Materials Chemistry Commons^™

Photoelectrochemical Water Splitting Cells: Methods For Improving Performance Of Electrodes And Recent Progress On Photocathodes, Kai-Jian Zhu, Wen-Jun Luo, Zhong-Jie Guan, Xin Wen, Zhi-Gang Zou, Wei Huang

Journal of Electrochemistry

Photoelectrochemical water splitting can convert solar energy into hydrogen which is an ideal way to utilize and store solar energy. A p-n tandem cell is considered as the most promising solar water splitting cell due to its high theory conversion efficiency, low cost and photoelectrode material flexibility. However, solar conversion efficiency of a tandem cell is still low in the experiment because of poor performance in a single photoelectrode. In this review, we have introduced some effective approaches to improve the performances of photoelectrodes by reducing recombination of photogenerated carriers in the bulk or on the surface, and suppressing back …

Preparations And Photoelectrochemical Properties Of Phosphate Modified Rgo-Biobr Nanocomposites, Shuang-Ying Chen, Zhi-Jun Li, Xu-Liang Zhang, Kang Hu, Rui Yan, Li-Qiang Jing

Journal of Electrochemistry

The RGO-BiOBr nanocomposites have been successfully synthesized by a hydrothermal process, and then modified with phosphorous acids. The photoelectrochemical properties of the fabricated RGO-BiOBr nanocomposite films were studied. The results indicate that the photocurrent densities of RGO-BiOBr were much larger compared with those of the bare BiOBr, and interestingly, the photocurrent densities were further improved after phosphate modification. Based on the analyses of the produced hydroxyl radical amounts, the enhanced photocurrent densities could be attributed to the introduction of RGO and to the formed negative fields of modified phosphate groups, which are favorable for electrons to be transferred and for …

Solvent Effect On The Anticorrosive Properties And Active Coating Area Of A Long Alkyd Varnish, Saadawy M., Abd-El-Nabey B.A., Gomaa A.Z., Ashour M.

Journal of Electrochemistry

The effects of solvent nature and composition on the anticorrosive properties of a long alkyd varnish after different days of immersion in 0.5 mol•L^-1 NaCl were studied using electrochemical impedance spectroscopy. The protection efficiencies of the long alkyd varnishes containing different solvents increased with increasing the volatility of solvent or the composition of a given volatile solvent, which was confirmed with the observations using scanning electron microscopy and energy-dispersive X-Ray spectroscopy. The delaminated area, the area where the organic coating is detached from the metal surface leaving it unprotected, was found to decrease by increasing the volatility of solvent.

Discrimination Of Chiral Copper(Ii) Complexes Upon Binding Of Galactonoamidine Ligands, Susanne Striegler, Jessica Pickens

Chemistry & Biochemistry Faculty Publications and Presentations

The coordination between N-p-methylbenzyl-D-galactonoamidine, a putative transition state analogue of the hydrolyis of glycosidic bonds, and symmetric and chiral binuclear copper(II) complexes was characterized by spectroscopic titration, isothermal titration calorimetry, circular dichroism spectroscopy, and DFT calculations to elucidate the binding sites in the carbohydrate upon coordination to selected metal complexes. For the formation of metal complex-glyconoamidine assemblies, contributions of the amidine site and of the hydroxyl group at C-2 in the glycon of the amidine are noted. The chiral complexes S- and R-Cu2bpdbo are discriminated by a third binding site in the carbohydrate that leads to higher stability of complexes …

Engineering Nanoarchitectures From Nanosheets, Nanoscrolls, And Nanoparticles, Taha Rostamzadeh

LSU New Orleans Theses and Dissertations

The ability to encapsulate/insert different kinds of nanoparticles (NPs) in scrolled nanosheets (NSs) may lead to the formation of new nanocomposite materials that yield novel properties. These nanostructures resemble “peapods” that consist of NPs chains (“peas”) located in a hollow space of desired nanoscrolls (“pods”). Depending on different combinations of “peas” and “pods” diverse families of nanopeapods (NPPs) can be synthesized which may exhibit interesting properties not accessible from the individual components. Though there exist various synthetic methods for the formation of NPPs, more development in terms of simplicity, flexibility, and productivity of synthetic approaches are needed so that different …

Assembly Of Nucleic Acid-Based Nanoparticles By Gas-Liquid Segmented Flow Microfluidics, Matthew L. Capek, Ross Verheul, David H. Thompson

The Summer Undergraduate Research Fellowship (SURF) Symposium

The development of novel and efficient mixing methods is important for optimizing the efficiency of many biological and chemical processes. Tuning the physical and performance properties of nucleic acid-based nanoparticles is one such example known to be strongly affected by mixing efficiency. The characteristics of DNA nanoparticles (such as size, polydispersity, ζ-potential, and gel shift) are important to ensure their therapeutic potency, and new methods to optimize these characteristics are of significant importance to achieve the highest efficacy. In the present study, a simple segmented flow microfluidics system has been developed to augment mixing of pDNA/bPEI nanoparticles. This DNA and …

Density Functional Theory Based Electrolyte Design Formulation For Lithium-Sulfur Batteries, Cynthia Ly, Carolyn Sturges, Vijay Murugesan

STAR Program Research Presentations

Lithium-ion (Li-ion) batteries are commonly used in portable electronics such as cellphones and laptops. Most Li-ion batteries operate on intercalation principle with typical theoretical specific energy of 400-600 (Wh/Kg). There is great scientific interest in lithium-sulfur (Li-S) batteries as a possible successor of traditional Li-ion batteries because Li-S holds the potential of being a very powerful (1550 Wh/kg theoretical specific energy) yet very cost-efficient battery (due the abundance and inexpensiveness of sulfur). However, one major problem in Li-S battery research is the polysulfide “shuttle phenomenon”, which is the shuttling of polysulfide species due to the dissolution of sulfide from the …

Calculating The Energy Barriers Required To Join Metal-Organic Framework Synthesis Intermediates With Non-Equilibrium Molecular Simulation, Marcus A. Tubbs, David Cantu, Roger Rousseau, Vassiliki-Alexandra Glezakou

STAR Program Research Presentations

Metal organic frameworks are synthetic porous materials with great capacity for adsorption of carbon dioxide and methane. They chemically appear as a chain-link fence with nodes of metal connected by organic linkers. The pores between the nodes define the characteristics of the material, allowing gas particles of specific size to pass through while blocking larger particulates. While there has been success in synthesizing small amounts of metal organic frameworks, the mechanistic details behind their assembly remain unknown. Understanding the synthesis mechanism is necessary to understand the kinetics involved and be able to produce this useful material on an industrial scale. …

Using In Situ Liquid Single Photon Ionization Mass Spectrometry (Spi-Ms) To Probe Lithium Polysulfide Electrolyte In Motion, Aala M. Al Hasan, Jiachao Yu, Juan Yao, Vijayakumar Murugesan, Manjula Nandasiri, Xiao-Ying Yu

STAR Program Research Presentations

The solid-liquid (s-l) interface is the most common interface encountered in electrochemical systems. The s-l interface has wide applications in energy storage, catalysis, and material sciences. In situ studies of chemical reactions taking place on the s-l interfaces can further our understanding of electron transfer and link to real-world device functions under challenging conditions. Direct probing of the solid electrode and liquid electrolyte interface has been realized using a vacuum compatible electrochemical microfluidic reactor, system for analysis at the liquid vacuum interface (SALVI) with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Most recently, the electrochemical version of SALVI was integrated to …

Correlation Of Polymer Performance And Hansen Solubility Parameters, Daniel Jobse Mania

Master's Theses

Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it is a fast-growing product that not only is creating its own space, but is beginning to supplant existing technology.

The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC).

Polymer architecture was also determined to be extremely important, but …

Mida Boronates Are Hydrolysed Fast And Slow By Two Different Mechanisms, Jorge A. Gonzalez, O. Maduka Ogba, Gregory F. Morehouse, Nicholas Rosson, Kendall N. Houk, Andrew G. Leach, Paul H.-Y. Cheong, Martin D. Burke, Guy C. Lloyd-Jones

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

MIDA boronates (N-methylimidodiacetic boronic acid esters) serve as an increasingly general platform for building-block-based small molecule construction, largely due to the dramatic and general rate differences with which they are hydrolysed under various basic conditions. Yet the mechanistic underpinnings of these rate differences have remained unclear, hindering efforts to address current limitations of this chemistry. Here we show that there are two distinct mechanisms for this hydrolysis: one is base-mediated and the other neutral. The former can proceed more than three orders of magnitude faster, and involves rate-limiting attack at a MIDA carbonyl carbon by hydroxide. The alternative ‘neutral’ hydrolysis …

Co7se8 Nanostructures As Catalysts For Oxygen Reduction Reaction With High Methanol Tolerance, Jahangir Masud, Manashi Nath

Chemistry Faculty Research & Creative Works

Co₇Se₈ nanostructures electrodeposited on glassy carbon (GC) electrodes show high efficiency for oxygen reduction reaction (ORR) with high methanol tolerance as compared to Pt electrocatalysts. In the presence of methanol, the onset potential for the ORR at Pt/GC is shifted from 0.931 V (vs reversible hydrogen electrode (RHE)) to 0.801 V (vs RHE), whereas it remains the same (0.811 V vs RHE) at Co₇Se₈/GC in the presence and absence of methanol in 0.5 M H₂SO₄ solution. The Co₇Se₈/GC electrodes also showed high cyclability in the presence …

Synthesis And Applications Of Lanthanide Sulfides And Oxides, Christopher Marin

Department of Chemistry: Dissertations, Theses, and Student Research

This dissertation focuses on two of the key fields where lanthanides find ready application: as optically active materials with a focus on the lanthanide sulfides, and as catalytic materials with a focus on cerium oxide.

The lanthanide sulfides have attracted considerable interest for their potential as solar energy conversion materials, pigments, infrared window materials, and phosphor host media. However, applications of these materials remain limited due to their synthetic difficulty along with their not well understood properties compounded by both their difficulty in manufacturing as well as in simulating largely due to the need to take into account f-shell electrons. …

Synthesis, Structural Diversity, And Redox Control Of Cyclometalated Monoruthenium Complexes, Zhong-Liang Gong, Jiang-Yang Shao, Yu-Wu Zhong

Journal of Electrochemistry

Cyclometalated ruthenium complexes have received increasing attractions recently due to their excellent redox and photophysical properties. One structural feature of these complexes is that there is a ruthenium-carbon (Ru-C) σ bond presented in the molecule. Three common methods, namely, the “late metalation”, “early metalation”, and “transmetalation” methods, for the synthesis of cyclometalated ruthenium complexes are discussed and summarized. General strategies for the design of cyclometalating ligand and cyclometalated ruthenium complexes are introduced. By using different ancillary ligands, such as pyridine, imidazole, triazole, and pyrimidine, a great number of ruthenium complexes can be prepared. The presence of the Ru-C bond significantly …

Electrochemical And In Situ X-Ray Absorption Fine Structure Study Of Li-Rich Cathode Materials, Meng-Yan Hou, Hong-Liang Bao, Ke Wang, Jian-Qiang Wang, Yong-Yao Xia

Journal of Electrochemistry

A series of the lithium-rich and manganese-based layered structure xLi₂MnO₃•(1-x)LiMn_1/3Ni_1/3Co_1/3O₂ (x = 0.3,0.5,0.7) materials were synthesized by a co-precipitation method, and followed by a solid-state reaction process. By comparing the first cycle efficiency, the reversible discharge capacity, the cycling stability and the voltage decay during the charge/discharge cycling process, the material with the composition of 0.5Li₂MnO₃•0.5LiMn_1/3Ni_1/3Co_1/3O₂was found to show the best electrochemical performance. The lithium storage mechanism and thermal stability of the de-lithiated compound were also investigated …

The Progress Of Order-Structured Membrane Electrode Assembly, Shang-Feng Jiang, Bao-Lian Yi

Journal of Electrochemistry

Performances of proton exchange membrane fuel cells (PEMFCs) have been recently improved. However, the cost and Pt loading must be further reduced for the commercialization of PEMFCs. Previous researches have proved that the order-structured electrode is beneficial to the effective utilization of Pt-based catalysts, decreasing the Pt loading and increasing the three-phase boundary for reaction. Especially, the nanostructure thin films (NSTFs) electrode, an ultra-thin catalytic layer developed by 3M Company, demonstrates high performance and durability. Besides, some other researchers have employed the high conductive carbon nanotube arrays or high stable metal oxide arrays as the order-structured catalyst supports for fundamental …

Recent Progress In Solid-State Nmr Study Of Electrode/Electrolyte Materials For Lithium/Sodium Ion Batteries, Gui-Ming Zhong, Zi-Geng Liu, Da-Wei Wang, Qi Li, Ri-Qiang Fu, Yong Yang

Journal of Electrochemistry

Solid state NMR technique is a powerful tool for characterizing the local structure and compositions of solid materials quantitatively. A comprehensive understanding of the structure evolution during the electrochemical reactions of the materials for lithium/sodium ion batteries will be obtained with the combination of solid state NMR, XRD, and XAS methods. Through analyzing solid state NMR spectra, we can obtain the compositions, local structures and ion diffusion dynamics of electrodes, electrolytes and surface layers for lithium/sodium ion batteries, providing an important theoretical support for the design and development of high-performance materials for batteries. In this paper, we review the recent …

3, 4-Ethylenedioxythiophene Monomer As Safety-Enhancing Additive For Lithium Ion Batteries, Wei-Xiao Ji, Feng Wang, Jiang-Feng Qian, Yu-Liang Cao, Xin-Ping Ai, Han-Xi Yang

Journal of Electrochemistry

Safety concern is a major obstacle hindering the wide applications of large-capacity lithium ion batteries (LIBs) in electric vehicles. In this paper, a polymerizable monomer of 3, 4-ethylenedioxythiophene (EDOT) was proposed and tested as an electrolyte additive for enhancing the safety of LIBs. The electro-oxidative polymerization behaviors and influence of PEDOT additive on the thermal behavior of LiCoO₂ cathode, as well as the safety performance and electrochemical properties of LiCoO₂-based LIBs were investigated. The results from cyclic voltammetry (CV) and transmission electron microscope (TEM) characterizations indicated that the monomer additive can be electro-oxidatively polymerized to form a …

Reduced Graphene Oxide (Rgo) Hollow Network Cages For High-Performance Electrochemical Energy Storage, Chi Zhang, Xu-Jun He, Gao-Ren Li

Journal of Electrochemistry

The reduced graphese oxide (RGO) hollow network cages were synthesized via zinc oxide (ZnO) template-assisted electrodeposition. The as-prepared RGO hollow network cages exhibited the multi-level architectures, from nano sheets, porous structures, networks, to 3D microscaled hollow cages, which can simultaneously optimize transport of electroactive species, utilization rate of electrode material, and super capacitive performance. Electrochemical measurements confirmed the superior performance of RGO hollow network cages for supercapacitors (SCs), such as high Csp (393 F⋅g^-1 at 1.0 A⋅g^-1), excellent rate capability (21.2% Csp loss from 1.0 to 20 A⋅g^-1), and superior cycling stability (< 1% Csp loss after 10000 cycles).

Electrochemiluminescence Immunosensor Based On Platinum Nanoparticles For The Determination Of Apolipoprotein A1, Ni Liao, Ying Zhuo, Ruo Yuan

Journal of Electrochemistry

In this paper, a novel electrochemiluminescence (ECL) immunosensor for the detection of apolipoprotein A1 was constructed based on flower-like platinum nanoparticles (PtNFs) via a one-pot chemical synthesis method. The PtNFs was used to immobilize the secondary antibody and enzyme (GOD). Then the prepared bioconjugates were introduced onto the electrode via sandwich immunoreactions. Accordingly, the ECL luminophore peroxydisulfate (S₂O₈^2-) was presented in the working buffer solution containing an appropriate amount of glucose. Through the ECL responses of S₂O₈^2- and O₂, a dramatically amplified ECL signal was obtained for the reason …