Chemistry Commons^™

Towards The Rational Design Of Organic Semiconductors Through Computational Approaches, Qianxiang Ai

Theses and Dissertations--Chemistry

Though organic semiconductors have illustrated potential as industry-relevant materials for electronics applications, there are few guidelines that can take one from molecular design to functional materials. This limitation is, in part, due to incomplete understanding as to how the atomic-scale construction of the π-conjugated molecules that comprise the organic semiconductors determines the nature and strength of both the noncovalent intramolecular interactions that govern molecular conformation and noncovalent intermolecular interactions that regulate the energetic preference for solid-state packing. Hence, there remain several fundamental questions that need to be resolved in order to design organic semiconductors from a priori knowledge, including: What …

Designing Metal-Halide Perovskites With Enhanced Optical Properties And Stability Using Surface Ligands, Md Aslam Uddin

Theses and Dissertations--Chemistry

Metal-halide perovskites (MHPs), with formula ABX₃ (A = methylammonium, formamidinium, or Cs⁺; B = Sn²⁺ or Pb²⁺; and X = Cl^-, Br^-, or I^-) are versatile and attractive materials because of their tunable optical and electronic properties. These optical and electronic properties include tunable direct band gaps, high absorption coefficients, low exciton binding energies, relatively high electron and hole mobilities, narrow emission line-widths, and high photoluminescence (PL) quantum yields (Φ_PL). Much of the initial excitement around organic metal-halide perovskites focused on their application in photovoltaics (PVs) …

Developing And Testing Redox Active Organic Molecules For Nonaqueous Redox Flow Battery Applications, Nuwan Harsha Attanayake

Theses and Dissertations--Chemistry

Non-emissive, sustainable energy sources such as solar, wind, and geothermal power have continued to provide an increasing amount of electricity to support electrical grids. Due to the intermittent nature of renewable energy sources like wind and solar, grid energy storage systems must adjust for variations in and mismatches between electricity production and consumption. Among the available energy storage technologies, redox flow batteries (RFBs) are expected to play a critical role in the grid energy storage due to their decoupled energy and power, long service life, and simple manufacturing. However, the worldwide market penetration of RFB systems is still limited due …

Identification Of Adsorbate Ft-Ir Bands Using In-Situ Techniques: Pd Speciation And Adsorption Chemistry Of Pd-Zeolites For Passive Nox Adsorption, Robert Bruce Pace Iii

Theses and Dissertations--Chemistry

To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NO_x) once the catalyst reaches operational temperature (~200 °C). NO_x emitted at lower catalyst temperatures now comprises most of the NO_x released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NO_x adsorbers present an appealing solution to the cold start problem, …

Cu(Ii) Phenanthroline-Phenazine Complexes Dysregulate Mitochondrial Function And Stimulate Apoptosis, Garret Rochford, Zara Molphy, Kevin Kavanagh, Malachy Mccann, Michael Devereux, Andrew Kellett, Orla L. Howe

Articles

Herein we report an in-depth study on the cytotoxic mechanism of action of four developmental cytotoxic copper(II) complexes: [Cu(phen)2]2+ (Cu-Phen); [Cu(DPQ)(Phen)]2+ (Cu-DPQ-Phen); [Cu(DPPZ)(Phen)]2+; and [Cu(DPPN)(Phen)]2+ (where Phen = 1,10-phenanthroline, DPQ = dipyrido[3,2-f:20,30-h]quinoxaline, DPPZ = dipyrido[3,2-a:20,30-c]phenazine, and DPPN = benzo[i]dipyrido[3,2-a:20,30-c]phenazine). This complex class is known for its DNA intercalative properties and recent evidence—derived from an in vivo proteomic study—supports the potential targeting of mitochondrial function. Therefore, we focused on mitochondrial-mediated apoptosis related to cytotoxic activity and the potential impact these agents have on mitochondrial function. The Cu(II) complexes demonstrated superior activity regardless of aromatic extension within the phenazine ligand to the …

Electrocatalytic Cathodes For Advanced Lithium–Sulfur Batteries, Ahmed Abdelkader

Theses and Dissertations

Energy demands are anticipated to increase in the next decades with the consumption of fossil fuels predicted to grow from the current levels. This will place an enormous burden on the non–renewable reserves of our energy sources and add to the preexisting environmental crisis with the emission of greenhouse gases like carbon dioxide (CO₂). Electrical energy storage (EES) is considered one of the most crucial needs of modern society to circumvent this crisis and potential applications include electric vehicles and devices, as well as storage systems for solar and wind sources.Lithium–ion batteries (LIBs) have proven to be …

Synthesis Of Supported Metal Nanoparticles On High Surface Area Supports For Application In Energy Conversion And Heterogeneous Catalysis, Nazgol Norouzi

Theses and Dissertations

Precise control of metal nanoparticles’ size, composition, and dispersity over high surface area supports are highly desirable to address current challenges in energy storage and conversion as well as catalytic processes involving precious metals. Therefore, developing viable synthetic routes that enable new catalytic systems derived from inexpensive transition metals or limited use of precious metals is vital for clean energy applications such as fuel cells and rechargeable batteries or affordable drugs in the pharmaceuticals arena. In addition to metal components of heterogeneous catalysts, the catalyst support is an integral part of catalyst design as it can impart both physical stability …

Structure, Morphology And Composition-Property Elucidation Of Ni–Mo And Ni−Mo−P Nanocrystals For Water Splitting Reactions And Group Iv Alloy And Silicate Nanocrystals For Visible To Near Ir Optoelectronics, Ebtesam Hassan Abuelenein Eladgham

Theses and Dissertations

Abstract

Structure, Morphology and Composition-Property Elucidation of Ni–Mo and Ni−Mo−P Nanocrystals for Water Splitting Reactions and Group IV Alloy and Silicate Nanocrystals for Visible to Near IR Optoelectronics

by

Ebtesam Hassan Abuelenein Eladgham

A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University.

Advisor: Indika U Arachchige

Associate Professor, Department of Chemistry

Nanomaterials have gained a great attention because of their unique physical properties with size intermediate between molecular materials and extended solids. They have a large surface to volume ratio and display size tunable physical properties that was not …

Metal-Oxide Nanostructures Fabricated From Reactive Laser Ablation In Liquid, Mallory G. John

Theses and Dissertations

The development of metal-oxide nanostructures is a growing area due to their applications in diverse fields spanning energy conversion and storage, chemical manufacturing, and en- vironmental technology. This interest in catalytically active nanomaterials has prompted the synthesis and investigation of highly functionalized nanoparticles (NPs), including core- shell, silicate-stabilized, and bi- and multi-metallic nanocomposites. While wet-chemical synthesis methods of metal-oxide nanostructures have led to several morphologies, compositions, and shapes, these syntheses often require high temperatures, toxic solvents or reducing agents, and long reaction times.

Laser synthesis and processing of colloids (LSPC) encompasses both ‘top down’ and ‘bottom up’ approaches to synthesize …

Synthesis Of Graphene Using Plasma Etching And Atmospheric Pressure Annealing: Process And Sensor Development, Andrew Robert Graves

Graduate Theses, Dissertations, and Problem Reports (ETD)

Having been theorized in 1947, it was not until 2004 that graphene was first isolated. In the years since its isolation, graphene has been the subject of intense, world-wide study due to its incredibly diverse array of useful properties. Even though many billions of dollars have been spent on its development, graphene has yet to break out of the laboratory and penetrate mainstream industrial applications markets. This is because graphene faces a ‘grand challenge.’ Simply put, there is currently no method of manufacturing high-quality graphene on the industrial scale. This grand challenge looms particularly large for electronic applications where the …

Morphology Controlled Preparations And Electrochemical Properties Of Znco2O4 Electrode Materials For Supercapacitors, Yue-Shen Zhou, Meng Li, Shuang Wu, Zhao-Lei Li, Yan-Min Gao

Journal of Electrochemistry

In this work, hydrothermal reaction and high temperature were used to grow ZnCo₂O₄ active materials on Ni foam. The crystal stuctures and surface morphlogies of four samples were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The electrochemical performances were characterized by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) testing and electrochemical impedance spectroscopy (EIS) on an electrochemical station. It can be seen that active materials tended to form denser stuctures with an increasing amount of NH₄F in the solution system and four different morphologies of ZnCo_{2 …}

Electrochemical Determination Of Trace Copper Ions In Drinking Water Source, Jing-Ji Peng, Hong Zheng, Yi-Song Zou, Guo-Kun Liu, Dong-Xing Yuan

Journal of Electrochemistry

Aiming at the on-site and quick safety evaluation of the dissolved trace copper ions (Cu²⁺) in drinking water source, an electrochemical detection platform was developed on the basis of the square wave anodic stripping voltammetry using the gold nanoparticles (Au NPs) modified glassy carbon electrode, where Au NPs were deposited via electrochemical cyclic voltammetry. The proposed method displayed the limit of detection as low as 1.3 μg·L^-1 in the linear range of 2 ~ 50 μg·L^-1. The proposed method was applied to the determination of Cu²⁺ in the midstream of Minjiang River, one of …

Electrochemical Behaviors Of Azopurine On Gold Electrodes, Ming-Xue Li, Hang Shi, Jia Liu, Meng Zhang, Jian-Zhang Zhou, De-Yin Wu, Zhong-Qun Tian

Journal of Electrochemistry

In this paper, we studied the electrochemical behaviors of azopurine on polished gold electrodes with cyclic voltammetry (CV). On the basis of analyzing scan rate and peak current, it was supposed that the redox process belonged to a reversible process controlled by adsorption in 0.2 mol·L^-1 PBS (pH = 4.0 ~ 10.0) solutions. The potentials of redox peaks moved more negatively with increasing pH value. This proved that the H⁺ proton has participcted in the electrochemical reaction. The further data analysis and the calculation of surface adsorption excess demonstrated that the reaction was a two-proton and two-electron process. …

Electrochemical Cycling Stability Of Polyaniline Films In Different Color Ranges, Kun Xu, Kai-Ling Zhou, Hao Wang, Jing-Bing Liu, Hui Yan

Journal of Electrochemistry

The electrochromic behaviors of polyaniline films were investigated by potential step and cyclic voltammetry coupled with UV viscosity photometer. The polyaniline films show colorful changes from pale yellow to green and then to blue. Electrochromic stability, electrochemical behavior, coloring performance, optical properties and surface formations of the produced films were studied in detail. The working electrode was the flexible PANI electrode, and the counter electrode and the reference electrode were a platinum sheet and Ag/AgCl, respectively. The in situ optical transmittance of the PANI film at 650 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (Shimadzu UV-3101PC) combining with a square …

Polyaniline Coated Hollow Sulfur Prepared Using Sublimate 2,4,6-Tri(Propan-2-Yl)-1,3,5-Trioxane As Template For Sulfur Electrode, Zhang-Feng Li, Xiao-Rui Wang, Wen-Sheng Tian, Jin-Ze Yang, Ping Zhang, Li-Ping Ma, Yang Chen, Xiao-Li Cui, Zhi-Yu Jiang

Journal of Electrochemistry

An advance method for preparing polyaniline-coated hollow sulfur material using sublimate material ADD(2,4,6-tri(propan-2-yl)-1,3,5-trioxane) as a template was developed for lithium-sulfur battery. At first, the smashed ADD particles were coated by a sulfur layer through the reaction of Na₂S₂O₃ with diluted HCl. Then polyaniline layer was coated again on the surface of sulfur layer through the reaction of aniline with (NH₄)₂S₂O₈. After being dried at 60 ^oC for 12 h, the ADD in such a composite evaporated totally, and resulted in the formation of polyaniline-coated hollow sulfur …

Study On Electro-Sorption Of Heavy Metals And Sulfamethoxazole On Activated Carbon Fibers, Wen-Jun Zhao, Bing-Xin Jia, Ya-Nan Zhang, Jiu-Nian Guan, Jiao Qu, Ying Lu

Journal of Electrochemistry

To study the optimal removal condition, adsorption mechanism and comparative analysis of the three typical cationic pollutants, i.e., Zn(II), anionic pollutant Cr(VI) and molecular pollutant sulfamethoxazole (SMX), using self-made upflowed electro-sorption device for adsorptions of above three pollutants by modified activated carbon fiber were researched. The activated carbon fiber (ACF) was modified by hydrochloric acid. The ACF morphology and structure before and after modification were characterized by SEM, BET and FTIR. The characterization results show that the modified ACF had fewer surface impurities than the modified surface and the gully is more obvious, the specific surface area was increased by …

Bipolar-Membrane Electrodialysis Method To Treat Industrial High Saline Perfume Wastewater, Jian Zhang, Dong-Fang Niu, Shuo-Zhen Hu, Xin-Sheng Zhang

Journal of Electrochemistry

Large amount of organic saline wastewater is generated from various chemical industries. The contents of organic saline wastewater are more and more complicated as they are created from different types of industries. Directly discharging the organic saline wastewater without pre-treatment can generate severe environmental problem and waste useful resources. It is necessary to use an economical method to treat the organic saline wastewater and recover the salt into useful materials to achieve resource reuse. Bipolar-membrane electrodialysis (BMED) is one of the methods that can remove salt from the wastewater and convert it into certain acid and base with higher value …

Transient Electrochemical Surface-Enhanced Raman Spectroscopic Study In Electrochemical Reduction Of P-Nitrothiophenol, Yun Ling, Jing Tang, Guo-Kun Liu, Cheng Zong

Journal of Electrochemistry

P-nitrothiophenol (PNTP) is one of the most common probe molecules studied by surface-enhanced Raman spectroscopy (SERS). The research in electrochemical reduction behavior of PNTP will help understanding the mechanism for the nitrobenzene reduction. In this paper, we used transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to study the SERS of PNTP with cyclic voltammetry and chronoamperometry on gold electrodes. The results show that the TEC-SERS provide a time resolution that equals the transient electrochemical methods, and we concluded that the reaction was so quick that we did not observe the spectral information of intermediate species described in the literatures with a …

Electrochemical Properties Of Sulfur In Different Carbon Support Materials, Bo Zhang, Jia Liu, Xiao-Chen Liu, De-Jun Li

Journal of Electrochemistry

In order to investigate the effect of carbon structure on electrochemical performance of sulfur/carbon composite in lithium-sulfur battery, in this paper, sublimation sulfur was incorporated into three types of carbon materials, namely, graphene, carbon black and porous carbon. The three sulfur/carbon composites were characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and X-ray diffraction (XRD) techniques, and their electrochemical performances were also studied. The results showed that the sulfur/porous carbon composite offered an initial discharge capacity of 1623.2 mA·h·g^-1 and remained 845 mA·h·g^-1 after 100 cycles. Compared with graphene and carbon black, the mesopores and micropores in porous …

Electrochemical Sensor Based On Magnetic Electrode Modified With Magnetic Molecularly Imprinted Nanoparticles Immobilized Hemoglobin For Determination Of Hydrogen Peroxide, Yang Yuan, Jia-Xin Wang, Yu-Hua Cao

Journal of Electrochemistry

In this work, the surface-imprinted technique was used to prepare magnetic hemoglobin (Hb) imprinted nanoparticles, using Fe₃O₄@SiO₂ NPs as the carrier, Hb as the template molecule, and tetraethyl orthosilicate (TEOS) as the imprinted polymer monomer. The nanoparticles had a core-shell structure, with magnetic Fe₃O₄ NPs as the core and Hb imprinted polymers as the shell. Therefore, Hb could be concentrated and fixed on the surface of the magnetic imprinted nanoparticles (MMIPs NPs). Furthermore, MMIPs NPs were immobilized with chitosan (CS) on the surface of a magnetic electrode to constitute Hb enzyme-like biosensor …

An Aptasensor Based On Aunps/Pani/Tnts Nanocomposite For Electrochemical Detection Of Tobramycin, Yong-Ling Nong, Ni-Na Qiao, Ying Liang

Journal of Electrochemistry

A novel well-constructed electrochemical aptamer-based sensor for the detection of tobramycin was presented, using differential pulse voltammetry (DPV) as a detection technique and methylene blue(MB) as an electrochemical indicator. A glassy carbon electrode modified with a nanocomposite of Au nanoparticles/polyaniline/titania nanotubes (AuNPs/PANI/TNTs) was constructed as the electrode scaffold. The nanocomposite was characterized by transmission electron microscopy and X-ray photoelectron spectroscopy in detail. The results of cyclic voltammetry and electrochemical impedance measurements demonstrated that the AuNPs/PANI/TNTs nanocomposites can improve greatly the electron transfer on the interface. For the detection of tobramycin, the DPV results showed a linear relationship between the current …

Zif-67-Derived Ag/Co-Embedded N-Enriched Mesoporous Carbon For Oxygen Reduction Reaction, Zheng-Ling Di, Jing Zhu, Lei Dai, Wei Meng, Yue-Hua Li, Zhang-Xing He, Ling Wang

Journal of Electrochemistry

Nitrogen-doped porous carbon materials are considered as one of the most promising catalysts for oxygen reduction reaction (ORR). Herein, in order to further improve the activity of the nitrogen-doped porous carbon, Ag/Co bimetal is embedded into nitrogendoped porous carbon to form Ag/Co-embedded nitrogen-doped porous carbon material (AgCo@NC). The AgCo@NC was derived by the wet impregnation of Ag+ into ZIF-67 precursor, followed by chemical reduction and a subsequent pyrolysis process under Ar atmosphere at different temperatures (500 ℃, 600 ℃, 700 ℃). The morphologic characterization shows that the Ag/Co nanoparticles were successfully embedded in the mesoporous carbon framework with abundant nitrogen …

Quantitative Detection Of Levofloxacin Hydrochloride By Differential Pulse Stripping Voltammetry With Electrodeposited Bismuth Film Electrodes, Zi-Ying Guo, Zuo-Peng Li, Jiang Li, Jian-Guo Zhao, Feng Feng

Journal of Electrochemistry

In this study, differential pulse stripping voltammetry was developed for the quantitative detection of levofloxacin hydrochloride indirectly. Levofloxacin hydrochloride contains organic amine, which can be precipitated upon interaction with Zn(SCN)₄^2-. By means of differential pulse stripping voltammetry, the concentration of Zn²⁺ can be determined using an in-situ formed bismuth film electrode, which allows determining indirectly the amount of levofloxacine hydrochloride. The linearity equation, I = 1.1401c - 0.5309 with the correlative coefficient R = 0.9979, was presented in the experiment. The results showed that this approach is very sensitive, having a limitation of detection of 3.18 …

Hydrogen Production Of Microbial Electrolysis Cell Using Scrap Metal Net As Cathode And The Analysis Of Microbial Community Structure In Anode, Hong-Yan Dai, Hui-Min Yang, Xian Liu, Xiu-Li Song, Zhen-Hai Liang

Journal of Electrochemistry

In order to find high quality and low price hydrogen catalyst, a scrap metal net was used as single-chamber microbial electrolytic cell (MEC) cathode, and its hydrogen production performance was investigated at different applied voltages. Meanwhile, the microbial community structures of original aerobic activated sludge, MFC and MEC anode microbes were analyzed by 16S rDNA amplicon sequencing technology. As the applied voltage increased, the maximum current density was increased and the running time was shortened. At an applied voltage of 0.7 V, the hydrogen production and electrical energy efficiency obtained with scrap metal mesh cathode MEC were, respectively, 0.330±0.012 m …

Ionic Liquid Assisted Synthesis Of Porous Carbons From Rice Husk For Supercapacitors, Han-Fang Zhang, Feng Wei, Jian Sun, Meng-Ying Jing, Xiao-Jun He

Journal of Electrochemistry

It is still a challenge to prepare carbon materials with high specific surface area at low cost from renewable resources. Herein, the authors report an efficient approach to synthesize porous carbons (PCs) from rice husk with ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆)) as a template and an activation agent. The as-made PCs featured the high specific surface area up to 1438 m²·g^-1. As electrodes for supercapacitors, PCs showed a high specific capacitance of 256 F·g^-1 at 0.05 A·g^-1 in 6 mol·L^-1 KOH aqueous electrolyte and a good rate performance of 211 F·g …

Hypervalent Iodine Compounds With Carboxylate And Tetrazolate Ligands, Avichal Vaish

Chemistry Theses and Dissertations

In modern organic chemistry, hypervalent (HV) iodine(III) compounds are frequently used as oxidizing agents but application of λ³-iodanes in polymer and material chemistry is still underexplored. This dissertation describes the preparation of dynamic and self-healing materials by employing ligand exchange reactions involving HV iodine(III) compounds of the type ArIL₂ (Ar = Aryl, L = ligand, e.g., carboxylate or (pseudo)halide). These compounds can undergo ligand exchange reactions in presence of nucleophiles (Nu^-) to form ArINu₂. Diacetoxyiodo benzene was successfully employed as a crosslinker to prepare dynamic and self-healing gels derived from carboxylate-containing polymers. Furthermore, …

Polyarylenes: Synthesis And Characterization Towards Advanced Applications, Stephen Budy

Chemistry Theses and Dissertations

A series of semi-fluorinated and non-fluorinated Diels−Alder step-growth polyarylene polymers and co-polymers were synthesized via typical oil bath heating (days/weeks) and more rapid microwave-assisted polymerization (hours). The polymers were characterized by multi-nuclear (¹H, ¹³C, and ¹⁹F) NMR and ATR−FTIR spectroscopy, thermal analysis (TGA, DSC, and DMA), GPC, XRD, water contact analysis (WCA), and refractive index (RI) measurements. The NMR spectra indicated a mixture of para and meta conformations through the polymer backbone increasing to more para with greater fluorine content. Thermal gravimetric analysis revealed the fluorine-containing polyarylenes possessed the highest char yields at almost 80% at …

Study Of Amorphous Boron Carbide And Hydrogenated Boron Carbide Materials Using Molecular Dynamics And Hybrid Reverse Monte Carlo, Rajan Khadka

Graduate Theses/Dissertations

We present a computational study of amorphous boron carbide (a-B_xC) models using Molecular Dynamics (MD) studied with Stillinger-Weber (SW) and ReaxFF potential. The atomic structure factor (S(Q)), radial distribution function (RDF) and bond lengths comparison with other experimental and ab initio models shows that a random arrangement of icosahedra (B₁₂, B₁₁C) interconnected by chains (CCC, CBC) are present in a-B_xC. Afterward, Hybrid Reverse Monte Carlo (HRMC) technique is used to recreate a-B_xC structures. The existing SW potential parameters of Boron are optimized for the α-rhombohedral (Icosahedral B_{12 …}

Understanding And Controlling Lithium Microstructure During Electroplating For Energy Applications, Yang Tian

Graduate Theses and Dissertations

Lithium-ion batteries are reaching the specific theoretical capacity limit, while lithium metal batteries are regarded as the ideal energy storage system for the next generation “beyond lithium-ion” battery systems. The lithium metal anode is considered as the “Holy grail” of anodes due to its relatively low electrochemical potential (-3.04 V vs SHE) and high theoretical capacity (3860 mAh g-1). However, the application of lithium metal anodes is hindered because of significant reaction between metallic lithium and electrolytes, as well as uneven electro-plating, which leads to dendrite formation, causing safety problems.

The kinetic parameters of Li ions such as diffusion coefficient …

Preparation Of Folic Acid-Carbon Dots-Doxorubicin Nanoparticles As Targeting Tumor Theranostics, Samson Dada

Electronic Theses and Dissertations

Carbon dots (CDs) have attracted much attention as an excellent gene/drug delivery and biological imaging agent for early cancer theranostics. In this study, we prepared two series of nanoparticles (NPs), which are composed of (CDs) with a targeting agent, folic acid (FA), and a chemotherapeutic agent Doxorubicin (Dox). All the NPs and their intermediates were characterized using ultraviolet-visible spectroscopy (UV-vis), fluorescence spectroscopy, and Fourier transform-infrared spectroscopy (FT-IR). The drug loading capacity (DLC) and drug loading efficiency (DLE) of two series of FA-CDs-Dox were assessed using UV-vis absorption spectroscopy at the wavelength of 485 nm. Both showed good DLE and DLC …