Chemistry Commons^™

Transport And Plugging Performance Evaluation Of A Novel Re-Crosslinkable Microgel Used For Conformance Control In Mature Oilfields With Super-Permeable Channels, Adel Alotibi, T. Song, Baojun Bai, Thomas P. Schuman

Geosciences and Geological and Petroleum Engineering Faculty Research & Creative Works

Preformed particle gels (PPG) have been widely applied in oilfields to control excessive water production. However, PPG has limited success in treating opening features because the particles can be flushed readily during post-water flooding. We have developed a novel micro-sized Re-crosslinkable PPG (micro-RPPG) to solve the problem. The microgel can re-crosslink to form a bulk gel, avoiding being washed out easily. This paper evaluates the novel microgels' transport and plugging performance through super-permeable channels. Micro-RPPG was synthesized and evaluated for this study. Its storage moduli after fully swelling are approximately 82 Pa. The microgel characterization, self-healing process, transportation behavior, and …

Intergranular And Pitting Corrosion Mechanisms Of Sensitized Aluminum Alloy Aa5083, Clayton Egleston

Williams Honors College, Honors Research Projects

The motivation and objectives of this project is to examine the mechanisms of intergranular corrosion (IGC) and pitting corrosion of sensitized AA5083. In this regard, different characterization techniques were used, including optical analysis of microstructure, cyclic potentiodynamic polarization with Tafel fitting, electrochemical impedance spectroscopy with electrical equivalent circuit (EEC) fitting, and potentiostatic current transient monitoring. The transition from IGC to pitting corrosion occurs when the grain boundaries become saturated with the β-phase (Mg₂Al₃). It was found that AA5083 becomes more vulnerable to pitting corrosion as the degree of sensitization increases.

Wetting Transition Of Texturized Surfaces, Jenna Stephens

Williams Honors College, Honors Research Projects

Building on previous research, this project aims to continue the investigation of the wettability of various liquids on a uniform, texturized surface. Different surface energies can impact the wettability of a surface. The surface can be hydrophilic, hydrophobic, or in between. The goal of this project is to research how features of texturized surfaces affect the wetting transition of water, oil, and a mixture of both. Additionally, this project aims to improve the quality of the 3D printed surfaces. The surfaces that will be studied are constructed using UV cured resin 3D printing and are made up of an array …

Facile Synthesis Of Nite2-Co2Te2@Rgo Nanocomposite For High-Performance Hybrid Supercapacitor, Maziar Farshadnia, Ali A. Ensafi, Kimia Zarean Mousaabadi, Behzad Rezaei, Muslum Demir

Chemistry & Biochemistry Faculty Publications and Presentations

The design of bimetallic tellurides that exhibit excellent electrochemical properties remains a huge challenge for high-performance supercapacitors. In the present study, tellurium is consolidated on CoNi₂@rGO for the first time, to synthesize NiTe₂-Co₂Te₂@rGO nanocomposite by using a facile hydrothermal method. As-prepared NiTe₂-Co₂Te₂@rGO nanocomposite was characterized by EDS, TEM, FESEM, Raman, BET, XRD, and XPS techniques to prove the structural transformation. Upon the electrochemical characterization, NiTe₂-Co₂Te₂@rGO has notably presented numerous active sites and enhanced contact sites with the electrolyte solution during …

Molecular Elucidation Of Reaction Mechanisms In Aluminum & Lithium Metal Batteries By Solid-State Nmr Spectroscopy And Electrochemical Methods, Leo W. Gordon

Dissertations and Theses

As society wrestles with the ever-growing climate consequences of burning fossil fuels, the increased demand for electric vehicles and renewable power generation mandates safe, sustainable, earth-abundant, low cost, and energy dense batteries. Different use cases will necessitate different types of batteries; for example, stationary storage systems prioritize minimal expense, whereas mobile applications like electric vehicles emphasize high energy densities. Aluminum and lithium metal batteries hold great promise for next-generation energy storage due to their large specific capacities (2980 mA h g^-1, and 3860 mA h g^-1, respectively). In particular, aluminum metal is low cost, has high …

Functionalizing Metal-Organic Super-Containers (Moscs) For Selective Anion Recognition, Hanying Li

Dissertations and Theses

Anions are ubiquitous in Nature and play critical roles in both chemistry and biology. Biologically important molecules like enzymes, DNA, and ATP (adenosine triphosphate) are either anionic or contain negatively charged regions. Inorganic anions such as Cl- and HCO3- play essential roles in various physiological, environmental, and technological processes. Compared to cations, anions have larger ionic radii and more diffuse charge distribution, resulting in weaker electrostatic interactions. Developing synthetic receptors for controlled anion recognition is vital but poses significant challenges. Recent decades have shown remarkable progress in anion recognition, yielding diverse synthetic receptors with promising binding abilities. However, traditional approaches …

Structural And Functional Modulation Of Metal-Organic Supercontainers (Moscs) And Their Applications In Supramolecular Catalysis, Shrijana Dc

Dissertations and Theses

Metal-organic supercontainers (MOSCs), a breakthrough development in our laboratory since 2012, have emerged as promising enzyme mimics, showcasing their prowess in encapsulating guest molecules and catalyzing confined chemical reactions. The intrigue surrounding MOSCs stems from their extraordinary traits, encompassing multiple binding domains, high stability, large surface area, tunable pore size, and structural modularity. Primarily comprising sulfonylcalix[4]arenes, divalent metal ions, and carboxylate linkers, MOSCs' quintessential architecture comprises both endo- and exo- nano-cavities, amenable to guest interaction, with geometry and functionality manipulation achievable through precise precursor selection. Nonetheless, early MOSC models exhibit limited reactivity, often necessitating more potent nucleophiles or electrophiles. This …

Mechanical And Adhesive Properties Of Supramolecular, Mussel-Inspired Hydrogels, Daniel Darby

Theses and Dissertations--Chemical and Materials Engineering

The exceptional mechanical and adhesive properties of mussel byssal threads come from supramolecular interactions of ligands found in the proteins comprising them. Ligands can form hydrophobic interactions, π-π stacking interactions, and hydrogen bonds, but the strongest supramolecular interaction they demonstrate is metal-ligand coordination. Specifically, Histidine (His-) and nitrodopamine (nDOPA) ligands coordinate to metals in a bidentate fashion and take on tris-, bis-, and mono- modalities (3, 2, or 1 ligand per ion, respectively). The distribution of these modalities is controlled by equilibrium thermodynamics. These same ligands can be used as crosslinks in supramolecular hydrogel networks. Supramolecular hydrogel networks are dissipative, …

Molecular Understanding Of Zwitterions And Quantum Computing For Sustainability, Manh Tien Nguyen

Theses and Dissertations--Chemical and Materials Engineering

The sustainable development of society needs sustainable energy solutions and the mitigation of greenhouse gas emissions. One key subject in this area is the development of safe and efficient ion-based batteries. Moreover, CO₂ capture is a crucial pathway in mitigating emissions from the combustion of fossil fuels. Ongoing efforts are to improve both technologies' safety and efficiency. This thesis presents our efforts to conduct computational research on understanding advanced zwitterionic electrolytes and CO₂ capture. Chapters 2-4 illustrate the computational research to understand ionic solvation in zwitterionic electrolytes. Solid-state electrolytes are essential for safer batteries. While solid polymer electrolytes …

Translating Chemistry, Structure, And Processing To The Solid-State Morphology And Function Of Organic Semiconductors Through Computational Modeling And Simulations, Chamikara D. Karunasena

Theses and Dissertations--Chemistry

The immense synthetic design space and material versatility have driven the exploration and development of organic semiconductors (OSC) over several decades. While many OSC designs focus on the chemistries of the molecular or polymer building blocks, a priori, multiscale control over the solid-state morphology is required for effective application of the active layer in a given technology. However, molecular assembly during solid-state formation is a complex function interconnecting the building block chemistry and the processing environment. Insufficient knowledge as to how these aspects engage, especially at the atomistic and molecular scales, has so far limited the ability to predict …

Developing And Deploying Data-Driven Tools For Accelerated Design Of Organic Semiconductors, Vinayak Bhat

Theses and Dissertations--Chemistry

Organic semiconductors have gained widespread attention due to their potential applications in flexible, low-cost, lightweight electronics, energy storage and generation technologies, and sensing applications. However, developing new organic semiconductors with improved performance remains a significant challenge due to the vast chemical space of possible molecular and materials structures. Furthermore, the high cost and time-consuming nature of experimental synthesis and characterization hinder the rapid discovery of new materials. To overcome these challenges, this dissertation presents a data-driven approach to organic semiconductor discovery. The primary focus of this work is the development of data-driven tools, namely machine learning models, to predict critical …

Surface Modification Of Carbon-Based Electrodes For Electrochemical Conversion Processes: Oxygen Reduction Reaction And Bicarbonate Conversion, Udari Shyamika Kodithuwakku Arachchige

Theses and Dissertations--Chemistry

Oxygen reduction reaction (ORR) and conversion of bicarbonate into value-added chemicals are two significant electrochemical processes for energy storage and conversion. ORR is an important electrochemical reaction in fuel cells and metal-air batteries that provide power conversion and storage capacity, respectively, for portable electronics, and electric vehicles. However, the performance of catalysts (e.g., platinum-based) is critically limited by slow kinetics, inefficient four-electron pathway, and surface deactivation. This limited performance of platinum-based catalysts, the scarcity of platinum, and vulnerable supply chains for critical minerals require the development of alternative electrocatalysts now more than ever. Carbon-based materials possess several key properties that …

Water-Soluble Palladium, Copper, And Nickel Catalysts And Their Formation In Ligand-Free Suzuki-Miyaura Cross-Coupling Reactions, Priya Karna

Theses and Dissertations--Chemistry

Transition-metal catalyzed Suzuki-Miyaura (SM) cross coupling is a powerful synthetic method for constructing carbon-carbon and carbon-heteroatom bonds in designing organic compounds, agrochemicals, pharmaceuticals, and precursors for materials. However, the nature of catalysis and identity of the transition metal catalysts used in these reactions remain under debate or unknown. This dissertation reports the studies of three metals: Pd, Cu, and Ni. Pd-nanocluster catalysts and their formation in ligand-free SM reactions with Pd(II) nitrate as a precatalyst was investigated. The catalysts are water-soluble neutral Pd tetramer and trimer in their singlet electronic states as identified by UV-Vis absorption spectroscopy and are formed …

Development Of An Effective Au:Pd Bimetallic Heterogeneous Catalyst For Oxidative Lignin Depolymerization To Low Molecular Weight Aromatics, Gayan P. Karunasinghe

Theses and Dissertations--Chemistry

The principal concept behind biorefining involves the transformation of lignocellulosic biomass into valuable products and energy resources. Historically, biorefinery strategies for lignocellulosic biomass have primarily focused on improving the conversion of cellulose into ethanol, often neglecting the underutilized lignin component. Lignin consists of phenolic subunits, from which it follows that value-added products can be obtained from lignin depolymerization. Unfortunately, lignin utilization is particularly challenging due to its high structural irregularity and recalcitrance. The goal of this study was to develop an AuPd/Li-Al layered double hydroxide (LDH) bimetallic catalyst for efficient lignin depolymerization, resulting in the production of high-value aromatic compounds. …

First Principles Calculations To Investigate Surface And Catalytic Properties Of Materials For Green Energy Generation, Keerthan Raghavendra Rao

Theses and Dissertations--Chemistry

Climate change due to greenhouse gas build up in the earth’s atmosphere is an existential threat to humanity. To mitigate climate change, a significant shift from fossil fuels is necessary. Over the years, several renewable energy sources like solar, wind, geothermal etc. have been explored with the aim providing carbon-free energy. In this work, we focus on using density functional theory (DFT) methods to investigate key functional properties of materials of interest for applications in solar cells and catalytic conversion for energy generation. We show geometric effects of carboxylic acid binding on a transition metal surface to impact the deoxygenation …

Exploring The Role Of Ring Annulation In Polycyclic Aromatic Hydrocarbons For Organic Electronic Applications, Tanner Smith

Theses and Dissertations--Chemistry

Organic materials offer promising potential for the next generation of electronic devices, as their tunability, processability, and low-temperature manufacturing make them a cheap and versatile alternative to traditional silicon-based electronics. The ability to systematically alter the electronic properties of organic materials is vital for their incorporation into device applications. Polycyclic aromatic hydrocarbons (PAHs) are of significant interest for organic electronic applications, as relevant properties are highly dependent on their size, structure, and functionalities, and thus can be tuned to fit a wide variety of applications. Due to the enormous number of structural isomers available in larger PAHs, the development of …

The Application Of Photoelectron Spectroscopies In Analyzing The Impact Of Interfacial Energetics On Perovskite Solar Cells, Tuo Liu

Theses and Dissertations--Chemistry

In recent years, organic-inorganic metal halide perovskites (HP) have garnered tremendous attention in photovoltaic research. This attention is attributed to their low cost and excellent optoelectronic properties, including large absorption coefficients, tunable bandgaps, long charge-carrier diffusion lengths, and low densities of deep trap states. Inverted p-i-n architecture perovskite solar cells (PSCs) are of intense interest and are generally regarded as more amenable to low-temperature solution processing. Nevertheless, the development of inverted PSCs is lagging the conventional architecture devices. Imperfect energy level alignments and charge carrier recombination, especially at the interface between perovskite and electron transport layers (ETLs), are two main …

Outstanding Advantages, Current Drawbacks, And Significant Recent Developments In Mechanochemistry: A Perspective View, Silvina Pagola

Chemistry & Biochemistry Faculty Publications

Although known since antiquity, mechanochemistry has remained dormant for centuries. Nowadays, mechanochemistry is a flourishing research field at the simultaneous stages of gathering data and (often astonishing) observations, and scientific argumentation toward their analysis, for which the combination of interdisciplinary expertise is necessary. Mechanochemistry’s implementation as a synthetic method is constantly increasing, although it remains far from being fully exploited, or understood on the basis of fundamental principles. This review starts by describing many remarkable advantages of mechanochemical reactions, simplifying and “greening” chemistry in solutions. This description is followed by an overview of the current main weaknesses to be addressed …

Chemistry Of Fluorinated Functional Groups: Impact On Molecular Packing, Optoelectronic Properties, Electrochemical Polymerization, Photochemistry, And Reagent Development, Shankar Gairhe

Dissertations and Theses

Fluorinated functional groups have attracted great interest in various aspects of chemistry applications including pharmaceuticals, organic electronics, and polymers. The aim of this study is to explore the impact of fluorinated functional groups on 1) optimization of crystal structures and electronic properties of organic semiconductor molecules, 2) electrochemical polymerization of fluorinated aromatics, 3) photochemical reactivity of carbonyl compounds, and 4) generating new nucleophilic fluorination reagents. Our initial work demonstrates that long fluoroalkyl side chains on planar aromatic systems give rise to fluorine-fluorine (F---F) attractive interactions, assisting formation of lamellar packing motif in the solid state. Surprisingly, introducing shorter perfluoroalkyl side …

Synthesis And Application Of Redox-Active Covalent Organic Frameworks In Rechargeable Batteries, Mohammad K. Shehab

Theses and Dissertations

Synthesis and Application of Redox-Active Covalent Organic Frameworks in Rechargeable Batteries

Mohammad K. Shehab

Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284, United States

Abstract

In recent years, lithium-ion batteries (LIBs) have been considered the dominant energy storage devices for portable electronics and electric vehicles due to their high energy density, low self-discharge rate, and long cycle life. In LIBs, the traditional positive electrodes employed are mainly derived from metal-containing inorganic compounds composed of cobalt, iron, nickel, or manganese (LiCoO₂, LiMn₂O₄, and LiFePO₄) coupled with graphite as the negative electrode. Despite …

Mechanistic Studies Of Co2 Electrochemical Reduction (Co2er) On Cu And Cuo Nanoparticles With In-Situ Atr-Ftir Spectroscopy, Jason Hsu

Theses and Dissertations (Comprehensive)

Global climate change is a major challenge facing the world in the 21st century. This environmental crisis originated from excess amounts of atmospheric carbon dioxide (CO2) released from burning fossil fuels. One promising remediation method to decrease atmospheric CO2 levels is called carbon dioxide electrochemical reduction (CO2ER). In CO2ER, the CO2 gas undergoes chemical reduction to other hydrocarbon fuels. For CO2ER to take place, an energy source and a catalyst are needed. In this thesis, three aspects of CO2ER were investigated using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy coupled with other surface sensitive characterization tools. First, we studied …

Electrolyte Synthesis And Engineering For Alkali Metal Batteries, Yiwen Zhang

Dartmouth College Ph.D Dissertations

Batteries have been in increasing demand over the last decade for portable electronic devices, electric vehicles, and grid-scale energy storage systems. While the electrode materials define the characteristic features of a battery system, the composition of the electrolyte is of critical importance and needs to be engineered for different battery systems to ensure superior electrochemical performance. In this thesis, the basic functionality and fundamental mechanism of the electrolytes in battery systems are first introduced. Then, three major electrolyte engineering strategies are demonstrated, including electrolyte composition formulation, electrolyte-electrode component modification, and function-oriented electrolyte design. Firstly, the low-temperature capacity restraint of lithium …

Feasibility Studies For Use Of Copper Slag In Clinker Manufacture, Suresh Vanguri, Suresh Palla, Gonthi Prasad, Sanjeev Kumar Chaturvedi, Bibekananda Mohapatra

Makara Journal of Science

This study investigated the feasibility of using copper slag (CS-C) as a raw material in the production of Portland cement (PC). The effect of addition of 0%-3.5% CS-C on the clinkerization process, mineralogy, microstructure, and compressive strength development was studied. The Presence of CS-C in the raw mix resulted in the reduced temperature of clinkerization by about 50 °C. The quality of clinker prepared from the raw mix containing 3% CS-C and burned at 1400 °C was comparable to that of clinker prepared from the raw mix containing no CS-C and burned at 1450 °C. Gradual polymorphic modification of alite …

Application Of Artificial Intelligence To Lithium-Ion Battery Research And Development, Zhen-Wei Zhu, Jing-Yi Qiu, Li Wang, Gao-Ping Cao, Xiang-Ming He, Jing Wang, Hao Zhang

Journal of Electrochemistry

Lithium-ion batteries (LIBs) have become one of the best solutions to the energy storage issue in modern society. However, the battery materials and device development are both complex, and involve multivariable problems. Traditional trial-and-error approach, which relies on researchers to conduct experiments, has encountered bottlenecks in the improvement of the battery performance. Artificial intelligence (AI) is the most potential technology to deal with this issue due to its powerful high-speed and capabilities of processing massive data. In particular, the capability of machine learning (ML) algorithms in assessing multidimensional data variables and discovering patterns in the sets are expected to assist …

Advances On Composite Cathodes For Lithium-Sulfur Batteries, Xi-Yao Li, Chang-Xin Zhao, Bo-Quan Li, Jia-Qi Huang, Qiang Zhang

Journal of Electrochemistry

Lithium-sulfur (Li-S) batteries are deemed as high-promising next-generation energy storage technique due to their ultrahigh theoretical energy density, where the sulfur cathodes with high specific capacity guarantee the energy density advantage and directly determine the battery performances. After decades of exploration, the most promising sulfur cathodes are sulfur/carbon composite (S/C) cathodes and sulfurized polyacrylonitrile (SPAN) cathodes. In this manuscript, recent advances on S/C and SPAN cathodes in Li-S batteries are comprehensively reviewed. The electrochemical reaction circumstances on S/C and SPAN cathodes are firstly introduced and compared to reveal the working mechanisms of the two types of Li-S batteries. The S/C …

Multi-Electron Reaction-Boosted High Energy Density Batteries: Material And System Innovation, Rui-Qi Guo, Feng Wu, Xin-Ran Wang, Ying Bai, Chuan Wu

Journal of Electrochemistry

The continuous development of the global energy structure transformation has put forward higher demands upon the development of batteries. The improvements of the energy density have become one of the important indicators and hot topic for novel secondary batteries. The energy density of existing lithium-ion battery has encountered a bottleneck due to the limitations of material and systems. Herein, this paper introduces the concept and development of multi-electron reaction materials over the past twenty years. Guided by the multi-electron reaction, light weight electrode and multi-ion effect, current development strategies and future trends of high-energy-density batteries are highlighted from the perspective …

Carbon-Al Interface Effect On The Performance Of Ionic Liquid-Based Supercapacitor At 3 V And 65 OC, Zhen-Zhen Ye, Shu-Ting Zhang, Xin-Qi Chen, Jin Wang, Ying Jin, Chao-Jie Cui, Lei Zhang, Lu-Ming Qian, Gang Zhang, Wei-Zhong Qian

Journal of Electrochemistry

Ionic liquid (IL) electrolyte-based supercapacitors (SCs) have advantages of high operating voltage window, high energy density and nonflammability, as compared to conventional acetonitrile-based organic electrolyte SCs, and are typically suitable for the large-scale energy storage in the era of carbon neutrality full of renewable, but unstable electricity. However, current efforts were concentrated on the study with coin-cell type of IL-SCs, and less has been reported on the pouch type of IL-SCs for a long cycling time yet. To fabricate a reliable SC for the life time test or for the accelerated aging test under high temperature, one should concern the …

Preparation Of Highly-Cyclized Sulfurized Polyacrylonitrile For Lithium-Sulfur Batteries, Xuan Ji, Jia-Yu Wang, An-Bang Wang, Wei-Kun Wang, Ming Yao, Ya-Qin Huang

Journal of Electrochemistry

Sulfurized polyacrylonitrile (SPAN) is regarded as an attractive cathode candidate of lithium-sulfur (Li-S) batteries for its non-dissolution mechanism and effective alleviation of polysulfides shuttling issue in Li-S batteries, displaying high utilization of cathode active material, outstanding cycle stability and structural stability. However, the relation between cyclization degree and cycle stability of SPAN is still unveiled. In this work, SPAN-C-V composites were synthesized by co-introduction of CuSO₄ and zinc n-ethyl-n-phenyldithiocarbamate (ZDB) in the co-heating of sulfur and polyacrylonitrile. The co-introduction of CuSO₄ and ZDB reduced the cyclization reaction onset temperature of PAN while increased the C—C/C=C within SPAN-C-V, thus …

Investigating The Electrochemical Behavior Of Dihydropyrrolopyroles For Use As Anodically Coloring Electrochromes, Perry Skiouris, Ally Kisiel, Valentino Sorto, Julia Mauro, Graham Collier

Symposium of Student Scholars

Electrochromic materials have found widespread use in consumer electronics, energy saving windows, and military applications. They contain unique electronic properties allowing them to undergo a color change in a redox reaction. One classification of these molecules is known as anodically coloring electrochromes (ACEs). When in solution, these compounds are transmissive in the neutral (ground) state and absorb visible light upon oxidation, by the formation of a radical cation, thus making them colored. The focus of this study is the electronic transitions of this radical cation and how chemical modifications to the structures produce a variable color profile. To design prospective …

Perfect Polar Alignment Of Parallel Beloamphiphile Monolayers: Synthesis, Characterization, And Crystal Architectures Of Unsymmetrical Phenoxy-Substituted Acetophenone Azines, Harmeet Bhoday, Michael Lewis, Steven P. Kelley, Rainer Glaser

Chemistry Faculty Research & Creative Works

It remains a great challenge to achieve polar order in organic molecular crystals because anti-parallel alignment of side-by-side molecules is intrinsically preferred. We have addressed this problem with a rational design that focuses on the polar stacking of parallel beloamphiphile monolayers (PBAMs) with strong lateral quadrupole-quadrupole attractions. We employ arene-arene interactions as lateral synthons. The first successes were achieved with unsymmetrical donor (X), acceptor (Y) substituted acetophenone azines which form polar PBAMs with double T-contacts between the azines. Near-perfect alignment was achieved with the methoxy series of (MeO, Y)-azines with Y=Cl, Br, I. Here, we report on the synthesis, the …