Materials Chemistry Commons^™

To Bend Or Not To Bend – Are Heteroatom Interactions Within Conjugated Molecules Effective In Dictating Conformation And Planarity?, Gary Conboy, Howard J. Spencer, Enrico Angioni, Alexander L. Kanibolotsky, Neil J. Findlay, Simon J. Coles, Claire Wilson, Mateusz B. Pitak, Chad Risko, Veaceslav Coropceanu, Jean-Luc Brédas, Peter J. Skabara

Chemistry Faculty Publications

We consider the roles of heteroatoms (mainly nitrogen, the halogens and the chalcogens) in dictating the conformation of linear conjugated molecules and polymers through non-covalent intramolecular interactions. Whilst hydrogen bonding is a competitive and sometimes more influential interaction, we provide unambiguous evidence that heteroatoms are able to determine the conformation of such materials with reasonable predictability.

Photocatalytic Properties Of G-C3n4–Tio2 Heterojunctions Under Uv And Visible Light Conditions, Rachel Fagan, Declan Mccormack, Steven J. Hinder, Suresh Pillai

Articles

Graphitic carbon nitride (g-C3N4) and titanium dioxide (TiO2) were chosen as a model system to investigate photocatalytic abilities of heterojunction system under UV and visible light conditions. The use of g-C3N4 has been shown to be effective in the reduction in recombination through the interaction between the two interfaces of TiO2 andg-C3N4. A simple method of preparing g-C3N4 through the pyrolysis of melamine was employed, which was then added to undoped TiO2 material to form the g-C3N4–TiO2 system. These materials were then fully characterized by X-ray diffraction (XRD), Brunauer Emmett Teller (BET), and various spectroscopic techniques including Raman, X-ray photoelectron …

Optimizing Chemical & Rheological Properties Of Rejuvenated Bitumen, Dominic Nguyen, Hamzeh Haghshenas Fatmehsari, Santosh Kommidi, Yong-Rak Kim

Department of Civil and Environmental Engineering: Dissertations, Theses, and Student Research

Bitumen has long been a material used in the construction of roadways, yet new pavement only consists of low fractions of recycled materials due to poor compatibility of aged bitumen and new materials. Thus, rejuvenators, chemical additives, have been used in an attempt to re-balance the chemical composition and restore the physical properties of aged bitumen back to its virgin state. A fundamental understanding of how one particular rejuvenator, soybean oil, revitalizes bitumen was investigated using a multi-scale approach.

Fourier-transform infrared spectroscopy (FTIR) was used to determine the changes in chemical properties of pure and rejuvenated virgin and aged samples. …

Biodegradable Copolymers Made With Magnesium Complexes, Reile M. Slattery, Joseph M. Fritsch

Seaver College Research And Scholarly Achievement Symposium

In this study, a bis-ligated magnesium complex was used to initiate the ring opening copolymerization of L-lactide (L-LA) and ϵ-caprolatone (ϵCL) and the isolated polymeric materials were characterized with NMR spectroscopy. First, the simultaneous feeding of both monomers resulted in the synthesis of homopolymer poly-lactic acid (PLA). Polymerization experiments with sequential addition of L-LA and ϵCL yielded surprising results. The ring opening polymerization of ϵCL yielded poly-caprolactone (PCL) which with the addition of L-LA yielded a di-block copolymer of PCL and PLA. The presence of the two homopolymer blocks in the copolymer was identified with ¹³C NMR where …

Synthesis And Characterization Of Organic-Inorganic Hybrid Materials For Thermoelectric Devices, Paige M. Huzyak

Masters Theses & Specialist Projects

The development of organic-inorganic hybrid materials is of great interest in thermoelectrics for its potential to combine the desirable characteristics of both classes of materials. Thermoelectric materials must combine low thermal conductivity with high electrical conductivity, but in most materials, thermal and electrical conductivity are closely related and positively correlated. By combining the low thermal conductivity, flexibility, facile processing, and low cost of organic components with the high electrical conductivity and stability of inorganic components, materials with beneficial thermoelectric properties may be realized.

Here, we describe the synthesis and characterization of anthracene-containing organic-inorganic hybrid materials for thermoelectric purposes. Specifically, POSS-ANT …

Colloidal Self-Assembly Of Multi-Fluorescent Silsesquioxane Microparticles, Niharika Neerudu Sreeramulu

Masters Theses & Specialist Projects

Self-assembly of colloidal microparticles is one of the strategies for making characteristic patterns. These versatile self-assemblies provide a route to elevate the efficiency of an electronic device. Silsesquioxane particles with various functionalities were synthesized by a modified Stöber condensation method. This thesis describes the synthesis of benzylchloride silsesquioxanes, benzylchloride-amine silsesquioxanes and amine-functionalized silsesquioxane particles with multi-fluorescent tags. The size and morphology of the particles were controlled by varying the concentration of base and anhydrous ethanol (solvent). The size distribution of particles was controlled by adjusting the molar ratios of organotrialkoxy silane, base, and ethanol concentrations. Through selective post-functionalization with fused …

Visible-Light-Responsible Co-Catalysts Enhanced By Graphene For Solar Energy Harvesting, Chen Ying

Masters Theses & Specialist Projects

This study focuses on the visible light response of hetero-structures of TiO2-graphene- MoS2 for solar energy harvestings. The commercial P25 TiO2 nano-particles, and selfprepared layered reduced graphene oxides (RG) and MoS2 were assembled for the targeted hetero-structure materials as visible-light responsible solar harvesting cocatalysts. The hydrothermal method was applied for nano-material synthesis, the reduction of graphene oxides, and bonding formation. Multiple characterization methods (SEM-TEM, XRD, XPS, UV-VIS, PL, FT-IR, TGA) have been applied to understand the electron-hole pair separation and recombination, and performance tuning in their visible-light photo-catalysis rhodamine B (Rh.B) degradations process

Compared to TiO2, an obvious red shift …

Enhancing The Photovoltaic Efficiency Of A Bulk Heterojunction Organic Solar Cell, Swapnil Ashok Sahare

Masters Theses & Specialist Projects

Active layer morphology of polymer-based solar cells plays an important role in improving power conversion efficiency (PCE). In this thesis, the focus is to improve the device efficiency of polymer-based solar cells. In the first objective, active layer morphology of polymer-solar cells was optimized though a novel solvent annealing technique. The second objective was to explore the possibility of replacing the highly sensitive aluminum cathode layer with a low-cost and stable alternative, copper metal. Large scale manufacturing of these solar cells is also explored using roll-to-roll printing techniques.

Poly (3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl (PCBM) were used as the …

Application Of Electrospray Ionization Mass Spectrometry For Ionic Liquids And Their Biodegradation Products, Sepideh Rahbarirad

Masters Theses

Ionic liquids (ILs) are organic salts with unique physico-chemical properties and are used as green alternatives to volatile organic solvents. ESI-MS is a sensitive technique to detect these stable, permanent ions. My research focused on (1) Identification of biodegradation products of ionic liquids and (2) Multiplexed tandem MS by modulation of ionization efficiency.

Studies, have demonstrated that ILs are toxic to the environment, which makes their biodegradability an important consideration. In this work, metabolites generated during the biodegradation of 1-butyl-3-methylimidazolium chloride (BMIM), a degradation resistant and commonly used ionic liquid, are identified using high performance liquid chromatography-mass spectrometry (LC-MS).

Multiplexed …

Characteristic Length Scales Of The Secondary Relaxations In Glass-Forming Glycerol, Sudipta Gupta, Eugene Mamontov, Niina Jalarvo, Laura Stingaciu, Michael Ohl

Faculty Publications

We investigate the secondary relaxations and their link to the main structural relaxation in glass-forming liquids using glycerol as a model system. We analyze the incoherent neutron scattering signal dependence on the scattering momentum transfer, Q , in order to obtain the characteristic length scale for different secondary relaxations. Such a capability of neutron scattering makes it somewhat unique and highly complementary to the traditional techniques of glass physics, such as light scattering and broadband dielectric spectroscopy, which provide information on the time scale, but not the length scales, of relaxation processes. The choice of suitable neutron scattering techniques depends …

An Effective Method For The Preparation Of High Temperature Stable Anatase Tio2 Photocatalysts, Rachel Fagan, Declan Mccormack, Suresh Pillai, Damian Synnott

Articles

An efficient, rapid and straightforward method for the preparation of nitrogen and fluorine (N, F) codoped high temperature stable anatase using a microwave pre-treatment is reported. Using a single source, ammonium fluoride (NH₄F) for both nitrogen and fluorine, effective doping of the precursor titanium isopropoxide (TTIP) was possible. These samples were characterised for their structural and optical properties using X-ray diffraction (XRD), Fourier transform IR (FTIR), Raman spectroscopy and UV-vis spectroscopy. In terms of the anatase to rutile transition enhancement using a novel microwave assisted technique, the sample prepared in a composition of 1:8 TiO₂: NH …

High Temperature Electrochemical Engineering And Clean Energy Systems, Brenda L. Garcia-Diaz, Luke Olson, Michael Martinez-Rodriguez, Roderick Fuentes, Hector Colon-Mercado, Josh Gray

Journal of the South Carolina Academy of Science

Global power demand is projected to more than double by 2050 and meeting this increased power demand will require maintaining or increasing power output from all existing energy sources while adding a large amount of new capacity. The power sources that have the greatest opportunity to fulfill this demand gap over this time period are clean energy sources including solar and nuclear power. One of the areas of expertise that SRNL has been applying to help with a variety of clean energy technologies is in high temperature electrochemistry. Savannah River National Laboratory (SRNL) in collaboration with industrial and university partners …

Toward High Performance Nanocarbon Fibers, Michaela R. Pfau

Master's Theses

High performance carbon fibers (CFs) have been a commercially available since their commercial boom in the 1970s, and are generally produced via carbonization of poly (acrylonitrile) (PAN). More recently, carbon nanomaterials like graphene and carbon nanotubes (CNTs) have been discovered and have shown excellent mechanical, thermal, and electrical properties due to their sp² carbon repeating structure. Graphene and CNTs can both be organized into macroscopic fibers using a number of different techniques, resulting in fibers with promising mechanical performance that can be readily multifunctionalized. In some cases, the two materials have been combined, and the resulting hybrid fibers have …

Electrochemical H2O2 Sensor Based On The Co-Immobilization Of Phosphmolybdic Acid And Graphene On Pedot Film Electrode With Nafion, Hao-Xian Zhou, Jun-Ming Zhang, Zhi-Yu Qu, Pan-Yu Zhang, You-Jun Fan

Journal of Electrochemistry

With a glassy carbon electrode (GCE) as the substrate, the poly(3,4-ethylenedioxythiophene) (PEDOT) film electrode was prepared through the electrochemical polymerization method, then a novel non-enzymatic electrochemical H₂O₂ sensor was fabricated by co-immobilizing phosphomolybdic acid and graphene with Nafion on the PEDOT/GCE electrode. The modified electrodes were characterized by scanning electron microscopy (SEM), while the responsive properties of the sensor to H₂O₂ were investigated by cyclic voltammetry and chronoamperometry. The results demonstrated that, under the optimized conditions, the sensor exhibited good electrocatalytic performance for H₂O₂ reduction. The current response of the sensor …

Improving The Electrochemical Properties Of Polyaniline By Doping With Silver Ions, Hui Xu, Jin-Juan Pu, Yong Chen, Jian Liu

Journal of Electrochemistry

Polyaniline (PANI) is an attractive candidate among the various conductive polymers based on its unique doping/de-doping behavior, intrinsic electrical conductivity, facile synthesis, and environmental stability. However, the poor conductivity and cycle stability in an acid medium have restricted its applications. Our work aims at solving the above problems effectively by doping silver ions into PANI. The PANI and PANI doped with silver ions (PANI/Ag⁺) were synthesized by a facile interfacial polymerization process, which used aniline as a starting material in toluene in contact with an aqueous solution of silver nitrate varied from 0.04 mol•L^-1 to 0.20 mol⋅L …

The Study On Comparison Of Electrochemical Performance In Microbial Fuel Cell With Glucose And Sodium Acetate Acting As Substrates, Lei Fan, Yu Zhao, Ting Li, Qin-Bo Yuan, En-Zhi Wang, Xiao-Bin Wang, Jun-Wen Wang

Journal of Electrochemistry

By inoculating aerobic sludge and anaerobic sludge from the sewage treatment plant, two sets of dual-chamber microbial fuel cells (MFCs) were built with either glucose or sodium acetate acting as a substrate. Accordingly, the electrochemical performances of MFCs were explored with the concentration of the substrates being 0.0335 mol⋅L^-1. The results of the comparative study in glucose system and sodium acetate system showed that the impedance values of anodic half cell were 222 Ω for glucose and 213.67 Ω for sodium acetate, implying no significant effect on the internal resistance in battery with the different substrates. The exchange …

Electrochemical Syntheses Of Graphene And Its Composites, Bo Zhao, Li Jiang, Ming-Hui Yuen, Xian-Zhu Fu, Rong Sun, Ching-Ping Wong

Journal of Electrochemistry

Graphene is a kind of ideal two-dimensional flat carbon nanomaterials which have unique chemical and physical properties. The attractive potential applications must be based on the high quality mass production of graphene. However, it remains a huge challenge. An electrochemical approach is a fast, environmental friendly and easy-operating method. single- or multi-layered graphene flakes can easily be produced in short periods of time. In this review, the structure, properties and preparation methods of graphene are first introduced. Accordingly, the electrochemical approaches used for the productions of graphene flakes, graphene/inorganic nanocomposites, graphene/polymer composites and graphene analogues are highlighted. Finally, challenges and …

Synthesis Of Fe, N-Doped Graphene/Carbon Black Composite With High Catalytic Activity For Oxygen Reduction Reaction, Chi Chen, Zhi-You Zhou, Xin-Sheng Zhang, Shi-Gang Sun

Journal of Electrochemistry

Oxygen reduction reaction (ORR) is a bottleneck for improving the efficiency of proton-exchange membrane fuel cells as a cathode reaction due to its sluggish kinetics. The exploitation of low cost and high performance non-precious metal catalysts such as Fe/N/C based materials toward ORR has attracted extensive attentions. In this work, the Fe, N-doped graphene nanosheets/carbon black composite was prepared by hydrothermal polymerization and followed by a twice-heat-treatment procedure using 2-aminoimidazole as an N precursor, FeCl₃ as an Fe precursor and KJ600 carbon black as a support. The TEM images revealed that the graphene nanosheets were separated by carbon black …

Adsorption Behavior Of Rhodamine 6g On Silver Surfaces Studied By Electrochemical Surface-Enhanced Raman Spectroscopy, Chan-Juan Chen, Cheng Zong, Guo-Kun Liu, Bin Ren

Journal of Electrochemistry

Rhodamine 6G (R6G) is one of the most common probe molecules employed in single molecule surface-enhanced Raman spectroscopy (SM-SERS). The study in adsorption behavior of R6G will help understand the interactions between R6G and surface. In this paper, we used electrochemical surface-enhanced Raman spectroscopy (SERS) to study the potential-dependent adsorption behavior of R6G on silver electrodes. Our results show that when the potential moved negatively, the orientation of R6G on silver surface changed from vertical to inclined adsorption. This result indicates that the abnormal SM-SERS spectra of R6G observed in the former SM-SERS studies from other research groups are due …

Effect Of Flame Retardant On Electrochemical Performances Of Lithium Ion Battery With Lini0.4Co0.2Mn0.4O2 As A Positive Electrode Material, Yan-Zhuo Lv, Yong-Xian Ge, Zhen-Bo Wang, Ke Ke

Journal of Electrochemistry

The effect of flame retardant on the electrochemical performances of lithium ion battery by using LiNi_0.4Co_0.2Mn_0.4O₂ as a positive material was studied by measuring the first charge-discharge, cycling, circulation, and AC impedance curves. The experimental data indicated that the discharge capacity of the battery decreased, while the charge transfer resistance and the lithium ion diffusion resistance increased with the increases in the concentrations of the flame retardant in the electrolyte solutions. Furthermore, the stability of the battery at small discharge ratios and the cyclic performance were also improved by the addition of flame …

Electricity Generation Of Microbial Fuel Cell Using Stainless Steel Mesh As Cathode, Hong-Yan Dai, Hui-Min Yang, Xian Liu, Xuan Jian, Xiu-Li Song, Zhen-Hai Liang

Journal of Electrochemistry

In the present work, a dual-chamber microbial fuel cell (MFC) was constructed with aeration tank sludge as an inoculum, carbon felt as an anode and stainless steel mesh without any modification as a cathode. The influence of the cathode size was investigated in terms of voltage output, power generation and electrochemical impedance. The long-term durability of the stainless steel mesh cathode was also evaluated. Results showed that the stainless steel mesh exhibited satisfactory long-term durability as MFC cathode. When the stainless steel mesh size was 2 × 2 cm², the maximum output voltage, power density, the internal resistance …

Electrochemical Detection Of Hydrogen Peroxide At Aunps Modified Electrode Using P-Hydroxyphenylboronic Acid As A Precursor, Chun-Yan Wang, Xiao-Qiu Liu, Ying-Xin Qi

Journal of Electrochemistry

We developed a new method for electrochemical detection of hydrogen peroxide (H₂O₂) based on boronate oxidation of p-hydroxyphenylboronic acid. This method using p-aminophenol which is produced from the reaction of H₂O₂ and p-aminophenylboronic acid as a well electrochemical probe, combined with a gold nanoparticles (AuNPs) modified electrode for an indirect detection of H₂O₂. Because of the large surface area and enhanced electrocatalytic behavior by the AuNPs modified electrode, the detection sensitivity was improved. The method could detect H₂O₂ in the concentration range of 1 ~ 100 …

Electrochemical Determination Of Hg(Ii) At Gold Nanoparticles@Carbonaceous Microspheres Modified Electrode, Tian-Yu Qiu, Ming-Chun Wang, Xian-Feng Du, Tian-Jia Jiang, Xing-Jiu Huang

Journal of Electrochemistry

The gold nanoparticles@carbonaceous microspheres (Au@CMSs) and  Au@CMSs modified glassy carbon electrode (GCE) were prepared. The Au@CMSs modified  GCE was further examined for possible sensitive detection of mercury ions (Hg(II)) in an aqueous solution by square wave anodic stripping voltammetry (SWASV). The excellent performance was found in the stripping analysis of Hg(II) in 0.1 mol•L^-1 NaAc-HAc(pH=5.0) with a sensitivity of 25.863 A•(mol•L^-1)^-1 and a detection limit of 3.69×10^-8 mol•L^-1 based on the 3σ method.

Fabrication Of Riboflavin Electrochemical Sensor Based On Au Nanoparticles/Polydopamine/Carbon Nanotubes Modified Glassy Carbon Electrode, Hua-Ping Peng, Mei-Ling Yu, Xin Liu, Pan Liu, Wei Chen, Ai-Lin Liu, Xin-Hua Lin

Journal of Electrochemistry

A novel electrochemical platform for the high sensitivity detection of riboflavin was constructed by Au nanoparticles/polydopamine/carbon nanotubes (Au-PDA-MWCNTs) nanocomposite modified glassy carbon electrode. The Au-PDA-MWCNTs nanocomposite was synthesized by in situ reduction method. The characteristics of the as-prepared Au-PDA-MWCNTs nanocomposite modified electrodes were investigated by using UV-Vis spectroscopy, scanning electron microscopy (SEM) and electrochemical methods. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to study the electrochemical behavior of riboflavin (RF) at Au-PDA-MWCNTs nanocomposite modified electrodes. The results demonstrated that the present electrochemical sensor exhibited a wide linear range from 5×10^-9 mol•L^-1to 1×10^-5 mol•L …

Sol-Gel Synthesis Of Intermediate Composition, Nanocrystalline Olivine, Corbin Cannon

Theses and Dissertations

Olivine is one of the most important rock forming minerals in our solar system. It forms in a solid-solution series between a magnesium-rich end member, forsterite (Mg2SiO4), and an iron-rich end member, fayalite (Fe2SiO4). For this reason, it is commonly used for experiments regarding the formation and evolution of planetary objects. Scarcity of iron-rich phases and the desirability of pure materials for research force the use of synthetic minerals for these experiments. Previous forsterite and fayalite synthesis methods were reexamined and combined to develop a new synthesis method that can produce a specific composition of olivine within the solid solution …

Design Rules For The Nucleation, Growth, And Encapsulation Of Gold Nanoparticles With Applications To Cancer Imaging, Matthew A. Wall

Dissertations, Theses, and Capstone Projects

Surface-enhanced Raman scattering (SERS) nanoparticles are exciting candidates for high-precision cancer imaging due to their highly specific spectral signature (Raman “fingerprint”) and propensity for passive targeting of cancerous tissues. However, the signal intensity of currently available SERS nanoparticles is insufficient for cancer imaging via passive targeting in most solid tumors. The overarching aim of this body of work is to develop a new generation of SERS nanoparticles with sufficiently low limits of detection to enable robust detection of various solid tumors in vivo.

The complexity of SERS nanoparticles requires significant advances to the theoretical and experimental understanding of metal …

Ultrafast Spectroscopy And Energy Transfer In An Organic/Inorganic Composite Of Zinc Oxide And Graphite Oxide, Jeff A. Secor

Dissertations, Theses, and Capstone Projects

The energy transfers and nature of defect levels of an organic/inorganic composite of Zinc Oxide and Graphite are studied with multidimensional spectroscopy. The edge and surface states of each composite are uncovered using excitation emission experiments showing which defect states are mediating the energy transfer from the metal oxide to the graphite oxide. Multidimensional time resolved spectroscopy further describes the effect of the carbon phase on the energy transfer pathways in the material.

Probing The Transport Properties Of Chemically-Doped Single-Walled Carbon Nantotube Polymer Composites, Tammy Pheuphong, Tamara El-Hayek, Jeffrey Blackburn, Andrew Ferguson

STAR Program Research Presentations

Thermoelectric (TE) materials are used to convert waste heat into electrical power. Semiconducting single-walled carbon nanotubes (s-SWCNT) have great potential to be used in thermoelectric devices, either on their own or in composites with conducting polymers. Certain polymers can selectively extract s-SWCNT from raw carbon nanotube soot (containing impurities such as metallic SWCNT, amorphous carbon, metal catalysts particles), but most of these polymers (e.g. polyfluorenes) are electrical insulators, rendering them inefficient in TE nanocomposites. On the other hand, conducting polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), have been used in efficient TE nanocomposites, but have never been rationally designed with …

Effect Of Spalled Particles Thermal Degradation On A Hypersonic Flow Field Environment, Raghava S. C. Davuluri, Huaibao Zhang, Alexandre Martin

Mechanical Engineering Faculty Publications

Two-way coupling is performed between a spallation code and a hypersonic aerothermodynamics CFD solver to evaluate the effect of spalled particles on the flow field. Time accurate solutions are computed in argon and air flow fields. A single particle simulations and multiple particles simulations are performed and studied. The results show that the carbon vapor released by spalled particles tend to change the composition of the flow field, particularly the upstream region of the shock.

Effects Of Surface Coatings On Crystalization Of Calcium Sulfate, Shawn Pj Kirby, Josiah Reams, Kamran Ghiassi, Jeffrey Alston

STAR Program Research Presentations

Deposits from hard water can be problematic as they can form scaling on boilers and cooling towers. Scaling can reduce thermal efficiency. Coatings can be used to prevent mineral fouling by changing the surface energy. Some deposits have inverse solubility; such as calcium sulfate. This means that as temperature rises, they become less soluble and can crystallize out of solution. Calcium sulfate is often found in hard water. Crystalization tests were done to determine how coatings such as various POSS (Polyhedral oligomeric silsesquioxane) compounds acted as nucleating surfaces for calcium sulfate. POSS compounds were tested in particular because they …