC …

Effect Of Mno2 Content On Electrochemical Capacitance Behavior Of Active Carbon Electrode, Kun Shen, Xian-Liang Zhou, Qi-Shun Duan

Journal of Electrochemistry

In this work, the manganese dioxide (MnO₂) materials were prepared by solution approach at low temperature, thermal decomposition and electrochemical deposition. The actived carbon (AC) and MnO₂ composite electrodes were used for aqueous supercapacitors. The morphologies and structures of the prepared materials were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the electrochemical behaviors were tested by cyclic voltammetry (CV) and galanostatic charge-discharge tests. Electrochemical test data show that the maximum specific capacitances of 151, 172 and 141 F•g^-1 were obtained with the contents of MnO₂ being 70, 60 and 70% in …

Special Issue: Electrochemistry Of Carbon Materials, Chen Wei

Journal of Electrochemistry

Carbon materials are traditional electrode materials due to their excellent electrical conductivities, high electrochemical stabilities and wide potential windows. Glassy carbon, graphite, various activated charcoals, carbon fibers etc. have been widely used in electrochemistry serving as electrode substrates or supports. In addition to their applications in basic electrochemistry, carbon materials have also played important roles in electrochemical energy storage and conversion. In recent years, various types of carbon structures, from zero-dimensional carbon nanodots, one-dimensional nanotubes, two-dimensional graphene to three-dimensional porous carbons, have attracted increasing attention in electrochemical field. It has been found that carbon materials have outstanding properties as advanced …

Colloidal Ionic Supercapacitors, Kun-Feng Chen, Dong-Feng Xue

Journal of Electrochemistry

Supercapacitors have high power density and long cycle life compared with battery systems, but they still suffer from low energy density at the same time. In order to increase the energy density of supercapacitors, we have developed a new type of pseudocapacitor, called colloidal ion supercapacitor, which can directly use commercial metal salts as electrode materials and form electroactive matter by in-situ electrochemical reactions without the need of additional materials synthesis processes. Colloidal ion supercapacitor can fully utilize the redox reaction of metal cations with multiple oxidation states, which can completely release the stored electrical energy of multiple-valence cations, leading …

Electrochemical Properties Of Graphene/Porous Nano-Silicon Anode, Chun-Li Li, Guang Yang, Ping Zhang, Zhi-Yu Jiang

Journal of Electrochemistry

Porous nano-silicon (Si) was prepared by acid etching Al-Si alloy powder method, and used as an active material for fabricating a grapene/porous nano-Si electrode. The results of SEM and TEM measurements indicated that porous nano-Si powder was uniformly mixed with graphene by emulsification dispersion-ultrasonication method. As an anode for lithium ion battery, the graphene/porous nano-Si electrode presented relatively high performance in 1 mol•L^-1 LiPF6/EC:DMC = 1:1(by volume) + 1.5% (by mass) VC solution. At the charge and discharge current densities of 0.5A•g^-1, the first discharge capacity was 1768.6 mAh•g^-1 with coulombic efficiency of 68.3%. The discharge …

Applications Of Carbon Materials In Electrochemical Energy Storage, Ji Liang, Lei Wen, Hui-Ming Cheng, Feng Li

Journal of Electrochemistry

An electrode material for electrochemical energy storage is one of the key components for high performance devices. In a variety of electrochemical energy storage systems, carbon materials, especially the lately emerged carbon nanomaterials including the carbon nanotube and graphene, have been playing a very important role and brought new vitality to the development and demonstration of the broad application prospects. In this review, we summarize the applications of various carbon materials in the typical electrochemical energy storage devices, namely lithium/sodium ion batteries, supercapacitors, and lithium-sulfur batteries, as well as flexible electrochemical energy storage and electrochemical catalysis. A perspective of novel …

Progress Of Self-Supported Supercapacitor Electrode Materials Based On Carbon Substrates, Shui-Jian He, Wei Chen

Journal of Electrochemistry

Self-supported electrode materials have been widely used in supercapacitors. Carbon materials are promising substrates in building self-supported electrode materials attributed to their diverse structures, rich resource, relatively low cost and high stability. Combined with our own research in this field, we summarize here the recent progress on the synthesis of self-supported electrode materials and their supercapacitance properties. The overall synthetic strategy could be divided into two categories: “top-down” and “bottom-up”. We hope this review is helpful for the development and application of renewable sources in self-supported electrode materials.

Synthesis Of Porous Carbon Nanosheets And Its Application In Sodium-Ion Battery, Jing-Fei Zhang, Jing Lu, Xiao-Yu Yang, Yun-Di Huang, Lin Xu, Dong-Mei Sun, Ya-Wen Tang

Journal of Electrochemistry

Owning to sodium’s high abundance, relatively low cost, similar chemical properties to Li and very suitable redox potential of E0(Na+/Na) = -2.71 V versus SHE which is only 0.3 V above that of lithium, rechargeable sodium ion battery hold much promise as potential alternatives to current lithium ion batteries for energy storage applications. Carbon material is regarded as the most promising anode candidate for sodium ion battery. Particularly, carbon nanosheet with porous structure and high conductivity is expected to have improved sodium ion storage properties. In this paper, we present a two-step pyrolysis-based method for facile synthesis of porous carbon …

Carbon Aerogel/Nickel Foam As Electrode For High-Performance Supercapacitor, Zhong Wu, Xin-Bo Zhang

Journal of Electrochemistry

Herein, a facile synthesis has been explored to prepare carbon aerogel/Ni foam. Graphene oxide, resorcinol and formaldehyde serve as precursors and polymerize in-situ on the Ni foam after hydrothermal synthesis at 85 oC. After lyophilization treatment, the carbon aerogel/Ni foam with porous structure can be obtained. Electrochemical investigations reveal that the carbon aerogel/Ni foam exhibits superior performances in both aqueous and organic electrolytes involving high specific capacitance and long-term cycling stability. The excellent properties can be ascribed to the unique formation and porous structure, which allows more effective transportations of electron and electrolyte ion.

Intercalation Of Clo4- Into Hopg Investigated By Ec-Stm, Xiao-Yan Hu, Alice Aliwowe, Jia-Wei Yan, Bing-Wei Mao

Journal of Electrochemistry

The electrochemical intercalation and surface morphology of highly oriented pyrolytic graphite (HOPG) electrode in 2 mol•L^-1 HClO₄ were studied by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). Based on the step-height changes observed before and after the intercalation, the effects of different step sites on intercalation are compared. The feasibility, reversibility and speed of intercalation are discussed. The intercalation of ClO₄^- into HOPG can be divided into three types depending on the number of graphite layers at the step site: When the layers of graphite are more than three, the intercalation becomes feasible; …

Photooxidation Reactions Of Small-Chain Methyl Esters, Aerosol Photoelectron Spectroscopy, And The Photodissociation Of Ethylenediamine, Giel Muller

Master's Theses

Research conducted at the University of San Francisco is presented within this masters thesis, including the Cl-initiated photooxidation reactions of methyl propanoate, methyl butanoate, and methyl valerate (pentanoate), the aerosol photoelectron spectroscopy of isoprene and gamma-valerolactone, and the TPEPICO investigation of ethylenediamine. Experiments were conducted at the Lawrence Berkeley National Lab Advanced Light Source (ALS), the National Synchrotron Radiation Research Center in Hsinchu City (NSRRC), and the University of Stockton in California, respectively.

Vibrational Imaging At The Nanoscale: Surpassing The Diffraction Limit Using Tip-Enhanced Raman Spectroscopy, Farshid Pashaee

Electronic Thesis and Dissertation Repository

A deep understanding of the chemical composition of surfaces, interfaces or nanoscale structure with a high spatial resolution is an important goal in nanoscience and nanotechnology. Structural information can be collected using a variety of high spatial resolution techniques such as atomic force microscopy (AFM), scanning tunneling microscopy (STM), scanning electron microscopy (SEM), or transmission electron microscopy (TEM). Nevertheless, these methods do not offer molecular information such as vibrational spectroscopy techniques that allow one to collect molecular or lattice vibrations yielding to a precise picture of the molecular interactions in bulk materials as well as in surfaces and interfaces. Unfortunately …

Understanding The Influence Of Non-Covalent Interactions And Nanoparticle Geometries In Carbon Based Polymer Nanocomposites, Bradley Carroll Miller

Doctoral Dissertations

Low-loading polymer nanocomposites (PNC) are an area of great interest in polymer science. As nanoparticles (NP) are typically expensive in comparison to matrix materials; the low loading regime makes the most efficient use of materials, and represents the optimum for realizing cost effective, high-performance PNCs. However, formulating effective low-loading composites is not without challenges. In addition to the typical requirement of good dispersion for efficient translation of NP properties to the bulk, low-loading composites can sometimes exhibit anomalous (non-classical) dynamics, and unpredictable properties. It is within this context that this thesis aims to examine the effects of NP geometry and …

Bombardment Simulations And Intercalation Studies Of Carbon Materials, Charles Lowe

All Dissertations

Molecular bombardment experiments have led to the possibility of altering materials with properties not normally associated with those materials. Molecular bombardment leads to defect formation in the material, potentially creating a pore, depending on the material and bombarding molecule. Carbon allotropes, specifically graphite and graphene, make excellent candidates for molecular bombardment experimentation. Depending on the bombarding molecule and the kinetic energy associated with that molecule, the defects induced will be sufficient to create a pore in the graphene. The AIREBO potential is used to simulate a graphene bilayer being bombarded with a single Ar atom, or a fullerene molecule, to …

Influence Of Shelling Temperature And Time On The Optical And Structural Properties Of Cuins2/Zns Quantum Dots, Colette Robinson

Graduate Theses and Dissertations

CIS/ZnS core/shell QDs are an important class of nanomaterials for optoelectronic, photovoltaic and photoluminescence applications. They consist of lower toxicity materials than the prototypical II-VI Cd-based QDs and show long fluorescence lifetimes, which generates prospective in biological imaging applications. It is vital to develop reproducible synthetic methods for this new class of nanomaterials in order to maintain small sizes with high QYs. CIS core QDs have been shelled with ZnS at various temperatures from 90-210°C for reaction times ranging from 20-140 minutes to examine the role of thermodynamics and kinetics on the shell growth. Using HR-TEM and ICP-MS, it was …

Porphyrin As A Spectroscopic Probe Of Net Electric Fields In Heme Proteins, Hannah Elizabeth Wagie

Theses and Dissertations

Heme proteins have diverse functions as well as varied structures but share the same organic, conjugated cofactor. Similarly varied approaches have been taken to deduce how heme can take on different roles based on its protein environment. A unique approach is to view the protein matrix as a constellation of point charges that generates a defined, reproducible, net internal electric field that has influence over the electronic properties of the heme cofactor. This work considers how porphyrins, the basic chromophore building block of heme, can be used as a native spectroscopic sensor of internal electric field at the active site …

Photochemistry Of A Series Of Weakly Coupled Dinuclear Ruthenium(Ii) Complexes, Latisha Michelle Puckett

Graduate Theses and Dissertations

An improved synthetic method was developed for symmetric ruthenium(II) polypyridine complexes with the form L2Ru(diphen)RuL2. The scope of the reaction was investigated in regards to the ligands, bridging ligands, and starting materials. Several ligands were successful in the synthesis, including 2,2’-bipyridine (bpy), 4,4’-dimethyl-2,2’-dipyridyl (dmb), 1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (dpphen), and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen). Ligands that did not react to form symmetric dimeric complexes were 2,2’-bipyrazine, bpz, and 2,2’-bipyrimidine, bpm.

Dpp, 2,3-bis(2-pyridyl)-pyrazine, effectively replaced diphen as the bridging ligand to produce (phen)2Ru(dpp)Ru(phen)24+. However, replacing the [Ru(CO)2Cl2]n with Ru(DMSO)4Cl2 did not prove successful. The newly developed synthesis was also applied to the synthesis of …

Validation Of The Global Distribution Of Co2 Volume Mixing Ratio In The Mesosphere And Lower Thermosphere From Saber, L. Rezac, Y. Jian, J. Yue, J. M. Russell Iii, A. Kutepov, R. Garcia, K. Walker, P. Bernath

Chemistry & Biochemistry Faculty Publications

The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on board the Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite has been measuring the limb radiance in 10 broadband infrared channels over the altitude range from ~ 400 km to the Earth's surface since 2002. The kinetic temperatures and CO₂ volume mixing ratios (VMRs) in the mesosphere and lower thermosphere have been simultaneously retrieved using SABER limb radiances at 15 and 4.3 μm under nonlocal thermodynamic equilibrium (non-LTE) conditions. This paper presents results of a validation study of the SABER CO₂ VMRs obtained with a two-channel, self-consistent …

Hybrid Sol–Gel Glasses With Glass-Transition Temperatures Below Room Temperature, Andrei Jitianu, Guadalupe Gonzalez, Lisa C. Klein

Publications and Research

Melting gels are hybrid gels that have the ability to soften and flow at around 100 ° C for some combinations of mono- and di-substituted alkoxysiloxanes, where substitutions are either all aromatic or all aliphatic. In this study, melting gels were prepared using phenyltriethoxysilane (PhTES) and dimethyldiethoxysilane (DMDES), meaning both an aromatic and aliphatic substitution. Differential scanning calorimetry was performed to identify glass-transition temperatures, and thermal gravimetric analysis coupled with differential thermal analysis (TGA-DTA) was performed to measure weight loss. The glass-transition temperatures ( T g ) ranged from – 61 ° C to + 5.6 ° C, which are …

From Dye Sensitized Solar Cells To Organic Field Effect Transistors: A Computational Investigation Into The Structural And Electronic Properties Of Novel Phthalocyanines, Patrick J. Dwyer

Seton Hall University Dissertations and Theses (ETDs)

Phthalocyanines (Pc) have gained intense research attention in many diverse application areas due to their highly tunable electronic and structural properties through modification of the molecular periphery and metal center. Throughout this work a series of novel perfluoro-isopropyl substituted MPc have been investigated through theoretical methods. First, the synthetic mechanisms of these Pcs will be explored to gain insight into the experimentally observed Pc product distribution. By examining the electronic structure and formation energies of the various Pc precursors, we explain the product distribution as well as propose the formation of additional Pcs, which were not currently believed to form. …

Hydrogen Bond-Mediated Structural Order In Hydroxylated Bis-Mpa Dendritic Polymers: Experimental And Molecular Dynamics Simulation Study, Maliha N. Syed

Dissertations

Dendritic architectures are echoed throughout nature. While the significance of these pervasive patterns is not entirely clear, connections between their structures and physical properties are fascinating to contemplate. Particular interest has been paid to a family of synthetically manufactured and commercially available dendritic polymers based on 2,2-bis(hydroxymethyl) propionic acid (bis-MPA) as a monomer. Composed of two hydroxyls and a carboxyl group, bis-MPA based structures hydrogen bond (H-bond) profusely. Given the high concentration and unique spatial orientation of end-groups, as well as the multitude of carbonyl, ester, and ether interior H-bond acceptors, a set of distinct H-bond organizations may be observed …

Development Of A Two-Fluid Drag Law For Clustered Particles Using Direct Numerical Simulation And Validation Through Experiments, Ahmadreza Abbasi Baharanchi

FIU Electronic Theses and Dissertations

This dissertation focused on development and utilization of numerical and experimental approaches to improve the CFD modeling of fluidization flow of cohesive micron size particles. The specific objectives of this research were: (1) Developing a cluster prediction mechanism applicable to Two-Fluid Modeling (TFM) of gas-solid systems (2) Developing more accurate drag models for Two-Fluid Modeling (TFM) of gas-solid fluidization flow with the presence of cohesive interparticle forces (3) using the developed model to explore the improvement of accuracy of TFM in simulation of fluidization flow of cohesive powders (4) Understanding the causes and influential factor which led to improvements and …

Contact Angles And Contact Lines Around Particles At Isotropic And Anisotropic Liquid Interfaces, Nesrin Senbil

Doctoral Dissertations

Liquid interfaces, capillarity and self-assembly of particles at interfaces are important in nature and technology. When a particle is adsorbed to a liquid interface, the contact line of the particle with the liquid interface and the associated contact angle are the crucial parameters that drive assembly of the particles. We looked at how the shape of the liquid interface and the shape of the particle affect the contact angle and the shape of the contact line. We used millimeter-sized PDMS-coated glass spheres and measured the contact angles at isotropic (planar) and anisotropic interfaces (saddle and cylindrical in shape). Anisotropy of …

Impact Of Fabrication Parameters On The Internal Structure Of Poly(3-Hexylthiophene) Nanoparticles, Dana Desiree Algaier

Doctoral Dissertations

Morphological control of organic functional materials is central to understanding and improving upon current technologies. The ability to create hierarchical assemblies with purposeful design from nano to meso scale has remained largely unattainable. This body of work aims to provide a foundation for creating nanoscale domains of poly (3-hexylthiophene) (P3HT) that can be used as building blocks to larger scale assemblies. We present a method for the fabrication of P3HT nanoparticles on the ability to vary the particle size and more importantly, the internal structure. We have identified the oil phase and surfactant as parameters able to influence the nature …

Quantum Calculations Of Aldol Condensation In Acidic Zeolites, Angela N. Migues

Doctoral Dissertations

We have used Density Functional Theory to model the mixed aldol condensation reaction catalyzed by acidic zeolites. We have studied the convergence of barriers for the keto-enol tautomerization of acetone in cluster models of HZSM-5 and HY ranging in size from 3-37T. A key finding was that activation barriers for keto-enol tautomerization of acetone in both zeolites (~20 kcal/mol) are significantly higher than those for the condensation reaction between the acetone enol and formaldehyde in 11T cluster models of HZSM-5 and HY. Moreover we found that three zeolite clusters of HZSM-5, similarly sized but including different structural features of the …

Protein Charge Anisotropy Mediated Self-Association And Phase Separation, Daniel P. Seeman

Doctoral Dissertations

Protein charge anisotropy results from the asymmetric distribution of charged residues on the exterior of a particular protein. Interactions between proteins and other macromolecules can be described in terms of attractive electrostatics; since electrostatic free energies, at optimal I, are on the order of kT, it is unlikely that such associations would result in desolvation, thus it is reasonable to consider such intermolecular attractions as being mediated by hydrated protein surfaces. Such interactions can be broken down in terms of a single protein interacting with a range of “binding partners”, including (1) protein-protein interactions, (2) protein-polymer interactions, and …

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Vladimir Benin

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified for the rotamer interconversion: TSsyn and TSanti, …

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Vladimir Benin

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.

The Tetrafluoroborate Salt Of 4-Methoxybenzyl N-2-(Dimethylamino)Ethyl-N-Nitrosocarbamate: Synthesis, Crystal Structure And Dft Calculations, Helene Hedian, Vladimir Benin

Vladimir Benin

The tetrafluoroborate salt of 4-methoxybenzyl N-2-(dimethylamino)ethyl-N-nitrosocarbamate was prepared in two steps, via the corresponding carbamate. Its crystal structure is monoclinic, space group P21/c. The unit cell dimensions are: a = 19.499(8) Å, b = 5.877(3) Å, c = 15.757(7) Å, α = 90°, β = 110.019(7)°, γ = 90°, V = 1696.5(12) Å3, Z = 4. The structure exhibits an unexpected, pseudo-gauche conformation with respect to the C2–C3 bond, due to a stabilizing hydrogen bond between the carbonyl oxygen (O1) and the hydrogen atom at the trialkylammonium center (H3n), with a distance between them of 2.37 Å. DFT calculations on …