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Full-Text Abstracts RM_MWGL Regional Meeting 1 Capping and passivation of aluminum nanoparticles with epoxy-alkenes Brandon J Thomas1, [email protected], Katherine Wentz2, Elena Guliants3, Christopher E Bunker4, Sophia E Hayes2, Paul A Jelliss1, Steven W Buckner1. (1) Department of Chemistry, Saint Louis University, Saint Louis, Missouri 63103, United States (2) Department of Chemistry, Washington University, Saint Louis, Missouri 63130, United States (3) Department of Electrical & Computer Engineering, University of Dayton Research Institute, Dayton, Ohio 45469, United States (4) Propulsion Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio, United States Aluminum nanoparticles (AlNPs) have applications in small-scale hydrogen production & high-density energy storage. However, production of air stable AlNPs has proved challenging as Al readily reacts with O2 & H2O. This leads to formation of a 2-6 nm Al2O3 layer on the AlNP surface. For particles on the order of 20 nm in diameter, this oxide layer can comprise a huge percentage of the particle's mass (> 70%). Our goal is to produce air-stable core-shell aluminum nanostructures that are resistant to reactions with H2O. We report on the synthesis of AlNPs capped & passivated with 1,2-epoxy-9- decene. Epoxides have proven to be an effective capping agent for AlNPs as the epoxide functionality can readily react with Al. By also inducing polymerization of the terminal alkene functionality of the epoxide, we produce AlNPs with long-term air stability on the order of 6 weeks. These nanostructures are embedded in an interconnected hydrophobic polymer matrix, preventing penetration of the Al core by water. Raman Spectroscopy and Solid-State NMR results are presented to confirm alkene polymerization. We also present results from PXRD, ATR-FTIR, DSC/TGA, & titrimetric analysis to confirm the presence of active aluminum. TEM images are presented to determine particle sizes. RM_MWGL Regional Meeting 2 Nanoneedles and Nanowires of superconducting FeSe encapsulated by carbon nanotubes Dr. Manashi Nath, Sukhada Patil, [email protected]. Department of Chemistry, Missouri University of Science and Technology, Rolla, MO 65401, United States Iron chalcogenides have attracted considerable attention due to their novel electronic and magnetic properties which make them useful in magnetic semiconductor and spintronic devices. Recently iron selenide, crystallizing in the tetragonal phase, has been in the center of attraction after sudden discovery of superconductivity (TC = 8K). We have synthesized FeSe nanowires encapsulated inside carbon nanotubes by a simple CVD reaction at 800°C from the volatile precursors, iron acetylacetonate and elemental Se. The core-shell FeSe/C nanotubes were grown on Au-coated Si substrates. The diameters of the nanotubes were 30-50 nm while the length exceeded several μm. The FeSe filling length could be varied by modifying the reaction conditions. In some cases the FeSe filling was pronounced and hollow at the tip and tapered down towards the tube interior forming a nanoneedle. The core-shell nanotubes were characterized by powder x-ray diffraction, SEM, HRTEM, EDAX, SAED with elemental mapping and magnetic measurements. RM_MWGL Regional Meeting 3 Aniline capped gold colloids by solvated metal atom dispersion method Yijun Sun, [email protected], Kenneth J Klabunde. Department of Chemistry, Kansas State University, Manhattan, KS 66502, United States Thoils were found to be very efficient ligands for the digestive-ripening process, during which a colloidal suspension in a solvent is refluxed at the solvent boiling temperature in the presence of a capping ligand to convert a highly polydisperse colloid into a nearly monodisperse one. Lots of work has been done by using thiols as the capping ligands to form gold colloids in our group. Apart from thiols, we are also interested in using amines, which were also found to have similar efficiency for this purpose. We want to differentiate between thiols and amines as the ligands in gold colloids. Our method is based on the solvated metal atom dispersion technique (SMAD), which is very suitable for preparation of large amounts of metal colloidal solutions. We prepared aniline capped Au colloids in butanone using our SMAD method and these colloids were characterized using electron microscopy and spectroscopic techniques such as UV- visible, NMR, FT-IR etc. The details about our findings towards aniline capped Au colloids would be discussed in the presentation. RM_MWGL Regional Meeting 4 Effects of the potential energy landscape on exciton delocalization in single 1-d quantum wires Virginia L Wayman1,2, [email protected], Robert A Burnett1,2, Benjamin S Hoener1,2, P J Morrison1,2, Fudong Wang1,2, William E Buhro1,2, Richard A Loomis1,2. (1) Department of Chemistry, Washington University, St Louis, MO 63130, United States (2) Center for Materials Innovation, Washington University, St Louis, MO 63130, United States Due to their one-dimensional (1-D) character, semiconductor quantum wires (QWs) have been considered for use in opto-electronic devices that implement charge- transport techniques. The potential energy landscape of a QW is not uniform due to varying surface passivation and structural defects. A photogenerated exciton in a QW will likely encounter a potential minima (or trap site), thus hampering its ability to behave as a free wave in a 1-D cylinder. In this work, we have modified the potential energy landscape of a single QW to investigate the quantum-mechanical behavior of excitons. Delocalization of bound excitons has been observed over an entire CdSe QW, with distances up to 10 microns. The role of subtle potential energy fluctuations in the landscape of a QW on exciton dynamics has been studied by performing temperature- dependent studies at 4 K. RM_MWGL Regional Meeting 5 Effect of doping transition metal ions on silica and titania aerogel systems Manindu N Weerasinghe, [email protected], Kenneth J Klabunde.Chemistry, Kansas State University, Manhattan, KS 66506, United States Transition metals and their respective ionic species show various properties depending on the number of d electrons available on their outermost electronic shell. There are a large number of reports on transition metal ions doped systems for catalytic, environmental remediation as well as in photo-catalytic water splitting studies. It is very interesting to study the effects of the doped transition metal ions and the host materials on textural, optical, and catalytic properties. We have synthesized a novel silicon dioxide (SiO2) and titanium dioxide (TiO2) based systems doped with different transition metal ions such as cobalt, chromium and vanadium ions using well-known aerogel synthesis method. These samples were characterized with X ray photoelectron spectroscopy, BET surface area analysis, X-ray diffraction studies and Diffuse reflectance UV-Vis spectroscopic measurements. Catalytic and photocatalytic activities were determined using acetaldehyde as a model pollutant. According to the kinetic studies chromium doped systems showed very high visible light photocatalytic activity while cobalt doped systems show dark catalytic activity towards acetaldehyde decomposition. Moreover, silica based systems tend to show higher catalytic activities compared to titania based systems. Oxygen absorption studies are currently carrying out in our lab to determine the ability of these catalysts to bind with oxygen and create reactive oxygen species. Detailed study of the catalysts will be carried out to understand the mechanisms of catalytic/photocatalytic activities of the systems. RM_MWGL Regional Meeting 6 Coaxial silicon coating on vertically aligned carbon nanofibers for high- performance lithium-ion batteries Steven Arnold Klankowski1, [email protected], Jun Li1, Ronald Rojeski2. (1) Department of Chemistry, Kansas State University, Manhattan, KS 66506, United States (2) 200 Carlyn Avenue, Suite C, Catalyst Power Technologies, Campbell, CA 95008, United States Improving the energy capacity, charging/discharging speed, and lifetime of Lithium-ion batteries is critical for their broader applications in portable electronics and hybrid electrical vehicles. We report a study on the development of a three-dimensional core- shell nanowire architecture anode for high-performance Li-ion batteries. This unique anode comprises of an amorphous silicon layer coaxially coated on a forest-like nanostructure of vertically aligned carbon nanofibers (VACNFs) that is grown on a substrate of 0.0033 inch thick Copper foil. The highly conductive VACNFs are firmly attached to the substrate and provide a good electron-conducting pathway while mechanically supporting the silicon coating upon charge/discharging cycling. The freedom in radial expansion also accommodates Silicon's large volume expansion upon lithiation (up to 300%) and thus improves the cycle stability. This nanostructured anode was characterized against a Lithium metal electrode with cyclic voltammetry and galvanostatic charging/discharging measurements to determine energy storage capacity, capacity retention, coulombic efficiency, and cycle lifetime. Our results demonstrated that the silicon coating with the nominal thickness of 500 nm and 1500 nm presents a Lithium storage capacity of ~3,000 to 3,500 mAh/g at C/2 power rate, close to the theoretical capacity of 4,200 mAh/g, and greater than 96% coulombic efficiency. This capacity is about an order of magnitude larger than that of commercial
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