Chemistry Commons^™

Infrared Spectroelectrochemistry Of Iron-Nitrosyl Triarylcorroles. Implications For Ligand Noninnocence, Md. Hafizur Rahman, Michael D. Ryan, Hugo Vazquez-Lima, Abraham Alemayehu, Abhik Ghosh

Chemistry Faculty Research and Publications

Recent DFT calculations have suggested that iron nitrosyl triarylcorrole complexes have substantial {FeNO}⁷–corrole^•2– character. With this formulation, reduction of Fe(C)(NO) complexes, where C = triarylcorrole, should be centered on the corrole macrocycle rather than on the {FeNO}⁷ moiety. To verify this proposition, visible and infrared spectroelectrochemical studies of Fe(C)(NO) were carried out and the results were interpreted using DFT (B3LYP/STO-TZP) calculations. The first reduction of Fe(C)(NO) led to significant changes in the Soret and Q-band regions of the visible spectrum as well as to a significant downshift in the ν_NO and changes in the corrole …

Inquiry Based Instruction In Chemistry With Games, Karen Ye

Professional Learning Day

Games can be a fun and motivating way to engage students, but they are often used as a means to practice, apply, or review learned content instead of introducing a new concept. In this session, participants will explore the use of common games as a tool for an inquiry-based approach to introducing topics in high school chemistry such as atomic structure and periodic trends.

Inquiry Based Instruction In Chemistry With Games, Karen Ye

Professional Learning Day

Games can be a fun and motivating way to engage students, but they are often used as a means to practice, apply, or review learned content instead of introducing a new concept. In this session, participants will explore the use of common games as a tool for an inquiry-based approach to introducing topics in high school chemistry such as atomic structure and periodic trends.

Structures And Electrochemical Properties Of Sn-Cl Co-Doped Li2Mno3 As Positive Materials For Lithium Ion Batteries, Fei Wang, Huan-Huan Zhai, Du-Dan Wang, Yu-Peng Li, Kang-Hua Chen

Journal of Electrochemistry

Positive material Li₂MnO₃ shows the highest ratio of lithium to manganese among lithium-rich materials and exhibites the theoretical capacity up to 458 mAh·g^-1, making it one of the most promising cathode materials. However, this material has the intrinsic low electrical conductivity and poor cycle stability. In this paper, Li₂MnO₃, the lithium-rich positive material, was prepared by sol-gel method using acetate as raw material and citric acid as a complexing agent. By using SnC₂O₄ as a tin source, Sn⁴⁺ instead of Mn⁴⁺ was introduced to obtain the …

Lithium Storage Performance Of High Capacity Material Si@CPzs In Lithium Ion Batteries, Qing-Nuan Zhang, Fang-Fang Zhang, Hong-Xia Li, Bing-Jun Yang, Xiao-Cheng Li, Juan Yang

Journal of Electrochemistry

Carbon layers with different thicknesses were introduced into the surfaces of silicon (Si) nanoparticles by sol-gel method using poly (cyclotriphosphazene-co-4, 4'-sulfonyldiphenol) as the carbon source. Technologies of X-ray diffraction, thermo-gravimetric analysis, Brunauer-Emmett-Teller and transmission electron microscopy were employed to analyze the structures and components of the as-prepared Si@C_PZS composites. Electrochemical performance of Si@C_PZS with different carbon thicknesses was studied. The results showed that Si@C_PZS with carbon thickness of 10 nm possessed the best performance. Its capacity remained 940 mAh·g^-1 after 290 cycles under 500 mA·g^-1. As the addictive, the graphite-based anode contained 30% of …

Preparations Of Nickel-Iron Hydroxide/Sulfide And Their Electrocatalytic Performances For Overall Water Splitting, Hang-Shuo Lu, Xiao-Bo He, Feng-Xiang Yin, Guo-Ru Li

Journal of Electrochemistry

The Ni-Fe/Ti oxygen evolution electrode was prepared by electrodeposition on a titanium mesh substrate. Then, the as prepared Ni-Fe/Ti electrode was used to derive the Ni-Fe-S/Ti hydrogen evolution electrode through solid phase sulfuration. The effects of the molar ratio of Ni²⁺ to Fe³⁺ in the electrolyte and the amount of thiourea on the structures and electrochemical performances of Ni-Fe/Ti and Ni-Fe-S/Ti electrodes were investigated. The results show that the oxygen evolution performance of Ni-Fe/Ti electrode was first increased and then decreased with the increase of nickel ion content in the electrolyte. The Ni9Fe1/Ti electrode exhibited the best oxygen …

Atomic Force Microscopic Characterization Of Solid Electrolyte Interphase In Lithium Ion Batteries, Qing-Yu Dong, Yan-Li Chu, Yan-Bin Shen, Li-Wei Chen

Journal of Electrochemistry

In recent years, the rapid growing in the electric vehicle market has raised higher requirement on the lithium-ion batteries (LIBs) performance towards energy density and safety. However, considering the successful development of LIBs techniques in the past 30 years, there is little room left for improving the LIBs performance on the aspects related to the electrode materials, battery structure design and production processes. It is important to pursue more comprehensive fundamental understanding in the entire system and working principle of LIBs. Solid electrolyte interphase (SEI), existing between the electrode material and the electrolyte, has been proved to be an important …

Electrochemical Impedance Spectroscopy For Electrocatalytic Interfaces And Reactions: Classics Never Die, Jun Huang

Journal of Electrochemistry

This review article recapitulates electrochemical impedance spectroscopy (EIS) studies in the field of electrocatalysis. The history of this specialized field, ranging from the beginning of the twentieth century to now, is outlined. We then chronicle milestones of the impedance theory. Special emphases are put on the Dolin-Ershler model, the prevailing model for analyzing adsorption impedance data. Afterwards, we narrow into a very specific and fundamental topic, the double-layer capacitance at platinum (Pt) single crystals. We discuss the challenges in experimentation and theoretical understanding thereof. We cast doubts into the validity of using the Dolin-Ershler model to obtain the double-layer capacitance …

Electrochemical Preparations And Applications Of Nano-Catalysts With High-Index Facets, Chi Xiao, Na Tian, Zhi-You Zhou, Shi-Gang Sun

Journal of Electrochemistry

The performance of catalysts highly depends on their surface structure and composition. Nanocrystals bounded by high-index facets usually exhibit high catalytic activity due to their high-density low-coordinated step atoms with high reactivity. In this paper, we have reviewed the preparations of noble metals (e.g., Pt, Pd and Rh) nanocatalysts with high-index facets by electrochemical square-wave potential method developed in our group. The square-wave potential method includes a nucleation procedure to generate nuclei, followed by a square-wave potential procedure for a certain period of time for the growth of nuclei into nanocrystals. The formation mechanism of high-index facets is also discussed. …

Insight Into The Important Solid/Liquid Double Layer From First-Principles Calculations, Ya-Hui Fang, Zhi-Pan Liu

Journal of Electrochemistry

Solid/liquid double layer is of fundamental importance in electrochemistry. It has been a challenge and focus to understand the equilibrium and the dynamic phenomena (e.g., chemical reactions) at the electrode/electrolyte double layer in a unified theoretical framework. In recent years, rapid expansion and development have been done in the application of first principles density function theory (DFT) simulation on the double layer. This article reviews the current theoretical methods for electrochemistry modeling, such as reaction center model, thermodynamic method and double reference model. The progress in the computation procedures based on first principles periodic continuum solvation method (DFT/CM-MPB) for obtaining …

Recent Progress In The Mechanistic Understanding Of Co2 Reduction On Copper, Matthew M Sartin, Wei Chen, Fan He, Yan-Xia Chen

Journal of Electrochemistry

In this review, we present the major developments in the understanding of the mechanisms of the electrochemical reduction of CO₂ from a historical perspective. Most of the work discussed in this review was carried out at copper electrodes, as this is the only material at which hydrocarbons are produced in reasonable quantities. The emphasis focuses on the differentiation of mechanisms for the generation of C1 and C2 products as well as factors and methods for controlling the product selectivity of CO₂ reduction. We have highlighted ambiguities, assumptions, and important methodologies, such as differential electrochemical mass spectrometry and electrochemical …

In-Situ Raman Spectroscopic Study Of Electrochemical Reactions At Single Crystal Surfaces, Min Su, Jin-Chao Dong, Jian-Feng Li

Journal of Electrochemistry

Since the 1970s, in-situ spectroscopy (Raman, infrared, etc.) has been used to systematically study the electrochemical interfacial reactions which can provide more information about surface reactions and reveal the mechanisms from microscopic view due to its excellent surface sensitivity and energy resolution. With the development of nano-technology, surface-enhanced Raman scattering effect spectroscopy has made rapid progress. Recently, the emergence of SHINERS provides a good in-situ spectroscopic technique for the study of catalytic reactions on single crystal model electrodes with deterministic surface structure. In this paper, we have summarized the application of SHINERS in the study of …

Encouraging More Frogs In Electrochemistry, Yan-Xia Chen, Jun Huang, Dong-Ping Zhan

Journal of Electrochemistry

No abstract provided.

Research Progresses In Ni-Co-Mn/Al Ternary Concentration Gradient Cathode Materials For Li-Ion Batteries, Chun-Fang Zhang, Wen-Gao Zhao, Shi-Yao Zheng, Yi-Xiao Li, Zheng-Liang Gong, Zhong-Ru Zhang, Yong Yang

Journal of Electrochemistry

Nickel-rich ternary materials with large reversible capacity as well as high operating voltage are considered as the most promising candidate for next generation lithium-ion batteries (LIBs). However, the inferior cycle stability and thermal stability have limited their widely commercial applications. Concentration gradient design of Ni-Co-Mn/Al ternary concentration gradient materials have been extensively studied in the past decade, which can ensure high cycle capacity while maintaining excellent cycle stability. In this paper, the latest research progresses in Ni-Co-Mn/Al ternary concentration gradient materials for LIBs are reviewed. Firstly, we summarize the different synthesis methods of ternary concentration-gradient materials, especially focusing on the …

Effect Of Nitrogen Content In Catalyst Precursor On Activity Of Fen/C Catalyst For Oxygen Reduction Reaction, Zhi Yang, Ya-Yun Shen, E Zhou, Cheng-Ling Wei, Hao-Li Qin, Juan Tian

Journal of Electrochemistry

Non-noble metal catalysts with high activity and low cost have attracted increasing interest as potential catalysts for oxygen reduction reaction (ORR) to replace Pt-based catalysts. In this paper, the effect of nitrogen content in catalyst precursor on ORR activity of FeN/C catalyst was investigated by X-ray diffraction (XRD), Brunauer-Emmet-Teller (BET) surface area and pore size distribution measurements, transmission electron microscope (TEM), thermogravimetric analysis (TGA), and rotating disk electrode (RDE) techniques. The results show that the most active catalyst was obtained by pyrolysis in argon at 1050 °C with a catalyst precursor containing 20wt% 1,10-phenanthroline, 1wt% Fe and Black Pearl 2000. …

Challenges In The Activity And Stability Of Pt-Based Catalysts Toward Orr, Tuo Zhao, Er-Gui Luo, Xian Wang, Jun-Jie Ge, Chang-Peng Liu, Wei Xing

Journal of Electrochemistry

The development of highly efficient oxygen reduction reaction (ORR) catalysts is the key to the commercialization of fuel cells, where the sluggish ORR reaction rate needs to be overcome by adjusting the intermediates adsorption energies on the catalytic surfaces. To-date, platinum (Pt)-based materials are the-state-of-the-art catalysts in terms of both activity and stability in ORR, making them the preferred choice for commercial applications. However, the high cost of Pt-based catalysts limits their widespread use, leading to massive effects paid in reducing Pt loading, improving catalyst activity and stability. This article illustrates the challenges in the ORR reaction and introduces the …

Preparation And Electrocatalytic Performance Of Nico2O4/Ni Foam For Hydrogen Peroxide Electrooxidation, Wei-Wei Chen, Fei-Fan Zhang, Jia-Liang Du, Yi Wang, Chun-Lin Zhao, Kai Zhu, Dian-Xue Cao, Gui-Ling Wang

Journal of Electrochemistry

The electrodes of Ni foam supported NiCo₂O₄ nanowires were prepared by hydrothermal method, followed by a thermal treatment in air, and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the NiCo₂O₄ nanowires had a diameter of about 50 nm with a length up to 3 ~ 5 μm. The catalytic performances of the Ni foam supported NiCo₂O₄ nanowires for H₂O₂ electrooxidation were studied by cyclic voltammetry and chronoamperometry. The results show that the Ni foam supported NiCo …

Research Progresses In Polymeric Proton Exchange Membranes For Fuel Cells, Xu-Po Liu, Yun-Feng Zhang, Shao-Feng Deng, De-Li Wang, Han-Song Cheng

Journal of Electrochemistry

Proton exchange membrane (PEM) is one of the key components in PEM fuel cells, which possesses the function of separating the cathode and anode, affording proton transport channels and preventing fuel permeability. The property of PEM significantly influences the performance and service life of fuel cells. Nowadays, the commercially used Nafion membranes have the shortcomings of serious fuel permeability, low proton conductivity at elevated temperature and high price, which limits the rapid development of PEM fuel cells. Therefore, it seems to be urgent to develop novel PEMs with low cost and good comprehensive properties. Polymeric proton exchange membrane is an …

Surface Reservoirs Dominate Dynamic Gas-Surface Partitioning Of Many Indoor Air Constituents, Chen Wang, Douglas B. Collins, Caleb Arata, Allen H. Goldstein, James M. Mattila, Delphine K. Farmer, Laura Ampollini, Peter F. Decarlo, Atila Novoselac, Marina E. Vance, William W. Nazaroff, Jonathan P.D. Abbatt

Faculty Journal Articles

Human health is affected by indoor air quality. One distinctive aspect of the indoor environment is its very large surface area that acts as a poorly characterized sink and source of gas-phase chemicals. In this work, air-surface interactions of 19 common indoor air contaminants with diverse properties and sources were monitored in a house using fast-response, on-line mass spectrometric and spectroscopic methods. Enhanced-ventilation experiments demonstrate that most of the contaminants reside in the surface reservoirs and not, as expected, in the gas phase. They participate in rapid air-surface partitioning that is much faster than air exchange. Phase distribution calculations are …

Assessment Of Soil Protein And Refractory Soil Organic Matter Across Two Chronosequences Of Newly Developing Marshes In Coastal Louisiana, Usa, Stuart Alexander Mcclellan

LSU Doctoral Dissertations

The impacts of sea-level rise and hydrologic manipulation are threatening the stability of coastal marshes throughout the world, thereby increasing the potential for re-mineralization of soil organic matter (SOM) in these systems. Such threats have prompted marsh restoration efforts, particularly in coastal Louisiana, yet it is unclear how the slowly decomposing (refractory) and quickly decomposing (labile) fractions of SOM may be differentially affected by different approaches to marsh restoration. Additionally, otherwise labile compounds may accumulate in the soil via a range of protective mechanisms, including rapid burial and association with organic compounds that are thought to enhance soil aggregation, such …

Yeast Copper Proteins And Reactive Oxygen Species In Effecting Lifespan, Megan Bestwick

Post-Grant Reports

Mitochondria are essential organelles in most eukaryotic cells because of their role in metabolism and the production of ATP by the oxidative phosphorylation (OXPHOS) pathway, as well as other key cellular processes. Metal cofactors, such as copper (Cu) and iron (Fe), are incorporated into OXPHOS protein complexes of yeast located within the inner membrane of the mitochondria. Misincorporation or modulation of these available metals in mitochondrial enzymes leads to the production of reactive oxygen species (ROS). ROS are reactive molecules containing oxygen such as peroxides, superoxide, and hydroxyl radicals. Yeast are a good model for studying aging and the effect …

The Allometry Of Daily Energy Expenditure In Hummingbirds: An Energy Budget Approach, Anushu Shankar, Donald R. Powers, Liliana M. Dávalos, Catherine H. Graham

Faculty Publications - Department of Biological & Molecular Science

1. Within-clade allometric relationships represent standard laws of scaling between energy and size, and their outliers provide new avenues for physiological and ecological research. According to the metabolic-level boundaries hypothesis, metabolic rates as a function of mass are expected to scale closer to 0.67 when driven by surface-related processes (e.g. heat or water flux), while volume-related processes (e.g. activity) generate slopes closer to one.

2. In birds, daily energy expenditure (DEE) scales with body mass (M) in the relationship log (DEE)=2.35+0.68×log (M), consistent with surface-level processes driving the relationship. However, taxon-specific patterns differ from the scaling slope of all birds. …

Force Field Development Of Β-Lactam Class Antibiotics, Trevor Heinzmann

SMU Journal of Undergraduate Research

Molecular dynamics (MD) simulation is a computational chemistry technique used to observe how a molecular system behaves as time passes. MD is based on solving Newton’s equations of motion. This requires the use of force fields to describe the potential energy function of each different molecule type in molecular system. In order to develop a force field, charges, bonds, angles, and dihedrals must be parameterized to fit quantum mechanics (QM) data. By basing the force field on QM data, MD simulations have higher accuracy while still using the low computational cost of molecular mechanics. This project focuses on developing well-fit …

Quantitative Trait Loci (Qtl) Underlying Phenotypic Variation In Bioethanol-Related Processes In Neurospora Crassa, Joshua C. Waters, Deval Jhaveri, Justin C. Biffinger, Kwangwon Lee

Chemistry Faculty Publications

Bioethanol production from lignocellulosic biomass has received increasing attention over the past decade. Many attempts have been made to reduce the cost of bioethanol produc- tion by combining the separate steps of the process into a single-step process known as consolidated bioprocessing. This requires identification of organisms that can efficiently decompose lignocellulose to simple sugars and ferment the pentose and hexose sugars lib- erated to ethanol. There have been many attempts in engineering laboratory strains by add- ing new genes or modifying genes to expand the capacity of an industrial microorganism. There has been less attention in improving bioethanol-related processes …

Assessing Differences Between Three Virtual General Chemistry Experiments And Similar Hands-On Experiments, Cory Hensen, Gosia Glinowiecka-Cox, Jack Barbera

Chemistry Faculty Publications and Presentations

To date the efficacy of virtual experiments is not well understood. To better understand what differences may exist between a hands-on learning environment and a virtual learning environment, three experiments were chosen for investigation. For each experiment, approximately half of the students completed a hands-on version of the experiment and the other half completed a virtual version. After completing the given experiment, students were compared on: their ability to meet the learning objectives for that experiment, their responses to six affective scales, and their grade on a laboratory report. Differences were found on four learning objectives. Two of these learning …

Polymers For Extrusion‐Based 3d Printing Of Pharmaceuticals: A Holistic Materials–Process Perspective, Mohammad A. Azad, Deborah Olawuni, Georgia Kimbell, Abu Zayed Badruddoza, Md. Shahadat Hossain, Tasnim Sultana

Publications and Research

Three dimensional (3D) printing as an advanced manufacturing technology is progressing to be established in the pharmaceutical industry to overcome the traditional manufacturing regime of ʹone size fits for allʹ. Using 3D printing, it is possible to design and develop complex dosage forms that can be suitable for tuning drug release. Polymers are the key materials that are necessary for 3D printing. Among all 3D printing processes, extrusion‐based (both fused deposition modeling (FDM) and pressure‐assisted microsyringe (PAM)) 3D printing is well researched for pharmaceutical manufacturing. It is important to understand which polymers are suitable for extrusion‐based 3D printing of pharmaceuticals …

Advancing Equity Amongst General Chemistry Students With Variable Preparations In Mathematics, Vanessa R. Ralph

USF Tampa Graduate Theses and Dissertations

Reducing the inequities propagating the lack of representation in Science, Technology, Engineering, and Mathematics (STEM) careers has become a national imperative made increasingly complex given the inequitable preparations in science and mathematics students experience before college. A common institutional-level approach to promoting equity is the use of math and science prerequisites to prepare students who seek to enroll in lower-level STEM coursework. However, the literature does not support the efficacy of this approach, finding no substantive improvement to student performance despite considerable financial and time costs to students, instructors, and universities alike. Set in first-semester General Chemistry courses taken early …

Electrochemical Studies Of Cobalt(Ii) Diphenylazodioxide Complexes, Lakshmi Balarama, Kylin A. Emhoff, Ahmed M.H. Salem, Jovana Hanna, Mohamed N. Alsabony, Mekki Bayachou, Jerry Mundell, W. Christropher Boyd

Chemistry Faculty Publications

The electrochemical behavior of the unusual cobalt(II) diphenylazodioxide complex salts [Co(az)₄](PF₆)₂ 1 and [Co(bpy)(az)₂](PF₆)₂ 2 has been studied by cyclic voltammetry. Each complex displays two quasireversible redox couples, which are proposed to correspond to a reduction of Co(II) to Co(I), followed by a ligand-based reduction. Irreversible reductions of 1 are observed at more negative potentials, and are proposed to arise from deposition of elemental Co and the decomposition of transiently formed Co(-I) species. Spectroelectrochemical experiments on both 1 and 2, involving electrolytic reduction followed by reoxidation, are consistent with …

Competition Between Intra And Intermolecular Triel Bonds. Complexes Between Naphthalene Derivatives And Neutral Or Anionic Lewis Bases, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

A TrF₂ group (Tr = B, Al, Ga, In, Tl) is placed on one of the α positions of naphthalene, and its ability to engage in a triel bond (TrB) with a weak (NCH) and strong (NC⁻) nucleophile is assessed by ab initio calculations. As a competitor, an NH₂ group is placed on the neighboring C^α, from which point it forms an intramolecular TrB with the TrF₂ group. The latter internal TrB reduces the intensity of the π-hole on the Tr atom, decreasing its ability to engage in a second external TrB. The …

Polyphenols In Alzheimer’S Disease And In The Gut–Brain Axis, V. Prakash Reddy, Puspa Aryal, Sara Robinson, Raheemat Rafiu, Mark Obrenovich, George Perry

Chemistry Faculty Research & Creative Works

Polyphenolic antioxidants, including dietary plant lignans, modulate the gut–brain axis, which involves transformation of these polyphenolic compounds into physiologically active and neuroprotector compounds (called human lignans) through gut bacterial metabolism. These gut bacterial metabolites exert their neuroprotective effects in various neurodegenerative diseases, such as Alzheimer's disease (AD) and Parkinson's disease (PD), and also have protective effects against other diseases, such as cardiovascular diseases, cancer, and diabetes. For example, enterolactone and enterodiol, the therapeutically relevant polyphenols, are formed as the secondary gut bacterial metabolites of lignans, the non-flavonoid polyphenolic compounds found in plant-based foods. These compounds are also acetylcholinesterase inhibitors and …