Chemistry Commons^™

Functional Sulfate Electrolytes Enable The Enhanced Cycling Stability Of Nati2(Po4)3/C Anode Material For Aqueous Sodium-Ion Batteries, Shu-Jin Li, Zhi-Kang Cao, Wen-Kai Wang, Xiao-Han Zhang, Xing-De Xiang

Journal of Electrochemistry

Aqueous sodium-ion batteries show promising application in fields of large-scale storage of intermittent renewable energies owing to the earth-abundant sodium resources and incombustible aqueous electrolytes. Primary factors determining whether they can be commercially utilized are low cost and long lifetime. Among current electrode materials, NASICON-type NaTi₂(PO₄)₃ arouses wide interests as an anode material for aqueous sodium-ion batteries as it offers a high specific capacity, fast Na-transport ability and reasonable working potential, however, suffering from insufficient cycling performance caused by severe dissolution of active materials in traditional aqueous electrolytes. In this work, a functional sulfate electrolyte …

Influence Of Heat Treatment Time On Cathode Material Cr8O21 For Lithium Battery, Jiu-Kang Teng, Qing-Jie Wang, Liang Zhang, Hong-Mei Zhang, Xiao-Tao Chen, Peng Zhang, Jin-Bao Zhao

Journal of Electrochemistry

Chromium oxide (Cr₈O₂₁) cathode material for lithium batteries was synthesized by thermal decomposition of chromium trioxide (CrO₃) at high temperature. The electrochemical properties of chromium oxide depended on the time and temperature during the heat treatment. Pure phase chromium oxide was prepared, and the effects of heat treatment time on the structures and electrochemical properties of Cr₈O₂₁ were systematically studied. The first discharge mechanism of chromium oxide in lithium batteries was explored, and the results were similar to that in lithium-sulfur batteries. The crystal phases and electrochemical properties of the prepared …

Effect Of Glycol Based Coolant Pollution On Pem Fuel Cells Stack And Recovery Measures, Cong-Yi Zhu, Xiao-Hui Li, Quan-Quan Gan

Journal of Electrochemistry

As the heat conduction medium of fuel cell cooling system, coolant is very important for the thermal management of fuel cell stack. In practical application, coolant leakage into the stack often occurs. Due to the randomness of fault location of components, the location of coolant leakage is uncertain, which may occur on the cathode side or anode side of some or all single cells. The main effects of coolant pollution on fuel cell stack are as follows: the output of open circuit voltage decreases sharply, the consistency of single cells voltage decreases and so on, which seriously affects the normal …

Formation And Morphological Evolution Of Nanoporous Anodized Iron Oxide Films, Jin-Wei Cao, Nan Gao, Zhao-Qing Gao, Chen Wang, Sheng-Yan Shang, Yun-Peng Wang, Hai-Tao Ma

Journal of Electrochemistry

The preparation of iron oxide films with nanoporous structure by anodization has attracted much attention for its potential applications. However, the formation mechanism of porous structure during anodization is still unclear. In this paper, the composition of anodic current during the formation of nanoporous anodized iron oxide film was analyzed in combination with the current density-potential response (I-V curve) and the derivation of Faraday’s law. The results showed that the anodic current consisted of an ionic current (leading to the migration of ions to form oxide) and an electronic current (leading to the oxygen evolution), and the …

Copper Nanoparticles In-Situ Anchored On Nitrogen-Doped Carbon For High-Efficiency Oxygen Reduction Reaction Electrocatalyst, Hui-Fang Yuan, Yue Zhang, Xing-Wu Zhai, Li-Bing Hu, Gui-Xian Ge, Gang Wang, Feng Yu, Bin Dai

Journal of Electrochemistry

Compared with noble metal platinum (Pt)-based catalysts, inexpensive non-noble metal electrocatalysts have attracted extensive attention for oxygen reduction reaction (ORR). Herein, chitosan as a kind of biomass resource rich in nitrogen and carbon was used to prepare nitrogen-doped carbon (N-C) and N-C in-situ anchored by copper nanoparticles (Cu/N-C). The as-obtained N-C and Cu/N-C nanoparticles were successfully used as non-noble eletrocatalysts tested for ORR. Compared with the N-C, the Cu/N-C showed the high surface area of 607.3 m ²·g^-1 with the mean pore size of 2.5 nm and the pore volume of 0.40 cm³·g^{-1 …}

A Nanoscale Shape-Discovery Framework Supporting Systematic Investigations Of Shape-Dependent Biological Effects And Immunomodulation, Wei Zhang, Hender Lopez, Luca Boselli, Paolo Bigini, André Perez-Potti, Zengchun Xie, Valentina Castagnola, Qi Cai, Camila P. Silveira, Joao M. De Araujo, Laura Talamini, Nicolò Panini, Giuseppe Ristagno, Martina B. Violatto, Stéphanie Devineau, Marco P. Monopoli, Mario Salmona, Valeria A. Giannone, Sandra Lara, Kenneth A. Dawson, Yan Yan

Articles

Since it is now possible to make, in a controlled fashion, an almost unlimited variety of nanostructure shapes, it is of increasing interest to understand the forms of biological control that nanoscale shape allows. However, a priori rational investigation of such a vast universe of shapes appears to present intractable fundamental and practical challenges. This has limited the useful systematic investigation of their biological interactions and the development of innovative nanoscale shape-dependent therapies. Here, we introduce a concept of biologically relevant inductive nanoscale shape discovery and evaluation that is ideally suited to, and will ultimately become, a vehicle for machine …

Splashing Of Large Helium Nanodroplets Upon Surface Collisions, Paul Martini, Simon Albertini, Felix Laimer, Miriam Meyer, Michael Gatchell, Olof E. Echt, Fabio Zappa, Paul Scheier

Faculty Publications

In the present work we observe that helium nanodroplets colliding with surfaces can exhibit splashing in a way that is analogous to classical liquids. We use transmission electron microscopy and mass spectrometry to demonstrate that neutral and ionic dopants embedded in the droplets are efficiently backscattered in such events. High abundances of weakly bound He-tagged ions of both polarities indicate a gentle extraction mechanism of these ions from the droplets upon collision with a solid surface. This backscattering process is observed for dopant particles with masses up to 400 kilodaltons, indicating an unexpected mechanism that effectively lowers deposition rates of …

Discovery Of An Olivine-Type Lithium Manganese Thiophosphate, Limnps4,: Via A Building Block Approach, Srikanth Balijapelly, Kartik Ghosh, Aleksandr V. Chernatynskiy, Amitava Choudhury

Physics Faculty Research & Creative Works

An olivine-type orthothiophospate LiMnPS4 has been synthesized for the first time through a building block approach by reacting preformed ternary lithium thiophospate with MnCl2. Diffuse reflectance measurements show an optical band gap of 2.36 eV, which is further confirmed by DFT calculations. Irreversible weak ferromagnetic ordering and metamagnetism are verified through preliminary magnetic measurements.

Functional Structure Of Biomacromolecules In Plant Biomass Using Solid-State Nmr And Dynamic Nuclear Polarization, Alex Kipchirchir Kirui

LSU Doctoral Dissertations

This dissertation summarizes the recent findings on complex biomacromolecules in cell wall of plants and fungi which perform important roles in cell recognition, structural build up, and energy storage. Because of the technical difficulty in characterizing these biomacromolecules, which are often polymorphic and disordered in structure, the functional structure of these biomacromolecules remains elusive. In this dissertation, I present two solid-state nuclear magnetic resonance (ssNMR) and dynamic nuclear polarization (DNP) studies of carbohydrate-rich biosystems: the energy-rich plant biomass and disease-relevant, pathogenic fungi.

First, we have investigated the secondary cell wall of plant biomass which is a carbohydrate-rich biosystem using solid …

Electrodeless Electrochemistry Enabled By Nonthermal Plasma, Harold Oldham

McKelvey School of Engineering Graduate Student Theses & Dissertations

The increasing availability and decreasing cost of electricity generated by renewable resources have motivated research into electrified chemical processing, whereby electrical energy is used to drive chemical transformations. Electricity-intensive processing techniques such as electrochemistry using solid electrodes has attracted attention in this context for the synthesis of organic compounds, such as high-value pharmaceuticals and renewable chemical production. Selective chemical transformations are achieved in conventional aqueous electrochemical systems by using external circuitry to bias solid electrodes, allowing for the preferential transfer of electrons between the electrode-liquid interface. Despite having the ability to promote controlled electrochemical reactions, configurations using solid electrodes are …

Seasonal Flammability Comparisons Of Native And Exotic Plants In The Post Oak Savannah, Blackland Prairie, And Pineywoods Ecoregions Of Texas, Michael Tiller

Electronic Theses and Dissertations

East Texas’ diverse landscape can present year-round wildfire seasons that can be influenced by seasonal and regional differences in climate and physiography. Greater insight into the fundamental thermal behavior of wildland fuels can aid in fire behavior prediction and development of fire-resistant plant lists. This study focused on estimating seasonal and regional flammability characteristics of five evergreen species: yaupon (Ilex vomitoria), Chinese privet (Ligustrum sinense), greenbrier (Smilax spp.), eastern red cedar (Juniperus virginiana), and escarpment live oak (Quercus fusiformis); and two deciduous species: Chinese tallow (Triadica sebifera) and southern …

Computational Investigations Of The Photochemical Properties Of B12-Dependent Systems: From Solution To Enzymes., Megan Toda Mackintosh

Electronic Theses and Dissertations

The photochemical properties of the B₁₂ family of molecules (cobalamins = Cbls) have been known for many years yet only until the 21^st century have applications for the light-sensitivity of Cbls come to the surface. Photolabile Cbls can be used for the delivery of therapeutics with spatial and temporal control, in the generation of hydroxyl radicals, and in nature, as demonstrated in the catalytic cycle of coenzyme B₁₂-dependent photoreceptors. This dissertation describes the use of computational methods to explore the photochemical properties of Cbl systems including antivitamins B₁₂, a thiolato-cobalamin, and the coenzyme B …

Computational Analysis Of The Spin Trapping Properties Of Lipoic Acid And Dihydrolipoic Acid, Matthew Bonfield

Electronic Theses and Dissertations

While the spin trapping properties of thiols have been investigated through EPR analysis and kinetics studies, few groups have studied these properties using strictly computational methods. In particular, α-lipoic acid (ALA) and its reduced form, dihydrolipoic acid (DHLA), one of the strongest endogenously produced antioxidants, show potential for being effective, naturally occurring spin traps for the trapping of reactive oxygen species. This research covers electronic structure calculations of ALA, DHLA, and their corresponding hydroxyl radical spin adducts, performed at the cc-pVDZ/B3LYP/DFT level of theory. The effects on DHLA introduced by other radicals such as ·OOH, ·OCH₃, …

Theoretical Investigation Of The Co-C Bond Activation In Methylcobalamin And Adenosylcobalamin-Dependent Systems: Mechanistic Insights., Arghya Pratim Ghosh

Electronic Theses and Dissertations

The vitamin B₁₂ derivates, otherwise known as cobalamin (Cbl), are ubiquitous organometallic cofactors. The biologically active forms of Cbl, such as methylcobalamin (MeCbl) and adenosylcobalamin (AdoCbl), act as cofactors in different physiological reactions for both prokaryotes and eukaryotes. A crucial aspect of the Cbl-mediated systems is the activation of the organometallic Co-C bond that plays a critical role in its catalytic activity. One of the most remarkable features of this Co-C bond is its unusual activation in AdoCbl-dependent enzymatic reactions, where a trillion-fold rate acceleration of the Co-C bond cleavage is observed inside the enzyme compared to the isolated …

Adsorption Of Helium On A Charged Propeller Molecule: Hexaphenylbenzene, Siegfried Kollotzek, Florent Calvo, Serge Krasnokutski, Fabio Zappa, Paul Scheier, Olof E. Echt

Faculty Publications

Physisorption on planar or curved graphitic surfaces or aromatic rings has been investigated by various research groups, but in these studies the substrate was usually strictly rigid. Here we report a combined experimental and theoretical study of helium adsorption on cationic hexaphenylbenzene (HPB), a propeller-shaped molecule. The orientation of its propeller blades is known to be sensitive to the environment, with substantial differences between the molecule in the gas phase and in the crystalline solid. Mass spectra of He_nHPB⁺, synthesized in helium nanodroplets, indicate enhanced stability for ions containing n = 2, 4, 14, 28, 42, …

The Profound Photophysical Effects Of Organic Chromophore Connectivity And Coupling, David J. Walwark Jr

Nanoscience and Microsystems ETDs

Through-bond and through-space interactions between chromophores are shown to have wide-ranging effects on photophysical outcomes upon light absorption in organic molecules. In collapsed poly(3-hexylthiophene), through-space coupling creates hybrid chromophores that act as energy sinks for nearby excitons and favorable sites for molecular oxygen to dock. Upon excitation with visible light the highly-coupled chromophores react with the docked oxygen and subsequently do not quench nearby excitons as efficiently. In tetramer arrays of perylene diimide chromophores the central moiety through-bond connectivity is synthesized in two variants which exhibit vastly different single-molecule blinking behavior and theoretically-predicted electronic transition character. In the more-connected tetramer …

Exploring The Geometric And Electronic Properties Of Palladium Doped Silicon Clusters, Madison Winkeler, Ciara N. Richardson

Scholars Week

Transition metal-doped silicon clusters have unique properties and have been studied as building blocks for nanomaterials and microelectronics. Here, the structure and properties of candidate palladium doped silicon clusters (SinPd2: n=1-17) were determined using global optimization techniques on a high performance computing cluster at the San Diego Supercomputing Center. Then geometric structures were further optimized utilizing the B3LYP method with 6-311+G(d) basis sets for silicon and lanl2dz pseudopotential for palladium, followed by the larger DSDPBEP86 method with 6-311+G(2d) basis sets for silicon and SDD pseudopotential for palladium, as implemented in the Gaussian 16 program package. The energetics for each cluster …

Single-Molecule Localization Microscopy Of 3d Orientation And Anisotropic Wobble Using A Polarized Vortex Point Spread Function, Tianben Ding, Matthew D. Lew

Electrical & Systems Engineering Publications and Presentations

Within condensed matter, single fluorophores are sensitive probes of their chemical environments, but it is difficult to use their limited photon budget to image precisely their positions, 3D orientations, and rotational diffusion simultaneously. We demonstrate the polarized vortex point spread function (PSF) for measuring these parameters, including characterizing the anisotropy of a molecule’s wobble, simultaneously from a single image. Even when imaging dim emitters (∼500 photons detected), the polarized vortex PSF can obtain 12 nm localization precision, 4°–8° orientation precision, and 26° wobble precision. We use the vortex PSF to measure the emission anisotropy of fluorescent beads, the wobble dynamics …

Non-Adiabatic Excited State Molecular Dynamics Using Ehrenfest And Modulated X-Ray Absorption In Titania, Alexander Matthew Meyer

LSU Doctoral Dissertations

This dissertation contains two separate sections aside from an introduction (Chapter 1): theory and methods (Chapter 2), time dependent density functional theory with Ehrenfest for excited state lifetimes in materials (Chapter 3), and simulated field modulated X-ray absorption in titania (Chapter 4).

Excited state lifetime in insulators and semiconductors can be difficult to compute using quantum chemistry due to their dense excited states. Non-radiative decay in these materials requires the use of non-adiabatic effects to dissipate energy through the means of electron-nuclear coupling such as coherent phonon generation. One method of approaching this challenge in these materials is using Ehrenfest …

Colloidal Nanomaterial Surface Chemistry And Characterization Studied By Linear And Nonlinear Spectroscopy, Asela Sampath Dikkumbura

LSU Doctoral Dissertations

Recent studies have demonstrated the use of nanomaterials such as metallic nanoparticles, liposomes, and polymer microparticles for biomedical applications, encompassing the field of nanomedicine. For developing novel core-shell metallic nanoparticles with controlled surface morphology, the in situ growth dynamics of colloidal silver-gold core-shell (Ag@Au CS) nanoparticles (NPs) in water are monitored in a stepwise synthesis approach using time-dependent second harmonic generation (SHG) and extinction spectroscopy. Transmission electron microscopy images show that the CS NP surface morphology becomes more smooth and uniform as the reaction proceeds, corresponding to lower, stable SHG signals and narrower plasmonic spectra that are compared to finite-difference …

Performance And Mechanism Of PtXCuY/C Electrocatalyst For Methanol Oxidation, Jia Tang, Xiao-Ming Zhang, Shan-Sheng Yu, Su-Li Wang, Gong-Quan Sun

Journal of Electrochemistry

Direct methanol fuel cell (DMFC), which directly converts the chemical energy of methanol fuel into electrical energy, has the advantages of high energy conversion efficiency, environmental friendliness, and abundance of fuel sources. DMFC is considered as the promising substitutes in the field of portable devices, military applications, and stationary power stations, while the broad application is severely hindered by the sluggish kinetic of methanol oxidation reaction (MOR) in the anode and the high cost of platinum (Pt)-based anodic electrocatalysts. Herein, a series of carbon supported Pt_xCu_y (Pt_xCu_y/C) binary metal electrocatalysts, featured with high …

Electrochemical Synthesis Of P-(Β-Hydroxyethyl Sulfone) Aniline, Hao Guo, Dong-Fang Niu, Shuo-Zhen Hu, Xin-Sheng Zhang

Journal of Electrochemistry

Para-ester is the most important intermediate for the preparation of ethylene sulfone type reactive dyes, which is usually used in the dyeing of cellulose fibers and synthetic fibers. P-(β-hydroxyethyl sulfone) aniline is an important intermediate for the synthesis of para-ester. In this paper, p-(β-hydroxyethyl sulfone) aniline was prepared by electrochemical method, having the advantages of simple process, mild reaction condition, less environmental pollution, easy reaction control and so on. It has strong development potential and industrial application prospect. The electrochemical reduction of p-nitrophenyl-β-hydroxyethyl sulfone on a lead plate electrode to prepare p-(β-hydroxyethyl …

Numerical Study On The Influences Of Flow Channel And Rib Width Ratio On The Performance Of Gas Diffusion Layer, Rong-Qiang Wei, Shi-An Li, Yi-Hui Liu, Zhi Yang, Qiu-Wan Shen, Guo-Gang Yang

Journal of Electrochemistry

Proton exchange membrane fuel cell (PEMFC) has the advantages of low noise, high power density, and zero emission. It is widely used in ships, automobiles, aviation and other fields. PEMFC is composed of bipolar plate (BP), gas diffusion layer (GDL), catalytic layer (CL) and proton exchange membrane (PEM). GDL has a supporting catalytic layer and proton exchange membrane, which provides gas diffusion for the reaction and a channel for the reaction to produce water, and transmits the anodic oxidation reaction. In the assembly of fuel cells, a certain assembly pressure is required to ensure air-tightness and effective conductivity. The assembly …

Mathematical Expression And Quantitative Analysis Of Impedance Spectrum On The Interface Of Glassy Carbon Electrode, Lei Cheng, Pu-Xuan Yan, You-Jun Fan, Hua-Hong Zou, Hong Liang

Journal of Electrochemistry

Glassy carbon electrode (GCE) is a common basic electrode for various electrochemical sensors, and the detection properties are determined by its interfacial characteristics. In this paper, we established an equivalent circuit including electrolyte resistance (R_el), charge transport resistance (R_ct), diffusion impedance (R_di, C_di), electrochemical (oxidation/reduction) reaction impedance (R_R, C_R), surface adsorption impedance (R_ads , C_ads), double-layer capacitance (C_DL), and derived the mathematical expression for the equivalent circuit. The R_el and C_DL are contributed by inactive …

Preparation Of Modified Titanium Based Pbo2 Electrode And Its Rapid Detection Of Cod, Qi Sun, Yan-He Han, Xiao-Lu Fu

Journal of Electrochemistry

In the traditional Ti/β-PbO₂ electrode, the crystal lattice difference between β-PbO₂ and Ti matrix is large, and the prepared electrode is easy to fall off and has a short service life. It needs to be modified in actual use. Based on the advantages of α-PbO₂ material and Ag material in terms of adhesion and conductivity, respectively, the above two materials are selected as the intermediate layer of Ti/β-PbO₂ electrode to improve electrode performance. In this paper, by preparing Ti/α/β-PbO₂ and Ti/Ag/β-PbO₂ electrodes …

Fundamentals Of Electrochemical Impedance Spectroscopy For Macrohomogeneous Porous Electrodes, Xiang Li, Qiu-An Huang, Wei-Heng Li, Yu-Xuan Bai, Jia Wang, Yang Liu, Yu-Feng Zhao, Juan Wang, Jiu-Jun Zhang

Journal of Electrochemistry

Electrochemical impedance spectroscopy (EIS) can be used to diagnose charge transfer reactions and mass transport in porous electrodes. The charge transfer reactions include interfacial charge accumulation and charge conduction as well as electrochemical reaction. In this paper, the complex phasor method is developed under the macrohomogeneous assumption to build an impedance model of porous electrodes for clarifying several vague expressions in the traditional approaches. The following researches are carried out: (1) Identifying characteristic parameters for the porous electrodes, including electrode electronic conductivity σ₁, electrolyte ionic conductivity σ₂, interface charge transfer conductivity g_ct, unit area …

Janus-Tinbco2 For Hydrogen Evolution Reaction With High Conductivity And Catalytic Activity, Li-Li Xu, Dong-Yan Ren, Xiao-Feng Zhao, Yong Yi

Journal of Electrochemistry

Exploring the potential hydrogen evolution reaction (HER) catalysts with the high activity and high conductivity has always been a hot spot in the research of renewable energy development. Ti₂C, as one of the 2D-MXene, has excellent properties relating to many active sites, mechanical stability, conductivity, etc., and has become a potential HER catalyst. However, the modification of the surface of Ti₂C by terminal O will reduce the conductivity, thereby limiting the transport of electrons between the valence band and the conduction band. In this study, an electric double layer Janus-TiNbCO₂ was constructed by Nb doping. …

Application Of Ti/Ruo2-Iro2-Sno2-Sb2O5 Anode In Rural Drinking Water Disinfection, Jing-Ru Guo, Xue-Jiao Zhang, Shuai Liao, Xue-Ming Chen

Journal of Electrochemistry

Sodium hypochlorite disinfection has many advantages, including reliable operation, low cost, easily available raw materials. It is, therefore, suitable for disinfection of drinking water in remote rural areas. The service life and chlorine evolution efficiency of the anode are the main factors restricting the performance of the sodium hypochlorite generator. The special conditions of frequent shutdown and low electrolyte concentration in the rural drinking water application also put forward high requirements on the performance of the anode. In this study, Ti/RuO₂-IrO₂-SnO₂-Sb₂O₅,a new-type and efficient chlorine evolution anode, was prepared by …

Study On Improving The Production Of Ammonium Persulfate By Ion Membrane Electrolysis, Yi-Hang Qu, Min Cui, Cong Zhang, Chong Li, Peng Li, Ju-Jie Ren

Journal of Electrochemistry

In china, the production of ammonium persulfate in factories mostly adopts the electrolysis method with simple process and high purity. However, there exists the problem of high energy consumption in the electrolysis process, which restricts the further development of ammonium persulfate in many fields. Aiming at this phenomenon, the equipment and technology to produce ammonium persulfate using electrolysis were designed and studied in order to reduce energy consumption. A new type of zero-pole distance and ion-exchange membrane industrial electrolytic cell was provided for the electrolysis production of ammonium persulfate. An ion-exchange membrane was used to separate the electrolytic cell into …

Effect Of Alkyl Chain Length Of Symmetrical Quaternary Ammonium Hydroxide On Oxalic Acid Electroreduction Reaction, Bo Huang, Xin-Sheng Zhang, Dong-Fang Niu, Shuo-Zhen Hu

Journal of Electrochemistry

Glyoxylic acid with the dual characteristics of acid and aldehyde is an important chemical raw material and organic synthesis intermediate, which is extensively used in the perfumery, pharmaceutical and fine chemical industries. A family of symmetric quaternary ammonium hydroxides (QAHs) with different alkyl chain lengths was used as the additives in generating glyoxylic acid from oxalic acid electroreduction reaction (OAER). The effects of alkyl chain length on OAER and the corresponding side reaction, i.e., hydrogen evolution reaction (HER), were investigated. Linear sweep voltammetric (LSV) results showed that the adsorption of the additives suppressed more on the HER than that on …