Chemistry Commons^™

Special Issue: Electrochemistry Of Carbon Materials, Chen Wei

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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 …

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

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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

Journal of Electrochemistry

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

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

McKelvey School of Engineering 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. …

The Effect Of Frictional And Adhesion Forces Attributed To Slurry Particles On The Surface Quality Of Polished Copper, Yi-Koan Hong, Ja-Hyung Han, Tae-Gon Kim, Jin-Goo Park, Ahmed A. Busnaina

Ahmed A. Busnaina

The effect of frictional and adhesion forces attributed to slurry particles on the quality of copper surfaces was experimentally investigated during copper chemical mechanical planarization process. The highest frictional force of 9 Kgf and adhesion force of 5.83 nN were observed in a deionized water-based alumina slurry. On the other hand, the smallest frictional force of 4 Kgf and adhesion force of 0.38 nN were measured in an alumina slurry containing citric acid. However, frictional (6 Kgf) and adhesion (1 nN) forces of silica particles in the slurry were not significantly changed regardless of the addition of citric acid. These …

The Effect Of Frictional And Adhesion Forces Attributed To Slurry Particles On The Surface Quality Of Polished Copper, Yi-Koan Hong, Ja-Hyung Han, Tae-Gon Kim, Jin-Goo Park, Ahmed A. Busnaina

Ahmed A. Busnaina

The effect of frictional and adhesion forces attributed to slurry particles on the quality of copper surfaces was experimentally investigated during copper chemical mechanical planarization process. The highest frictional force of 9 Kgf and adhesion force of 5.83 nN were observed in a deionized water-based alumina slurry. On the other hand, the smallest frictional force of 4 Kgf and adhesion force of 0.38 nN were measured in an alumina slurry containing citric acid. However, frictional (6 Kgf) and adhesion (1 nN) forces of silica particles in the slurry were not significantly changed regardless of the addition of citric acid. These …

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

Electronic Thesis and Dissertation Repository

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

Solvothermal Synthesis And Characterization Of Cuins2, Cuinse2 And Agins2 Nanoparticles From Single Source Precursors, Xuzhao Zhao

Electronic Thesis and Dissertation Repository

Nanoscale semiconductors have emerged as alternative candidates for the absorber layer in solar cells. Group 11-13-16 semiconductors have received a lot attention because of their direct band gap energies, high absorption coefficients and environmental friendly nature. To date, CuInS₂, CuInSe₂ and AgInS₂ semiconductors are three of the main ternary nanomaterials investigated. Besides the application in solar cells, these nanoscale semiconductors can also be applied in areas such as biosensors and hydro catalysis.

However, it is often challenging to prepare small-sized nanoparticles with uniform size and shape, especially for large scale production. In this thesis, the synthesis …

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 …

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

Doctoral Dissertations

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

Interface And Morphology Engineering In Solution-Processed Electronic And Optoelectronic Devices, Sanjib Das

Doctoral Dissertations

The first part of this dissertation focuses on interface and morphology engineering in polymer- and small molecule-based organic solar cells. High-performance devices were fabricated, and the device performance was correlated with nanoscale structures using various electrical, spectroscopic and microscopic characterization techniques, providing guidelines for high-efficiency cell design.

The second part focuses on perovskite solar cells (PSCs), an emerging photovoltaic technology with skyrocketing rise in power conversion efficiency (PCE) and currently showing comparable PCEs with those of existing thin film photovoltaic technologies such as CIGS and CdTe. Fabrication of large-area PSCs without compromising reproducibility and device PCE requires formation of dense, …

Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis

Doctoral Dissertations

The spontaneous generation of complex structures from polymeric building blocks provides a simple yet effective route to create useful soft matter structures having potential application in a variety of nanotechnologies. The topology, chemical structure, block composition, and sequence of the constituent building blocks of polymers are tunable through synthetic chemistry. This tunability offers attractive opportunities to generate complex, yet well-defined structures with control over the geometry, packing symmetry, and microdomain structure. This thesis work involves the study of the self-assembly behaviors of architecturally complex amphiphilic block copolymers (ABCs). ABCs are composed of two or more chemically distinct blocks that are …

Novel Thermoplastic Elastomers Based On Benzofulvene: Synthesis And Mechanical Properties, Weiyu Wang

Doctoral Dissertations

Thermoplastic elastomers (TPEs) are of great importance both academically and technologically. Currently TPEs are the predominated form of styrene-diene copolymers. However, these styrenic TPEs have serious limitations in applications, especially at higher temperature, because of their low upper service temperature (UST). The work described in this dissertation aimed to developing thermoplastic elastomers with a higher UST and lower cost.

In order to develop TPEs with a higher UST, we employed benzofulvene, an anionically polymerizable monomer in hydrocarbon solvent at room temperature, as the glassy block and copolymerized it with isoprene to prepare polybenzofulvene-polyisoprene-polybenzofulvene (FIF) triblock copolymers. Among all triblock copolymers …

The Effect Of Composition And Architecture On Polymer Behavior In Homopolymer Blends And Inter-Filament Bonding In 3d Printed Models, Edward Roy Duranty

Doctoral Dissertations

This dissertation presents work that increases our understanding of the effects of composition and architecture on copolymer structure and dynamics and how they affect material diffusion between filaments in a 3D printed model. Copolymers are polymer chains made up of at least two different monomers. The ordering and arrangement of the two monomer species within a copolymer can have drastic effects on the behavior and properties of the copolymer.

The first chapter of this dissertation examines how the copolymer composition affects the structure and dynamics of the chain in a homopolymer blend. This study used a modified Monte Carlo BFM …

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 …

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. …

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 …

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 …

Studying Nanoparticle/Cell And Nanoparticle/Biosurface Interaction With Mass Spectrometry, Singyuk Hou

Masters Theses

Nanoparticles (NPs) have been used widely in various fields ranging from biomedical applications to life science due to their highly tunable properties. It is essential to understanding how NPs interact with biological systems of interest, therefore, analytical platforms to efficiently track NPs from cell to animal level are essential. In this thesis, laser desorption ionization mass spectrometry (LDI-MS) and inductively-coupled plasma mass spectrometry (ICP-MS) has been developed and applied to quantify NP/cell and NP/biological surface interactions. These two methods provide fast, label-free and quantitative analysis. New capability of LDI-MS to differentiate cell surface-bound and internalized NPs were established and ICP-MS …

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

FIU Electronic Theses and Dissertations

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

Inkjet Printing For Biosensing And Security Applications, Brian Creran

Doctoral Dissertations

The adaptation of inkjet printing technology has recently been used to create controlled high throughput micro- and nano-scaled structures. Coupling this technique with gold nanoparticles in our research has produced new platforms for biosensors, chemical patterning, and anti-counterfeiting applications. In this presentation, we will highlight promising fabrication strategies including the development of test strips for the determination of bacteria in drinking water as well as the use of patterned nanoparticles for security applications.

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

Doctoral Dissertations

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