Materials Chemistry Commons^™

Graphene-Like Bilayer Hexagonal Silicon Polymorph, Jaeil Bai, Hideki Tanaka, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

We present molecular dynamics simulation evidence for a freezing transition from liquid silicon to quasi-twodimensional (quasi-2D) bilayer silicon in a slit nanopore. This new quasi-2D polymorph of silicon exhibits a bilayer hexagonal structure in which the covalent coordination number of every silicon atom is four. Quantum molecular dynamics simulations show that the stand-alone bilayer silicon (without the confinement) is still stable at 400 K. Electronic band-structure calculations suggest that the bilayer hexagonal silicon is a quasi-2D semimetal, similar to a graphene monolayer, but with an indirect zero band gap.

Interaction Between Langmuir And Langmuir- Blodgett Films Of 5,11,17,23-Tetra-Tert-Butyl-25,27-Diethoxycarbonyl Methyleneoxy-26,28,Dihydroxycalix[4]Arene And 5,17-(9h-Fluoren-2-Yl)Methyleneamino)-11,23-Di-Tert-Butyl-25,27-Diethoxycarbonyl Methyleneoxy-26,28-Dihydroxycalix[4]Arene With Aqueous Copper And Lithium Ions., Mary Deasy, Fintan Kelleher, Faridah L. Supian, Tim H. Richardson, James P. Ward, Vickie Mckee

Articles

The binding interactions between aqueous copper (Cu2þ ) and lithium (Li þ ) ions and Langmuir monolayers and Langmuir-Blodgett (LB) multilayers have been investigated by studying surface pressure-area (Π-A) isotherms and surface potential-area (ΔV-A) behavior in order to find the effective dipole moment, μ^, of the calixarene molecules in the uncomplexed and complexed states. The orientation of both calix[4]arenes, namely, 5,11,17,23-tetra-tert-butyl- 25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene and 5,17-(9H-fluoren-2-yl)methyleneamino)- 11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene, is such that the plane of the calix ring is parallel with the plane of the water surface regardless of the ion content of the subphase. The Gibbs equation was used to interpret …

Corrosion Protection Properties Of Various Ligand Modified Organic Inorganic Hybrid Coating On Aa 2024-T3, Rajath Varma, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, John Colreavy, Brendan Duffy

Articles

The inclusion of zirconium precursors to prepare organosilane solgel coatings improves the corrosion protection performance of the coatings on aluminium and steel. The inherent differences in the hydrolysis rates of the silane and zirconium precursors, various ligands were used to control the hydrolysis by decreasing the number of reactive alkoxide group. Hybrid sols were synthesised using 3-(trimethoxysilyl) propylmethacrylate (MAPTMS) and zirconium n-propoxide chelated with organic ligands including different organic acids, acetyl acetone and 2 2’ bipyridyl. The effects of zirconia inclusion on the properties of the coatings were compared on the aerospace alloy AA 2024-T3. Electrochemical analysis and salt spray …

Corrosion Protection Of Aa 2024-T3 Aluminium Alloys Using 3, 4-Diaminobenzoic Acid Chelated Zirconium-Silane Hybrid Sol-Gels, P.C. Rajath Varma, John Colreavy, John Cassidy, Mohamed Oubaha, Colette Mcdonagh, Brendan Duffy

Articles

Organic-inorganic polymers formed by hydrolysis/condensation reactions of alkoxide precursors, such as organically modified silanes (Ormosils) have found applications as electronic, optical and protective coatings. Such coatings possess important characteristics such as chemical stability, physical strength and scratch resistance. Further performance improvement is achieved through the incorporation of zirconium and titanium based nanoparticles, also formed through the sol-gel process. However due to the inherent difference in the reactivity of the precursors, the hydrolysis of each precursor must be carried out separately before being combined for final condensation. Zirconium precursors are commonly chelated using acetic acid or acetyl acetonate prior to hydrolysis, …

Silver Nanoparticle Polymer Composite Based Humidity Sensor, Aoife Power, Tony Betts, John Cassidy

Articles

Silver nanoparticles were synthesised by a chemical reduction process in order to produce an aqueous colloidal dispersion. The resulting colloids were then characterised by a combination of UV-Vis spectroscopy, dynamic light scattering, X-ray diffraction and transmission electron microscopy and the nanoparticles were found to have an average diameter of 20–22 nm. The Ag/polymer nanocomposites were then applied to platinum interdigital electrodes as sensor coatings and the capability of the resulting sensor as a humidity detector investigated. With the application of 1 V, a current developed which was found to be directly proportional to humidity levels. The sensor gives a reversible, …

Charge Transfer And Nanostructure Formation During Electroless Etching Of Silicon, Kurt W. Kolasinski

Chemistry Faculty Publications

No abstract provided.

Dynamics Of Porous Silicon Formation By Etching In Hf + V2o5 Solutions, Kurt W. Kolasinski, Justin B. Hartline, Bryan T. Kelly, Julia Yadlovskiy

Chemistry Faculty Publications

No abstract provided.

Investigation Of Network Architecture Development And Properties In Thermoset Matrices, Jeremy Owen Swanson

Dissertations

Matrices employed in composite materials directly influence overall composite properties. In all thermoset materials, molecular level interactions and transformations during cure result in heterogeneous architecture. Variability in connectivity results from the often dramatic spatial and topological changes that occur during the crosslinking process. Compatibility (fillers, pigments, additives), temperature gradients and reactivity differences in the precursors only serve to increase the complexity of network formation. The objective of the research herein is to characterize and understand the relationships between cure conditions, conversion, connectivity, network architecture and properties in glassy thermosetting matrix resins.

In this research, epoxy and vinyl ester resins (VERs) …

Extraction Experiments Using Commerciallv Available Spices, Armando M. Guidote Jr, Maricar O. Ribo-Ramos, Dante Gilbert L. De Leon

Chemistry Faculty Publications

Safe and cost-effective experiments were designed for high school students to enhance their laboratory skills and knowledge on polarity and separation of mixtures. Annatto, Spanish paprika and turmeric were extracted yielding red-orange, light red-orange and yellow color, respectively. These were combined with a blue aqueous solution made from food color resulting to green mixtures. These were all extracted with kerosene or oil/kerosene. The non-polar solutes for each mixture combined with the kerosene or oil/kerosene layer, making the polar phase blue again. Students gained a better understanding of the concepts as shown in their laboratory report and test results.

Synthesis And Characterization Of Zinc Oxide Nanostructures., Khalifa Said Zahran Al-Azri

Student Works (2010-2019)

The growth mechanism, morphology, structure and optical properties of the ZnO nanostructures grown on bare and gold-coated silicon substrates using carbothermal reaction at atmospheric pressure were investigated under different growth conditions. The ZnO nanostructures formed were studied as a function of substrate location, furnace temperature, Ar gas flow rate, deposition time and ZnO powder to carbon powder mass ratio. The morphology and structure of the samples were characterized using the fieldemission scanning electron microscopy (FESEM), energy dispersive x-ray spectroscopy(EDX) spectrum, x-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). It was found that in both silicon and gold-coated silicon …

The Thermoluminescence Properties Of Manganese Doped Zns Nanophosphor., Khalid Humaid Zahir Al-Hinai

Student Works (2010-2019)

The thermoluminescence (TL) properties of Manganese (Mn) doped ZnS nanophosphors were investigated after gamma irradiation at room temperature. The ZnS:Mn nanophosphors were prepared by chemical precipitation method by using Zinc sulfate, Sodium sulfide and Manganese sulfate. 1 mole, 2 moles and 3 moles of Manganese sulfate were used to have different concentrations of Mn in doped ZnS. The formation of the nanophosphors was characterized by high resolution scanning electron microscopy FESEM, XRD and EDX. The obtained products consist of particles with the dimension about 85–150nm. Comparison between ZnS nanophosphors and commercial ZnS powder glow curves was studied. It was observed …

Synthesis And Characterization Of Silicon Oxide And Silicon Carbide Nanostructures., Majid Salim Mohammed Al-Ruqieshi

Student Works (2010-2019)

Silicon oxide nanostructures have attracted extensive interests in recent years due to their physical and optical properties. SiOx nanostructures are synthesized by catalytic and non-catalytic approaches. With catalytic approach, long and uniform amorphous silicon oxide nanowires, nanofibers (comet and tree like), nanocakes and nanocages were synthesized on Si substrate by carbothermal evaporation reactions of TiO2 at high temperature. The SiOx nanowires were about 13 nm to 243 nm in diameters and 194 nm to several microns in length and the nanofibres with diameter between 8 nm to 30 nm and around 50 nm to 2.5μm in length. The diameter and …

Production Of Multiwall Carbon Nanotube For Alcohol Sensor Application., Ebtehal Saleh Alshaqaq

Student Works (2010-2019)

Multiwall carbon nanotube/polyethylene oxide (PEO), multiwall carbon nanoube/polyvinyl alcohol(PVA) and multiwall carbon nanotube/ polyvinyl alcohol(PVA)/zinc oxide(ZnO) have been tested as chemical sensors and detailed study on the effect of different gas concentration and material properties on gas sensitivity is presented. Initial composites were prepared by a simple solution casting and characterized by x-ray diffraction for ZnO, Fourier transform infra-red spectroscopy (FTIR) and scanning electron microscopy (SEM) to demonstrate crystallite size of ZnO, the morphology and surface area respectively. On the other hand, MWCNT/PEO , MWCNT/PVA , MWCNT/PVA/ZnO were prepared with different loading MWCNT and ZnO. The chemical sensing properties of …

Investigation Of Novel Thiol "Click" Reactions, Justin William Chan

Dissertations

The thio-Michael addition reaction is traditionally considered a base catalyzed reaction which involves high catalyst concentrations and long reaction times. This reaction utilizes potent, simple nucleophiles to catalyze the reaction, decreases the catalyst concentration and greatly increases the reaction times. The free radical mediated thiol-ene click reaction uses light or heat and an initiator to catalyze the rapid and quantitative addition of thiols to most electron rich enes without the formation of side products and in the absence of solvent. Recently, the thiol-ene click reaction has been exploited for these reasons in materials science and organic synthesis. The research herein …

Investigation Of The Relationship Between Polymer Structures And Thermal, Mechanical, Viscoelastic Properties, Ethem Kaya

Dissertations

The research presented in this dissertation involves four distinct areas: physical crosslinking systems, UV curable coatings for enhanced oxygen and carbon dioxide barrier properties, synthesis, and investigation of melting behavior/crystallinity relations of linear polyamides with long alkyl chains, and synthesis and characterization of cyclic diamides as precursors to linear polyamides 6 4.

The physical crosslinking section involves synthesis of monomers and polymers bearing cyclodextrin and adamantane pendent groups, and investigation of non-covalent interactions between these polymers (Chapter II). Two methacrylate monomers bearing cyclodextrin and adamantane were synthesized, and copolymerized with poly(ethylene glycol) methyl ether methacrylate. The specific interaction between copolymers …

Random And Block Copolymers Of Poly(Dodecamethyleneterephthalamide), Theodore Frank Novitsky Jr.

Dissertations

The following dissertation focuses on the synthesis and characterization of poly(dodecamethylene terephthalamide) (PA-12,T) and novel copolymers. Chapter I details the synthesis of PA-12,T homopolymer by melt condensation polymerization. A series of homopolymers with different molecular weights were obtained by adjusting the stoichiometry of the polymerization using 1,12-diaminododecane, terephthalic acid and benzoic acid. End group 13C NMR spectroscopy resonances were obtained by correlating peak intensities with intrinsic viscosity values. From the NMR data, total end group concentrations and molecular weights were determined for each sample. The data exhibited a linear trend when plotting log (IV) versus log (Mn), and previously unknown …

Preparation And Characterization Of Thiol Based Polymeric Materials, Junghwan Shin

Dissertations

The thiol click-type reaction is one of the most efficient chemical processes that can undergo at room temperature in the benign organic solvent providing excellent opportunity in the fabrication of new materials as well as development of new manufacturing processes. Moreover, the versatility of thiol click-type reactions with many different functional groups such as ene, yne, epoxy, isocyanate, and alkyl halide is the important aspect that should be differentiated from the classic azide-alkyne click chemistry. Although, there are tremendous studies on many areas using thiol click-type reactions, the efficiency and utilities for the material applications have been barely explored. Especially, …

Kinetic Studies Of The Sulfoxidation Of Aryl Methyl Sulfides By Trans-Dioxoruthenium(Vi) Porphyrin Complexes, Chris Abebrese

Masters Theses & Specialist Projects

The development of an efficient, catalytically active, biomimetic model for cytochrome P-450 enzymes has been an area of intense research activity. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes, the epoxidation of alkenes and aromatic rings, and the N-oxidation of amines, among others. In this project, the kinetics of two-electron sulfoxidation of para-substituted phenyl methyl sulfides to the corresponding sulfoxides with well-characterized trans-dioxoruthenium(VI) porphyrin complexes were studied by rapid stopped-flow spectroscopy. The substituent effect in sulfides and in dioxoruthenium(VI) complexes were …

Off-Metal Synthesis Of Some Aryl Substituted Rhenium N5-Cyclopenta [C] Pyridazyl Complexes, James Leif Neathery

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (e.g. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to non-aromatic analogs (e.g. polyacetylene). Our current interests focus upon the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. Pyridazines, 6-membered aromatic rings with two adjacent nitrogens, are promising candidates for a variety of materials and commercial applications. These molecular electronic materials posses several advantages over traditional inorganic semiconducting materials including lower cost of production, higher processibility, and the ability to function on flexible …

Platinum Modified With Hydrogen Molybdenum/Tungsten Bronze As Electrocatalysts For Direct Small Organic Molecule Fuel Cell, Wei-Shan Li, Li-Peng Tian, Jun-Hua Du, Hong-Liang Huang, Wei Li, Li-Xia Zhang, Hong-Yan Yang, Pan-Pan Guo, Zhi-Hui Zhou, Xing-De Xiang, Zhao Fu

Journal of Electrochemistry

There are several problems that limit the application of direct small organic fuel cell,including the use of precious platinum and the activity loss of platinum due to the intermediates poisons from the oxidation of small organic molecules.These problems have attracted wide interest and many solutions have been proposed.We have developed a new method to reduce the platinum usage and improve its activity,based on the modification of platinum with hydrogen molybdenum/tungsten bronze(HxMo(W)O₃) was reviewed.

Preparation Of Pt Nanoflower/Zno Composites Arrays And Their Electrocatalysis For Methanol Oxidation, Li Gao, Yi-Feng E, Lou-Zhen Fan

Journal of Electrochemistry

The Pt nanoflower/ZnO(PtNF/ZnO) nanorod composites arrays were electrochemically prepared by controlling the hydrophobicity and the hydrophilicity of ZnO nanorods arrays.The Pt nanoflowers grew on the tip of ZnO nanorods,which maintain the vertical array of Zno nanorods with a high degree of size uniformity and high surface area.Compared with Pt nanoparticle covered ZnO nanorod arrays,which were prepared by controlling the hydrophilicities of ZnO nanorods and Pt nanoparticles,the PtNF/ZnO displayed highest electrocatalytic activities for the oxidation of methanol.

Indirect Electrosynthesis Of Double Aldehyde Starch Using Pb-(Bro3-/Br-) As Electro-Catalytic Mediator, Ni-Na Chen, Ri-Yao Chen, Xi Zheng, Xiao Chen, Zhen Chen

Journal of Electrochemistry

In this paper,Nafion membrane was used as the separator in the electrolysis cell to indirectly electro-generating the double aldehyde starch(DAS) with BrO₃^-/Br^-as a redox mediator and Pb as an anode.Effects of temperature,concentration of sulfuric acid and starch on the electro-oxidation of DAS were discussed.The steady state polarization curves were obtained.The experiment results showed that the current efficiency was over 50% when the electrolysis current density was 15mA/ cm².

Preparation Of Polyaniline/Polyester Conductive Fabric Via In-Situ Polymerization, Fang Na, Wei Wang

Journal of Electrochemistry

The formation of PANI coating on the surface of PET fiber and fabric was obtained by in-situ polymerization method.The coating′s thickness was about 1～2 μm.Orthogonal test methodology was used to analyze the main factors of preparation of PANI / PET conductive fabric.The effects of the aniline monomer concentration,oxidant: aniline molar ratio,doping acid concentration and types,reaction time on the conductivities of the fabric were studied.The structure of the polymer were characterized by SEM,FTIR and XRD.The results indicated that there was uniform and continuous polyaniline film on the surface of polyester fabric.The contents of oxidation and reduction of polyaniline molecular chain structure …

Electrocatalytic Activities Of Au-Mmni(3.2)Al(0.2)Mn(0.6)Co(1.00) For Borohydride Oxidation, Gui-Ling Wang, Jin-Cheng Liu, Ke-Ning Sun, Dian-Xue Cao

Journal of Electrochemistry

In this work,the electrocatalytic activities of MmNi_3.2Al_0.2Mn_0.6Co_1.0, NaOH treated MmNi_3.2Al_0.2Mn_0.6Co_1.0 and Au-MmNi_3.2Al_0.2Mn_0.6Co_1.0 obtained after NaOH treatment(Mm: misch metal) for NaBH₄ oxidation were reported. The electrodes were prepared by electrodeposition, their morphologies were analysized by SEM, their electrocatalytic properties were studied by the linear sweeping test. It was found that the oxidation current density of the Au-MmNi_3.2Al_0.2Mn_0.6Co_1.0 was 60 mA·cm^-2, it was 3.5 times higher than that at the …

Electrocatalytic Performance Of Carbon Supported Ir Catalysts With Different Ir Loadings For Ammonia Oxidation, Yu-Zhi Jiang, Qing-Mei Kong, Tian-Hong Lu, Yi-Ming Zhou, Ya-Wen Tang

Journal of Electrochemistry

The electrocatalytic performance of the Ir/C catalyst as the anodic catalyst in the amperometric and electrochemical NH₃ sensor was investigated.The experimental results illustrated that in the NaClO₄ neutral electrolyte,the electrocatalytic performance of the Ir/C catalyst for the NH₃ oxidation is related to the Ir loading in the Ir/C catalyst.Among the Ir/C catalysts with different Ir loading,the best electrocatalytic activity,stability and sensitivity were achieved by the Ir/C catalyst with 10% Ir loadings.In addition,the current densities of the NH₃ oxidation at the Ir/C catalysts with the different Ir loadings were linearly proportional to the NH₃ concentration.The Ir/C …

Progresses In Electrocatalysis Of Nanomaterials—Tuning The Surface Structure And Property Of Electrocatalysts, Yan-Xia Jiang, Na Tian, Zhi-You Zhou, Sheng-Pei Chen, Shi-Gang Sun

Journal of Electrochemistry

The property of an electrocatalyst depends strongly on its surface structure.The study of surface structure-catalytic functionality is the base of design and preparation of electrocatalysts of high activity,high stability and high selectivity at microstructure level.In this paper,based mainly on our results concering hydrogen and oxygen adsorption-desorption,ethylene glycol oxidation and CO₂ reduction,the research progresses in tuning the surface structure and property of electrocatalysts are summarized.This paper overviews firstly the cyclic voltammetric characteristics,electrocatalytic properties of platinum single crystal planes lying on different crystallographic zones of the unit stereographic triangle of face-centered cubic(fcc) metals.Next,the innovation of electrochemical methods to control the surface …

Synthesis And Electrocatalytic Properties Of Ni-Pd/C Catalysts With Pd-Enriched Surface, Yu-Mei Chen, Zhi-Xiu Liang, Sheng-Li Chen

Journal of Electrochemistry

The Ni-Pd alloy catalysts with Pd-enriched surface were synthesized through a modified polyol process.The synthesized materials were investigated by XRD and electrochemical methods,and tested as electrocatalysts for CH₃OH-tolerant oxygen reduction.The results indicated that the synthesized Ni-Pd nanoparticles possess multiple phases containing Pd-Ni alloy and pure Ni.Comparing with Pd/C,the prepared Ni-Pd/C nanoparticles exhibited better resolved voltammetric peaks between the hydrogen absorption and adsorption,and positively shifted current peaks for the reduction of Pd oxide.The prepared Ni-Pd alloys with Pd-enriched surface have significantly enhanced ORR activity and improved CH₃OH tolerance as comparing with Pd/C catalysts.

Electrooxidation Of Formic Acid On Pd-Ni Alloy Film Electrode-The Effect Of Dealloying, Chao Wang, Fei-Fei Shi, Jin-Yi Wang, Han-Xuan Zhang, Wen-Bin Cai

Journal of Electrochemistry

A Pd-Ni alloy film was electrodeposited on Au disc electrode at a constant potential from a weakly basic bath containing PdCl₂,NiSO₄ and ethylenediamine.The as-deposited film was then subjected to potential cycling in a perchloric acid solution for surface dealloying treatment.The dealloyed Pd-Ni film electrode was examined for the electrocatalytic oxidation of formic acid,and compared with the as-deposited one as well as a Pd film electrode.The FE-SEM and electrochemical measurements on the Pd-Ni films revealed that the dealloying treatment caused a surface roughening and an increase in specific surface reaction area.The ICP-AES and XPS analyses demonstrated that the …

Complex Reduction Preparation Of Carbon Supported Pd Nanoparticle Catalyst And Its Electrocatalysis For Formic Acid Oxidation, Wei He, Yong-Yin Kang, Chong Du, Zhi-Qing Zou, Xiao-Gang Zhang, Hui Yang

Journal of Electrochemistry

A simple procedure involved the complexing of PdCl₂ with sodium citrate followed by ethylene glycol reduction has been employed for the preparation of carbon-supported Pd nanoparticles(Pd/C).The XRD and TEM characterizations indicate that Pd nanoparticles with a small particle size were well-dispersed on carbon support.The mean particle sizes of the Pd/C catalysts were found to be increased from 2.7 to 5.8 nm with heat-treatments at different temperature.The mass activity of the Pd/C catalyst for formic acid electrooxidation increased with the decrease in Pd particle size.However,the specific activity increased with Pd particle size.Furthermore,the Pd/C catalyst with a particle size of ca.3.6 …

Cyclic Voltammetric And In-Situ Ftir Spectroscopic Studies Of Adsorption And Reduction Of No On Electrode Of Pt Nanoparticles, Qian Cheng, Yan-Xia Jiang, Dong-Mei Zeng, Shi-Gang Sun

Journal of Electrochemistry

Adsorption and reduction of NO on electrode of Pt nanoparticles in acid solutions were studied by means of cyclic voltammetry(CV) and in-situ FTIR spectroscopy.The results indicated that the reduction of NO is a complicated process including the adsorption of NO on electrode surface.Two types of surface-bonded NO were determined on Pt nanoparticles.The weakly adsorbed NO was reduced between 0.6 V and-0.05 V,which yielded nitrous oxide(N₂O) and ammonium(NH₄⁺) as products;while the strongly bonded NO was reduced at more negative potentials between-0.05V and-0.15V,producing only NH₄⁺ species.