Chemistry Commons^™

Research And Application Of Key Materials For Sodium-Ion Batteries, Yong-Chang Liu, Cheng-Cheng Chen, Ning Zhang, Liu-Bin Wang, Xing-De Xiang, Jun Chen

Journal of Electrochemistry

Sodium-ion batteries (SIBs) have been considered as a potential large-scale energy storage technology owing to the abundance, wide distribution, and low price of sodium resources. However, the larger and heavier sodium ion as compared to lithium ion makes it difficult to identify appropriate electrode materials with the capability for fast and stable sodium-ion insertion/extraction. Furthermore, the optimization of electrolyte, the matching of cathode and anode materials, and the construction of sodium-ion full batteries with high-performance, high-safety, and low-cost are urgently needed in order to make SIBs commercially available. This review summarizes the up-to-date research progresses in key materials (including cathode, …

Advances And Prospects Of Lithium-Sulfur Batteries, Shou-Yi Yuan, Ying Pang, Li-Na Wang, Yong-Gang Wang, Yong-Yao Xia

Journal of Electrochemistry

Lithium-sulfur batteries have recently attracted worldwide attention due to the high specific theoretical energy density of sulfur cathode (2600 Wh⋅kg^-1), low cost and wide availability of sulfur. However, the practical application of lithium-sulfur batteries has been hindered by several challenges, such as the shuttling of polysulfide intermediates, the large volume expansion of sulfur during charge/discharge and the dendrites formation on lithium anode. Foremost among these is the shuttling effect arising from the dissolution of lithium polysulfides intermediate into the electrolyte from the cathode reaction and their diffusion to the anode where they react with metal lithium to form …

Micro/Nano-Structured Electrode Materials For Sodium-Ion Batteries, Shuang Yuan, Yun-Hai Zhu, Sai Wang, Tao Sun, Xin-Bo Zhang, Qiang Wang

Journal of Electrochemistry

Sodium has similar physics and chemical properties to lithium, alternatively, sodium (Na)-ion batteries have again aroused a great deal of interest recently, particularly for large-scale stationary energy storage applications due to the practically infinite sodium resources and low cost. However, the technics and materials for Na-ion batteries are immature. Therefore, development of advanced anode and cathode materials for Na-ion batteries is urgently desired but remains a great challenge. This paper briefly reviews some recent progresses in this field, addressing the morphology effects, as well as functions of carbon composite materials toward Na-ion batteries. Several electrode materials with micro/nano-structures based on …

Research Progress Of Si-Based Anode Materials For Lithium-Ion Batteries, Ding-Qiong Chen, Yang Yang, Qiu-Li Li, Jin-Bao Zhao

Journal of Electrochemistry

Owing to its high theoretical specific capacity (4200 mAh·g^-1), silicon is a promising candidate to replace graphite as the anode in lithium ion batteries (LIBs). However, low intrinsic electric conductivity and dramatic volume change (~ 300%) during the process of lithiation and delithiation result in electrode pulverization and capacity loss with cycling, accordingly, the application of silicon as an anode in LIBs has been severely hindered. We will discuss the structure of silicon electrode including synthesis of Si-based composites,the selection of binder for silicon and the fabrication of binder-free Si-based electrode, as well as the electrolyte additive to …

Electrochemical Performance Of Crystalline Li12Si7 As Anode Material For Lithium Ion Battery, Ya-Xiong Yang, Rui-Jun Ma, Ming-Xia Gao, Hong-Ge Pan, Yong-Feng Liu

Journal of Electrochemistry

Crystalline Li₁₂Si₇ is successfully synthesized by heating the mixture of LiH and Si with a molar ratio of 12:7, which avoids the huge difference of the melting points between Li and Si. The electrochemical performance and lithium storage mechanism of the as-prepared Li12Si7 are studied in this work. It is found that only a change in cell volume takes place without a phase change during the lithiation/delithiation of Li₁₂Si₇ at a voltage range of 0.02 ~ 0.6 V, exhibiting a solid-solution lithium storage mechanism. Such a lithium storage process effectively retards the volume effect …

Continuous Synthesis And Condition Exploration Of Precursor Ni1/3Co1/3Mn1/3(Oh)2 Ternary Cathode Material, Zhi-Jun Jiang, Ya-Li Zhang, Qian Wang, Hui Zhang

Journal of Electrochemistry

Commercial LiNi_1/3Co_1/3Mn_1/3(OH)₂ ternary material is generally prepared by a combination of co-precipitation and solid state reaction method. The particle size distribution and morphology of Ni_1/3Co_1/3Mn_1/3(OH)₂ precursor have a great impact on the electrochemical performance of LiNi_1/3Co_1/3Mn_1/3O₂. In this work, the precursor Ni_1/3Co_1/3Mn_1/3(OH)₂ ternary cathode material was prepared by co-precipitation method with MnSO₄, NiSO₄, and CoSO₄ as raw materials, NaOH as a precipitating agent and NH_{3 …}

The Study Of Dynamical Electrochemical Impedance Spectroscopy For Oxygen Reduction Reaction On Pt/C Catalyst, Kun-Ming Shi, Jian-Wei Guo, Jia Wang

Journal of Electrochemistry

With joint techniques of rotating disc electrode(RDE) and electrochemical impedance spectroscopy(EIS), and further establishment on equivalent circuit model, this paper studied oxygen reduction reaction(ORR) on commercial Pt/C catalyst in acid medium. Our results found that the dynamical interface on Pt/C consists of two independent processes: 1) the PtO reduction from Pt surface, 2) the new PtO formation from ORR, thus providing key clues for catalyst stability and activity. This also implied that the dynamical interface facilitates reconstruction for porous electrode, and matches with mass transfer. One important issue is discovered that at high overpotential, the high reaction rate for ORR …

Construction And Sodium Storage Performance Of Complex One-Dimensional Nanomaterials, Yuan-Jie Zhang, Wei Li, Xuan-Peng Wang, Chao-Jiang Niu, Li-Qiang Mai

Journal of Electrochemistry

One-dimensional nanomaterials have been widely studied in energy storage and conversion fields because of their unique structure and physicochemical properties. Sodium-ion batteries are highly promising and attractive for large-scale energy storage due to the truly abundant sodium resources and low cost. With the growing demand of energy and deepening of research, the evolution of structures and properties of one-dimensional nanomaterials are also experiencing from simplicity to complexity and from ordinary to excellence. Therefore, constructing complex superior one-dimensional nanomaterials has become one of the hotspot in energy storage. Based on the new advance in this field and Mai group’s work, this …

Research Progress In Cycle Stability Of Silicon Based Li-Ion Battery Anodes, Ze-Liang Guo, Hui Wu

Journal of Electrochemistry

Silicon(Si), with the highest specific capacity currently known, is a promising anode material for Li-ion battery. However, in the charging and discharging process, with Li atoms inserting into and breaking out of the Si crystal lattices, the Si anode undergoes enormous volume expansion and contraction, ending in pulverization. The fact that the specific capacity of bulk Si anodes drop quickly is a challenging problem. In this review, we summarize recent progresses in Si anode. We concern about the nanostructure of silicon, cooperation of silicon with other additives and macrostructure design of anodes. We discuss strengths and shortcomings of different methods, …

Template-Assisted Hydrothermal Synthesis Of Nio@Co3O4 Hollow Spheres With Hierarchical Porous Surfaces For Supercapacitor Applications, Wen Zhou, Xue-Feng Lu, Ming-Mei Wu, Gao-Ren Li

Journal of Electrochemistry

Hollow structures have shown great potentials in a variety of important applications, such as energy conversion and storage. In order to further enhance the performance, the rational design of hollow structures with higher complexity in terms of composition and structure is highly desirable and still remains a great challenge. In this work, an efficient strategy was established for the fabrication of novel NiO@Co₃O₄ hollow spheres (HSs) with hierarchical porous surfaces by silica spheres template-assisted hydrothermal synthesis. The as-fabricated NiO@Co₃O₄ HSs showed high specific surface area of 219.68 m²·g^-1, and significant …

Effects Of Lithium Salts On The Properties Of Hyperbrandched/Comb-Like Composite Polymer Electrolytes, Xian-Lei Hu, Xiao-Xu Liang, Ming-Qiu Zhang, Ruo-Xin Zhang, Li-Ping Zhang, Wen-Hong Ruan

Journal of Electrochemistry

Based on the chemical characteristics of the hydroxyl group of PVA side-chain, the hyperbrandched poly(amine-ester) (HBPAE) was used to hypergraftingly pretreated nano-silica (SiO₂) and polyving akohol (PVA). And different lithium salts were added to fabricate the SiO₂-g-HBPAE/PVA-g-HBPAE hyperbrandched/comb-like composite polymer electrolytes (CPEs). The dispersion of nanoparticles in matrix was observed by SEM. The effects of different lithium salts on the properties of CPEs were studied by DSC, tensile test and dielectric spectra. The results showed that the hypergrafting method improved the interphase compatibility between SiO₂ and matrix. Sulfonic acid type lithium salts accelerated self-plasticizing with …

Assessment Of The Presence And Strength Of H-Bonds By Means Of Corrected Nmr, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The downfield shift of the NMR signal of the bridging proton in a H-bond (HB) is composed of two elements. The formation of the HB causes charge transfer and polarization that lead to a deshielding. A second factor is the mere presence of the proton-accepting group, whose electron density and response to an external magnetic field induce effects at the position of the bridging proton, exclusive of any H-bonding phenomenon. This second positional shielding must be subtracted from the full observed shift in order to assess the deshielding of the proton caused purely by HB formation. This concept is applied …

Infrared Spectroscopy Of The Nitrogenase Mofe Protein Under Electrochemical Control: Potential-Triggered Co Binding, P. Paengnakorn, Philip A. Ash, Sudipta K. Shaw, Karamatullah Danyal, T. Chen, Dennis R. Dean, Lance C. Seefeldt, Kylie A. Vincent

Chemistry and Biochemistry Faculty Publications

We demonstrate electrochemical control of the nitrogenase MoFe protein, in the absence of Fe protein or ATP, using europium(III/II) polyaminocarboxylate complexes as electron transfer mediators. This allows the potential dependence of proton reduction and inhibitor (CO) binding to the active site FeMo-cofactor to be established. Reduction of protons to H2 is catalyzed by the wild type MoFe protein and Β-98^Tyr→His and Β-^99Phe→His variants of the MoFe protein at potentials more negative than -800 mV (vs. SHE), with greater electrocatalytic proton reduction rates observed for the variants compared to the wild type protein. Electrocatalytic proton reduction is strongly …

The Tribology And Chemistry Of Phosphorus Containing Lubricant Additives, David W. Johnson

Chemistry Faculty Publications

Phosphate esters, thiophosphate esters and metal thiophosphates have been used as lubricant additives for over 50 years. Recently, phosphorus‐containing ionic liquids have emerged as a new class of lubricant additives. While the use of phosphorus compounds has been extensive, a detailed knowledge of how they work has been a much more recent development. In this chapter, the use of phosphate esters, thiophosphate esters, metal thiophosphates and phosphorus‐containing ionic liquids as antiwear or extreme pressure additives is discussed. The primary emphasis will be on how they form a protective film, which is both durable and reduces friction. The first part of …

Asymmetric Transformations Catalyzed By Chiral Binol Alkaline Earth Metal Phosphate Complexes, Sri Krishna Nimmagadda

USF Tampa Graduate Theses and Dissertations

Small molecule hydrogen bond donors have emerged as versatile catalysts in asymmetric synthesis. Within this class, chiral BINOL phosphoric acid is regarded as one of the pioneer catalysts used in several asymmetric transformations. The ability of the catalyst to activate the substrates could be controlled in two different ways. (1) Dual activation/bifunctional activation of substrate by hydrogen bond interactions or ion pairing with phosphoric acid or (2) By forming chiral BINOL phosphate metal complex that could significantly alter the interactions in chiral space. In particular, chiral alkaline earth metal phosphate complexes have unique advantages as catalysts owing to the ubiquitous …

Evolution From The Plasmon To Exciton State In Ligand-Protected Atomically Precise Gold Nanoparticles, Meng Zhou, Chenjie Zeng, Yuxiang Chen, Shuo Zhao, Matthew Y. Sfeir, Manzhou Zhu, Rongchao Jin

Publications and Research

The evolution from the metallic (or plasmonic) to molecular state in metal nanoparticles constitutes a central question in nanoscience research because of its importance in revealing the origin of metallic bonding and offering fundamental insights into the birth of surface plasmon resonance. Previous research has not been able to probe the transition due to the unavailability of atomically precise nanoparticles in the 1-3 nm size regime. Herein, we investigate the transition by performing ultrafast spectroscopic studies on atomically precise thiolate-protected Au₂₅, Au₃₈, Au₁₄₄, Au₃₃₃, Au_∼520 and Au_∼940 nanoparticles. Our results …

Block Ionomer Complexes Consisting Of Sirna And ARaft-Synthesized Hydrophilic-Block-Cationic Copolymers Ii: The Influence Of Cationic Block Charge Density On Gene Suppression, Keith Hampton Parsons, Andrew Christopher Holley, Gabrielle A. Munn, Alex S. Flynt, Charles L. Mccormick

Faculty Publications

Block ionomer complex (BIC)–siRNA interactions and effectiveness in cell transfection are reported. Aqueous RAFT polymerization was used to prepare a series of hydrophilic-block-cationic copolymers in which the cationic block statistically incorporates increasing amounts of neutral, hydrophilic monomer such that the number of cationic groups remains unchanged but the cationic charge density is diluted along the polymer backbone. Reduced charge density decreases the electrostatic binding strength between copolymers and siRNA with the goal of improving siRNA release after targeted cellular delivery. However, lower binding strength resulted in decreased transfection and RNA interference pathway activation, leading to reduced gene knockdown. Enzymatic siRNA …

Design And Development Of Peptidomimetic Ligands For Targeting Radiopharmaceuticals, Imaging Probes, And Immunotherapeutics In Oncologic Disease, Michael Lawrence Doligalski

USF Tampa Graduate Theses and Dissertations

Cancer is a leading cause of morbidity and mortality in the developed world. While much has been learned about these diseases in the last few decades, one of the main barriers to widespread advancement is the heterogeneity of cancer biology. A growing body of evidence supports the idea that certain protein receptors are overexpressed on the surface of tumor cells as compared to normal tissues. These extracellular biomarkers provide a unique opportunity to selectively target the tumor with both imaging and therapeutic modalities. The research in this dissertation focuses on targeting proteins on the tumor cell surface with peptidomimetic ligands. …

Synthesis, Structure And Antimicrobial Property Of Green Composites From Cellulose, Wool, Hair And Chicken Feather, Chieu D. Tran, Franja Prosenc, Mladen Franko, Gerald Benzi

Chemistry Faculty Research and Publications

Novel composites between cellulose (CEL) and keratin (KER) from three different sources (wool, hair and chicken feather) were successfully synthesized in a simple one-step process in which butylmethylimidazolium chloride (BMIm⁺Cl⁻), an ionic liquid, was used as the sole solvent. The method is green and recyclable because [BMIm⁺Cl⁻] used was recovered for reuse. Spectroscopy (FTIR, XRD) and imaging (SEM) results confirm that CEL and KER remain chemically intact and homogeneously distributed in the composites. KER retains some of its secondary structure in the composites. Interestingly, the minor differences in the structure of KER …

Green Chemistry: Progress And Barriers, Sarah A. Green

Michigan Tech Publications, Part 1

Green chemistry can advance both the health of the environment and the primary objectives of the chemical enterprise: to understand the behavior of chemical substances and to use that knowledge to make useful substances. We expect chemical research and manufacturing to be done in a manner that preserves the health and safety of workers; green chemistry extends that expectation to encompass the health and safety of the planet. While green chemistry may currently be treated as an independent branch of research, it should, like safety, eventually become integral to all chemistry activities. While enormous progress has been made in shifting …

A Thermodynamic Description Of The Adsorption Of Simple Water-Soluble Peptoids To Silica, Anna L. Calkins, Jennifer Yin, Jacenda L. Rangel, Madeleine R. Landry, Amelia A. Fuller, Grace Y. Stokes

Chemistry and Biochemistry

The first report of a water-soluble peptoid adsorbed to silica monitored by second harmonic generation (SHG) at the liquid/solid interface is presented here. The molecular insights gained from these studies will inform the design and preparation of novel peptoid coatings. Simple 6- and 15-residue peptoids were dissolved in phosphate buffered saline and adsorbed to bare silica surfaces. Equilibrium binding constants and relative surface concentrations of adsorbed peptoids were determined from fits to the Langmuir model. Complementary fluorescence spectroscopy studies were used to quantify the maximum surface excess. Binding constants, determined here by SHG, were comparable to those previously reported for …

Effects Of Sintering Parameters On The Microstructure And Tensile Properties Of In Situ (Ti5si3 + Tibw)/Ti6al4v Composites With Two-Scale Network Architecture, Yang Jiao, L. J. Huang, L. Geng

The 8th International Conference on Physical and Numerical Simulation of Materials Processing

No abstract provided.

Highly Selective Halide Receptors Based Upon Chalcogen, Pnicogen, And Tetrel Bonds, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The interactions of halides with a number of bipodal receptors are examined via quantum chemical methods. The receptors are based upon a dithieno thiophene framework in which two S atoms can engage in a pair of chalcogen bonds with a halide. These two S atoms are replaced by P and As atoms to compare chalcogen with pnicogen bonding, and by Ge which engages in tetrel bonds with the receptor. Zero, one, and two O atoms are added to the thiophene S atom which is not directly involved in the interaction with the halides. Fluoride is bound the most strongly, followed …

Recent Approaches In Designing Bioadhesive Materials Inspired By Mussel Adhesive Protein, Pegah Kord Forooshani, Bruce P. Lee

Department of Biomedical Engineering Publications

Marine mussels secret protein-based adhesives, which enable them to anchor to various surfaces in a saline, intertidal zone. Mussel foot proteins (Mfps) contain a large abundance of a unique, catecholic amino acid, Dopa, in their protein sequences. Catechol offers robust and durable adhe-sion to various substrate surfaces and contributes to the curing of the adhesive plaques. In this article, we review the unique features and the key functionalities of Mfps, catechol chemistry, and strategies for preparing catechol-functionalized poly- mers. Specifically, we reviewed recent findings on the contributions of various features of Mfps on interfacial binding, which include coacervate formation, surface …

Atomic Tiles: Manipulative Resources For Exploring Bonding And Molecular Structure, Alan L. Kiste, Rebecca G. Hooper, Gregory E. Scott, Seth Bush

Chemistry and Biochemistry

A simple manipulative resource, Atomic Tiles, is described for scaffolding the learning of Lewis structures without using algorithmic, rule-based methods of drawing. Students use Atomic Tiles to (1) create models of bonding that lead to drawing Lewis structures, (2) use the structures they create to infer patterns required for rational structures and common organic functional groups, (3) translate between Lewis structures and molecular models, and (4) use molecular models to identify isomers.

The Structure Of The Antibiotic Deactivating, N-Hydroxylating Rifampicin Monooxygenase, Li Kai Liu, Heba Abdelwahab, Julia S. Martin Del Campo, Ritcha Mehra-Chaudhary, Pablo Sobrado, John J. Tanner

Chemistry Faculty Research & Creative Works

Rifampicin monooxygenase (RIFMO) catalyzes the N-hydroxylation of the natural product antibiotic rifampicin (RIF) to 2′-N-hydroxy-4-oxo-rifampicin, a metabolite with much lower antimicrobial activity. RIFMO shares moderate sequence similarity with well characterized flavoprotein monooxygenases, but the protein has not been isolated and characterized at the molecular level. Herein, we report crystal structures of RIFMO from Nocardia farcinica, the determination of the oligomeric state in solution with small angle x-ray scattering, and the spectrophotometric characterization of substrate binding. The structure identifies RIFMO as a class A flavoprotein monooxygenase and is similar in fold and quaternary structure to MtmOIV and OxyS, which are enzymes …

The Missing Electrostatic Interactions Between Dna Substrate And Sulfolobus Solfataricus Dna Photolyase: What Is The Role Of Charged Amino Acids In Thermophilic Dna Binding Proteins?, Yvonne Gindt, Ban H. Edani, Antonia Olejnikova, Ariana N. Roberts, Sudipto Munshi, Robert J. Stanley

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

DNA photolyase can be used to study how a protein with its required cofactor has adapted over a large temperature range. The enzymatic activity and thermodynamics of substrate binding for protein from Sulfolobus solfataricus were directly compared to protein from Escherichia coli. Turnover numbers and catalytic activity were virtually identical, but organic cosolvents may be necessary to maintain activity of the thermophilic protein at higher temperatures. UV-damaged DNA binding to the thermophilic protein is less favorable by ∼2 kJ/mol. The enthalpy of binding is ∼10 kJ/mol less exothermic for the thermophile, but the amount and type of surface area buried …

A Simple Model Of The Chromatographic Process, Charles F. Babbs

Weldon School of Biomedical Engineering Faculty Working Papers

No abstract provided.

Synthesis And Characterization Of Polycyclic Aromatic Hydrocarbon ( Pah )-Porphyrin Hybrids, Ruixiao Gao

Theses and Dissertations

Carbaporphyrins are porphyrin analogs where one or more pyrrole units are replaced with a carbocyclic ring. Benziporphyrins are porphyrin analogues with a 1,3-phenylene unit replacing one of the pyrrole subunits. Because of cross-conjugation, benziporphyrins are not aromatic species. However, protonation of benziporphyrins can afford some aromatic characteristics. Although the synthesis of many examples of monocarbaporphyrins have been successfully executed, no examples of porphyrinoids with pyrene subunits have been prepared. Pyrene-containing porphyrinoids, which have been named as pyreniporphyrins, are theoretically significant molecules that provide insights into the aromaticity and reactivity of porphyrinoid systems.

In this thesis, two projects were conducted to …

The Origin Of Efficient Triplet State Population In Sulfur-Substituted Nucleobases, Marvin Pollum, Nicholas Dunn, Carlos E. Crespo-Hernández

Faculty Scholarship

Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces …