Materials Chemistry Commons^™

Organometallic Materials: Ferroceno[C]Thiophenes And 1,2-Bisthienylmetallocenes, Surya R. Banks

Theses and Dissertations--Chemistry

Development of synthetic routes toward two general organometallic frameworks was undertaken. The first project involved synthetic attempts of substituted and unsubstituted ferroceno[c]thiophene while the second one was the synthesis of 1,2-dithienylmetallocenes. The long-term goal of this work is to lay the foundations for study of electronic, electrochromic, redox, and optical properties of thiophene-based materials integrated with organometallic systems such as ferrocene, ruthenocene and cymantrene. The synthetic pathway for the target molecule in the first project involved converting 1,2-bis(hydroxymethyl)ferrocene to 1,2-bis(thiouroniummethyl)ferrocene with thiourea under acidic conditions. Refluxing the salt in base followed by acidification resulted in 1,2-bis(mercaptomethyl)ferrocene, which is …

Understanding Electrical Conduction In Lithium Ion Batteries Through Multi-Scale Modeling, Jie Pan

Theses and Dissertations--Chemical and Materials Engineering

Silicon (Si) has been considered as a promising negative electrode material for lithium ion batteries (LIBs) because of its high theoretical capacity, low discharge voltage, and low cost. However, the utilization of Si electrode has been hampered by problems such as slow ionic transport, large stress/strain generation, and unstable solid electrolyte interphase (SEI). These problems severely influence the performance and cycle life of Si electrodes. In general, ionic conduction determines the rate performance of the electrode, while electron leakage through the SEI causes electrolyte decomposition and, thus, causes capacity loss. The goal of this thesis research is to design Si …

Using Conventional And In Situ Transmission Electron Microscopy Techniques To Understand Nanoscale Crystallography, Bethany M. Hudak

Theses and Dissertations--Chemistry

Transmission electron microscopy (TEM) is a powerful tool for studying solidstate crystalline systems. With the advances in aberration correction, monochromation, and in situ capabilities, these microscopes are now more useful for addressing fundamental materials chemistry problems than ever before. This dissertation will illustrate the ways in which I have been using high-resolution imaging and in situ heating in the TEM during my Ph.D. research to investigate unique solid state chemistry questions.

This dissertation will focus on four unique crystal systems: thermoelectric skutterudite crystals, vapor-liquid-solid (VLS) grown nanowires, and hafnium dioxide nanorods. Although these systems are very different from one another, …

Artscience, Dustin Swiers

All Graduate Theses, Dissertations, and Other Capstone Projects

My thesis show opened on Friday, March 11, 2016 at the 410 project's art gallery, located in downtown Mankato.

The artwork consisted of sculptures displayed on pedestals, hanging on the walls, sitting on specifically constructed arrangements, and hanging from the ceiling. The materials I used to create these sculptures have a dramatically contrasting appearance, but have one universal similarity. At some point most of the materials used were liquid or fluid. I used metals, ceramics, hand blown glass, plastics, and wax. I like to work with these materials in that fluid state because of the added flexibility and forgiveness they …

Fabrication Of Multifunctional Nanostructured Porous Materials, Ahmed A. Farghaly

Theses and Dissertations

Nanostructured porous materials generally, and nanoporous noble metals specifically, have received considerable attention due to their superior chemical and physical properties over nanoparticles and bulk counterparts. This dissertation work aims to develop well-established strategies for the preparation of multifunctional nanostructured porous materials based on the combination of inorganic-chemistry, organic-chemistry and electrochemistry. The preparation strategies involved one or more of the following processes: sol-gel synthesis, co-electrodeposition, metal ions reduction, electropolymerization and dealloying or chemical etching. The study did not stop at the preparation limits but extended to investigate the reaction mechanism behind the formation of these multifunctional nanoporous structures in order …

Systematic Postsynthetic Modification Of Nanoporous Organic Frameworks And Their Performance Evaluation For Selective Co2 Capture, Timur Islamoglu

Theses and Dissertations

Porous organic polymers (POPs) with high physicochemical stability have attracted significant attention from the scientific community as promising platforms for small gas separation adsorbents. Although POPs have amorphous morphology in general, with the help of organic chemistry toolbox, ultrahigh surface area materials can be synthesized. In particular, nitrogen-rich POPs have been studied intensively due to their enhanced framework-CO₂ interactions. Postsynthetic modification (PSM) of POPs has been instrumental for incorporating different functional groups into the pores of POPs which would increase the CO₂ capture properties. We have shown that functionalizing the surface of POPs with nitro and amine groups …

Laser Vaporization Controlled Condensation And Laser Irradiation In Solution For The Synthesis Of Supported Nanoparticle Catalysts, Vitaly Kisurin Mr.

Theses and Dissertations

Solid catalyst supports of SiOx-RGO (Reduced Graphene Oxide) and UiO-67 (Universitet i Oslo) have been successfully synthesized and were loaded with palladium nanoparticles to test for a series of heterogeneous reactions. The SiOx/RGO catalysts were synthesized through laser ablation of silicon and graphite oxide micron powder and UiO-67 metal-organic framework (MOF) was synthesized through mixing of precursors with DMF/HCl solution and washing the resultant powder from impurities. The SiOx/RGO supports were later impregnated with palladium precursors which were then subject to Microwave Irradiation (MWI). The UiO-67 framework was impregnated with palladium precursors and was irradiated with pulsed Nd:YAG 532 nm …

Dynamic Atomistic Study Of Tunnel Functions In Nanostructured Transitional Metal Oxides, Yifei Yuan

Dissertations, Master's Theses and Master's Reports

Alpha (α-) MnO₂ is a well know transitional metal oxide possessing one dimensional 2×2 (4.6 × 4.6 Ų) tunnels for accommodation of various ions. Such a characteristic tunneled structure has enabled the wide applications of α-MnO₂ in the fields of ion exchange, molecular sieves, biosensor, catalysis and energy storage. This PhD dissertation focuses on the dynamic study of ion transport functionality of α-MnO₂ at atomic level using an aberration corrected scanning transmission electron microscopy equipped with a special holder with a scanning tunneling microscopy probe.

The wide application of in situ TEM studying the dynamic …

Special Issue: Electrochemistry Of Carbon Materials, Wei Chen

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 …

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 …

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 …

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 °C and …

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 …

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 ℃. 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 ofClO₄^- 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; when …

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 MnO₂composite 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^-1were obtained with the contents of MnO₂being 70, 60 and 70% in …

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 …

Applying Bayesian Machine Learning Methods To Theoretical Surface Science, Shane Carr

McKelvey School of Engineering Graduate Student Theses & Dissertations

Machine learning is a rapidly evolving field in computer science with increasingly many applications to other domains. In this thesis, I present a Bayesian machine learning approach to solving a problem in theoretical surface science: calculating the preferred active site on a catalyst surface for a given adsorbate molecule. I formulate the problem as a low-dimensional objective function. I show how the objective function can be approximated into a certain confidence interval using just one iteration of the self-consistent field (SCF) loop in density functional theory (DFT). I then use Bayesian optimization to perform a global search for the solution. …

Uses Of Diaryliodonium Salts And Methods For Their Synthesis, Jordan M. Veness

Department of Chemistry: Dissertations, Theses, and Student Research

Diaryliodonium salts have been studied continuously since the first report of their synthesis in 1894. Diaryliodonium salts are I(III) derivatives that are air- and moisturestable. The reactivity of these compounds resembles the organometallic chemistry of heavy transition metal ions such as Pb(IV), Hg(II), Th(III), and Pd(II). A significant advantage of diaryliodonium salts is that they can carry undergo many of the aryl functionalization reactions of heavy metal organometallic complexes, yet they have little to no toxicity and they are relatively inexpensive to prepare. The DiMagno laboratory uses diaryliodonium salts as precursors in the final synthetic step of radiopharmaceuticals; given that …

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 …

The Unique Electrochemical Reactivity Of Small Metal Nanoparticles., Rafael A. Masitas

Electronic Theses and Dissertations

This dissertation describes the factors controlling metal nanoparticle (NP) oxidation, using Au oxidation in Br- and Ag oxidation in acid as model systems. We found that the oxidation potential depends on size, surface charge, and electrode material. Size has a dramatic effect, shifting about 200 mV from > 200 nm diameter down to 4 nm diameter. The shift is more dramatic below 4 nm. 2.3 nm average diameter Au NPs oxidized in the 300-500 mV range and 1.5 nm average diameter Au NPs displayed several sharp peaks from 200 mV to as low as -200 mV. These smallest Au NPs show …

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 …

Sulfonated-Graphene/Nafion Composite Membrane For All Vanadium Redox Flow Batteries, Da-Wei Yang, Yan-Qing Dong, Jing-Min Fan, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

Nafion membrane has been widely used in fuel cells due to its good proton conductivity, chemical and mechanical stabilities. However, the well-developed water channels in Nafion membrane have restricted its application in all vanadium redox flow batteries owing to the high permeation of vanadium ions and the cost. In this work, the water adsorption rate, resistivity and transference number of vanadium ions of sulfonated-graphene/Nafion composite membrane were investigated and compared with those of Nafion membrane in an effort to overcome the abovementioned drawbacks. It was found that the area resistivity and permeation rate of sulfonated-graphene/Nafion composite membrane were significantly reduced …

Application Of Pd/Graphene Modified Electrode In The Detection Of 4-Chlorophenol, Peng Shi, Bo-Xuan Wang, Quan-Lin Song, Hui Wang, Xin Liu, Zhao-Yong Bian

Journal of Electrochemistry

The Pd/graphene composites were synthesized by a modified Hummers method and NaBH4 reduction process, and then were characterized using XRD, SEM, XPS, and TEM. The Pd/graphene modified glassy carbon electrode (Pd/graphene/GCE) was prepared based on this method. Cyclic voltammetry was used to study the optimum operation conditions for the 4-chlorophenol detection. It was shown that the surface of the graphene was smooth and Pd nanoparticles were uniformly dispersed on graphene. The average particle size was calculated to be 6.5 ± 0.05 nm. These nanoparticles exhibited high catalytic activity and sensitivity toward chlorophenols. PBS with a concentration of 0.1 mol·L^{-1 …}

Latest Progresses In Vanadium Flow Battery Technologies And Applications, Xiao-Li Wang, Yu Zhang, Hua-Min Zhang

Journal of Electrochemistry

With virtues of high safety, long cycle life, friend environment and state of charge easy monitoring, vanadium flow battery has become an effective technique for large scale energy storage. United States, Japan, Europe and other developed countries are actively promoting the developments of vanadium flow battery technology and related equipments. In this paper, the performance of containerized vanadium flow battery, which was newly developed by Rongke Power (RKP) and Dalian Institute of Chemical Physics, was introduced. The operation data of 5 MW/10 MWh vanadium flow battery energy storage station was displayed. Finally, it is pointed out that reducing the cost, …

Short Review On Electrochemical Energy Storage, Hong Li, Ying-Chun Lyu

Journal of Electrochemistry

Energy storage is a critical supporting technology in many fields such as energy, information, transportation, and healthcare, aerospace, advanced manufacture, advanced equipment, national security. Electrochemical energy storage technique has been widely applied and is developing continuously. In this article, the energy storage mechanism, technical indicators and technology ready level in electrochemical energy storage are summarized. Mainly based on lithium ion batteries, untraditional electrochemical issues in electrochemical energy storage devices are described from the perspective of fundamental science. These issues deal mainly with thermodynamics, kinetics, size effect, asymmetric system, asymmetric reaction path, surface phenomenon, hybrid ion transportation, and solid state battery. …

Research Progress Of Secondary Sodium-Air Batteries, San-Pei Zhang, Zhao-Yin Wen, Jun Jin, Xiang-Wei Wu, Ying-Ying Hu, Mei-Fen Wu

Journal of Electrochemistry

Rechargeable sodium-air batteries have been the focus in the fields of batteries and energy storage recently, owing to their high specific energy density (1600 Wh·kg^-1), an equilibrium discharge potential of 2.3 V and earth-abundant sodium element However, research on sodium-air cells is still in an infant age and presents many scientific issues. Based on recently reported work and our own experience on sodium-based batteries, this review summarizes the research progress related to the critical scientific is sues of secondary sodium-air batteries and the application prospect of sodium-air battery.