Science.gov

Sample records for metal alkoxides templates

  1. Metal alkoxides: templates for organometallic chemistry and catalysis. Final technical report on DE FG 02-86ER13570

    SciTech Connect

    Chisholm, Malcolm H.

    2002-11-01

    The physical properties and chemical reactivities of a series of alkoxide, fluoroalkoxide and thiolate compounds of molybdenum and tungsten having M{triple_bond}M or M{triple_bond}N bonds have been examined which reveal the influence of the pi-donor properties of the ligands: RO > R{sub f}O{approx}RS. Single-site metal alkoxide catalysts for the ring-opening polymerization of lactides have been prepared for the metals magnesium, zinc, and aluminum.

  2. Metal alkoxides and methods of making same

    DOEpatents

    Hentges, Patrick J.; Greene, Laura H.; Pafford, Margaret Mary; Westwood, Glenn; Klemperer, Walter G.

    2005-01-04

    A method of making a superconducting structure includes depositing a metal alkoxide on a surface of a metal and hydrolyzing the metal alkoxide on the surface to form a pinhole-free film. The metal is a superconductor. The metal alkoxide may be a compound of formula (I): where M is zirconium or hafnium, and the purity of the compound is at least 97% as measured by NMR spectroscopy.

  3. All-alkoxide synthesis of strontium-containing metal oxides

    DOEpatents

    Boyle, Timothy J.

    2001-01-01

    A method for making strontium-containing metal-oxide ceramic thin films from a precursor liquid by mixing a strontium neo-pentoxide dissolved in an amine solvent and at least one metal alkoxide dissolved in a solvent, said at least one metal alkoxide selected from the group consisting of alkoxides of calcium, barium, bismuth, cadmium, lead, titanium, tantalum, hafnium, tungsten, niobium, zirconium, yttrium, lanthanum, antimony, chromium and thallium, depositing a thin film of the precursor liquid on a substrate, and heating the thin film in the presence of oxygen at between 550 and 700.degree. C.

  4. Virus templated metallic nanoparticles.

    PubMed

    Aljabali, Alaa A A; Barclay, J Elaine; Lomonossoff, George P; Evans, David J

    2010-12-01

    Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. ≤35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron. PMID:20877898

  5. Preparation of oxide glasses from metal alkoxides by sol-gel method

    NASA Technical Reports Server (NTRS)

    Kamiya, K.; Yoko, T.; Sakka, S.

    1987-01-01

    An investigation is carried out on the types of siloxane polymers produced in the course of the hydrolysis of silicon tetraethoxide, as well as the preparation of oxide glasses from metal alkoxides by the sol-gel method.

  6. Virus templated metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Aljabali, Alaa A. A.; Barclay, J. Elaine; Lomonossoff, George P.; Evans, David J.

    2010-12-01

    Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron.Plant viruses are considered as nanobuilding blocks that can be used as synthons or templates for novel materials. Cowpea mosaic virus (CPMV) particles have been shown to template the fabrication of metallic nanoparticles by an electroless deposition metallization process. Palladium ions were electrostatically bound to the virus capsid and, when reduced, acted as nucleation sites for the subsequent metal deposition from solution. The method, although simple, produced highly monodisperse metallic nanoparticles with a diameter of ca. <=35 nm. CPMV-templated particles were prepared with cobalt, nickel, iron, platinum, cobalt-platinum and nickel-iron. Electronic supplementary information (ESI) available: Additional experimental detail, agarose gel electrophoresis results, energy dispersive X-ray spectra, ζ-potential measurements, dynamic light scattering data, nanoparticle tracking analysis and an atomic force microscopy image of Ni-CPMV. See DOI: 10.1039/c0nr00525h

  7. Impact of metal-alkoxide functionalized linkers on H2 binding: A density functional study

    NASA Astrophysics Data System (ADS)

    Banu, Tahamida; Ghosh, Avik; Das, Abhijit K.

    2016-08-01

    The effect of metal-alkoxide functionalization of different organic linkers on the H2 binding is investigated employing DFT approach. While analyzing the H2 binding interaction of magnesium-alkoxide modified benzene, naphthalene, anthracene and pyrene linkers, we find their comparable affinity toward H2 molecules. Six-member alkoxide ring containing naphthalene and pyrene systems interact with the H2 molecules in a comparatively better way than their five-member analogues. AIM, NBO and LMO-EDA analyses have been performed to comprehend the bonding nature between Mg center and the H2 molecules. Polarization along with the charge transfer interactions play significant role in stabilizing the systems.

  8. Metal nanodisks using bicellar templates

    DOEpatents

    Song, Yujiang; Shelnutt, John A

    2013-12-03

    Metallic nanodisks and a method of making them. The metallic nanodisks are wheel-shaped structures that that provide large surface areas for catalytic applications. The metallic nanodisks are grown within bicelles (disk-like micelles) that template the growth of the metal in the form of approximately circular dendritic sheets. The zero-valent metal forming the nanodisks is formed by reduction of a metal ion using a suitable electron donor species.

  9. Growth versus cyclization in the early stages of the polycondensation of metal alkoxides.

    PubMed

    In, Martin; Sanchez, Clément

    2005-12-22

    The early steps of the polycondensation of transition metal alkoxide have been studied from the chemical and structural points of view. Polyoxoalkoxides are described like macromolecules by the composition of the repeating unit, the degree of polymerization (N), and the radius of gyration (R). The fraction p of binding sites of the coordination sphere of the metal centers occupied by terminal ligands determines N as follows: N proportional, variant pdf (dA-df), where df is the fractal dimension and dA is defined by Np proportional, variant RdA. This approach addresses difficulties raised by both coordinative unsaturation and cyclization in the modelization of the polycondensation of metal alkoxides. The coordinative unsaturation is accounted for by a particularly small value of dA= 1 in the very early steps, while the cyclization frequency is measured by the difference dA-df. This difference is not constant along the polycondensation process, and its dependence on the extent of reaction provides clues for understanding the high apparent kinetics order of gelation often reported in the literature. PMID:16375372

  10. Hard template synthesis of metal nanowires.

    PubMed

    Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

    2014-01-01

    Metal nanowires (NWs) have attracted much attention because of their high electron conductivity, optical transmittance, and tunable magnetic properties. Metal NWs have been synthesized using soft templates such as surface stabilizing molecules and polymers, and hard templates such as anodic aluminum oxide, mesoporous oxide, carbon nanotubes. NWs prepared from hard templates are composites of metals and the oxide/carbon matrix. Thus, selecting appropriate elements can simplify the production of composite devices. The resulting NWs are immobilized and spatially arranged, as dictated by the ordered porous structure of the template. This avoids the NWs from aggregating, which is common for NWs prepared with soft templates in solution. Herein, the hard template synthesis of metal NWs is reviewed, and the resulting structures, properties and potential applications are discussed. PMID:25453031

  11. Hard template synthesis of metal nanowires

    NASA Astrophysics Data System (ADS)

    Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

    2014-11-01

    Metal nanowires (NWs) have attracted much attention because of their high electron conductivity, optical transmittance and tunable magnetic properties. Metal NWs have been synthesized using soft templates such as surface stabilizing molecules and polymers, and hard templates such as anodic aluminum oxide, mesoporous oxide, carbon nanotubes. NWs prepared from hard templates are composites of metals and the oxide/carbon matrix. Thus, selecting appropriate elements can simplify the production of composite devices. The resulting NWs are immobilized and spatially arranged, as dictated by the ordered porous structure of the template. This avoids the NWs from aggregating, which is common for NWs prepared with soft templates in solution. Herein, the hard template synthesis of metal NWs is reviewed, and the resulting structures, properties and potential applications are discussed.

  12. Hard template synthesis of metal nanowires

    PubMed Central

    Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

    2014-01-01

    Metal nanowires (NWs) have attracted much attention because of their high electron conductivity, optical transmittance, and tunable magnetic properties. Metal NWs have been synthesized using soft templates such as surface stabilizing molecules and polymers, and hard templates such as anodic aluminum oxide, mesoporous oxide, carbon nanotubes. NWs prepared from hard templates are composites of metals and the oxide/carbon matrix. Thus, selecting appropriate elements can simplify the production of composite devices. The resulting NWs are immobilized and spatially arranged, as dictated by the ordered porous structure of the template. This avoids the NWs from aggregating, which is common for NWs prepared with soft templates in solution. Herein, the hard template synthesis of metal NWs is reviewed, and the resulting structures, properties and potential applications are discussed. PMID:25453031

  13. Low temperature synthesis of monolithic transparent Ta2O5 gels from hydrolysis of metal alkoxide

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1993-01-01

    Tantalum oxide gels in the form of transparent monoliths and powder were prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC2H5)5:C2H50H:H20:HCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide:water:HCl ratio, time of gel formation increased with the alcohol to alkoxide mole ratio. Thermal evolution of the physical and structural changes in the gel was monitored by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. On heating to approximately 400 C, the amorphous gel crystallized into the low temperature orthorhombic phase Beta-Ta2O5, which transformed into the high temperature tetragonal phase Alpha-Ta2O5 when further heated to approximately 1450 C. The volume fraction of the crystalline phase increased with the firing temperature. The Alpha-Ta205 converted back into the low temperature phase, Beta-Ta2O5, on slow cooling through the transformation temperature of 1360 C indicating a slow but reversible transformation.

  14. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

    DOE PAGESBeta

    Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; Cramer, Roger

    2016-03-15

    In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing weremore » found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

  15. Surfactant-Templated Mesoporous Metal Oxide Nanowires

    DOE PAGESBeta

    Luo, Hongmei; Lin, Qianglu; Baber, Stacy; Naalla, Mahesh

    2010-01-01

    We demore » monstrate two approaches to prepare mesoporous metal oxide nanowires by surfactant assembly and nanoconfinement via sol-gel or electrochemical deposition. For example, mesoporous Ta 2 O 5 and zeolite nanowires are prepared by block copolymer Pluronic 123-templated sol-gel method, and mesoporous ZnO nanowires are prepared by electrodeposition in presence of anionic surfactant sodium dodecyl sulfate (SDS) surfactant, in porous membranes. The morphologies of porous nanowires are studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses.« less

  16. Structure, photochemistry and applications of metal-doped polyoxotitanium alkoxide cages.

    PubMed

    Matthews, Peter D; King, Timothy C; Wright, Dominic S

    2014-11-01

    Metal-doped polyoxotitanium cages (M-POTs) of the type [TixOy(OR)zMnXm] (M = a main group, transition metal or lanthanide; X = an anion such as a halide) can be regarded as molecular fragments of metal-doped TiO2. As such M-POTs can be used as structural models for the inclusion of metal ions into the TiO2 lattice and the ways in which well-defined microstructural changes affect photo-induced hole-electron separation. They are also potential organically-soluble redox-catalysts for a range of organic transformations and have been shown to be useful single-source precursors for the deposition of metal-doped TiO2. The applications of M-POTs as molecular precursors to metal-doped TiO2 offers a high degree of atomic control in the low temperature fabrication of photocatalytic thin films, which have applications in pollution control and water splitting. This perspective highlights the structural trends in M-POTs, their electronic behaviour and their applications as single-source precursors, looking at current and future trends in the development of inorganic precursors for device applications. PMID:25056360

  17. Templated Dry Printing of Conductive Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Rolfe, David Alexander

    Printed electronics can lower the cost and increase the ubiquity of electrical components such as batteries, sensors, and telemetry systems. Unfortunately, the advance of printed electronics has been held back by the limited minimum resolution, aspect ratio, and feature fidelity of present printing techniques such as gravure, screen printing and inkjet printing. Templated dry printing offers a solution to these problems by patterning nanoparticle inks into templates before drying. This dissertation shows advancements in two varieties of templated dry nanoprinting. The first, advective micromolding in vapor-permeable templates (AMPT) is a microfluidic approach that uses evaporation-driven mold filling to create submicron features with a 1:1 aspect ratio. We will discuss submicron surface acoustic wave (SAW) resonators made through this process, and the refinement process in the template manufacturing process necessary to make these devices. We also present modeling techniques that can be applied to future AMPT templates. We conclude with a modified templated dry printing that improves throughput and isolated feature patterning by transferring dry-templated features with laser ablation. This method utilizes surface energy-defined templates to pattern features via doctor blade coating. Patterned and dried features can be transferred to a polymer substrate with an Nd:YAG MOPA fiber laser, and printed features can be smaller than the laser beam width.

  18. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    SciTech Connect

    Jacobs, Benjamin W.; Herberg, Julie L.; Highley, Aaron M.; Grossman, Jeffrey; Wagner, Lucas; Bhakta, Raghu; Peaslee, D.; Allendorf, Mark D.; Liu, X.; Behrens, Richard, Jr.; Majzoub, Eric H.

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  19. Two axles threaded using a single template site: active metal template macrobicyclic [3]rotaxanes.

    PubMed

    Goldup, Stephen M; Leigh, David A; McGonigal, Paul R; Ronaldson, Vicki E; Slawin, Alexandra M Z

    2010-01-13

    Template approaches to rotaxanes normally require at least n - 1 template sites to interlock n components. Here we describe the one-pot synthesis of [3]rotaxanes in which a single metal template site induces formation of axles through each cavity of a bicyclic macrocycle. Central to the approach is that a portion of the bicyclic molecule acts as a ligand for a transition metal ion that mediates covalent bond formation through one or other macrocyclic cavity, depending on the ligand's orientation, making a mechanical bond. The ligand can then rotate so that the transition metal can catalyze the formation of a second axle through the other macrocycle. Using this strategy with the Cu(I)-catalyzed azide-alkyne cycloaddition (the CuAAC reaction) generates a [3]rotaxane with two identical axles in up to 86% yield. [3]Rotaxanes with two different axles threaded through the macrobicyclic rings can also be created using a single template site, either by having copper(I) sequentially form both mechanical bonds (via the CuAAC reaction) using different sets of building blocks for each axle or by using two different reactions catalyzed by two different metal ions: a palladium(II)-mediated alkyne homocoupling to assemble the first thread through one cavity, followed by a copper(I)-mediated CuAAC reaction to form the second axle through the other ring. PMID:19968281

  20. Silver nanowires-templated metal oxide for broadband Schottky photodetector

    NASA Astrophysics Data System (ADS)

    Patel, Malkeshkumar; Kim, Hong-Sik; Park, Hyeong-Ho; Kim, Joondong

    2016-04-01

    Silver nanowires (AgNWs)-templated transparent metal oxide layer was applied for Si Schottky junction device, which remarked the record fastest photoresponse of 3.4 μs. Self-operating AgNWs-templated Schottky photodetector showed broad wavelength photodetection with high responsivity (42.4 A W-1) and detectivity (2.75 × 1015 Jones). AgNWs-templated indium-tin-oxide (ITO) showed band-to-band excitation due to the internal photoemission, resulting in significant carrier collection performances. Functional metal oxide layer was formed by AgNWs-templated from ITO structure. The grown ITO above AgNWs has a cylindrical shape and acts as a thermal protector of AgNWs for high temperature environment without any deformation. We developed thermal stable AgNWs-templated transparent oxide devices and demonstrated the working mechanism of AgNWs-templated Schottky devices. We may propose the high potential of hybrid transparent layer design for various photoelectric applications, including solar cells.

  1. Synthesis and Reactions of 3d Metal Complexes with the Bulky Alkoxide Ligand [OC(t)Bu2Ph].

    PubMed

    Bellow, James A; Yousif, Maryam; Fang, Dong; Kratz, Eric G; Cisneros, G Andrés; Groysman, Stanislav

    2015-06-15

    Treatment of NiCl2(dme) and NiBr2(dme) (dme = dimethoxyethane) with 2 equiv of LiOR (OR = OC(t)Bu2Ph) forms the distorted trigonal planar complexes [NiLiX(OR)2(THF)2] (THF = tetrahydrofuran) 5 (X = Cl) and 6 (X = Br). The reaction of CuX2 (X = Cl, Br) with 2 equiv of LiOR affords the Cu(I) product Cu4(OR)4 (7). The same product can be obtained using the Cu(I) starting material CuCl. NMR studies indicated that the reduction of Cu(II) to Cu(I) is accompanied by the oxidation of the alkoxide RO(-) to form the alkoxy radical RO(•), which subsequently forms tert-butyl phenyl ketone by β-scission. Treatment of compounds 1-4 ([M2Li2Cl2(OR)4], M = Cr-Co) with thallium hexafluorophosphate allowed the isolation of the distorted tetrahedral complexes of the form M(OR)2(THF)2 for M = Mn (8), Fe (9), and Co (10). Cyclic voltammetry performed on compounds 8-10 demonstrated irreversible oxidations for all complexes, with the iron complex 9 being the most reducing. Complex 9 shows a reactivity toward PhIO and Ph3SbS to form the corresponding dinuclear iron(III) complexes Fe2(O)(OR)4(THF)2 (11) and Fe2(S)(OR)4(THF)2 (12), respectively. X-ray structural studies were performed, showing that the Fe-O-Fe angle for complex 11 is 176.4(1)° and that the Fe-S-Fe angle for complex 12 is 164.83(3)°. PMID:26043187

  2. Evolution of Metal Selectivity in Templated Protein Interfaces

    PubMed Central

    Brodin, Jeffrey D.; Medina-Morales, Annette; Ni, Thomas; Salgado, Eric N.; Ambroggio, Xavier I.; Tezcan, F. Akif

    2010-01-01

    Selective binding by metalloproteins to their cognate metal ions is essential to cellular survival. How proteins originally acquired the ability to selectively bind metals and evolved a diverse array of metal-centered functions despite the availability of only a few metal-coordinating functionalities remains an open question. Using a rational design approach (Metal-Templated Interface Redesign), we describe the transformation of a monomeric electron transfer protein, cytochrome cb562, into a tetrameric assembly (C96RIDC-1) that stably and selectively binds Zn2+, and displays a metal-dependent conformational change reminiscent of a signaling protein. A thorough analysis of the metal binding properties of C96RIDC-14 reveals that it can also stably harbor other divalent metals with affinities that rival (Ni2+) or even exceed (Cu2+) those of Zn2+ on a per site basis. Nevertheless, this analysis suggests that our templating strategy also introduces an increased bias towards binding a higher number of Zn2+ ions (4 high affinity sites) versus Cu2+ or Ni2+ (2 high affinity sites), ultimately leading to the exclusive selectivity of C96RIDC-14 for Zn2 over those ions. More generally, our results indicate that an initial metal-driven nucleation event followed by the formation of a stable protein architecture around the metal provides a straightforward path for generating structural and functional diversity. PMID:20515031

  3. Alkoxide routes to Inorganic Materials

    SciTech Connect

    Thomas, George H

    2007-12-01

    An all alkoxide solution chemistry utilizing metal 2-methoxyethoxide complexes in 2-methoxyethanol was used to deposit thin-films of metal oxides on single-crystal metal oxide substrates and on biaxially textured metal substrates. This same chemistry was used to synthesize complex metal oxide nanoparticles. Nuclear Magnetic Resonance spectroscopy was used to study precursor solutions of the alkaline niobates and tantalates. Film crystallization temperatures were determined from x-ray diffraction patterns of powders derived from the metal oxide precursor solutions. Film structure was determined via x-ray diffraction. Film morphology was studied using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Epitaxial thin-films of strontium bismuth tantalate (SrBi{sub 2}Ta{sub 2}O{sub 9}, SBT) and strontium bismuth niobate (SrBi{sub 2}Nb{sub 2}O{sub 9}, SBN) were deposited on single crystal [1 0 0] magnesium oxide (MgO) buffered with lanthanum manganate (LaMnO{sub 3}, LMO). Epitaxial thin films of LMO were deposited on single crystal [100] MgO via Rf-magnetron sputtering and on single crysal [100] lanthanum aluminate (LaAlO{sub 3}) via the chemical solution deposition technique. Epitaxial thin-films of sodium potassium tantalate (na{sub 0.5}K{sub 0.5}TaO{sub 3}, NKT), sodium potassium niobate (Na{sub 0.5}K{sub 0.5}NbO{sub 3}, NKN) and sodium potassium tantalum niobate (Na{sub 0.5}K{sub 0.5}Ta{sub 0.5}O{sub 3}, NKTN) were deposited on single crystal [1 0 0] lanthanum aluminate and [1 0 0] MgO substrates (NKT and NKN) and biaxially textured metal substrates via the chemical solution deposition technique. Epitaxial growth of thin-films of NKT, NKN and NKTN was observed on LAO and Ni-5% W. Epitaxial growth of thin-films of NKN and the growth of c-axis aligned thin-films of NKT was observed on MgO. Nanoparticles of SBT, SBN, NKT and NKN were synthesized in reverse micelles from alkoxide precursor solutions. X-ray diffraction and transmission electron

  4. Titanium alkoxide compound

    DOEpatents

    Boyle, Timothy J.

    2007-08-14

    A titanium alkoxide composition is provided, as represented by the chemical formula (OC.sub.6H.sub.5N).sub.2Ti(OC.sub.6H.sub.5NH.sub.2).sub.2. As prepared, the compound is a crystalline substance with a hexavalent titanium atom bonded to two OC.sub.6H.sub.5NH.sub.2 groups and two OC.sub.6H.sub.5N groups with a theoretical molecular weight of 480.38, comprising 60.01% C, 5.04% H and 11.66% N.

  5. The fabrication of short metallic nanotubes by templated electrodeposition

    NASA Astrophysics Data System (ADS)

    Huang, Chienwen; Hao, Yaowu

    2009-11-01

    Template-based electrochemical synthesis has widely been used to produce metal nanowires and nanorods. Commercially available filtration membranes, such as anodic aluminum oxide (AAO) and polycarbonate track etch membranes, have commonly been utilized as hard templates for this purpose. In this process, a thick metal film is usually sputtered or vacuum evaporated onto one side of the membrane to block the pores and serve as the working electrode for the subsequent electrodeposition. Here, we show that during the deposition of the metal electrode for AAO membranes, the electrode metal diffuses into the pores and is deposited on the pore walls which leads to preferential electrodeposition of metal on the walls and therefore forms metal tubes. This phenomenon has been utilized to fabricate short nanotubes by carefully controlling the electrodeposition conditions. The process is a straightforward method for any electroplatable materials to form nanoscale tubular structures. The effects of working electrodes and electrodeposition conditions on the formation of tubular structures are discussed in detail. A new mechanism based on this simple fact is proposed to explain the formation of Ni tubes by Ni-Cu co-deposition. Also, we demonstrate how to distinguish magnetic nanotubes from nanorods by a simple magnetic measurement.

  6. Mechanistic and synthetic studies aimed at the development of single-site metal alkoxide catalysts for the generation of polyesters and polycarbonates

    SciTech Connect

    Chisholm, Malcolm

    2010-06-30

    The work proposed herein focuses on the chemistry of metal-oxygen bonds with respect to insertion/enchainment reactions involving epoxides, cyclic esters and carbonates, acid anhydrides and carbon dioxide leading to the formation of polyethers, polyesters and polycarbonates from renewable resources. Particular emphasis is placed on the use of the biologically benign metals magnesium and calcium and the M(3+) ions of aluminum, chromium and cobalt that have a similar ionic radii but different coordination properties arising from their respective d0, d3 and d6 valence shell configurations. The work emphasizes the design and use of single-site metal catalysis involving LMOR initiating and propagating species. For M = Mg and Ca, L is a pyrazolyl borate ligand specifically tailored to the coordination properties of the metal. In addition the ligand is inert with respect to reactions of the substrates under consideration. For the M(3+) ions, L is a substituted porphyrin, namely 5,10,15,20-tetraphenylporphyrin, TPP, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, TFPP or 2,3,7,8,12,13,17,18-octaethylporphyrin, which together with Lewis base co-catalysts will allow the elucidation of factors leading to polyethers, polycarbonates and cyclic carbonates in reactions involving epoxides and CO2. Specific attention is given to reactions involving propylene oxide and styrene oxide which commonly show competitive formation of products. Electronic structure calculations employing Density Functional Theory will be carried out to elucidate the ring opening of the epoxide by alkylcarbonate and alkoxide ligands and the chain growth mechanism. Polymerization of lactide will be investigated using inexpensive solid supports and catalytic routes to cyclic esters are proposed wherein complexation to metal ions may allow chemical amplification of specific rings. With an understanding of mechanisms involving the reactions of M-OR bonds the development of single-site catalysis for the

  7. Template Synthesis of Nanostructured Metals using Cellulose Nanocrystal

    SciTech Connect

    Shin, Yongsoon; Exarhos, Gregory J.

    2009-11-01

    In this chapter, cellulose nanocrystal (CNXL) has been used as a template and reducing agent for synthesizing nanoscale inorganic solids such as metal oxide, metal carbide, and nanocrystalline metals. CNXL selectively nucleates metal or metal oxide phases in ordered arrangements commensurate with the attendant structure and chemistry of the fiber. The reaction has an analogy to the well-known Tollen’s reagent where addition of an aldehyde or glucose analyte to a glass vessel containing a soluble ammoniacal silver complex causes reduction of the silver to form a mirror on the vessel surface. For the synthesis of TiO2, CNXL produced mesoporous anatase with 5-10 nm particle sizes and 170-200 m2/g surface area after air-calcination. Silica-infiltrated CNXL produced very homogeneous SiC nanowires with 70 nm in diameter at 1400 oC in Ar. For the syntheses of metal nanoparticles, upon addition of aqueous metal ion containing solutions (Cu(II), Ni(II), Ag(I), Au(III), Pd(II), Pt(IV), or even selenite, Se(IV)) into the CNXL suspension, reduction to the metal occurs under hydrothermal conditions to form ordered metal nanostructures. Ni (II) and Cu(II) ions required high temperature (300-400 oC) to be reduced due to their low reduction potentials. However, metal ions including Ag(I), Au(III), Pt(IV), Pd(II), Se(IV) needed lower temperatures (160-200 oC) to be reduced. Enhanced catalytic activity on these templated surfaces has been demonstrated for a methylene-blue dye photo-induced decomposition (Se nanocrystals resident on crystalline cellulose).

  8. Mechanistic studies aimed at the development of single site metal alkoxide catalysts for the production of polyoxygenates from renewable resources.

    SciTech Connect

    Chisholm, Malcolm H.

    2015-12-15

    The work proposed herein follows on directly from the existing 3 year grant and the request for funding is for 12 months to allow completion of this work and graduation of current students supported by DOE. The three primary projects are as follows. 1.) A comparative study of the reactivity of LMg(OR) (solvent), where L= a β-diiminate or pyrromethene ligand, in the ring-opening of cyclic esters. 2.) The homopolymerization of expoxides, particularly propylene oxide and styrene oxide, and their copolymerizations with carbon dioxide or organic anhydrides to yield polycarbonates or polyesters, respectively. 3.) The development of well-defined bismuth (III) complexes for ring-opening polymerizations that are tolerant of both air and water. In each of these topics special emphasis is placed on developing a detailed mechanistic understanding of the ring-opening event and how this is modified by the employment of specific metal and ligand combinations. This document also provides a report on findings of the past grant period that are not yet in the public domain/published and shows how the proposed work will bring the original project to conclusion.

  9. Apoferritin-Templated Synthesis of Encoded Metallic Phosphate Nanoparticle Tags

    SciTech Connect

    Liu, Guodong; Wu, Hong; Dohnalkova, Alice; Lin, Yuehe

    2007-07-31

    Encoded metallic-phosphate nanoparticle tags, with distinct encoding patterns, have been prepared using an apoferritin template. A center-cavity structure as well as the disassociation and reconstructive characteristics of apoferritin at different pH environments provide a facile route for preparing such encoded nanoparticle tags. Encapsulation and diffusion approaches have been investigated during the preparation. The encapsulation approach, which is based on the dissociation and reconstruction of apoferritin at different pHs, exhibits an effective route to prepare such encoded metallic-phosphate nanoparticle tags. The compositionally encoded nanoparticle tag leads to a high coding capacity with a large number of distinguishable voltammetric signals, reflecting the predetermined composition of the metal mixture solution (and hence the nanoparticle composition). Releasing the metal components from the nanoparticle tags at pH 4.6 acetate buffer avoids harsh dissolution conditions, such as strong acids. Such a synthesis of encoded nanoparticle tags, including single-component and compositionally encoded nanoparticle tags, is substantially simple, fast, and convenient compared to that of encoded metal nanowires and semiconductor nanoparticle (CdS, PbS, and ZnS) incorporated polystyrene beads. The encoded metallic-phosphate nanoparticle tags thus show great promise for bioanalytical or product-tracking/identification/protection applications.

  10. Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

    NASA Technical Reports Server (NTRS)

    Bridson, P. K.; Fakhrai, H.; Lohrmann, R.; Orgel, L. E.; Van Roode, M.

    1981-01-01

    The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

  11. Fabrication and characterization of metal-semiconductor-metal nanorod using template synthesis

    SciTech Connect

    Kim, Kyohyeok; Kwon, Namyong; Hong, Junki; Chung, Ilsub

    2009-07-15

    The authors attempted to fabricate and characterize one dimensional metal-semiconductor-metal (MSM) nanorod using a template. Cadmium selenide (CdSe) and polypyrrole (Ppy) were chosen as n-type and p-type semiconductor materials, respectively, whereas Au was chosen as a metal electrode. The fabrication of the nanorod was achieved by ''template synthesis'' method using polycarbonate membrane. The structure of the fabricated nanorod was analyzed using scanning electron microscopy and energy dispersive spectroscopy. In addition, the electrical properties of MSM nanorods were characterized using scanning probe microscopy (Seiko Instruments, SPA 300 HV) by probing with a conductive cantilever. I-V characteristics as a function of the temperature give the activation energy, as well as the barrier height of a metal-semiconductor contact, which is useful to understand the conduction mechanism of MSM nanorods.

  12. Metal-organic framework templated inorganic sorbents for rapid and efficient extraction of heavy metals.

    PubMed

    Abney, C W; Gilhula, J C; Lu, K; Lin, W

    2014-12-17

    An innovative wet-treatment with Na2 S transforms two indium metal-organic frameworks (MOFs) into a series of porous inorganic sorbents. These MOF-templated materials display remarkable affinity for heavy metals with saturation occurring in less than 1 h. The saturation capacity for Hg(II) exceeds 2 g g(-1) , more than doubling the best thiol-functionalized sorbents in the literature. PMID:25348588

  13. Tridentate ligated heteronuclear tin(II) alkoxides for use as base catalysts

    DOEpatents

    Boyle, Timothy J.

    2001-01-01

    Tin alkoxide compounds are provided with accessible electrons. The tin alkoxide compound have the general formula (THME).sub.2 Sn.sub.3 (M(L).sub.x).sub.y, where THME is (O--CH.sub.2).sub.3 C(CH.sub.3), M is a metal atom selected from Sn and Ti, L is an organic/inorganic ligand selected from an alkoxide, a phenoxide or an amide, x is selected from 2 and 4 and y is selected from 0 and 1. These compounds have applicability as base catalysts in reactions and in metal-organic chemical vapor depositions processes.

  14. Dextran templating for the synthesis of metallic and metal oxide sponges

    NASA Astrophysics Data System (ADS)

    Walsh, Dominic; Arcelli, Laura; Ikoma, Toshiyuki; Tanaka, Junzo; Mann, Stephen

    2003-06-01

    Silver or gold-containing porous frameworks have been used extensively in catalysis, electrochemistry, heat dissipation and biofiltration. These materials are often prepared by thermal reduction of metal-ion-impregnated porous insoluble supports (such as alumina and pumice), and have surface areas of about 1 m2 g-1, which is typically higher than that obtained for pure metal powders or foils prepared electrolytically or by infiltration and thermal decomposition of insoluble cellulose supports. Starch gels have been used in association with zeolite nanoparticles to produce porous inorganic materials with structural hierarchy, but the use of soft sacrificial templates in the synthesis of metallic sponges has not been investigated. Here we demonstrate that self-supporting macroporous frameworks of silver, gold and copper oxide, as well as composites of silver/copper oxide or silver/titania can be routinely prepared by heating metal-salt-containing pastes of the polysaccharide, dextran, to temperatures between 500 and 900 °C. Magnetic sponges were similarly prepared by replacing the metal salt precursor with preformed iron oxide (magnetite) nanoparticles. The use of dextran as a sacrificial template for the fabrication of metallic and metal oxide sponges should have significant benefits over existing technologies because the method is facile, inexpensive, environmentally benign, and amenable to scale-up and processing.

  15. Active-Metal Template Synthesis of a Halogen-Bonding Rotaxane for Anion Recognition.

    PubMed

    Langton, Matthew J; Xiong, Yaoyao; Beer, Paul D

    2015-12-21

    The synthesis of an all-halogen-bonding rotaxane for anion recognition is achieved by using active-metal templation. A flexible bis-iodotriazole-containing macrocycle is exploited for the metal-directed rotaxane synthesis. Endotopic binding of a Cu(I) template facilitates an active-metal CuAAC iodotriazole axle formation reaction that captures the interlocked rotaxane product. Following copper-template removal, exotopic coordination of a more sterically demanding rhenium(I) complex induces an inversion in the conformation of the macrocycle component, directing the iodotriazole halogen-bond donors into the rotaxane's interlocked binding cavity to facilitate anion recognition. PMID:26500150

  16. Templated synthesis for highly ordered metal/support nanocomposite materials with catalytic applications

    NASA Astrophysics Data System (ADS)

    Sarkar, Jayashri

    Template synthesis is a powerful method of synthesizing materials with tunable properties. Tailorability of the templates makes it a viable method for high performance material synthesis. Surfactant, polymers and semiconductors have been used as templating tools for a long time. In the present work, we demonstrate the ability to synthesize hexagonally organized porous titania, zirconia and zirconia/titania mixed oxide supports and their respective nanocomposites of Pt from their alkoxide precursors using a highly viscous mixed surfactant template, separating nanoscopic bicontinuous channels of water and isooctane. Oil soluble precursor that eventually forms the support, precipitates at the oil-water interface mimicking the microstructure of the template. Subsequent reduction of Pt precursor in the aqueous nanochannels decorates the surface of the macropore walls with well-separated platinum (Pt) nanoparticles. This technique enables us to synthesize two components in a single template system by utilizing both oil and water phases. The composite formed possess a bimodal pore size distribution with one mean pore size ˜3.5nm (nanopores) and the other in the larger mean pore diameter regions ˜100nm-2mum (macropores), depending on the oxide support. Because of the decreased mass transfer resistance provided by the ordered and interconnected macropores in the support, the Pt/TiO2 nanocomposite exhibits a significantly higher carbon monoxide oxidation efficiency than that obtained with a commercial support that has a 4-fold larger specific surface area (at equivalent Pt loadings). We further demonstrate that simple changes in the post-synthesis processing can improve the properties of the material. Altering the drying technique and calcination temperature result in a substantial improvement in the specific surface area of the support material making them better than or comparable to the commercial support materials. We are able to synthesize materials with very low Pt

  17. Versatile method for template-free synthesis of single crystalline metal and metal alloy nanowires

    NASA Astrophysics Data System (ADS)

    Scott, John A.; Totonjian, Daniel; Martin, Aiden A.; Tran, Toan Trong; Fang, Jinghua; Toth, Milos; McDonagh, Andrew M.; Aharonovich, Igor; Lobo, Charlene J.

    2016-01-01

    Metal and metal alloy nanowires have applications ranging from spintronics to drug delivery, but high quality, high density single crystalline materials have been surprisingly difficult to fabricate. Here we report a versatile, template-free, self-assembly method for fabrication of single crystalline metal and metal alloy nanowires (Co, Ni, NiCo, CoFe, and NiFe) by reduction of metal nitride precursors formed in situ by reaction of metal salts with a nitrogen source. Thiol reduction of the metal nitrides to the metallic phase at 550-600 °C results in nanowire growth. In this process, sulfur acts as a uniaxial structure-directing agent, passivating the surface of the growing nanowires and preventing radial growth. The versatility of the method is demonstrated by achieving nanowire growth from gas-phase, solution-phase or a combination of gas- and solution-phase precursors. The fabrication method is suited to large-area CVD on a wide range of solid substrates.Metal and metal alloy nanowires have applications ranging from spintronics to drug delivery, but high quality, high density single crystalline materials have been surprisingly difficult to fabricate. Here we report a versatile, template-free, self-assembly method for fabrication of single crystalline metal and metal alloy nanowires (Co, Ni, NiCo, CoFe, and NiFe) by reduction of metal nitride precursors formed in situ by reaction of metal salts with a nitrogen source. Thiol reduction of the metal nitrides to the metallic phase at 550-600 °C results in nanowire growth. In this process, sulfur acts as a uniaxial structure-directing agent, passivating the surface of the growing nanowires and preventing radial growth. The versatility of the method is demonstrated by achieving nanowire growth from gas-phase, solution-phase or a combination of gas- and solution-phase precursors. The fabrication method is suited to large-area CVD on a wide range of solid substrates. Electronic supplementary information (ESI) available

  18. Active‐Metal Template Synthesis of a Halogen‐Bonding Rotaxane for Anion Recognition

    PubMed Central

    Langton, Matthew J.; Xiong, Yaoyao

    2015-01-01

    Abstract The synthesis of an all‐halogen‐bonding rotaxane for anion recognition is achieved by using active‐metal templation. A flexible bis‐iodotriazole‐containing macrocycle is exploited for the metal‐directed rotaxane synthesis. Endotopic binding of a CuI template facilitates an active‐metal CuAAC iodotriazole axle formation reaction that captures the interlocked rotaxane product. Following copper‐template removal, exotopic coordination of a more sterically demanding rhenium(I) complex induces an inversion in the conformation of the macrocycle component, directing the iodotriazole halogen‐bond donors into the rotaxane’s interlocked binding cavity to facilitate anion recognition. PMID:26500150

  19. Preparation of Mesoporous Silica Templated Metal Nanowire Films on Foamed Nickel Substrates

    SciTech Connect

    Campbell, Roger; Kenik, Edward A; Bakker, Martin; Havrilla, George; Montoya, Velma; Shamsuzzoha, Mohammed

    2006-01-01

    A method has been developed for the formation of high surface area nanowire films on planar and three-dimensional metal electrodes. These nanowire films are formed via electrodeposition into a mesoporous silica film. The mesoporous silica films are formed by a sol-gel process using Pluronic tri-block copolymers to template mesopore formation on both planar and three-dimensional metal electrodes. Surface area increases of up to 120-fold have been observed in electrodes containing a templated film when compared to the same types of electrodes without the templated film.

  20. Versatile method for template-free synthesis of single crystalline metal and metal alloy nanowires.

    PubMed

    Scott, John A; Totonjian, Daniel; Martin, Aiden A; Tran, Toan Trong; Fang, Jinghua; Toth, Milos; McDonagh, Andrew M; Aharonovich, Igor; Lobo, Charlene J

    2016-02-01

    Metal and metal alloy nanowires have applications ranging from spintronics to drug delivery, but high quality, high density single crystalline materials have been surprisingly difficult to fabricate. Here we report a versatile, template-free, self-assembly method for fabrication of single crystalline metal and metal alloy nanowires (Co, Ni, NiCo, CoFe, and NiFe) by reduction of metal nitride precursors formed in situ by reaction of metal salts with a nitrogen source. Thiol reduction of the metal nitrides to the metallic phase at 550-600 °C results in nanowire growth. In this process, sulfur acts as a uniaxial structure-directing agent, passivating the surface of the growing nanowires and preventing radial growth. The versatility of the method is demonstrated by achieving nanowire growth from gas-phase, solution-phase or a combination of gas- and solution-phase precursors. The fabrication method is suited to large-area CVD on a wide range of solid substrates. PMID:26763153

  1. Nanofabrication of highly ordered, tunable metallic mesostructures via quasi-hard-templating of lyotropic liquid crystals

    PubMed Central

    Zhang, Xinyi; Lu, Wei; Dai, Jiyan; Bourgeois, Laure; Yao, Jianfeng; Wang, Huanting; Friend, James R.; Zhao, Dongyuan; MacFarlane, Douglas R.

    2014-01-01

    The synthesis of metal frameworks perforated with nanotunnels is a challenge because metals have high surface energies that favor low surface area structures; traditional liquid-crystal templating techniques cannot achieve the synthetic control required. We report a synthetic strategy to fabricate metal nanomaterials with highly ordered, tunable mesostructures in confined systems based on a new quasi-hard-templating liquid-crystals mechanism. The resulting platinum nanowires exhibit long range two-dimensional hexagonally ordered mesopore structures. In addition, single crystalline hexagonal mesoporous platinum nanowires with dominant {110} facets have been synthesized. Finally, we demonstrate that the mesostructures of metal nanomaterials can be tuned from hexagonal to lamellar mesostructures. PMID:25502015

  2. Microscopic mechanism of templated self-assembly: Indium metallic atomic wires on Si(553)-Au

    NASA Astrophysics Data System (ADS)

    Kang, Pil-Gyu; Jeong, Hojin; Yeom, Han Woong

    2009-03-01

    We report on the self-assembly of metallic atomic wires utilizing a templated semiconductor surface. A well-ordered template is provided by a vicinal Si surface reacted with Au, Si(553)-Au, which has a regular and robust step array. The scanning tunneling microscopy study shows that In atoms preferentially adsorb and diffuse actively along step edges to form well-ordered atomic wires. The local spectroscopy indicates the metallic property of In atomic wires formed. Ab initio calculations reveal the microscopic mechanism of the templated self-assembly as based on well-aligned preferential adsorption sites and the strongly anisotropic surface diffusion. This template can, thus, be widely applied to fabricate various atomic or molecular wires.

  3. Rational Design of Biomolecular Templates for Synthesizing Multifunctional Noble Metal Nanoclusters toward Personalized Theranostic Applications.

    PubMed

    Yu, Yong; Mok, Beverly Y L; Loh, Xian Jun; Tan, Yen Nee

    2016-08-01

    Biomolecule-templated or biotemplated metal nanoclusters (NCs) are ultrasmall (<2 nm) metal (Au, Ag) particles stabilized by a certain type of biomolecular template (e.g., peptides, proteins, and DNA). Due to their unique physiochemical properties, biotemplated metal NCs have been widely used in sensing, imaging, delivery and therapy. The overwhelming applications in these individual areas imply the great promise of harnessing biotemplated metal NCs in more advanced biomedical aspects such as theranostics. Although applications of biotemplated metal NCs as theranostic agents are trending, the rational design of biomolecular templates suitable for the synthesis of multifunctional metal NCs for theranostics is comparatively underexplored. This progress report first identifies the essential attributes of biotemplated metal NCs for theranostics by reviewing the state-of-art applications in each of the four modalities of theranostics, namely sensing, imaging, delivery and therapy. To achieve high efficacy in these modalities, we elucidate the design principles underlying the use of biomolecules (proteins, peptides and nucleic acids) to control the NC size, emission color and surface chemistries for post-functionalization of therapeutic moieties. We then propose a unified strategy to engineer biomolecular templates that combine all these modalities to produce multifunctional biotemplated metal NCs that can serve as the next-generation personalized theranostic agents. PMID:27377035

  4. Fabrication of Smooth Patterned Structures of Refractory Metals, Semiconductors, and Oxides via Template Stripping

    PubMed Central

    2013-01-01

    The template-stripping method can yield smooth patterned films without surface contamination. However, the process is typically limited to coinage metals such as silver and gold because other materials cannot be readily stripped from silicon templates due to strong adhesion. Herein, we report a more general template-stripping method that is applicable to a larger variety of materials, including refractory metals, semiconductors, and oxides. To address the adhesion issue, we introduce a thin gold layer between the template and the deposited materials. After peeling off the combined film from the template, the gold layer can be selectively removed via wet etching to reveal a smooth patterned structure of the desired material. Further, we demonstrate template-stripped multilayer structures that have potential applications for photovoltaics and solar absorbers. An entire patterned device, which can include a transparent conductor, semiconductor absorber, and back contact, can be fabricated. Since our approach can also produce many copies of the patterned structure with high fidelity by reusing the template, a low-cost and high-throughput process in micro- and nanofabrication is provided that is useful for electronics, plasmonics, and nanophotonics. PMID:24001174

  5. Quasi-radial growth of metal tube on si nanowires template

    NASA Astrophysics Data System (ADS)

    Huang, Zhipeng; Liu, Lifeng; Geyer, Nadine

    2011-12-01

    It is reported in this article that Si nanowires can be employed as a positive template for the controllable electrochemical deposition of noble metal tube. The deposited tube exhibits good crystallinity. Scanning electron microscope and transmission electron microscope characterizations are conducted to reveal the growth process of metal tube, showing that the metal tube grows quasi-radially on the wall of Si nanowire. The quasi-radial growth of metal enables the fabrication of thickness-defined metal tube via changing deposition time. Inner-diameter-defined metal tube is achieved by choosing Si nanowires with desired diameter as a template. Metal tubes with inner diameters ranging from 1 μm to sub-50 nm are fabricated.

  6. Quasi-radial growth of metal tube on si nanowires template

    PubMed Central

    2011-01-01

    It is reported in this article that Si nanowires can be employed as a positive template for the controllable electrochemical deposition of noble metal tube. The deposited tube exhibits good crystallinity. Scanning electron microscope and transmission electron microscope characterizations are conducted to reveal the growth process of metal tube, showing that the metal tube grows quasi-radially on the wall of Si nanowire. The quasi-radial growth of metal enables the fabrication of thickness-defined metal tube via changing deposition time. Inner-diameter-defined metal tube is achieved by choosing Si nanowires with desired diameter as a template. Metal tubes with inner diameters ranging from 1 μm to sub-50 nm are fabricated. PMID:21711672

  7. Tantalum Aluminum Alkoxide as a Double-Metal Precursor for Metalorganic Chemical Vapor Deposition of Sr2AlTaO6

    NASA Astrophysics Data System (ADS)

    Zama, Hideaki; Takahashi, Yoshihiro; Tanabe, Keiichi; Morishita, Tadataka

    2001-02-01

    We proposed resolving the poor controllability in the metalorganic chemical vapor deposition (MOCVD) of a complex oxide film consisting of a few metal elements, Sr2AlTaO6 (SAT) film, by using a double-metal source, tantalum aluminum isopropoxide TaAl(O-iC3H7)8. It had a melting point as low as 93°C and generated suitable vapor pressure for MOCVD at a temperature of 100°C. The supply metal ratio, Al/Ta, was ˜ 1, because it remained a double-metal structure in the vapor phase. We grew stoichiometric SAT films using it as a metal source.

  8. Periodic arrays of metal nanorings and nanocrescents fabricated by a scalable colloidal templating approach.

    PubMed

    Liu, Xuefeng; Choi, Baeck; Gozubenli, Numan; Jiang, Peng

    2013-11-01

    Here, we report a scalable bottom-up approach for fabricating periodic arrays of metal nanorings and nanocrescents. Wafer-scale monolayer silica colloidal crystals with an unusual non-close-packed structure prepared by a simple and rapid spin-coating technology are used as both etching and shadowing masks to create nanoring-shaped trenches in between templated polymer posts and sacrificial nanoholes. Directional deposition of metals in the trenches followed by liftoff of the polymer posts and the sacrificial nanoholes results in forming ordered metal nanorings. The inner and outer radii of the final nanorings are determined by the sizes of the templated polymer posts and the silica microspheres which can be easily adjusted by tuning the spin-coating and templating conditions. Most importantly, by simply controlling the tilt angle of the substrate toward the directional metal beams, continuous geometric transition from concentric nanorings to eccentric nanorings to nanocrescents can be achieved. This new colloidal templating approach is compatible with standard semiconductor microfabrication, promising for mass-production and on-chip integration of periodic nanorings and nanocrescents for a wide spectrum of technological applications ranging from nanooptical devices and ultrasensitive biosensing to magnetic memories and logic circuits. PMID:23978286

  9. Formation of 3D graphene foams on soft templated metal monoliths.

    PubMed

    Tynan, Michael K; Johnson, David W; Dobson, Ben P; Coleman, Karl S

    2016-07-21

    Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene's high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a methane chemical vapour deposition (CVD). Cobalt metal gels were shown to afford the highest quality material as determined by electron microscopy (SEM and TEM) and Raman spectroscopy. PMID:27341076

  10. Replicative generation of metal microstructures by template-directed electrometallization

    SciTech Connect

    Thom, I.; Haehner, G.; Buck, M.

    2005-07-11

    Copper structures were produced by electrochemical deposition onto patterned self-assembled monolayers (SAMS) of thiols adsorbed on polycrystalline gold substrates and subsequent transfer to an insulating substrate. Selective metal deposition was achieved by use of thiols which differ in their electrochemical blocking properties, namely hexadecane thiol [CH{sub 3}(CH{sub 2}){sub 15}SH] and {omega}-(4{sup '}-methyl-biphenyl-4-yl)-methanethiol (CH{sub 3}-C{sub 6}H{sub 4}-C{sub 6}H{sub 4}-CH{sub 2}-SH). Besides control of the blocking properties, the SAM served to minimize adhesion between the metal deposit and the substrate, thus, allowing the transfer of the metal pattern. Since the process is replicative, it represents a very simple and fast route to generating metal patterns.

  11. Replicative generation of metal microstructures by template-directed electrometallization

    NASA Astrophysics Data System (ADS)

    Thom, I.; Hähner, G.; Buck, M.

    2005-07-01

    Copper structures were produced by electrochemical deposition onto patterned self-assembled monolayers (SAMS) of thiols adsorbed on polycrystalline gold substrates and subsequent transfer to an insulating substrate. Selective metal deposition was achieved by use of thiols which differ in their electrochemical blocking properties, namely hexadecane thiol [CH3(CH2)15SH] and ω-(4'-methyl-biphenyl-4-yl)-methanethiol (CH3-C6H4-C6H4-CH2-SH). Besides control of the blocking properties, the SAM served to minimize adhesion between the metal deposit and the substrate, thus, allowing the transfer of the metal pattern. Since the process is replicative, it represents a very simple and fast route to generating metal patterns.

  12. Transition metal-chelating surfactant micelle templates for facile synthesis of mesoporous silica nanoparticles

    SciTech Connect

    Lee, Hye Sun; Kim, Won Hee; Lee, Jin Hyung; Choi, Doo Jin; Jeong, Young-Keun; Chang, Jeong Ho

    2012-01-15

    Highly ordered mesoporous silica nanoparticles with tunable morphology and pore-size are prepared by the use of a transition metal-chelating surfactant micelle complex using Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}, and Zn{sup 2+} ions. These metal ions formed a metal-P123 micelle complex in an aqueous solution, while the metal ions are chelated to the hydrophilic domain such as the poly(ethylene oxide) group of a P123 surfactant. The different complexation abilities of the utilized transition metal ions play an important role in determining the formation of nano-sized ordered MSNs due to the different stabilization constant of the metal-P123 complex. Consequently, from a particle length of 1700 nm in the original mesoporous silica materials, the particle length of ordered MSNs through the metal-chelating P123 micelle templates can be reduced to a range of 180-800 nm. Furthermore, the variation of pore size shows a slight change from 8.8 to 6.6 nm. In particular, the Cu{sup 2+}-chelated MSNs show only decreased particle size to 180 nm. The stability constants for the metal-P123 complex are calculated on the basis of molar conductance measurements in order to elucidate the formation mechanism of MSNs by the metal-chelating P123 complex templates. In addition, solid-state {sup 29}Si, {sup 13}C-NMR and ICP-OES measurements are used for quantitative characterization reveal that the utilized metal ions affect only the formation of a metal-P123 complex in a micelle as a template. - Graphical abstract: Metal-chelating surfactant micelle templates support a simple and facile preparations of size-tunable ordered MSNs. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Facile preparation of mesoporous silica nanoparticles (MSNs) was achieved by metal-chelating surfactant micelle complex using Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}, and Zn{sup 2+} ions. Black-Right-Pointing-Pointer Different complexation of metal ions plays an important role in determining the formation of

  13. Template-Free Synthesis of Hierarchical Porous Metal-Organic Frameworks

    SciTech Connect

    Yue, Yanfeng; Qiao, Zhen-an; Fulvio, Pasquale F; Dai, Sheng; Binder, Andrew J; Tian, Chengcheng; Nelson, Kimberly M; Zhu, Xiang

    2013-01-01

    A template-free synthesis of a hierarchical microporous-mesoporous metal-organic framework (MOF) of Zn(II)-2,5-dihydroxy-1,4-benzenedicarboxylate, namely Zn-MOF-74, is reported. The surface morphology and porosity of the bimodal materials can be modified by etching the pore walls with the synthesis solvent under different reaction times and different solvents. This template-free strategy allows for the preparation of stable frameworks with mesopores exceeding 15 nm, which was previously unattained by the synthesis of MOFs by ligand exten-sion method.

  14. Templated fabrication of periodic arrays of metallic and silicon nanorings with complex nanostructures

    NASA Astrophysics Data System (ADS)

    Liu, Xuefeng; Gozubenli, Numan; Choi, Baeck; Jiang, Peng; Meagher, Timothy; Jiang, Bin

    2015-02-01

    Here we report a scalable colloidal templating approach for fabricating periodic arrays of metallic and silicon nanorings with complex nanostructures. Non-close-packed monolayer silica colloidal crystal prepared by a simple spin-coating technology is first used as template for making periodic arrays of mushroom-like composite nanostructures consisting of silica spherical caps and polymer stems. Subsequent metal sputtering and reactive ion etching lead to the formation of ordered asymmetric nickel nanorings which can be further utilized as etching masks for patterning periodic arrays of symmetric silicon nanorings. Moreover, periodic arrays of metallic and silicon concentric double nanorings can be fabricated by using the asymmetric nickel nanorings as templates. We have also demonstrated that gold concentric double nanorings show strong surface-enhanced Raman scattering (SERS) with a SERS enhancement factor of ˜9.5 × 107 from adsorbed benzenethiol molecules. The SERS enhancement and the electric field amplitude distribution surrounding gold concentric double nanorings have been calculated by using finite element electromagnetic modeling. This new colloidal templating technique is compatible with standard microfabrication and enables wafer-scale production of a variety of periodic nanorings with hierarchical structures that could find important technological applications in plasmonic and magnetic devices.

  15. Engineering Hybrid Metallic Nanostructures Using a Single Domain of Block Copolymer Templates.

    PubMed

    Liu, Zhicheng; Chang, Tongxin; Huang, Haiying; He, Tianbai

    2015-11-25

    Building complex nanostructures using a simple patterned template is challenging in material science and nanotechnology. In the present work, three different strategies have been exploited for the successful fabrication of hybrid dots-on-wire metallic nanostructures through combining an in-situ method with an ex-situ method. Basically, plasma etching was applied to generate a metallic wire-like nanostructure, and preformed nanoparticles could be placed through multiple means before or after the formation of the wire-like nanostructure. Various monometallic and bimetallic nanostructures have been obtained by utilizing only one functional domain of block copolymer templates. In these cases, full utilization of the functional domain or introduction of the molecular linker is critical to engineering hybrid metallic nanostructures. Other complex and multifunctional hybrid nanostructures can be developed via these strategies similarly, and these nanostructures are promising for useful applications such as optics and surface-enhanced Raman spectroscopy (SERS). PMID:26517409

  16. Apoferritin Templated Synthesis of Metal Phosphate Nanoparticle Labels for Electrochemical Immunoassay

    SciTech Connect

    Liu, Guodong; Wu, Hong; Wang, Jun; Lin, Yuehe

    2006-08-29

    W have introduced template-synthesized metal phosphate nanoparticle labels for electrochemical immunoassay. Such use of an apoferritin template offers a simple and convenient route to prepare metallic nanoparticle labels for electrochemical immunoassays and avoid the complicated and time-consuming nanoparticle synthesis process (QD synthesis). Releasing metal ions from metal phosphate in an acetate buffer (pH 4.6) eliminates the harsh condition in the traditional metallic nanoparticle dissolution (e.g., strong acid dissolution of QDs and gold nanoparticles). This method is ultrasensitive and its DL is low to 77fM. The simultaneous detection of multiple protein targets is easily performed by using different metal phosphate nanoparticle labels (cadmium phosphate and lead phosphate). This approach can be extended to prepare multiple metal (such as zinc, lead, cadmium, copper, indium, gold, silver) phosphate nanoparticle labels or hybrid metal (bimetallic or trimetallic with predetermined ratios) phosphate nanoparticle labels for a multiplex electrochemical immunoassay. The new nanoparticle labels could be applicable to other electrochemical bioassays, such as DNA, and is thus expected to lead to wide applications for protein diagnostics and for bioanalysis in general.

  17. Formation of 3D graphene foams on soft templated metal monoliths

    NASA Astrophysics Data System (ADS)

    Tynan, Michael K.; Johnson, David W.; Dobson, Ben P.; Coleman, Karl S.

    2016-07-01

    Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene's high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a methane chemical vapour deposition (CVD). Cobalt metal gels were shown to afford the highest quality material as determined by electron microscopy (SEM and TEM) and Raman spectroscopy.Graphene foams are leading contenders as frameworks for polymer thermosets, filtration/pollution control and for use as an electrode material in energy storage devices, taking advantage of graphene's high electrical conductivity and the porous structure of the foam. Here we demonstrate a simple synthesis of a macroporous 3D graphene material templated from a dextran/metal salt gel, where the metal was cobalt, nickel, copper, and iron. The gel was annealed to form a metal oxide foam prior to a methane chemical vapour deposition (CVD). Cobalt metal gels were shown to afford the highest quality material as determined by electron microscopy (SEM and TEM) and Raman spectroscopy. Electronic supplementary information (ESI) available: Raman, EDX, PXRD, TGA, electrical conductivity data and SEM. See DOI: 10.1039/c6nr02455f

  18. Structure of reverse microemulsion-templated metal hexacyanoferrate nanoparticles

    PubMed Central

    2012-01-01

    The droplet phase of a reverse microemulsion formed by the surfactant cetyltrimethylammonium ferrocyanide was used as a matrix to synthesize nanoparticles of nickel hexacyanoferrate by adding just a solution of NiCl2 to the microemulsion media. Dynamic light scattering and small-angle neutron scattering measurements show that the reverse microemulsion droplets employed have a globular structure, with sizes that depend on water content. Transmission electron microscopy and electron diffraction are used to obtain information about the structure of the synthesized nanoparticles. The results show that the size and shape of the coordination compound nanoparticles correspond with the size and shape of the droplets, suggesting that the presented system constitutes an alternative method of the synthesis of metal hexacyanoferrate nanoparticles. PMID:22264404

  19. Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.

    SciTech Connect

    Vamvasakis, Ioannis; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.; Armatas, Gerasimos S.

    2015-04-01

    Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the pore surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.

  20. High aspect ratio 10-nm-scale nanoaperture arrays with template-guided metal dewetting.

    PubMed

    Wang, Ying Min; Lu, Liangxing; Srinivasan, Bharathi Madurai; Asbahi, Mohamed; Zhang, Yong Wei; Yang, Joel K W

    2015-01-01

    We introduce an approach to fabricate ordered arrays of 10-nm-scale silica-filled apertures in a metal film without etching or liftoff. Using low temperature (<400°C) thermal dewetting of metal films guided by nano-patterned templates, apertures with aspect ratios up to 5:1 are demonstrated. Apertures form spontaneously during the thermal process without need for further processing. Although the phenomenon of dewetting has been well studied, this is the first demonstration of its use in the fabrication of nanoapertures in a spatially controllable manner. In particular, the achievement of 10-nm length-scale patterning at high aspect ratio with thermal dewetting is unprecedented. By varying the nanotemplate design, we show its strong influence over the positions and sizes of the nanoapertures. In addition, we construct a three-dimensional phase field model of metal dewetting on nano-patterned substrates. The simulation data obtained closely corroborates our experimental results and reveals new insights to template dewetting at the nanoscale. Taken together, this fabrication method and simulation model form a complete toolbox for 10-nm-scale patterning using template-guided dewetting that could be extended to a wide range of material systems and geometries. PMID:25858792

  1. High aspect ratio 10-nm-scale nanoaperture arrays with template-guided metal dewetting

    PubMed Central

    Wang, Ying Min; Lu, Liangxing; Srinivasan, Bharathi Madurai; Asbahi, Mohamed; Zhang, Yong Wei; Yang, Joel K. W.

    2015-01-01

    We introduce an approach to fabricate ordered arrays of 10-nm-scale silica-filled apertures in a metal film without etching or liftoff. Using low temperature (<400°C) thermal dewetting of metal films guided by nano-patterned templates, apertures with aspect ratios up to 5:1 are demonstrated. Apertures form spontaneously during the thermal process without need for further processing. Although the phenomenon of dewetting has been well studied, this is the first demonstration of its use in the fabrication of nanoapertures in a spatially controllable manner. In particular, the achievement of 10-nm length-scale patterning at high aspect ratio with thermal dewetting is unprecedented. By varying the nanotemplate design, we show its strong influence over the positions and sizes of the nanoapertures. In addition, we construct a three-dimensional phase field model of metal dewetting on nano-patterned substrates. The simulation data obtained closely corroborates our experimental results and reveals new insights to template dewetting at the nanoscale. Taken together, this fabrication method and simulation model form a complete toolbox for 10-nm-scale patterning using template-guided dewetting that could be extended to a wide range of material systems and geometries. PMID:25858792

  2. Synthesis and photocatalytic property of porous metal oxides nanowires based on carbon nanofiber template

    NASA Astrophysics Data System (ADS)

    Fan, Weiqiang; Li, Meng; Xu, Jinfu; Bai, Hongye; Zhang, Rongxian; Chen, Chao

    2015-11-01

    A series of porous metal oxides nanowires (Fe2O3, Co3O4, NiO and CuO) have been successfully synthesized, where commercial carbon nanofibers were used as the template. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-Vis diffuse reflectance (UV-Vis DR) spectra and transmission electron microscope (TEM). According to the photodegradation data, the porous metal oxides nanowires exhibit significantly photocatalytic activity for degrading tetracycline (TC). Furthermore, the porous Fe2O3 nanowires show the best photocatalytic performance among all the samples.

  3. Self-aligned grating couplers on template-stripped metal pyramids via nanostencil lithography

    NASA Astrophysics Data System (ADS)

    Klemme, Daniel J.; Johnson, Timothy W.; Mohr, Daniel A.; Oh, Sang-Hyun

    2016-05-01

    We combine nanostencil lithography and template stripping to create self-aligned patterns about the apex of ultrasmooth metal pyramids with high throughput. Three-dimensional patterns such as spiral and asymmetric linear gratings, which can couple incident light into a hot spot at the tip, are presented as examples of this fabrication method. Computer simulations demonstrate that spiral and linear diffraction grating patterns are both effective at coupling light to the tip. The self-aligned stencil lithography technique can be useful for integrating plasmonic couplers with sharp metallic tips for applications such as near-field optical spectroscopy, tip-based optical trapping, plasmonic sensing, and heat-assisted magnetic recording.

  4. Non-equilibrium self-assembly of metals on diblock copolymer templates

    NASA Astrophysics Data System (ADS)

    Lopes, Ward Antone

    Typically, the most perfectly ordered, self-assembled structures correspond to equilibrium states of the system. Here, I show that a high degree of order can arise out of strongly non-equilibrium conditions. I report on a systematic study of non-equilibrium aspects of the decoration of diblock copolymer ultrathin films by evaporated metals. I observe two distinct behaviors for selectively decorating the diblock copolymer: either the metal decorates the diblock copolymer template with nanoparticles or the metal decorates the template with nanowires. Remarkably, these nanowires remain stable under non-equilibrium conditions. I focus on results obtained with evaporated gold and silver on asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA). Gold and a number of other metals (indium, tin, lead, bismuth, aluminum) decorate the diblock copolymer with chains of nanoparticles and don't form wires. Silver forms chains of nanoparticles at low coverage (<30 A), but at high coverage (>100 A), silver forms nanowires. One can understand the formation of the chains of nanoparticles by understanding the equilibrium state of the system (metal + polymer). The silver nanowires, however, are highly non-equilibrium structures. To understand their formation, I modeled the self-assembly of the nanowires with a Monte Carlo simulation. This Monte Carlo simulation qualitatively agrees with the formation of the silver nanowires and their relaxation to equilibrium upon moderate heating.

  5. Predicting Sizes of Hexagonal and Gyroid Metal Nanostructures from Liquid Crystal Templating.

    PubMed

    Asghar, Kaleem A; Rowlands, Daniel A; Elliott, Joanne M; Squires, Adam M

    2015-11-24

    We describe a method to predict and control the lattice parameters of hexagonal and gyroid mesoporous materials formed by liquid crystal templating. In the first part, we describe a geometric model with which the lattice parameters of different liquid crystal mesophases can be predicted as a function of their water/surfactant/oil volume fractions, based on certain geometric parameters relating to the constituent surfactant molecules. We demonstrate the application of this model to the lamellar (Lα), hexagonal (H1), and gyroid bicontinuous cubic (V1) mesophases formed by the binary Brij-56 (C16EO10)/water system and the ternary Brij-56/hexadecane/water system. In this way, we demonstrate predictable and independent control over the size of the cylinders (with hexadecane) and their spacing (with water). In the second part, we produce mesoporous platinum using as templates hexagonal and gyroid phases with different compositions and show that in each case the symmetry and lattice parameter of the metal nanostructure faithfully replicate those of the liquid crystal template, which is itself in agreement with the model. This demonstrates a rational control over the geometry, size, and spacing of pores in a mesoporous metal. PMID:26493862

  6. Alcohol-free alkoxide process for containing nuclear waste

    DOEpatents

    Pope, James M.; Lahoda, Edward J.

    1984-01-01

    Disclosed is a method of containing nuclear waste. A composition is first prepared of about 25 to about 80%, calculated as SiO.sub.2, of a partially hydrolyzed silicon compound, up to about 30%, calculated as metal oxide, of a partially hydrolyzed aluminum or calcium compound, about 5 to about 20%, calculated as metal oxide, of a partially hydrolyzed boron or calcium compound, about 3 to about 25%, calculated as metal oxide, of a partially hydrolyzed sodium, potassium or lithium compound, an alcohol in a weight ratio to hydrolyzed alkoxide of about 1.5 to about 3% and sufficient water to remove at least 99% of the alcohol as an azeotrope. The azeotrope is boiled off and up to about 40%, based on solids in the product, of the nuclear waste, is mixed into the composition. The mixture is evaporated to about 25 to about 45% solids and is melted and cooled.

  7. Alcohol-free alkoxide process for containing nuclear waste

    SciTech Connect

    Pope, J.M.; Lahoda, E.J.

    1984-02-07

    Disclosed is a method of containing nuclear waste. A composition is first prepared of about 25 to about 80%, calculated as SiO/sub 2/, of a partially hydrolyzed silicon compound, up to about 30%, calculated as metal oxide, of a partially hydrolyzed aluminum or calcium compound, about 5 to about 20%, calculated as metal oxide, of a partially hydrolyzed boron or calcium compound, about 3 to about 25%, calculated as metal oxide, of a partially hydrolyzed sodium, potassium or lithium compound, an alcohol in a weight ratio to hydrolyzed alkoxide of about 1.5 to about 3% and sufficient water to remove at least 99% of the alcohol as an azeotrope. The azeotrope is boiled off and up to about 40%, based on solids in the product, of the nuclear waste, is mixed into the composition. The mixture is evaporated to about 25 to about 45% solids and is melted and cooled.

  8. Size-Reduction Template Stripping of Smooth Curved Metallic Tips for Adiabatic Nanofocusing of Surface Plasmons.

    PubMed

    Johnson, Timothy W; Klemme, Daniel J; Oh, Sang-Hyun

    2016-06-01

    We present a new technique to engineer metallic interfaces to produce sharp tips with smooth curved surfaces and variable tip angles, as well as ridges with arbitrary contour shapes, all of which can be integrated with grating couplers for applications in plasmonics and nanophotonics. We combine template stripping, a nanofabrication scheme, with atomic layer deposition (ALD) to produce the ultrasharp nanoscale tips and wedges using only conventional photolithography. Conformal ALD coating of insulators over silicon trench molds of various shapes reduces their widths to make nanoscale features without high-resolution lithography. Along with a metal deposition and template stripping, this size-reduction scheme can mass-produce narrow and ultrasharp (<10 nm radius of curvature) metallic wedges and tips over an entire 4 in. wafer. This size-reduction scheme can create metallic tips out of arbitrary trench patterns that have smooth curved surfaces to facilitate efficient adiabatic nanofocusing which will benefit applications in near-field optical spectroscopy, plasmonic waveguides, particle trapping, hot-electron plasmonics, and nonlinear optics. PMID:27156522

  9. Complexation of metal ion with poly(1-vinylimidazole) resin prepared by radiation-induced polymerization with template metal ion. [Gamma radiation

    SciTech Connect

    Kato, M.; Nishide, H.; Tsuchida, E.; Sasaki, T.

    1981-07-01

    Poly(1-vinylimidazole) (PVI) resin was prepared with Ni/sup 2 +/, CO/sup 2 +/, or Zn/sup 2 +/ as a template to study the adsorption of metal ions. The metal-1-vinylimidazole complex was copolymerized and cross-linked with 1-vinyl-2-pyrrolidone by ..gamma..-ray irradiation and the template metal ion was removed by treating the polymer complex with an acid. These PVI resins adsorbed metal ions more effectively than the PVI resin prepared without the template. The number of adsorption sites (As) and the stability constant (K) of Ni/sup 2 +/ complex were larger for the PVI resin prepared with the Ni ion template caused by the smaller dissociation rate constant of Ni ion from the resin. The composition of the Ni/sup 2 +/ complex in the resin remained constant. This suggests that the complexation proceeded via a one-step mechanism.

  10. Fabrication of transition metal-containing nanostructures via polymer templates for a multitude of applications

    NASA Astrophysics Data System (ADS)

    Lu, Jennifer Qing

    Nanostructures such as carbon nanotubes and semiconducting nanowires offer great technological promise due to their remarkable properties. The lack of a rational synthesis method prevents fabricating these nanostructures with desirable and consistent properties at predefined locations for device applications. In this thesis, employing polymer templates, a variety of highly ordered catalytically active transition metal nanostructures, ranging from single metallic nanoparticles of Fe, Co, Ni, Au and bimetallic nanoparticles of Ni/Fe and Co/Mo to Fe-rich silicon oxide nanodomains with uniform and tunable size and spacing have been successfully synthesized. These nanostructures have been demonstrated to be excellent catalyst systems for the synthesis of carbon nanotube and silicon nanowire. High quality, small diameter carbon nanotubes and nanowires with narrow size distribution have been successfully attained. Because these catalytically active nanostructures are uniformly distributed and do not agglomerate at the growth temperatures, uniform, high density and high quality carbon nanotube mats have been obtained. Since this polymer template approach is fully compatible with conventional top-down photolithography, lithographically selective growth of carbon nanotubes on a surface or suspended carbon nanotubes across trenches have been produced by using existing semiconductor processing. We have also shown the feasibility of producing carbon nanotubes and silicon nanowires at predefined locations on a wafer format and established a wafer-level carbon nanotube based device fabrication process. The ability of the polymer template approach to control catalyst systems at the nano-, micro- and macro-scales paves a pathway for commercialization of these 1D nanostructure-enabled devices. Beside producing well-defined, highly ordered discrete catalytically active metal-containing nanostructures by the polymer template approach, Au and Ag nanotextured surfaces have also been

  11. New template for metal decoration and hydrogen adsorption on graphene-like C 3N 4

    NASA Astrophysics Data System (ADS)

    Zhang, Yi; Sun, Hong; Chen, Changfeng

    2009-07-01

    From density functional theory calculations we identify a graphene-like C 3N 4 (g-C 3N 4) as an excellent template for stable and well dispersed decoration of alkali (Li) and 3 d transition metal (TM) atoms. The porous sites of g-C 3N 4 accommodate excessive N lone-pair electrons and promote hybridization between the orbitals of N and the metal atoms. The most stable TM decorations (Ti and Sc) on g-C 3N 4 exhibit high capacities of hydrogen adsorption with binding energies suitable for mobile applications. These metal decorated g-C 3N 4 may also prove useful in catalytic and sensing applications for their unique nanoscale structural features unavailable in conventional nano-clusters.

  12. Self-ordering of small-diameter metal nanoparticles by dewetting on hexagonal mesh templates

    NASA Astrophysics Data System (ADS)

    Meshot, Eric R.; Zhao, Zhouzhou; Lu, Wei; Hart, A. John

    2014-08-01

    Arrays of small-diameter nanoparticles with high spatial order are useful for chemical and biological sensors, data storage, synthesis of nanowires and nanotubes, and many other applications. We show that self-ordered metal nanoparticle arrays can be formed by dewetting of thin films on hexagonal mesh substrates made of anodic aluminum oxide (AAO). Upon heating, the metal (Fe) film dewets onto the interstitial sites (i.e., the node points) between pores on the top surface of the AAO. We investigated the particle morphology and dynamics of dewetting using a combination of atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), and numerical simulations. Templated metal particles are more monodisperse and have higher local order than those formed by the same dewetting process on flat, nonporous alumina. The degree of order depends on the initial film thickness, and for the optimal thickness tested (nominally 2 nm), we achieved uniform coverage and high order of the particles, comparable to that of the AAO template itself. Computational modeling of dewetting on templates with various pore order and size shows that the order of AAO pores is primarily influential in determining particle position and spacing, while the variance in pore size is less impactful. Potential uses of these ordered nanoparticle arrays on porous materials include plasmonic sensors and spatially controlled catalysts.Arrays of small-diameter nanoparticles with high spatial order are useful for chemical and biological sensors, data storage, synthesis of nanowires and nanotubes, and many other applications. We show that self-ordered metal nanoparticle arrays can be formed by dewetting of thin films on hexagonal mesh substrates made of anodic aluminum oxide (AAO). Upon heating, the metal (Fe) film dewets onto the interstitial sites (i.e., the node points) between pores on the top surface of the AAO. We investigated the particle morphology and dynamics of dewetting using

  13. In-situ deposition of Pd nanoparticles on tubular halloysite template for initiation of metallization.

    PubMed

    Fu, Yubin; Zhang, Lide; Zheng, Jiyong

    2005-04-01

    Halloysite template has a tubular microstructure; its wall has a multi-layer aluminosilicate structure. A new catalytic method is adopted here, through the in-situ reduction of Pd ions on the surface of tubular halloysite by methanol to initiate electroless plating; the detailed deposition features of Pd nanoparticles are investigated for the first time. The results indicate that an in-situ reduction and deposition of Pd occurs at room temperature, in which the halloysite template plays an important role. Impurities in halloysite (such as ferric oxide) influence the formation and distribution of the Pd nanoparticles. The Pd nanoparticles are of a non-spherical shape in most cases, which would be caused by the irregular appearance of halloysite. No intercalation of the nanoparticles occurs between the aluminosilicate layers in the halloysite. The diameter of Pd nanoparticles increases with time; the average diameter ranges from 1 nm to 4 nm. Pd nanoparticles on a halloysite template can catalyze electroless deposition of Ni to prepare a novel nano-sized cermet at low cost. This practicable catalytic method could also be used on other clay substrates for the initiation of metallization. PMID:16004119

  14. Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered double hydroxides

    SciTech Connect

    Wang Jun; Zhou Jideng; Li Zhanshuang; He Yang; Lin Shuangshuang; Liu Qi; Zhang Milin; Jiang Zhaohua

    2010-11-15

    We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs having different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted

  15. Ionothermal synthesis of chiral metal phosphite open frameworks with in situ generated organic templates.

    PubMed

    Li, Li-Ming; Cheng, Kai; Wang, Fei; Zhang, Jian

    2013-05-20

    Two novel three-dimensional chiral metal phosphite open frameworks with 4-connected quartz topology, [Me2-DABCO][M2(HPO3)3] [M = Co (1), Zn (2); Me2-DABCO = N,N'-dimethyl-1,4-diazabicyclo[2.2.2]octane], have been ionothermally synthesized in deep eutectic solvents (choline chloride/1,3-dimethylurea). It is interesting that the organic template, Me2-DABCO, is in situ generated from the alkylation reaction of 1,4-diazabicyclo[2.2.2]octane and dimethyl phosphites. PMID:23621695

  16. Template-controlled reactivity: Following nature's way to design and construct metal-organic polyhedra and polygons

    SciTech Connect

    Hamilton, Tamara D.; Papaefstathiou, Giannis S.; MacGillivray, Leonard R. . E-mail: len-macgillivray@uiowa.edu

    2005-08-15

    We show how a template-controlled reaction performed in the organic solid state can be used to construct a molecule that functions as an organic building unit of both a metal-organic polyhedron and polygon. The template is a small organic molecule that organizes two olefins via hydrogen bonds for a [2+2] photodimerization. The process of utilizing a molecule to build a molecule that is subsequently used for self-assembly is inspired by the general two-step process of template-directed synthesis and self-assembly of Nature that is used to construct large, functional self-assembled structures.

  17. Fabrication of Porous Matrix Membrane (PMM) Using Metal-Organic Framework as Green Template for Water Treatment

    PubMed Central

    Lee, Jian-Yuan; Tang, Chuyang Y.; Huo, Fengwei

    2014-01-01

    Pressure-driven membranes with high porosity can potentially be fabricated by removing template, such as low water stability metal-organic frameworks (MOFs) or other nanoparticles, in polymeric matrix. We report on the use of benign MOFs as green template to enhance porosity and interconnectivity of the water treatment membranes. Significantly enhanced separation performance was observed which might be attributed to the mass transfer coefficient of the substrate layer increased in ultrafiltration (UF) application. PMID:24435326

  18. Metal-organic frameworks as templates for nanoscale NaAlH4.

    PubMed

    Bhakta, Raghunandan K; Herberg, Julie L; Jacobs, Benjamin; Highley, Aaron; Behrens, Richard; Ockwig, Nathan W; Greathouse, Jeffery A; Allendorf, Mark D

    2009-09-23

    Metal-organic frameworks (MOFs) offer an attractive alternative to traditional hard and soft templates for nanocluster synthesis because their ordered crystalline lattice provides a highly controlled and inherently understandable environment. We demonstrate that MOFs are stable hosts for metal hydrides proposed for hydrogen storage and their reactive precursors, providing platform to test recent theoretical predictions that some of these materials can be destabilized with respect to hydrogen desorption by reducing their critical dimension to the nanoscale. With the MOF HKUST-1 as template, we show that NaAlH(4) nanoclusters as small as eight formula units can be synthesized. The confinement of these clusters within the MOF pores dramatically accelerates the desorption kinetics, causing decomposition to occur at approximately 100 degrees C lower than bulk NaAlH(4). However, using simultaneous thermogravimetric modulated beam mass spectrometry, we also show that the thermal decomposition mechanism of NaAlH(4) is complex and may involve processes such as nucleation and growth in addition to the normally assumed two-step chemical decomposition reactions. PMID:19719170

  19. Self-Assembled Collagen-like Peptide Fibers as Templates for Metallic Nanowires

    PubMed Central

    Gottlieb, Daniel; Morin, Stephen A.

    2009-01-01

    Inspired by nature’s ability to fabricate supramolecular nanostructures from the bottom-up, materials scientist have become increasingly interested in the use of biomolecules like DNA, peptides, or proteins as templates for the creation of novel nanostructures and nanomaterials. Although the advantages of self-assembling biomolecular structures clearly lie in their chemical diversity, spatial control, and numerous geometric architectures, it is challenging to elaborate them into functional hybrid inorganic–bionanomaterials without rendering the biomolecular scaffold damaged or dysfunctional. In this study, attachment of gold nanoparticles to collagen-related self-assembling peptides at L-lysine residues incorportated within the peptides sequence and the N-terminus led to metal nanoparticle–decorated fibers. After electroless silver plating, these fibers were completely metalized, creating electrically conductive nanowires under mild conditions while leaving the peptide fiber core intact. This study demonstrates the bottom-up assembly of synthetic peptidic fibers under mild conditions and their potential as templates for other complex inorganic–organic hybrid nanostructures. PMID:20130788

  20. Self-Assembled Collagen-like Peptide Fibers as Templates for Metallic Nanowires.

    PubMed

    Gottlieb, Daniel; Morin, Stephen A; Jin, Song; Raines, Ronald T

    2008-01-01

    Inspired by nature's ability to fabricate supramolecular nanostructures from the bottom-up, materials scientist have become increasingly interested in the use of biomolecules like DNA, peptides, or proteins as templates for the creation of novel nanostructures and nanomaterials. Although the advantages of self-assembling biomolecular structures clearly lie in their chemical diversity, spatial control, and numerous geometric architectures, it is challenging to elaborate them into functional hybrid inorganic-bionanomaterials without rendering the biomolecular scaffold damaged or dysfunctional. In this study, attachment of gold nanoparticles to collagen-related self-assembling peptides at L-lysine residues incorportated within the peptides sequence and the N-terminus led to metal nanoparticle-decorated fibers. After electroless silver plating, these fibers were completely metalized, creating electrically conductive nanowires under mild conditions while leaving the peptide fiber core intact. This study demonstrates the bottom-up assembly of synthetic peptidic fibers under mild conditions and their potential as templates for other complex inorganic-organic hybrid nanostructures. PMID:20130788

  1. Metal patterning on silicon surface by site-selective electroless deposition through colloidal crystal templating.

    PubMed

    Asoh, Hidetaka; Sakamoto, Seiji; Ono, Sachiko

    2007-12-15

    Site-selective Cu deposition on a Si substrate was achieved by a combination of colloidal crystal templating, hydrophobic treatment, and electroless plating. Uniformly sized nano/microstructures were produced on the substrate using a monolayer coating of colloidal spheres instead of a conventional resist. The Cu patterns obtained were of two different types: networklike honeycomb and isolated-island patterns with a minimum period of 200 nm. Each ordered pattern with the desired intervals was composed of clusters of Cu nanoparticles with a size range of 50-100 nm. By the present method, it is possible to control the periodicity of metal arrays by changing the diameter of the colloidal spheres used as an initial mask and to adjust the shape of the metal patterns by changing the mask structure for electroless plating. PMID:17915242

  2. Spirulina-Templated Metal Microcoils with Controlled Helical Structures for THz Electromagnetic Responses

    PubMed Central

    Kamata, Kaori; Piao, Zhenzi; Suzuki, Soichiro; Fujimori, Takahiro; Tajiri, Wataru; Nagai, Keiji; Iyoda, Tomokazu; Yamada, Atsushi; Hayakawa, Toshiaki; Ishiwara, Mitsuteru; Horaguchi, Satoshi; Belay, Amha; Tanaka, Takuo; Takano, Keisuke; Hangyo, Masanori

    2014-01-01

    Microstructures in nature are ultrafine and ordered in biological roles, which have attracted material scientists. Spirulina forms three-dimensional helical microstructure, one of remarkable features in nature beyond our current processing technology such as lithography in terms of mass-productivity and structural multiplicity. Spirulina varies its diameter, helical pitch, and/or length against growing environment. This unique helix is suggestive of a tiny electromagnetic coil, if composed of electro-conductive metal, which brought us main concept of this work. Here, we describe the biotemplating process onto Spirulina surface to fabricate metal microcoils. Structural parameters of the microcoil can be controlled by the cultivation conditions of Spirulina template and also purely one-handed microcoil can be fabricated. A microcoil dispersion sheet exhibited optically active response attributed to structural resonance in terahertz-wave region. PMID:24815190

  3. Spirulina-Templated Metal Microcoils with Controlled Helical Structures for THz Electromagnetic Responses

    NASA Astrophysics Data System (ADS)

    Kamata, Kaori; Piao, Zhenzi; Suzuki, Soichiro; Fujimori, Takahiro; Tajiri, Wataru; Nagai, Keiji; Iyoda, Tomokazu; Yamada, Atsushi; Hayakawa, Toshiaki; Ishiwara, Mitsuteru; Horaguchi, Satoshi; Belay, Amha; Tanaka, Takuo; Takano, Keisuke; Hangyo, Masanori

    2014-05-01

    Microstructures in nature are ultrafine and ordered in biological roles, which have attracted material scientists. Spirulina forms three-dimensional helical microstructure, one of remarkable features in nature beyond our current processing technology such as lithography in terms of mass-productivity and structural multiplicity. Spirulina varies its diameter, helical pitch, and/or length against growing environment. This unique helix is suggestive of a tiny electromagnetic coil, if composed of electro-conductive metal, which brought us main concept of this work. Here, we describe the biotemplating process onto Spirulina surface to fabricate metal microcoils. Structural parameters of the microcoil can be controlled by the cultivation conditions of Spirulina template and also purely one-handed microcoil can be fabricated. A microcoil dispersion sheet exhibited optically active response attributed to structural resonance in terahertz-wave region.

  4. Controlled DNA-templated metal deposition: towards ultra-thin nanowires.

    PubMed

    Berti, Lorenzo; Alessandrini, Andrea; Menozzi, Claudia; Facci, Paolo

    2006-08-01

    In this paper, we report the metallization of a dsDNA template using a novel photography-derived two-step strategy in which dsDNA is first complexed with Ag(I) ions and then irradiated with UV light at 254 nm. The nucleobases act as light harvesters and sensitizers, triggering the photoreduction of the complexed silver ions. This process yields a silver nanoparticles blueprint along the DNA strand. The silver latent image is then developed by depositing metallic nickel through an electroless plating process. This photography-derived procedure generates very homogeneous and evenly distributed strings of silver-core/nickel-shell nanoparticles. Although still discontinuous, we believe that such chains can serve as the base for obtaining continuous metal nanowires. Furthermore, this process can most likely be extended to other plating metals, resulting in a broadly general procedure for metallizing DNA with a variety of different materials. Because of the intrinsic simplicity in using light as the key step, this methodology might be amenable to large-scale development, eventually leading to a very efficient molecular-photolithography process. PMID:17037844

  5. FtsZ Cytoskeletal Filaments as a Template for Metallic Nanowire Fabrication.

    PubMed

    Ostrov, Nili; Fichman, Galit; Adler-Abramovich, Lihi; Gazit, Ehud

    2015-01-01

    Supramolecular protein assemblies can serve as templates for the fabrication of inorganic nanowires due to their morphological reproducibility and innate proclivity to form well-ordered structures. Amongst the variety of naturally occurring nano-scale assemblies, cytoskeletal fibers from diverse biological sources represent a unique family of scaffolds for biomimetics as they efficiently self-assemble in vitro in a controllable manner to form stable filaments. Here, we harness the bacterial FtsZ filament system as a scaffold for protein-based metal nanowires, and further demonstrate the control of wire alignment with the use of an external magnetic field. Due to the ease at which the bacterial FtsZ is overexpressed and purified, as well as the extensive studies of its ultrastructural properties and physiological significance, FtsZ filaments are an ideal substrate for large-scale production and chemical manipulation. Using a biologically compatible electroless metal deposition technique initiated by adsorption of platinum as a surface catalyst, we demonstrate the coating of assembled FtsZ filaments with iron, nickel, gold, and copper to fabricate continuous nanowires with diameters ranging from 10-50 nm. Organic-inorganic hybrid wires were analyzed using high-resolution field-emission-gun transmission and scanning electron microscopy, and confirmed by energy-dispersive elemental analysis. We also achieved alignment of ferrofluid-coated FtsZ filaments using an external magnetic field. Overall, we provide evidence for the robustness of the FtsZ filament system as a molecular scaffold, and offer an efficient, biocompatible procedure for facile bottom-up assembly of metallic wires on biological templates. We believe that bottom-up fabrication methods as reported herein significantly contribute to the expanding toolkit available for the incorporation of biological materials in nano-scale devices for electronic and electromechanical applications. PMID:26328401

  6. Concentration effect of the solutions for alumina template ac filling by metal arrays

    NASA Astrophysics Data System (ADS)

    Jagminas, A.; Lichušina, S.; Kurtinaitien≐, M.; Selskis, A.

    2003-04-01

    The influence of the cMe z+ in acidic solutions of Cu, Ni, Co, and Sn salts on the amount of deposited metal, mMe, by ac electrolysis in the pores of various alumina templates grown in commonly used aluminium anodizing solutions of sulfuric, oxalic, phosphoric and chromo-boric acids was investigated. Behaviour of the porous alumina under ac voltage control manifests itself through mMe- cMe z+ parabola dependencies. The peaks of mMe- cMe z+ plots was found to be dependent on the alumina pore diameter, dp, and composition of the metal salt solution used. An increase in dp and decrease in a solution pH shifts mMe versus cMe z+ dependencies and the optimal cMe z+ toward smaller solution concentrations. From the results of the voltammetric and chronopotentiometric studies a surprisingly large value of a few seconds of the transition time for hydrogen ions discharge, occurring before the metal ion reduction at the bottom of alumina pores, was obtained. This result makes it reasonable to suggest that the amount of Me(OH) x, formed in the pore base region due to the hydrogen evolution from the acidic solutions with bulk concentration 0.1-0.2 M, is the most favourable to the deposition of metal arrays at the highest rate if 13.5≤ dp≤37.5 nm.

  7. Synthesis, structure and characterization of five new organically templated metal sulfates with 2-aminopyridinium.

    PubMed

    Bednarchuk, Tamara J; Kinzhybalo, Vasyl; Pietraszko, Adam

    2016-05-01

    The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C5H7N2)[Al(H2O)6](SO4)2·4H2O, (I); type 2 for bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Co(H2O)6]3(SO4)4·2H2O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Mg(H2O)6]3(SO4)4·2H2O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C5H7N2)2[Ni(H2O)6](SO4)2, (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C5H7N2)2[Zn(H2O)6](SO4)2, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence of π-π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures. PMID:27146574

  8. Solution-Processed Self-Assembled Nanodielectrics on Template-Stripped Metal Substrates.

    PubMed

    McMorrow, Julian J; Walker, Amanda R; Sangwan, Vinod K; Jariwala, Deep; Hoffman, Emily; Everaerts, Ken; Facchetti, Antonio; Hersam, Mark C; Marks, Tobin J

    2015-12-01

    The coupling of hybrid organic-inorganic gate dielectrics with emergent unconventional semiconductors has yielded transistor devices exhibiting record-setting transport properties. However, extensive electronic transport measurements on these high-capacitance systems are often convoluted with the electronic response of the semiconducting silicon substrate. In this report, we demonstrate the growth of solution-processed zirconia self-assembled nanodielectrics (Zr-SAND) on template-stripped aluminum substrates. The resulting Zr-SAND on Al structures leverage the ultrasmooth (r.m.s. roughness <0.4 nm), chemically uniform nature of template-stripped metal substrates to demonstrate the same exceptional electronic uniformity (capacitance ∼700 nF cm(-2), leakage current <1 μA cm(-2) at -2 MV cm(-1)) and multilayer growth of Zr-SAND on Si, while exhibiting superior temperature and voltage capacitance responses. These results are important to conduct detailed transport measurements in emergent transistor technologies featuring SAND as well as for future applications in integrated circuits or flexible electronics. PMID:26479833

  9. Metallic Nanostructures Based on Self-Assembling DNA Templates for Studying Optical Phenomena

    NASA Astrophysics Data System (ADS)

    Pilo-Pais, Mauricio

    DNA origami is a novel self-assembly technique that can be used to form various 2D and 3D objects, and to position matter with nanometer accuracy. It has been used to coordinate the placement of nanoscale objects, both organic and inorganic, to make molecular motor and walkers; and to create optically active nanostructures. In this dissertation, DNA origami templates are used to assemble plasmonic structures. Specifically, engineered Surface Enhanced Raman Scattering (SERS) substrates were fabricated. Gold nanoparticles were selectively placed on the corners of rectangular origami and subsequently enlarged via solution-based metal deposition. The resulting assemblies exhibited "hot spots" of enhanced electromagnetic field between the nanoparticles. These hot spots significantly enhanced the Raman signal from Raman molecules covalently attached to the assemblies. Control samples with only one nanoparticle per DNA template, which therefore lacked inter-particle hot spots, did not exhibit strong enhancement. Furthermore, Raman molecules were used to map out the hot spots' distribution, as the molecules are photo-damaged when experiencing a threshold electric field. This method opens up the prospect of using DNA origami to rationally engineer and assemble plasmonic structures for molecular spectroscopy.

  10. Metal-Templated Ligand Architectures for Trinuclear Chemistry: Tricopper Complexes and Their O2 Reactivity

    PubMed Central

    Lionetti, Davide; Day, Michael W.

    2013-01-01

    A trinucleating framework was assmbled by templation of a heptadentate ligand around yttrium and lanthanides. The generated complexes orient three sets of two or three N-donors each for binding additional metal centers. Addition of three equivalents of copper(I) leads to the formation of tricopper(I) species. Reactions with dioxygen at low temperatures generate species whose spectroscopic features are consistent with a μ3,μ3-dioxo-tricopper complex. Reactivity studies were performed with a variety of substrates. The dioxo-tricopper species deprotonates weak acids, undergoes oxygen atom transfer with one equivalent of triphenylphosphine to yield triphenylphosphine oxide, and abstracts two hydrogen atom equivalents from tetramethylpiperidine-N-hydroxide (TEMPO-H). Thiophenols reduce the oxygenated species to a CuI3 complex and liberate two equivalents of disulfide, consistent with a four-electron four-proton process. PMID:23539341

  11. Water-soluble titanium alkoxide material

    DOEpatents

    Boyle, Timothy J.

    2010-06-22

    A water soluble, water stable, titanium alkoxide composition represented by the chemical formula (OC.sub.6H.sub.6N).sub.2Ti(OC.sub.6H.sub.2(CH.sub.2N(CH.sub.3).sub.2).sub- .3-2,4,6).sub.2 with a theoretical molecular weight of 792.8 and an elemental composition of 63.6% C, 8.1% H, 14.1% N, 8.1% O and 6.0% Ti.

  12. Fabrication of periodic arrays of metallic nanoparticles by block copolymer templates on HfO2 substrates.

    PubMed

    Frascaroli, Jacopo; Seguini, Gabriele; Spiga, Sabina; Perego, Michele; Boarino, Luca

    2015-05-29

    Block copolymer-based templates can be exploited for the fabrication of ordered arrays of metal nanoparticles (NPs) with a diameter down to a few nanometers. In order to develop this technique on metal oxide substrates, we studied the self-assembly of polymeric templates directly on the HfO₂ surface. Using a random copolymer neutralization layer, we obtained an effective HfO₂ surface neutralization, while the effects of surface cleaning and annealing temperature were carefully examined. Varying the block copolymer molecular weight, we produced regular nanoporous templates with feature size variable between 10 and 30 nm and a density up to 1.5 × 10¹¹ cm⁻². With the adoption of a pattern transfer process, we produced ordered arrays of Pt and Pt/Ti NPs with diameters of 12, 21 and 29 nm and a constant size dispersion (σ) of 2.5 nm. For the smallest template adopted, the NP diameter is significantly lower than the original template dimension. In this specific configuration, the granularity of the deposited film probably influences the pattern transfer process and very small NPs of 12 nm were achieved without a significant broadening of the size distribution. PMID:25948389

  13. Bicontinuous ceramics with high surface area from block copolymer templates.

    PubMed

    Hsueh, Han-Yu; Ho, Rong-Ming

    2012-06-01

    Mesoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by hydrolysis of PLLA block. Well-defined polymer/ceramic nanohybrid materials with inorganic gyroid nanostructures in a PS matrix can be obtained by using the mesoporous PS as a template for sol-gel reaction. Titanium tetraisopropoxide (TTIP) is used as a precursor to give a model system for the fabrication of metal oxide nanostructures from reactive transition metal alkoxides. By controlling the rates of capillary-driven pore filling and sol-gel reaction, the templated synthesis can be well-developed. Also, by taking advantage of calcination, bicontinuous TiO(2) with controlled crystalline phase (i.e., anatase phase) can be fabricated after removal of the PS template and crystallization of TiO(2) by calcination leading to high photocatalytic efficiency. This new approach provides an easy way to fabricate high-surface-area and high-porosity ceramics with self-supporting structure and controlled crystalline phase for practical applications. As a result, a platform technology to fabricate precisely controlled polymer/ceramic nanohybrids and mesoporous ceramic materials can be established. PMID:22530553

  14. The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

    NASA Astrophysics Data System (ADS)

    Amelina, Anna; Grinberg, Evgenii

    A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used

  15. Scalable salt-templated synthesis of two-dimensional transition metal oxides.

    PubMed

    Xiao, Xu; Song, Huaibing; Lin, Shizhe; Zhou, Ying; Zhan, Xiaojun; Hu, Zhimi; Zhang, Qi; Sun, Jiyu; Yang, Bo; Li, Tianqi; Jiao, Liying; Zhou, Jun; Tang, Jiang; Gogotsi, Yury

    2016-01-01

    Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide. Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300 F cm(-3) in an Al2(SO4)3 electrolyte). The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications. PMID:27103200

  16. Scalable salt-templated synthesis of two-dimensional transition metal oxides

    PubMed Central

    Xiao, Xu; Song, Huaibing; Lin, Shizhe; Zhou, Ying; Zhan, Xiaojun; Hu, Zhimi; Zhang, Qi; Sun, Jiyu; Yang, Bo; Li, Tianqi; Jiao, Liying; Zhou, Jun; Tang, Jiang; Gogotsi, Yury

    2016-01-01

    Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide. Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300 F cm−3 in an Al2(SO4)3 electrolyte). The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications. PMID:27103200

  17. Graphene-Templated Synthesis of Magnetic Metal Organic Framework Nanocomposites for Selective Enrichment of Biomolecules.

    PubMed

    Cheng, Gong; Wang, Zhi-Gang; Denagamage, Sachira; Zheng, Si-Yang

    2016-04-27

    Successful control of homogeneous and complete coating of graphene or graphene-based composites with well-defined metal organic framework (MOF) layers is a great challenge. Herein, novel magnetic graphene MOF composites were constructed via a simple strategy for self-assembly of well-distributed, dense, and highly porous MOFs on both sides of graphene nanosheets. Graphene functionalized with magnetic nanoparticles and carboxylic groups on both sides was explored as the backbone and template to direct the controllable self-assembly of MOFs. The prepared composite materials have a relatively high specific surface area (345.4 m(2) g(-1)), and their average pore size is measured to be 3.2 nm. Their relatively high saturation magnetization (23.8 emu g(-1)) indicates their strong magnetism at room temperature. Moreover, the multifunctional composite was demonstrated to be a highly effective affinity material in selective extraction and separation of low-concentration biomolecules from biological samples, in virtue of the size-selection property of the unique porous structure and the excellent affinity of the composite materials. Besides providing a solution for the construction of well-defined functional graphene-based MOFs, this work could also contribute to selective extraction of biomolecules, in virtue of the universal affinity between immobilized metal ions and biomolecules. PMID:27046460

  18. Scalable salt-templated synthesis of two-dimensional transition metal oxides

    DOE PAGESBeta

    Xiao, Xu; Song, Huaibing; Lin, Shizhe; Zhou, Ying; Zhan, Xiaojun; Hu, Zhimi; Zhang, Qi; Sun, Jiyu; Yang, Bo; Li, Tianqi; et al

    2016-04-22

    Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide.more » Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300Fcm-3 in an Al2(SO4)3 electrolyte). Furthermore, the synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications.« less

  19. Scalable salt-templated synthesis of two-dimensional transition metal oxides

    NASA Astrophysics Data System (ADS)

    Xiao, Xu; Song, Huaibing; Lin, Shizhe; Zhou, Ying; Zhan, Xiaojun; Hu, Zhimi; Zhang, Qi; Sun, Jiyu; Yang, Bo; Li, Tianqi; Jiao, Liying; Zhou, Jun; Tang, Jiang; Gogotsi, Yury

    2016-04-01

    Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide. Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300 F cm-3 in an Al2(SO4)3 electrolyte). The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications.

  20. Simultaneous immunoassay of phosphorylated proteins based on apoferritin templated metallic phosphates as voltammetrically distinguishable signal reporters.

    PubMed

    Ge, Xiaoxiao; Zhang, Aidong; Lin, Yuehe; Du, Dan

    2016-06-15

    A novel electrochemical immunosensor has been developed to detect phosphorylated proteins, phospho-p53(15) and phospho-p53(392), simultaneously. Different apoferritin templated metal phosphates were used as distinguishable signal reporters (apoferritin templated cadmium phosphates (ATCP) and apoferritin templated lead phosphates (ATLP)) to enhance the detection sensitivity. Here, magnetic Fe3O4 nanoparticles functionalized phospho-p53(15) capture antibody (MP-p53(15)c-Ab) and phospho-p53(392) capture antibody (MP-p53(392)c-Ab), respectively, were used to specifically capture phospho-p53(15) and phospho-p53(392) antigens, followed by immunorecognition with p53(15) detection antibody (p53(15)d-Ab) and p53(392) detection antibody (p53(392)d-Ab) to form sandwich-like immunocomplexes. SiO2@Au nanocomposites served as nanocarriers for co-immobilization of both d-Ab and signal reporters (ATCP/SiO2@Au/p53(15)d-Ab, ATLP/SiO2@Au/p53(392)d-Ab), which greatly amplified the detection signal. The distinguished current responses were achieved by electrochemical detection of cadmium ions and lead ions with square wave voltammetry (SWV) after dissolution with acid. The proposed immunoassay exhibited high sensitivity and selectivity for the detection of phospho-p53(15) and phospho-p53(392) simultaneously. The linear relationships between electrochemical responses and the concentrations of phospho-p53(15) and phospho-p53(392) were obtained in the range of 0.1-20ng/mL and 0.05-20ng/mL, respectively. The detection limits were 0.05 and 0.02ng/mL (S/N=3), respectively. This strategy provides a new platform for simultaneous immunoassay of multiple protein biomarkers. PMID:26844908

  1. Controlled fabrication of DNA molecular templates for the deposition and electrical measurement of 1D metal nanowires

    NASA Astrophysics Data System (ADS)

    Barreda, Jorge; Hu, Longqian; Yu, Liuqi; Wang, Zhibin; Xia, Junfei; Guan, Jingjiao; Xiong, Peng; Guan's group Team; Xiong's group Team

    Stretched DNA nanowires (NWs) offer a convenient substrate for the fabrication and measurement of 1D metal NWs of width down to nm.So far the fabrication of the DNA templates has replied on somewhat random self-assembly processes. Here we demonstrate a process with high degree of control over the length, spacing, diameter , and orientation of the metal NWs: A one-step dewetting of a DNA solution on a PDMS stamp with an array of micropillars with well-defined pitch yields DNA NWs suspended across the micropillars along a chosen direction. The DNA NWs are then transferred via micro-contact printing onto a Si/SiO2/SiNx substrate with a lithographically fabricated trench defined by an opening in the SiNx layer and undercut in the SiO2 layer. The template with DNA NWs stretched across the trench is placed in a high-vacuum evaporator for metal deposition, resulting in a metal NW of width defined by the diameter of the DNA template (<10 nm) and length determined by the width of the trench. Quasi-four terminal I-V measurements are performed in situ with incremental metal deposition. Concomitant with a transition from strongly nonlinear IV to Ohmic behavior with increasing thickness, the NW resistance is observed to decrease exponentially.

  2. Preparation of multicomponent oxides via non-hydrolytic sol-gel routes from novel bimetallic alkoxides

    SciTech Connect

    Athar, Taimur; Oh Kwon, Jeong; Seok, Sang Il . E-mail: seoksi@pado.krict.re.kr

    2005-05-15

    New series of double alkoxides of erbium and its oxides have been prepared by non-hydrolytic sol-gel reactions for the first time. These compounds were characterized with the help of FT-IR, NMR, Mass, DTA-TGA and SEM. The mass spectra show similar types of fragmentation pattern in all compounds. The XRD diffraction pattern shows an enhanced homogeneity at high temperature. TGA/DTA measurements show that thermal decomposition occurs in steps and entirely depends on the chemical compositions and the synthesis routes. The SEM observation reveals a high dense and smooth microstructural uniformity of polycrystalline nature. The physico-chemical properties show that crystallization behaviors can be controlled with the help of fine-tuning the chemical properties of chelating agents in order to increase the solubility of metal alkoxides.

  3. Metal-Organic-Framework-Templated Polyelectrolyte Nanocapsules for the Encapsulation and Delivery of Small-Molecule-Polymer Conjugates.

    PubMed

    Liu, Shuo; Chen, Jianbin; Bao, Xiaojia; Li, Tao; Ling, Yunyang; Li, Chunxiang; Wu, Chuanliu; Zhao, Yibing

    2016-06-21

    Herein, we report a strategy for exploiting nanoscale metal-organic frameworks (nano-MOFs) as templates for the layer-by-layer (LbL) assembly of polyelectrolytes. Because small-molecule drugs or imaging agents cannot be efficiently encapsulated by polyelectrolyte nanocapsules, we investigated two promising and biocompatible polymers (comb-shaped polyethylene glycol (PEG) and hyperbranched polyglycerol-based PEG) for the conjugation of model drugs and imaging agents, which were then encapsulated inside the nano-MOF-templated nanocapsules. Furthermore, we also systemically explored the release kinetics of the encapsulated conjugates, and examined how the encapsulation and/or release processes could be controlled by varying the composition and architecture of the polymers. We envision that our nano-MOFs-templated nanocapsules, through combining with small-molecule-polymer conjugates, will represent a new type of delivery system that could open up new opportunities for biomedical applications. PMID:27123998

  4. Directing Colloidal Assembly and a Metal-Insulator Transition Using a Quench-Disordered Porous Rod Template

    NASA Astrophysics Data System (ADS)

    Jadrich, Ryan B.; Schweizer, Kenneth S.

    2014-11-01

    Replica and effective-medium theory methods are employed to elucidate how to massively reconfigure a colloidal assembly to achieve globally homogeneous, strongly clustered, and percolated equilibrium states of high electrical conductivity at low physical volume fractions. A key idea is to employ a quench-disordered, large-mesh rigid-rod network as a templating internal field. By exploiting bulk phase separation frustration and the tunable competing processes of colloid adsorption on the low-dimensional network and fluctuation-driven colloid clustering in the pore spaces, two distinct spatial organizations of greatly enhanced particle contacts can be achieved. As a result, a continuous, but very abrupt, transition from an insulating to metallic-like state can be realized via a small change of either the colloid-template or colloid-colloid attraction strength. The approach is generalizable to more complicated template or colloidal architectures.

  5. Correlation of photobleaching, oxidation and metal induced fluorescence quenching of DNA-templated silver nanoclusters

    NASA Astrophysics Data System (ADS)

    Morishita, Kiyoshi; Maclean, James L.; Liu, Biwu; Jiang, Hui; Liu, Juewen

    2013-03-01

    Few-atom noble metal nanoclusters have attracted a lot of interest due to their potential applications in biosensor development, imaging and catalysis. DNA-templated silver nanoclusters (AgNCs) are of particular interest as different emission colors can be obtained by changing the DNA sequence. A popular analytical application is fluorescence quenching by Hg2+, where d10-d10 metallophilic interaction has often been proposed for associating Hg2+ with nanoclusters. However, it cannot explain the lack of response to other d10 ions such as Zn2+ and Cd2+. In our effort to elucidate the quenching mechanism, we studied a total of eight AgNCs prepared by different hairpin DNA sequences; they showed different sensitivity to Hg2+, and DNA with a larger cytosine loop size produced more sensitive AgNCs. In all the cases, samples strongly quenched by Hg2+ were also more easily photobleached. Light of shorter wavelengths bleached AgNCs more potently, and photobleached samples can be recovered by NaBH4. Strong fluorescence quenching was also observed with high redox potential metal ions such as Ag+, Au3+, Cu2+ and Hg2+, but not with low redox potential ions. Such metal induced quenching cannot be recovered by NaBH4. Electronic absorption and mass spectrometry studies offered further insights into the oxidation reaction. Our results correlate many important experimental observations and will fuel the further growth of this field.Few-atom noble metal nanoclusters have attracted a lot of interest due to their potential applications in biosensor development, imaging and catalysis. DNA-templated silver nanoclusters (AgNCs) are of particular interest as different emission colors can be obtained by changing the DNA sequence. A popular analytical application is fluorescence quenching by Hg2+, where d10-d10 metallophilic interaction has often been proposed for associating Hg2+ with nanoclusters. However, it cannot explain the lack of response to other d10 ions such as Zn2+ and Cd2+. In

  6. Preparation of silica stabilized biological templates for the production of metal and layered nanoparticles

    DOEpatents

    Culver, James N; Royston, Elizabeth; Brown, Adam; Harris, Michael

    2013-02-26

    The present invention relates to a system and method providing for increased silica growth on a bio-template, wherein the bio-template is pretreated with aniline to produce a uniform silica attractive surface and yielding a significant silica layers of at least 10 nm, and more preferably at least 20 nm in thickness, thereby providing for a high degree of stability to the bio-template.

  7. Self-assembled bifunctional surface mimics an enzymatic and templating protein for the synthesis of a metal oxide semiconductor.

    PubMed

    Kisailus, David; Truong, Quyen; Amemiya, Yosuke; Weaver, James C; Morse, Daniel E

    2006-04-11

    The recent discovery and characterization of silicatein, a mineral-synthesizing enzyme that assembles to form the filamentous organic core of the glassy skeletal elements (spicules) of a marine sponge, has led to the development of new low-temperature synthetic routes to metastable semiconducting metal oxides. These protein filaments were shown in vitro to catalyze the hydrolysis and structurally direct the polycondensation of metal oxides at neutral pH and low temperature. Based on the confirmation of the catalytic mechanism and the essential participation of specific serine and histidine residues (presenting a nucleophilic hydroxyl and a nucleophilicity-enhancing hydrogen-bonding imidazole nitrogen) in silicatein's catalytic active site, we therefore sought to develop a synthetic mimic that provides both catalysis and the surface determinants necessary to template and structurally direct heterogeneous nucleation through condensation. Using lithographically patterned poly(dimethylsiloxane) stamps, bifunctional self-assembled monolayer surfaces containing the essential catalytic and templating elements were fabricated by using alkane thiols microcontact-printed on gold substrates. The interface between chemically distinct self-assembled monolayer domains provided the necessary juxtaposition of nucleophilic (hydroxyl) and hydrogen-bonding (imidazole) agents to catalyze the hydrolysis of a gallium oxide precursor and template the condensed product to form gallium oxohydroxide (GaOOH) and the defect spinel, gamma-gallium oxide (gamma-Ga(2)O(3)). Using this approach, the production of patterned substrates for catalytic synthesis and templating of semiconductors for device applications can be envisioned. PMID:16585518

  8. Assembly of new polyoxometalate-templated metal-organic frameworks based on flexible ligands

    NASA Astrophysics Data System (ADS)

    Li, Na; Mu, Bao; Lv, Lei; Huang, Rudan

    2015-03-01

    Four new polyoxometalate(POM)-templated metal-organic frameworks based on flexible ligands, namely, [Cu6(bip)12(PMoVI12O40)2(PMoVMoVI11O40O2)]·8H2O(1), [CuI3CuII3(bip)12(PMoVI12O40)2(PMoV12O34)]·8H2O(2), [Ni6(bip)12(PMoVI12O40)(PMoVI11MoVO40)2]Cl·6H2O(3), [CoII3CoIII2(H2bib)2(Hbib)2(PW9O34)2(H2O)6]·6H2O(4) (bip=1,3-bis(imidazolyl)propane, bib=1,4-bis(imidazolyl)butane) have been obtained under hydrothermal condition and characterized by single-crystal X-ray diffraction analyses, elemental analyses, and thermogravimetric (TG) analyses. The studies of single crystal X-ray indicate that compounds 1-3 crystallize in the trigonal space group P-3, and compound 4 crystallizes in the triclinic space group P-1. Compounds 1 and 3 represent 3D frameworks, and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals, while compounds 2 and 4 show 3D frameworks by hydrogen bonds. This compounds provide new examples of host-guest compounds based on flexible bis(imidazole) ligands. In addition, the electrochemical property and the catalytic property of compound 1 have also been investigated.

  9. A template-free method for stable CuO hollow microspheres fabricated from a metal organic framework (HKUST-1)

    NASA Astrophysics Data System (ADS)

    Zhang, Suoying; Liu, Hong; Liu, Pengfei; Yang, Zhuhong; Feng, Xin; Huo, Fengwei; Lu, Xiaohua

    2015-05-01

    Uniform CuO hollow microspheres were successfully achieved from a non-uniform metal organic framework by using a template-free method. The process mechanism has been revealed to be spherical aggregation and Ostwald ripening. When tested in CO oxidation and heat treatment, these assembled microspheres exhibited an excellent catalytic performance and show a much better stability than the inherited hollow structure from MOFs.Uniform CuO hollow microspheres were successfully achieved from a non-uniform metal organic framework by using a template-free method. The process mechanism has been revealed to be spherical aggregation and Ostwald ripening. When tested in CO oxidation and heat treatment, these assembled microspheres exhibited an excellent catalytic performance and show a much better stability than the inherited hollow structure from MOFs. Electronic supplementary information (ESI) available: The experiment details, auxiliary FESEM, XRD, BET and TG results of synthesized products. See DOI: 10.1039/c5nr01443c

  10. A template-free method for stable CuO hollow microspheres fabricated from a metal organic framework (HKUST-1).

    PubMed

    Zhang, Suoying; Liu, Hong; Liu, Pengfei; Yang, Zhuhong; Feng, Xin; Huo, Fengwei; Lu, Xiaohua

    2015-06-01

    Uniform CuO hollow microspheres were successfully achieved from a non-uniform metal organic framework by using a template-free method. The process mechanism has been revealed to be spherical aggregation and Ostwald ripening. When tested in CO oxidation and heat treatment, these assembled microspheres exhibited an excellent catalytic performance and show a much better stability than the inherited hollow structure from MOFs. PMID:25955660

  11. Minimization of Surface Energies and Ripening Outcompete Template Effects in the Surface Growth of Metal-Organic Frameworks.

    PubMed

    Yu, Xiu-Jun; Zhuang, Jin-Liang; Scherr, Julian; Abu-Husein, Tarek; Terfort, Andreas

    2016-07-11

    As well-oriented, surface-bound metal-organic frameworks become the centerpiece of many new applications, a profound understanding of their growth mode becomes necessary. This work shows that the currently favored model of surface templating is in fact a special case valid only for systems with a more or less cubic crystal shape, while in less symmetric systems crystal ripening and minimization of surface energies dominate the growth process. PMID:27258394

  12. Reconstruction of Colloidal Spheres by Targeted Etching: A Generalized Self-Template Route to Porous Amphoteric Metal Oxide Hollow Spheres.

    PubMed

    Pan, Jia Hong; Bai, Yuqing; Wang, Qing

    2015-04-21

    Despite the significant progress in developing various synthetic strategies for metal oxide hollow spheres (h-MO), the so-far explored materials are mostly chemically inert metal oxides. Very few attempts have been made for amphoteric metal oxides such as Al2O3 and ZnO due to the difficulties in the control of the dissolution and recrystallization process. Herein, a facile self-template route to the synthesis of amphoteric h-MO with tunable size and shell thickness is developed by targeted etching via an acid-base reaction. With the protection of polyvinylpyrrolidone (PVP) on the surface, the interior of metal oxide solid colloidal spheres (c-MOs) that possess radially divergent structures could be selectively etched with acid/alkali as an etchant, forming h-MO of Al2O3 and ZnO. Our results also show that a wide variety of metal oxide colloidal spheres can be potential self-templates for targeted etching, which paves the way for developing a generalized strategy for the synthesis of various metal oxide hollow spheres. PMID:25835084

  13. Fast microwave treatments of single source alkoxides for nanostructured Li-ion battery electrodes.

    PubMed

    Laveda, Josefa Vidal; Chandhok, Vibhuti; Murray, Claire A; Paterson, Gary W; Corr, Serena A

    2016-07-12

    Microwave or ultrasonic treatment of metal alkoxides presents a fast, low cost route to both anode and cathode nanomaterials for Li-ion battery applications. Here, we demonstrate the formation of LiMPO4 (M = Fe, Mn) and Mn3O4 nanostructures via this simple route which exhibit excellent electrochemical performances. This approach opens up a new avenue for the targeted design of nanostructured materials, where co-location of the desired metals in a single starting material shortens reaction times and temperatures since there is a decrease in diffusional energy requirements usually needed for these reactions to proceed. PMID:26486274

  14. An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Huang, Hongliang; Li, Jian-Rong; Wang, Keke; Han, Tongtong; Tong, Minman; Li, Liangsha; Xie, Yabo; Yang, Qingyuan; Liu, Dahuan; Zhong, Chongli

    2015-11-01

    Metal-organic frameworks (MOFs) have recently emerged as a new type of nanoporous materials with tailorable structures and functions. Usually, MOFs have uniform pores smaller than 2 nm in size, limiting their practical applications in some cases. Although a few approaches have been adopted to prepare MOFs with larger pores, it is still challenging to synthesize hierarchical-pore MOFs (H-MOFs) with high structural controllability and good stability. Here we demonstrate a facile and versatile method, an in situ self-assembly template strategy for fabricating stable H-MOFs, in which multi-scale soluble and/or acid-sensitive metal-organic assembly (MOA) fragments form during the reactions between metal ions and organic ligands (to construct MOFs), and act as removable dynamic chemical templates. This general strategy was successfully used to prepare various H-MOFs that show rich porous properties and potential applications, such as in large molecule adsorption. Notably, the mesopore sizes of the H-MOFs can be tuned by varying the amount of templates.

  15. An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks

    PubMed Central

    Huang, Hongliang; Li, Jian-Rong; Wang, Keke; Han, Tongtong; Tong, Minman; Li, Liangsha; Xie, Yabo; Yang, Qingyuan; Liu, Dahuan; Zhong, Chongli

    2015-01-01

    Metal-organic frameworks (MOFs) have recently emerged as a new type of nanoporous materials with tailorable structures and functions. Usually, MOFs have uniform pores smaller than 2 nm in size, limiting their practical applications in some cases. Although a few approaches have been adopted to prepare MOFs with larger pores, it is still challenging to synthesize hierarchical-pore MOFs (H-MOFs) with high structural controllability and good stability. Here we demonstrate a facile and versatile method, an in situ self-assembly template strategy for fabricating stable H-MOFs, in which multi-scale soluble and/or acid-sensitive metal-organic assembly (MOA) fragments form during the reactions between metal ions and organic ligands (to construct MOFs), and act as removable dynamic chemical templates. This general strategy was successfully used to prepare various H-MOFs that show rich porous properties and potential applications, such as in large molecule adsorption. Notably, the mesopore sizes of the H-MOFs can be tuned by varying the amount of templates. PMID:26548441

  16. Soft-Templating Synthesis and Properties of Mesoporous Alumina-Titania

    SciTech Connect

    Morris, Stacy M; Horton, Jr, Joe A; Jaroniec, Mietek

    2010-01-01

    Mesoporous alumina-titania materials, having various molar compositions of aluminum and titanium, were synthesized via cooperative self-assembly of the corresponding metal alkoxides and Pluronic P123 triblock copolymer (soft template) in ethanolic solution under acidic conditions. The resulting mixed metal oxides possess ordered mesopores at low to equal molar compositions of titanium in relation to aluminum (up to 50%) and worm-like mesostructures at higher molar compositions of titanium (50-75%). In addition, these mesoporous oxides exhibit high BET surface areas (up to 438 m2/g), large pore widths (from 7.37 to 18.55 nm) and pore volumes (from 0.16 to 0.64 cm3/g), narrow pore size distributions, crystalline pore walls and high thermal stability.

  17. Zirconium alkoxide interfaces for adhesion enhancement and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Vanderkam, Susan Killian

    Tetra(tert-butoxy)zirconium was chemisorbed onto the native oxide layers of aluminum, iron, copper, and porous silicon, forming surface bound di- or tri-alkoxy zirconium species. Poly(ethylene- co-acrylic acid) was subsequently reacted with the surface forming chemically bound copolymer through carboxyzirconium linkages. Copolymer bound through the zirconium complex adhered to the metal oxide surfaces better than without the zirconium alkoxide intermediate, as determined by FTIR spectroscopy. Copper substrates were subjected to a variety of stability tests, including exposure to ambient conditions, base washing, and chronocoulometry. The copper-zirconium-copolymer ensemble was shown to be very stable in all of these tests. Indium tin oxide (ITO) powder was titrated to determine surface hydroxyl content per unit area. ITO-coated glass slides were reacted with tetra( tert-butoxy)zirconium, and subsequently with both carboxylic acid and phenol derivatives. Ferrocene-carboxyzirconium-coated ITO was characterized electrochemically, and the surface loading of ferrocene was found to be approximately one monolayer. Phenoxyzirconium-coated ITO was also characterized electrochemically and tested for electrocatalytic properties for the oxidation of several compounds in solution. Phenoxyzirconium-coated ITO was found to improve the oxidation kinetics for ferrocene and tetramethylphenylenediamine in acetonitrile.

  18. Formation of three-dimensional ordered hierarchically porous metal oxides via a hybridized epoxide assisted/colloidal crystal templating approach.

    PubMed

    Davis, Marauo; Ramirez, Donald A; Hope-Weeks, Louisa J

    2013-08-28

    Three-dimensionally ordered hierarchically porous alumina, iron(III) oxide, yttria, and nickel oxide have been prepared through the hybridization of colloidal crystal-templating and a modified sol-gel method. Simply, highly ordered arrays of poly(methyl methacrylate) (PMMA) were infiltrated with a precursor solution of metal salt and epoxide. Calcination after solidification of the material removed the polymer template while forming the inverse replicas, simultaneously. These hierarchical structures possessing macropore windows and mesopore walls were characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and N2 adsorption/desorption techniques to probe the structural integrity. It was revealed by PXRD that the prepared 3D frameworks were single-phase polycrystalline structures with grain sizes between 5 and 27 nm. The thermal stability as studied by TGA illustrates expected weight losses and full decomposition of the PMMA template. SEM reveals the bimodal, hierarchical macroporous frameworks with well-defined macropore windows and mesoporous walls. Gas sorption measurements of the ordered materials display surface areas as high as 93 m(2) g(-1), and average mesopore diameter up to 33 nm. Due to the versatility of this method, we expect these materials will be ideal candidates for applications in catalysis, adsorption, and separations. Furthermore, the implementation of this technology for production of three-dimensionally ordered macroporous materials can improve the cost and efficiency of metal oxide frameworks (MOFs) due to its high versatility and amenability to numerous systems. PMID:23926949

  19. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    PubMed Central

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-01-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

  20. Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

    2014-12-01

    Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

  1. Crackle template based metallic mesh with highly homogeneous light transmission for high-performance transparent EMI shielding

    NASA Astrophysics Data System (ADS)

    Han, Yu; Lin, Jie; Liu, Yuxuan; Fu, Hao; Ma, Yuan; Jin, Peng; Tan, Jiubin

    2016-05-01

    Our daily electromagnetic environment is becoming increasingly complex with the rapid development of consumer electronics and wireless communication technologies, which in turn necessitates the development of electromagnetic interference (EMI) shielding, especially for transparent components. We engineered a transparent EMI shielding film with crack-template based metallic mesh (CT-MM) that shows highly homogeneous light transmission and strong microwave shielding efficacy. The CT-MM film is fabricated using a cost-effective lift-off method based on a crackle template. It achieves a shielding effectiveness of ~26 dB, optical transmittance of ~91% and negligible impact on optical imaging performance. Moreover, high–quality CT-MM film is demonstrated on a large–calibre spherical surface. These excellent properties of CT-MM film, together with its advantages of facile large-area fabrication and scalability in processing on multi-shaped substrates, make CT-MM a powerful technology for transparent EMI shielding in practical applications.

  2. Poly(cyclohexylethylene)-block-poly(ethylene oxide) block polymers for metal oxide templating

    SciTech Connect

    Schulze, Morgan W.; Sinturel, Christophe

    2015-09-01

    A series of poly(cyclohexylethylene)-block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation produces an ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.

  3. Poly(cyclohexylethylene)-block-poly(ethylene oxide) block polymers for metal oxide templating

    DOE PAGESBeta

    Schulze, Morgan W.; Sinturel, Christophe; Hillmyer, Marc A.

    2015-09-01

    A series of poly(cyclohexylethylene)-block-poly(ethylene oxide) (CEO) diblock copolymers were synthesized through tandem anionic polymerizations and heterogeneous catalytic hydrogenation. Solvent-annealed CEO diblock films were used to template dense arrays of inorganic oxide nanodots via simple spin coating of an inorganic precursor solution atop the ordered film. The substantial chemical dissimilarity of the two blocks enables (i) selective inclusion of the inorganic precursor within the PEO domain and (ii) the formation of exceptionally small feature sizes due to a relatively large interaction parameter estimated from mean-field analysis of the order–disorder transition temperatures of compositionally symmetric samples. UV/ozone treatment following incorporation produces anmore » ordered arrangement of oxide nanodots and simultaneously removes the block polymer template. However, we report the smallest particles (6 ± 1 nm) templated from a selective precursor insertion method to date using a block polymer scaffold.« less

  4. Influence of lead(II) lone pairs on the serpentine structures for heterometallic alkoxides

    SciTech Connect

    Teff, D.J.; Huffman, J.C.; Caulton, K.G.

    1995-05-10

    Heterometallic alkoxides, M{sub a}M{sub b}{prime}(OR){sub m}, most often adopts closed polyhedral structures, in part to give suitably high coordination numbers to all metals. In general, the ratio m/(a + b) is typically low (because one or more of M and M{prime} are low valent) so that {mu}{sub 2}- and {mu}{sub 3}-OR functionalities are required, and a closed polyhedron best accommodates such demands. Thus the metals of KZr{sub 2}(O{sup i}Pr){sub 9}{sup 2} and [BaZr{sub 2}(O{sup i}Pr){sub 10}]{sub 2}{sup 3} form triangles, those of K{sub 2}Zr{sub 2}(O{sup t}Bu){sub 10}{sup 4} form a diamond, and those of K{sub 4}Zr{sub 2}O(O{sup i}Pr){sub 10}{sup 2} form an octahedron. The authors report here the very different outcome of combining Zr(IV) with the soft divalent metal Pb(II). These results demonstrate that rational synthetic control of two different stoichiometries can be effected in heterometallic alkoxide chemistry.

  5. Rapid (<3 min) microwave synthesis of block copolymer templated ordered mesoporous metal oxide and carbonate films using nitrate-citric acid systems.

    PubMed

    Zhang, Yuanzhong; Bhaway, Sarang M; Wang, Yi; Cavicchi, Kevin A; Becker, Matthew L; Vogt, Bryan D

    2015-03-25

    Rapid chemical transformation from micelle templated precursors (metal nitrate and citric acid) to ordered mesoporous metal carbonates and oxides is demonstrated using microwave heating for cobalt, copper, manganese and zinc. Without aging requirements, <3 min of microwave processing yields highly ordered mesoporous films. PMID:25714045

  6. DEXTROSE-TEMPLATED MICROWAVE-ASSISTED COMBUSTION SYNTHESIS OF SPONGY METAL OXIDES

    EPA Science Inventory

    Microwave-assisted combustion synthesis of porous nanocrystalline titania and carbon coated titania is reported using dextrose as template and the product was compared with the one obtained using conventional heating furnace. Out of three compositions viz., 1:1, 1:3, and 1:5 (met...

  7. Synthesis and nanostructure characterization of carbon base hybrid ceramics derived from Si H containing resin alkoxide mixtures

    NASA Astrophysics Data System (ADS)

    Narisawa, M.; Endoh, Y.; Tanaka, E.; Nishimura, R.; Mabuchi, H.; Okamura, K.; Itoh, M.; Kamiyama, T.

    2005-02-01

    Si H containing thermosetting resin, poly[(phenylsilylene)-ethynylene-1,3-phenylene ethynylene] which shows high ceramic yield after pyrolysis, was modified with various metal (Ti, Ta, Zr, Si and Al) alkoxides. The modified resins were shaped to sheet form by solution casting and pyrolyzed at high temperatures to give amorphous materials with Si M(metal elements in alkoxides) C O compositions. The small angle X-ray scattering (SAXS) analysis was performed to give nanostructure information on the pyrolyzed sheets, in which metal oxide particles are considered to be dispersed in carbon rich matrix. The size and distribution of particles derived from the SAXS pattern fittings depended on kinds of the used alkoxide and the pyrolysis temperature. For the practical application for these hybridized gel systems, the flow coating of precursor solutions on stainless steels were attempted. The coated layer on the substrate showed black and glassy surface with no obvious cracks even after pyrolysis at 1073 K with a coating thickness of 2 3 μm.

  8. Template copolymerization to control site structure around metal ions: Applications towards sensing and gas storage and release

    NASA Astrophysics Data System (ADS)

    Mitchell-Koch, Jeremy T.

    The development of functional materials for sensing and gas storage and release is useful in a number of chemical and biological applications. Investigating function of molecularly imprinted polymers (MIP), often used for these purposes, has relied on circumstantial evidence because direct examination of immobilized sites is not possible. Described in this dissertation is the design, synthesis, characterization and function studies of materials synthesized by template copolymerization methods. Metal ions exhibit unique spectroscopic properties and their utilization makes site examination more feasible. Ligand binding modulates these properties such that the event can be measured by spectroscopy. The metal ion's secondary coordination environment can also be tuned to increase or decrease function of the material. In Chapter Two the utilization of template copolymerization to immobilize a europium-containing compound for the detection of volatile organic compounds is described. Luminescence of the immobilized complex is quenched in the presence of volatile organic compounds (VOC). The quenching effect is dependent on concentration of VOC and the nature of polymeric host. Chapters Three and Four describe the development of materials for the photolytic release of nitric oxide (NO). In Chapter Three, a novel manipulation of the immobilized complex is employed to produce binding sites that contain ligands covalently embedded into the host in a position to bind the metal ion upon NO release in order to block rebinding. Incompatible binding affinities of the iron-containing templates made it impossible to study NO photo-release from this material. Second-row transition metals are more compatible with NO binding, and Chapter Four describes a ruthenium salen-containing polymer that releases NO in response to light. Additionally, transfer of NO to a metalloporphyrin and myoglobin has been achieved. This is the first report of photolytic heterogeneous NO transfer by a material

  9. General Self-Template Synthesis of Transition-Metal Oxide and Chalcogenide Mesoporous Nanotubes with Enhanced Electrochemical Performances.

    PubMed

    Wang, Huan; Zhuo, Sifei; Liang, Yu; Han, Xiling; Zhang, Bin

    2016-07-25

    The development of a general strategy for synthesizing hierarchical porous transition-metal oxide and chalcogenide mesoporous nanotubes, is still highly challenging. Herein we present a facile self-template strategy to synthesize Co3 O4 mesoporous nanotubes with outstanding performances in both the electrocatalytic oxygen-evolution reaction (OER) and Li-ion battery via the thermal-oxidation-induced transformation of cheap and easily-prepared Co-Asp(cobalt-aspartic acid) nanowires. The initially formed thin layers on the precursor surfaces, oxygen-induced outward diffusion of interior precursors, the gas release of organic oxidation, and subsequent Kirkendall effect are important for the appearance of the mesoporous nanotubes. This self-template strategy of low-cost precursors is found to be a versatile method to prepare other functional mesoporous nanotubes of transition-metal oxides and chalcogenides, such as NiO, NiCo2 O4 , Mn5 O8 , CoS2 and CoSe2 . PMID:27239778

  10. Low-temperature oriented growth of vanadium dioxide films on CoCrTa metal template on Si and vertical metal-insulator transition

    SciTech Connect

    Okimura, Kunio; Mian, Md.Suruz

    2012-09-15

    The authors achieved oriented growth of vanadium dioxide (VO{sub 2}) films on CoCrTa metal template grown on an Si substrate. Low-temperature ({approx}250 Degree-Sign C) deposition of VO{sub 2} films using inductively coupled-plasma-assisted sputtering technique realized an abrupt interface between VO{sub 2} and CoCrTa layers, suppressing the oxidation and diffusion of metal components. The films revealed a metal-insulator transition with resistance change of over 2 orders of magnitude. The CoCrTa film, in which Co hexagonal crystalline grains with c-axis orientation were surrounded by segregated Cr and Ta, serves for the oriented growth of VO{sub 2} crystalline film, enabling higher orders of transition in resistance and low voltage switching, even for the vertical (out-of-plane) direction.

  11. Syntheses and crystal structures of the first organically templated metal tellurites

    SciTech Connect

    Feng Meiling; Mao Jianggao . E-mail: mjg@ms.fjirsm.ac.cn

    2005-07-15

    The first organically templated vanadium tellurites, [H{sub 2}en][(VO{sub 2})(TeO{sub 3})]{sub 2}.H{sub 2}O (1, en=ethylenediamine) and [H{sub 2}pip][(VO{sub 2})(TeO{sub 3})]{sub 2} (2, pip=piperazine) have been synthesized by hydrothermal reactions and structurally characterized. Both compounds feature a [(VO{sub 2})(TeO{sub 3})]{sup -} anionic layer containing V{sub 2}Te{sub 2} four-member rings and V{sub 4}Te{sub 4} eight member rings. The vanadium (V) atom is five coordinated by three tellurite oxygens and two terminal oxygen atoms in a distorted trigonal bipyramidal geometry. The interconnection of the VO{sub 5} polyhedra by bridging tellurite groups leads to a 2D corrugated anionic inorganic layer. The doubly protonated template cations and the lattice water molecules in 1 are located at the interlayer space and are involved in hydrogen bonding. The doubly protonated template cation in 2 is not involved in hydrogen bonding with the anionic inorganic layer.

  12. Crackle template based metallic mesh with highly homogeneous light transmission for high-performance transparent EMI shielding

    PubMed Central

    Han, Yu; Lin, Jie; Liu, Yuxuan; Fu, Hao; Ma, Yuan; Jin, Peng; Tan, Jiubin

    2016-01-01

    Our daily electromagnetic environment is becoming increasingly complex with the rapid development of consumer electronics and wireless communication technologies, which in turn necessitates the development of electromagnetic interference (EMI) shielding, especially for transparent components. We engineered a transparent EMI shielding film with crack-template based metallic mesh (CT-MM) that shows highly homogeneous light transmission and strong microwave shielding efficacy. The CT-MM film is fabricated using a cost-effective lift-off method based on a crackle template. It achieves a shielding effectiveness of ~26 dB, optical transmittance of ~91% and negligible impact on optical imaging performance. Moreover, high–quality CT-MM film is demonstrated on a large–calibre spherical surface. These excellent properties of CT-MM film, together with its advantages of facile large-area fabrication and scalability in processing on multi-shaped substrates, make CT-MM a powerful technology for transparent EMI shielding in practical applications. PMID:27151578

  13. Crackle template based metallic mesh with highly homogeneous light transmission for high-performance transparent EMI shielding.

    PubMed

    Han, Yu; Lin, Jie; Liu, Yuxuan; Fu, Hao; Ma, Yuan; Jin, Peng; Tan, Jiubin

    2016-01-01

    Our daily electromagnetic environment is becoming increasingly complex with the rapid development of consumer electronics and wireless communication technologies, which in turn necessitates the development of electromagnetic interference (EMI) shielding, especially for transparent components. We engineered a transparent EMI shielding film with crack-template based metallic mesh (CT-MM) that shows highly homogeneous light transmission and strong microwave shielding efficacy. The CT-MM film is fabricated using a cost-effective lift-off method based on a crackle template. It achieves a shielding effectiveness of ~26 dB, optical transmittance of ~91% and negligible impact on optical imaging performance. Moreover, high-quality CT-MM film is demonstrated on a large-calibre spherical surface. These excellent properties of CT-MM film, together with its advantages of facile large-area fabrication and scalability in processing on multi-shaped substrates, make CT-MM a powerful technology for transparent EMI shielding in practical applications. PMID:27151578

  14. Metal phthalocyanine: fullerene composite nanotubes via templating method for enhanced properties.

    PubMed

    Ahmad Makinudin, Abdullah Haaziq; Fakir, Muhamad Saipul; Supangat, Azzuliani

    2015-01-01

    The use of templating method to synthesize the vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine (VOPcPhO):[6,6]-phenyl C71 butyric acid methyl ester (PC71BM) composite nanotubes is presented here. VOPcPhO is a p-type material and PC71BM is an n-type material which acts as an electron donor and electron acceptor, respectively. Both materials have been studied due to their potential applications as solar energy converter and organic electronics. High-resolution transmission electron microscope (HRTEM) and field emission scanning electron microscope (FESEM) images have shown the replication of the porous template diameter of approximately 200 nm with a superior incorporation of both VOPcPhO and PC71BM. VOPcPhO:PC71BM composite nanotubes showed the significant properties improvement if compared over their bulk heterojunction counterpart. UV-vis spectra of composite nanotubes show a shift to a longer wavelength at the absorption peaks. Significant quenching has been attained by the photoluminescence spectra of VOPcPhO:PC71BM composite nanotubes which supports the redshift of UV-vis absorption spectra. Presumably, the photo-induced charge transfer and charge carrier dissociation can be enhanced from the VOPcPhO:PC71BM composite nanotubes rather than the bulk heterojunction. PMID:25852350

  15. Metal phthalocyanine: fullerene composite nanotubes via templating method for enhanced properties

    NASA Astrophysics Data System (ADS)

    Ahmad Makinudin, Abdullah Haaziq; Fakir, Muhamad Saipul; Supangat, Azzuliani

    2015-02-01

    The use of templating method to synthesize the vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine (VOPcPhO):[6,6]-phenyl C71 butyric acid methyl ester (PC71BM) composite nanotubes is presented here. VOPcPhO is a p-type material and PC71BM is an n-type material which acts as an electron donor and electron acceptor, respectively. Both materials have been studied due to their potential applications as solar energy converter and organic electronics. High-resolution transmission electron microscope (HRTEM) and field emission scanning electron microscope (FESEM) images have shown the replication of the porous template diameter of approximately 200 nm with a superior incorporation of both VOPcPhO and PC71BM. VOPcPhO:PC71BM composite nanotubes showed the significant properties improvement if compared over their bulk heterojunction counterpart. UV-vis spectra of composite nanotubes show a shift to a longer wavelength at the absorption peaks. Significant quenching has been attained by the photoluminescence spectra of VOPcPhO:PC71BM composite nanotubes which supports the redshift of UV-vis absorption spectra. Presumably, the photo-induced charge transfer and charge carrier dissociation can be enhanced from the VOPcPhO:PC71BM composite nanotubes rather than the bulk heterojunction.

  16. Surprisingly facile CO2 insertion into cobalt alkoxide bonds: A theoretical investigation

    PubMed Central

    Offermans, Willem K; Bizzarri, Claudia; Leitner, Walter

    2015-01-01

    Summary Exploiting carbon dioxide as co-monomer with epoxides in the production of polycarbonates is economically highly attractive. More effective catalysts for this reaction are intensively being sought. To promote better understanding of the catalytic pathways, this study uses density functional theory calculations to elucidate the reaction step of CO2 insertion into cobalt(III)–alkoxide bonds, which is also the central step of metal catalysed carboxylation reactions. It was found that CO2 insertion into the cobalt(III)–alkoxide bond of [(2-hydroxyethoxy)CoIII(salen)(L)] complexes (salen = N,N”-bis(salicyliden-1,6-diaminophenyl)) is exothermic, whereby the exothermicity depends on the trans-ligand L. The more electron-donating this ligand is, the more exothermic the insertion step is. Interestingly, we found that the activation barrier decreases with increasing exothermicity of the CO2 insertion. Hereby, a linear Brønsted–Evans–Polanyi relationship was found between the activation energy and the reaction energy. PMID:26425188

  17. Templated assembly of Co-Pt nanoparticles via thermal and laser-induced dewetting of bilayer metal films.

    PubMed

    Oh, Yong-Jun; Kim, Jung-Hwan; Thompson, Carl V; Ross, Caroline A

    2013-01-01

    Templated dewetting of a Co/Pt metal bilayer film on a topographic substrate was used to assemble arrays of Co-Pt alloy nanoparticles, with highly uniform particle size, shape and notably composition compared to nanoparticles formed on an untemplated substrate. Solid-state and liquid-state dewetting processes, using furnace annealing and laser irradiation respectively, were compared. Liquid state dewetting produced more uniform, conformal nanoparticles but they had a polycrystalline disordered fcc structure and relatively low magnetic coercivity. In contrast, solid state dewetting enabled formation of magnetically hard, ordered L1(0) Co-Pt single-crystal particles with coercivity >12 kOe. Furnace annealing converted the nanoparticles formed by liquid state dewetting into the L1(0) phase. PMID:23175433

  18. High-dimensional assembly depending on polyoxoanion templates, metal ion coordination geometries, and a flexible bis(imidazole) ligand.

    PubMed

    Dong, Bao-xia; Peng, Jun; Gómez-García, Carlos J; Benmansour, Samia; Jia, Heng-qing; Hu, Ning-hai

    2007-07-23

    By introducing the flexible 1,1'-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the polyoxovanadate system, five novel polyoxoanion-templated architectures based on [As(8)V(14)O(42)](4-) and [V(16)O(38)Cl](6-) building blocks were obtained: [M(bbi)(2)](2)[As(8)V(14)O(42)(H(2)O)] [M = Co (1), Ni (2), and Zn (3)], [Cu(bbi)](4)[As(8)V(14)O(42)(H(2)O)] (4), and [Cu(bbi)](6)[V(16)O(38)Cl] (5). Compounds 1-3 are isostructural, and they exhibit a binodal (4,6)-connected 2D structure with Schläfli symbol (3(4) x 4(2))(3(4) x 4(4) x 5(4) x 6(3))(2), in which the polyoxoanion induces a closed four-membered circuit of M(4)(bbi)(4). Compound 4 exhibits an interesting 3D framework constructed from tetradentate [As(8)V(14)O(42)](4-) cluster anions and cationic ladderlike double chains. There exists a bigger M(8)(bbi)(6)O(2) circuit in 4. The 3D extended structure of 5 is composed of heptadentate [V(16)O(38)Cl](6-) anions and flexural cationic chains; the latter consists of six Cu(bbi) segments arranged alternately. It presents the largest 24-membered circuit of M(24)(bbi)(24) so far observed made of bbi molecules and transition-metal cations. Investigation of their structural relations shows the important template role of the polyoxoanions and the synergetic interactions among the polyoxoanions, transition-metal ions, and flexible ligand in the assembly process. The magnetic properties of compounds 1-3 were also studied. PMID:17592834

  19. Fast and reversible insertion of carbon dioxide into zirconocene-alkoxide bonds. A mechanistic study.

    PubMed

    Brink, Alice; Truedsson, Ida; Fleckhaus, André; Johnson, Magnus T; Norrby, Per Ola; Roodt, Andreas; Wendt, Ola F

    2014-06-21

    In two consecutive equilibria the compound (Cp*)2Zr(OMe)2 undergoes insertion of CO2 to form the mono- and bis-hemicarbonates. Both equilibria are exothermic but entropically disfavoured. Magnetisation transfer experiments gave kinetic data for the first equilibrium showing that the rate of insertion is overall second order with a rate constant of 3.20 ± 0.12 M(-1) s(-1), which is substantially higher than those reported for other early transition metal alkoxides, which are currently the best homogeneous catalysts for dimethyl carbonate formation from methanol and CO2. Activation parameters for the insertion reaction point to a highly ordered transition state and we interpret that as there being a substantial interaction between the CO2 and the metal during the C-O bond formation. This is supported by DFT calculations showing the lateral attack by CO2 to have the lowest energy transition state. PMID:24796283

  20. Template-directed covalent conjugation of DNA to native antibodies, transferrin and other metal-binding proteins

    NASA Astrophysics Data System (ADS)

    Rosen, Christian B.; Kodal, Anne L. B.; Nielsen, Jesper S.; Schaffert, David H.; Scavenius, Carsten; Okholm, Anders H.; Voigt, Niels V.; Enghild, Jan J.; Kjems, Jørgen; Tørring, Thomas; Gothelf, Kurt V.

    2014-09-01

    DNA-protein conjugates are important in bioanalytical chemistry, molecular diagnostics and bionanotechnology, as the DNA provides a unique handle to identify, functionalize or otherwise manipulate proteins. To maintain protein activity, conjugation of a single DNA handle to a specific location on the protein is often needed. However, preparing such high-quality site-specific conjugates often requires genetically engineered proteins, which is a laborious and technically challenging approach. Here we demonstrate a simpler method to create site-selective DNA-protein conjugates. Using a guiding DNA strand modified with a metal-binding functionality, we directed a second DNA strand to the vicinity of a metal-binding site of His6-tagged or wild-type metal-binding proteins, such as serotransferrin, where it subsequently reacted with lysine residues at that site. This method, DNA-templated protein conjugation, facilitates the production of site-selective protein conjugates, and also conjugation to IgG1 antibodies via a histidine cluster in the constant domain.

  1. A metal-organic framework-templated synthesis of γ-Fe2O3 nanoparticles encapsulated in porous carbon for efficient and chemoselective hydrogenation of nitro compounds.

    PubMed

    Li, Yang; Zhou, Yu-Xiao; Ma, Xiao; Jiang, Hai-Long

    2016-03-18

    The γ-Fe2O3 nanoparticles well dispersed in porous carbon were fabricated via a Fe-based metal-organic framework-templated pyrolysis. The resultant product exhibits excellent catalytic activity, chemoselectivity and magnetic recyclability for the hydrogenation of diverse nitro compounds under mild conditions. PMID:26908070

  2. Ammonium-crown ether supramolecular cation-templated assembly of an unprecedented heterobicluster-metal coordination polymer with enhanced NLO properties.

    PubMed

    Zhang, Jinfang; Jia, Ding; Humphrey, Mark G; Meng, Suci; Zaworotko, Michael J; Cifuentes, Marie P; Zhang, Chi

    2016-03-01

    An ammonium-crown ether host-guest supramolecular cation-templated synthetic methodology has been developed to construct a structurally unprecedented heterobicluster-metal coordination polymer (HCM-CP 1) based on tetranuclear clusters [WS4Cu3](+) with different connection environments, pentanuclear clusters [WS4Cu4](2+), and Cu(+) building metal ions. HCM-CP 1 exhibits enhanced NLO properties, which may be ascribed to the incorporation of diverse building cluster components. PMID:26864604

  3. Uranium complexes with amide, alkoxide and thiolate ligands

    NASA Astrophysics Data System (ADS)

    Ephritikhine, Michel

    1994-10-01

    Alkoxide, hydroxide and mu-oxo complexes of U(IV) have been synthesized by (a) the reaction of alcohols, ketones and water with hydride or borohydride derivatives, (b) the coupling reaction of ketones with UCl4 in the presence of sodium amalgam; (c) the reduction of CO2 by (U(C5H4SiMe3)3) or (U(C5H4SiMe3)3H); (d) the deoxygenation of CO by (U(C5H5)3R) complexes; and (e) condensation reactions of alkoxide and hydroxide compounds. Thiolate complexes were made by the treatment of uranium borohydride or hydride compounds with thiols. The reaction of UCl4 with NaSR reagents afforded the homoleptic thiolate complexes ((THF)3Na(mu-SR)3U(mu-SR)3Na(THF)3). Amide compounds, including U(V) derivatives, were prepared from U(NEt 2)4.

  4. Highly Soluble Alkoxide Magnesium Salts for Rechargeable Magnesium Batteries

    SciTech Connect

    Liao, Chen; Guo, Bingkun; Jiang, Deen; Custelcean, Radu; Mahurin, Shannon Mark; Sun, Xiao-Guang; Dai, Sheng

    2014-01-01

    A unique class of air-stable and non-pyrophoric magnesium electrolytes has been developed based on alkoxide magnesium compounds. The crystals obtained from this class of electrolytes exhibit a unique structure of tri-magnesium cluster, [Mg3Cl3(OR)2(THF)6]+ [(THF)MgCl3] . High reversible capacities and good rate capabilities were obtained in Mg-Mo6S8 batteries using these new electrolytes at both 20 and 50 oC.

  5. Metal-Templated Design: Enantioselective Hydrogen-Bond-Driven Catalysis Requiring Only Parts-per-Million Catalyst Loading.

    PubMed

    Xu, Weici; Arieno, Marcus; Löw, Henrik; Huang, Kaifang; Xie, Xiulan; Cruchter, Thomas; Ma, Qiao; Xi, Jianwei; Huang, Biao; Wiest, Olaf; Gong, Lei; Meggers, Eric

    2016-07-20

    Based on a metal-templated approach using a rigid and globular structural scaffold in the form of a bis-cyclometalated octahedral iridium complex, an exceptionally active hydrogen-bond-mediated asymmetric catalyst was developed and its mode of action investigated by crystallography, NMR, computation, kinetic experiments, comparison with a rhodium congener, and reactions in the presence of competing H-bond donors and acceptors. Relying exclusively on weak forces, the enantioselective conjugate reduction of nitroalkenes can be executed at catalyst loadings as low as 0.004 mol% (40 ppm), representing turnover numbers of up to 20 250. A rate acceleration by the catalyst of 2.5 × 10(5) was determined. The origin of the catalysis is traced to an effective stabilization of developing charges in the transition state by carefully orchestrated hydrogen-bonding and van der Waals interactions between catalyst and substrates. This study demonstrates that the proficiency of asymmetric catalysis merely driven by hydrogen-bonding and van der Waals interactions can rival traditional activation through direct transition metal coordination of the substrate. PMID:27336458

  6. Metal-organic gel templated synthesis of magnetic porous carbon for highly efficient removal of organic dyes.

    PubMed

    Wang, Luhuan; Ke, Fei; Zhu, Junfa

    2016-03-21

    Magnetic porous carbon composites are promising materials in various applications, such as adsorbents, supercapacitors and catalyst supports, due to their high surface area, thermal and chemical stability, and easy separation. However, despite the increasing number of reports of magnetic porous carbon composites, the preparation of these materials with environmentally friendly procedures still remains a great challenge. Herein, we report a facile method to prepare a magnetic porous carbon composite with high surface area from a Fe-based metal-organic gel (MOG) template, an extended structure of a metal-organic framework (MOF). The obtained magnetic porous carbon composite was applied to remove organic dyes from an aqueous solution by selecting methyl orange (MO) as a model molecule. It exhibits excellent adsorption capacity (182.82 mg g(-1)), fast adsorption kinetics (8.13 × 10(-3) g mg(-1) min(-1)), and a perfect magnetic separation performance for the MO removal. This study demonstrates a new way to achieve clean synthesis of magnetic porous carbon materials, and opens a new door for the application of MOGs in organic dye removal. PMID:26842305

  7. Polymer grafting surface as templates for the site-selective metallization

    NASA Astrophysics Data System (ADS)

    Yang, Fang; Li, Peiyuan; Li, Xiangcheng; Huo, Lini; Chen, Jinhao; Chen, Rui; Na, Wei; Tang, Wanning; Liang, Lifang; Su, Wei

    2013-06-01

    We report a simple, low-cost and universal method for the fabrication of copper circuit patterns on a wide range of flexible polymeric substrates. This method relies on procedures to modify the polymeric substrates with grafted polymer template to form surface-bound N-containing groups, which can bind palladium catalysts that subsequently initiate the site-selective deposition of copper granular layer patterns. The fabrications of patterned copper films were demonstrated on three kinds of flexible polymeric films including poly(imide) (PI), poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) with minimum feature sizes of 200 μm. The films were characterized by ATR FT-IR, contact angle, XPS, XRD, TEM, SEM. Furthermore, the copper layered structure shows good adhesion with polymeric film. This method, which provides a promising strategy for the fabrication of copper circuit patterns on flexible polymeric substrates, has the potential in manufacturing conductive features adopted in various fields including modern electronics, opto-electronics and photovoltaic applications.

  8. Photochemical Fabrication of Transition Metal Nanoparticles Using CdS Template and Their Co-Catalysis Effects for TiO2 Photocatalysis

    NASA Astrophysics Data System (ADS)

    Badhwar, Nidhi; Gupta, Nidhi; Pal, Bonamali

    2013-06-01

    Transition metal nanoparticles were prepared by chemical dissolution of CdS template from metal photodeposited CdS nanorod (length = 70-85 nm and width = 5-6 nm) heterocomposites. Size (9-10 nm) of metal nanoparticles obtained after CdS removal was larger than the size (4-6 nm) of metal nanodeposits over CdS template. The obtained Au nanoparticles displayed a broad red shifted absorption band at 660 nm, whereas Pt, Pd and Rh nanoparticles exhibit featureless absorption spectra. Elemental analysis confirms the complete removal of CdS template from Au-CdS (Au — 2.65 at.%) and Ag-CdS (Ag — 2.06 at.%) composites showing no Cd peak. These metal nanoparticles imparted dissimilar co-catalytic activity of TiO2 for photocatalytic degradation of salicylic acid in the order Au > Pt > Pd > Ag > Rh as a function of their nature, electronegativity, redox potential and work function.

  9. Mixed protein-templated luminescent metal clusters (Au and Pt) for H2O2 sensing

    PubMed Central

    2013-01-01

    A simple and cost-effective method to synthesize the luminescent noble metal clusters (Au and Pt) in chicken egg white aqueous solution at room temperature is reported. The red-emitting Au cluster is used as fluorescent probe for sensitive detection of H2O2. PMID:23601828

  10. Metallotropic liquid crystals formed by surfactant templating of molten metal halides.

    PubMed

    Martin, James D; Keary, Cristin L; Thornton, Todd A; Novotnak, Mark P; Knutson, Jeremey W; Folmer, Jacob C W

    2006-04-01

    Liquid crystals consist of anisotropic molecular units, and most are organic molecules. Materials incorporating metals into anisotropic molecules, described as metallomesogens, have been prepared. Anisotropic structures such as one-dimensional chains and two-dimensional layers are frequently observed in solid-state inorganic materials, however, little is understood about structural organization in melts of such materials. Achieving liquid-crystalline behaviour in inorganic fluids should be possible if the anisotropic structure can be retained or designed into the molten phase. We demonstrated the ability to engineer zeolite-type structures into metal halide glasses and liquids. In this work we have engineered lamellar, cubic and hexagonal liquid-crystalline structure in metal-halide melts by controlling the volume fraction and nature of the inorganic block (up to 80 mol%) with respect to alkylammonium surfactants. The high metal content of these liquid-crystalline systems significantly advances the field of metallomesogens, which seeks to combine magnetic, electronic, optical, redox and catalytic properties common to inorganic materials with the fluid properties of liquid crystals. PMID:16547520

  11. Aryl- and heteroaryl-thiosemicarbazone derivatives and their metal complexes: a pharmacological template.

    PubMed

    Moorthy, Narayana S H N; Cerqueira, Nuno M F S A; Ramos, Maria J; Fernandes, Pedro A

    2013-05-01

    In this review, we discuss the current patents concerning aryl/heteroaryl thiosemicarbazone derivatives as regards to their activities and properties, including coordination (chelation) properties. The mode of action of the aryl/heteroaryl thiosemicarbazone derivatives involves metal coordination with proteins or biological fluids that have metal ions in their structure. Additionally, these molecules can also form multiple hydrogen bonds through their (thio) amide and N3 nitrogen that ensure a strong interaction with the receptor. In some cases, strong π-π interactions can be observed too. Special attention is given to pyridyl, bis-pyridyl, benzoylpyridyl and isatin thiosemicarbazone derivatives that exhibit significant anticancer, antiviral and other activities in free and in metal complexed forms. This key biological role is often related with their capability to inhibit the enzyme ribonucleotide reductase, similar to what is observed with potent anticancer drugs such as Triapine and methisazone. Recent studies have revealed that thiosemicarbazone can also inhibit topoisomerase II α enzyme. Thiosemicarbazone derivatives form coordination complex with various metals such as Zn, Cu, Fe, Co, Ni, Pt, Pd, etc., and these complexes provide better activities than the free thiosemicarbazones. Recent patents show that the controlled or sustained release dosage form of the thiosemicarbazone derivatives along with ionizing radiations is used for the treatment of proliferative diseases (US20110152281, US20110245304, US20120172217). PMID:22963201

  12. Templating hydrogels.

    PubMed

    Texter, John

    2009-03-01

    Templating processes for creating polymerized hydrogels are reviewed. The use of contact photonic crystals and of non-contact colloidal crystalline arrays as templates are described and applications to chemical sensing and device fabrication are illustrated. Emulsion templating is illustrated in the formation of microporous membranes, and templating on reverse emulsions and double emulsions is described. Templating in solutions of macromolecules and micelles is discussed and then various applications of hydrogel templating on surfactant liquid crystalline mesophases are illustrated, including a nanoscale analogue of colloidal crystalline array templating, except that the bead array in this case is a cubic array of nonionic micelles. The use of particles as templates in making core-shell and hollow microgel beads is described, as is the use of membrane pores as another illustration of confinement templating. PMID:19816529

  13. Site-selective metallization of polymeric substrates by the hyperbranched polymer templates

    NASA Astrophysics Data System (ADS)

    Li, Peiyuan; Yang, Fang; Li, Xiangcheng; He, Chunling; Su, Wei; Chen, Jinhao; Huo, Lini; Chen, Rui; Lu, Chensheng; Liang, Lifang

    2013-09-01

    We demonstrate a simple, cost-effective and universal technique for the fabrication of copper circuit pattern on flexible polymeric substrate. This method relies on a ternary polyethylenimine-poly(acrylic acid)-substrate film incorporating palladium catalysts, which are used as adhesive interlayers for the copper metallization of flexible polymeric substrates. We demonstrated the fabrication of patterned copper films on a variety of flexible polymers with minimum feature sizes of 200 μm. And the resulting copper circuit showed strong adhesion with underlying flexible polymeric substrates. The films were characterized by ATR FT-IR, contact angle, XPS, XRD, TEM and SEM. The direct patterning of metallic circuit on flexible polymeric substrate indicates great potential for the use in electronics industry.

  14. Synthesis of the Cortistatin Pentacyclic Core by Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling.

    PubMed

    Aquino, Claudio; Greszler, Stephen N; Micalizio, Glenn C

    2016-06-01

    The pentacyclic core skeleton of the cortistatins has been prepared in a stereoselective fashion by strategic use of an alkoxide-directed metallacycle-mediated annulative cross-coupling. This metal-centered tandem reaction delivers a polyunsaturated hydrindane and establishes the C13 stereodefined quaternary center with high levels of stereocontrol. Subsequent regio- and stereoselective global hydroboration results in the realization of the DE-trans ring fusion and a tertiary alcohol at C8. Establishment of the ABC-tricyclic subunit was then accomplished through phenolic oxidation/trans-acetalization, chemoselective reduction, regioselective cleavage, and intramolecular alkylation at C5. PMID:27193994

  15. Nanoparticle-based immunosensor with apoferritin templated metallic phosphate label for quantification of phosphorylated acetylcholinesterase

    SciTech Connect

    Du, Dan; Chen, Aiqiong; Xie, Yunying; Zhang, Aidong; Lin, Yuehe

    2011-05-15

    A new sandwich-like electrochemical immunosensor has been developed for quantification of organophosphorylated acetylcholinesterase (OP-AChE), an exposure biomarker of organophosphate pesticides and nerve agents. Zirconia nanoparticles (ZrO2 NPs) were anchored on a screen printed electrode (SPE) to preferably capture OP-AChE adducts by metal chelation with phospho-moieties, which was selectively recognized by lead phosphate-apoferritin labeled anti-AChE antibody (LPA-anti-AChE). The sandwich-like immunoreactions were performed among ZrO2 NPs, OP-AChE and LPA-anti-AChE to form ZrO2/OP-AChE/LPA-anti-AChE complex and the released lead ions were detected on a disposable SPE. The binding affinity was investigated by both square wave voltammetry (SWV) and quartz crystal microbalance (QCM) measurements. The proposed immunosensor yielded a linear response current over a broad OP-AChE concentrations range from 0.05 nM to 10 nM, with detection limit of 0.02 nM, which has enough sensitivity for monitoring of low-dose exposure to OPs. This method avoids the drawback of unavailability of commercial OP-specific antibody as well as amplifies detection signal by using apoferritin encoded metallic phosphate nanoparticle tags. This nanoparticle-based immunosensor offers a new method for rapid, sensitive, selective and inexpensive quantification of phosphorylated adducts for monitoring of OP pesticides and nerve agents exposures.

  16. Explosives: Metal-Organic Framework Templated Synthesis of Copper Azide as the Primary Explosive with Low Electrostatic Sensitivity and Excellent Initiation Ability (Adv. Mater. 28/2016).

    PubMed

    Wang, Qianyou; Feng, Xiao; Wang, Shan; Song, Naimeng; Chen, Yifa; Tong, Wenchao; Han, Yuzhen; Yang, Li; Wang, Bo

    2016-07-01

    On page 5837, L. Yang, B. Wang, and co-workers describe a metal-organic framework (MOF) templating method to synthesize copper azide uniformly anchored in a 3D interconnected carbon matrix and evenly spaced by the electron-conductive joints. This strategy sheds light on the preparation of powerful yet safe primary explosives and fulfills the need for controllable explosive systems. PMID:27442967

  17. Graphene/graphene-tube nanocomposites templated from cage-containing metal-organic frameworks for oxygen reduction in Li-O₂ batteries.

    PubMed

    Li, Qing; Xu, Ping; Gao, Wei; Ma, Shuguo; Zhang, Guoqi; Cao, Ruiguo; Cho, Jaephil; Wang, Hsing-Lin; Wu, Gang

    2014-03-01

    Nitrogen-doped graphene/graphene-tube nanocomposites are prepared by a hightemperature approach using a newly designed cage-containing metal-organic framework (MOF) to template nitrogen/carbon (dicyandiamide) and iron precursors. The resulting N-Fe-MOF catalysts universally exhibit high oxygen-reduction activity in acidic, alkaline, and non-aqueous electrolytes and superior cathode performance in Li-O2 batteries. PMID:24277526

  18. Cadmium amido alkoxide and alkoxide precursors for the synthesis of nanocrystalline CdE (E=S,Se, Te).

    SciTech Connect

    Boyle, Timothy J.; Avilucea, Gabriel; Bunge, Scott D.; Alam, Todd Michael; Headley, Thomas Jeffrey; Holland, Gregory P.

    2004-12-01

    The synthesis and characterization of a family of alternative precursors for the production of CdE nanoparticles (E = S, Se, and Te) is reported. The reaction of Cd(NR{sub 2}){sub 2} where NR{sub 2} = N(SiMe{sub 3}){sub 2} with n HOR led to the isolation of the following: n = 1 [Cd({mu}-OCH{sub 2}CMe{sub 3})(NR{sub 2})(py)]{sub 2} (1, py = pyridine), Cd[({mu}-OC{sub 6}H{sub 3}(Me){sub 2}-2,6){sub 2}Cd(NR{sub 2})(py)]{sub 2} (2), [Cd({mu}-OC{sub 6}H{sub 3}(CHMe{sub 2}){sub 2}-2,6)(NR{sub 2})(py)]{sub 2} (3), [Cd({mu}-OC{sub 6}H{sub 3}(CMe{sub 3}){sub 2}-2,6)(NR{sub 2})(py)]{sub 2} (4), [Cd({mu}-OC{sub 6}H{sub 2}(NH{sub 2}){sub 3}-2,4,6)(NR{sub 2})(py)]{sub 2} (5), and n = 2 [Cd({mu}-OC{sub 6}H{sub 3}(Me){sub 2}-2,6)(OC{sub 6}H{sub 3}(Me){sub 2}-2,6)(py){sub 2}]{sub 2} (6), and [Cd({mu}-OC{sub 6}H{sub 3}(CMe{sub 3}){sub 2}-2,6)(OC{sub 6}H{sub 3}(CMe{sub 3}){sub 2}-2,6)(THF)]{sub 2} (7). For all but 2, the X-ray crystal structures were solved as discrete dinuclear units bridged by alkoxide ligands and either terminal -NR{sub 2} or -OR ligands depending on the stoichiometry of the initial reaction. For 2, a trinuclear species was isolated using four {mu}-OR and two terminal -NR{sub 2} ligands. The coordination of the Cd metal center varied from 3 to 5 where the higher coordination numbers were achieved by binding Lewis basic solvents for the less sterically demanding ligands. These complexes were further characterized in solution by {sup 1}H, {sup 13}C, and {sup 113}Cd NMR along with solid-state {sup 113}Cd NMR spectroscopy. The utility of these complexes as 'alternative precursors' for the controlled preparation of nanocrystalline CdS, CdSe, and CdTe was explored. To synthesize CdE nanocrystals, select species from this family of compounds were individually heated in a coordinating solvent (trioctylphosphine oxide) and then injected with the appropriate chalcogenide stock solution. Transmission electron spectroscopy and UV-vis spectroscopy were used to characterize

  19. Accelerated subcritical drying of large alkoxide silica gels

    NASA Astrophysics Data System (ADS)

    Wang, Shiho; Kirkbir, Fikret; Chaudhuri, S. R.; Sarkar, Arnab

    1992-12-01

    Fracture during drying has been the key hurdle in fabrication of large monolithic silica glass from alkoxide gels. Although existing literature suggests pore enlargement, aging, chemical additives, supercritical drying and freeze drying as helpful in avoiding fracture during drying, successful accelerated sub-critical drying of large silica monoliths from alkoxide gels has not yet been reported. In the present approach, acid catalyzed sols of TEOS, ethanol and water (pH equals 2) were cast as cylindrical rods in plastic molds of 8.0 and 10.0 cm diameter with volumes of 2000 cc and 3000 cc respectively. The resultant gels were aged for about 7 days and dried in a specially designed chamber under sub-critical conditions of the pore field. We have obtained monolithic dry gels in drying times of 3 - 7 days for sizes of 2000 - 3000 cc. The dry gels have narrow unimodal pore size distributions, with average pore radius of about 20 angstroms as measured by BET. Although capillary stress during drying increases with reduction of pore size, it was found that in this approach it is easier to dry gels of smaller pore size.

  20. Method for making monolithic metal oxide aerogels

    SciTech Connect

    Coronado, P.R.

    1999-09-28

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The containment vessel is enclosed within an aqueous atmosphere that is above the supercritical temperature and pressure of the solvent of the metal alkoxide solution.

  1. Method for making monolithic metal oxide aerogels

    DOEpatents

    Coronado, Paul R.

    1999-01-01

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The containment vessel is enclosed within an aqueous atmosphere that is above the supercritical temperature and pressure of the solvent of the metal alkoxide solution.

  2. Reactivity of divalent germanium alkoxide complexes is in sharp contrast to the heavier tin and lead analogues.

    PubMed

    Ferro, Lorenzo; Hitchcock, Peter B; Coles, Martyn P; Fulton, J Robin

    2012-02-01

    The chemistry of β-diketiminate germanium alkoxide complexes has been examined and shown to be in sharp contrast to its heavier congeners. For instance, (BDI)GeOR (BDI = [{N(2,6-(i)Pr(2)C(6)H(3))C(Me)}(2)CH], R = (i)Pr, (s)Bu, (t)Bu) does not react with carbon dioxide to form a metal carbonate complex. Addition of aliphatic electrophiles, such as methyl iodide or methyl triflate, results in the net oxidative addition to the germanium, giving cationic tetravalent germanium complexes, [(BDI)Ge(Me)OR][X] (X = I, OTf). An examination of the contrasting reactivities of the alkoxide ligand and the germanium loan pair with Lewis acids yielded the unusual germanium(II)-copper(I) adduct, {μ(2)-Cu(2)I(2)}[(BDI)GeO(t)Bu](2). This complex not only displays a rare example of a divalent Ge-Cu bond, but is the first example in which a planar Cu(2)I(2) diamond core possesses a three-coordinate copper bound to another metal center. PMID:22242862

  3. Synthesis, structural characterization, IR- and Raman spectroscopy, magnetic properties of new organically templated metal sulfates with 4-aminopyridinium

    NASA Astrophysics Data System (ADS)

    Bednarchuk, Tamara J.; Kinzhybalo, Vasyl; Bednarchuk, Oleksandr; Pietraszko, Adam

    2016-09-01

    Crystal structures of the series of twelve 4-aminopyridinium templated metal sulfates: (C5H7N2)2[MeII(H2O)6](SO4)2 (MeII = Cu (1), Co (2), Mg (3), Zn (4), Fe (5), Mn (6a)), (C5H7N2)2[MeII(H2O)4(SO4)2]·4H2O (MeII = Mn (6b), Cd (7a)), (C5H7N2)2[MnII(H2O)4(SO4)2] (6c), (C5H7N2)2[Cd(H2O)4(SO4)2] (7b), (C5H7N2)[Al(H2O)6](SO4)2·4H2O (low (8lt) and room temperature (8rt) phases) and (C5H7N2)[FeIII(H2O)4(SO4)2] (9) were determined by single-crystal X-ray diffraction. Compounds 1-6a are isostructural, crystal structure consists of [Me(H2O)6]2+ octahedra, 4-aminopyridinium cations (4ap) and sulfate anions. Crystal packing in 1-6a series is characterized by alternating 4ap and inorganic layers. In the structure of 1 Cu2+ coordination environment is axially deformed due to Jahn-Teller effect to tetragonal bipyramidal. Compounds 6 (a, b) and 7a at ambient conditions dehydrate to produce isostructural complexes 6c and 7b, respectively. In structures of 6c, 7b and 9 sulfate anions are involved in slightly distorted octahedral metal coordination composed of six O atoms from four water molecules and two sulfate anions. Room temperature phase of 8 is characterized by disorder of 4ap around center of inversion. Continuous phase transition at ≈185 K leads to the cell doubling and ordering of 4ap. All of the structures are governed by an extensive three-dimensional hydrogen bond networks, as well as π-π interactions visualized by Hirshfeld surface analysis. Moreover, selected compounds were characterized by the IR and Raman spectroscopy and magnetic measurement studies.

  4. A Qualitative Analysis of a "Bora-Brook Rearrangement": The Ambident Reactivity of Boryl-Substituted Alkoxide Including the Carbon-to-Oxygen Migration of a Boryl Group.

    PubMed

    Kisu, Haruki; Sakaino, Hirotoshi; Ito, Fumihiro; Yamashita, Makoto; Nozaki, Kyoko

    2016-03-16

    A bora-Brook rearrangement, i.e., the migration of boryl group from a carbon to an oxygen atom in an isolated α-boryl-substituted alkoxide, was examined, and decisive factors for the acceleration of this reaction are disclosed. In this rearrangement, the boryl-substituted alkoxide exhibited ambiphilic reactivity toward electrophiles to afford two types of products, which are electrophiles bound either at the oxygen or at the carbon atom. Using polar solvents, a saturated backbone of the boron-containing heterocycle, or larger alkali metal cations resulted in a significantly increased reaction rate of base-catalyzed isomerization of α-borylbenzyl alcohol including the bora-Brook rearrangement. PMID:26907676

  5. Assembly of a Metal-Organic Framework into 3 D Hierarchical Porous Monoliths Using a Pickering High Internal Phase Emulsion Template.

    PubMed

    Zhu, He; Zhang, Qi; Zhu, Shiping

    2016-06-20

    3D Hierarchical porous metal-organic framework (MOF) monoliths are prepared by using Pickering high internal phase emulsion (HIPE) template. Pickering HIPEs were stabilized solely by UiO-66 MOF particles with internal phase up to 90 % of the volume. The effects of internal phase type and volume, as well as MOF particle concentration on the stability of resulting Pickering HIPEs were investigated. Furthermore, by adding small amount of polyvinyl alcohol (PVA) as binder or polymerization in the continuous aqueous phase, followed by freeze-drying, two types of MOF-based 3D hierarchical porous monoliths with ultralow density (as low as 12 mg cm(-3) ) were successfully prepared. This Pickering HIPE template approach provides a facile and practical way for assembling of MOFs into complex structures. PMID:27123547

  6. Investigations of the effects of photocatalysis on the molecular assembly behavior of titanium alkoxide materials

    NASA Astrophysics Data System (ADS)

    Musgraves, Jonathan David

    The present work focuses on the use of engineered, photoactive metal alkoxide precursors in the sol-gel processing of metal-oxide materials. The strategy under investigation seeks to integrate photoinduced structural modification with conventional sol-gel chemical preparations to enable the selective photo-activation of reaction points about the metal center during material formation. The approach thus has the potential to influence the development of intermolecular bonding geometry and to provide an opportunity to enforce or bias longer range structural development processes and resulting network topology. This ability to bias the long range structural development has been shown to provide opportunities both for photoinduced material formation and the potential to control multi-length scale structural characteristics of these materials. The response of a mononuclear, heteroleptic titanium alkoxide (OPy) 2Ti(4MP)2 [where OPy = pyridine carbinoxide and 4MP = 4-mercaptophenoxide] to ultraviolet (UV) irradiation in dilute solution and in solid-state samples has been measured. Vibrational spectroscopy (FTIR absorption and Raman scattering) was used to monitor changes in molecular structure upon exposure to 337.1 and 365 nm light. Assignment of spectral features to vibrational modes of the molecule was aided by a normal-mode analysis of the energy-minimized molecular structure within a density functional theory (DFT) framework. Photoinduced decreases in peak areas were observed in both FTIR spectra of the precursor solutions and Raman data collected from solution-cast films of the precursor material. These changes were associated with vibrational modes localized at the 4MP ligands. Conversely, no significant modification of vibrational structure associated with the OPy moiety was observed under the excitation conditions examined. Excitation, with 248 nm light, of a solution of (OPy)2Ti(TAP) 2 [where OPy = pyridine carbinoxide and TAP = 2,4,6 tris

  7. Covalent heterogenization of discrete bis(8-quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes by a metal-template/metal-exchange method: Cyclooctene epoxidation catalysts with enhanced performances

    SciTech Connect

    Yang, Ying; Chattopadhyay, Soma; Shibata, Tomohiro; Ren, Yang; Lee, Sungsik; Kan, Qiubin

    2014-10-01

    A metal-template/metal-exchange method was used to imprint covalently attached bis(8- quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes onto large surface-area, mesoporous SBA-15 silica to obtain discrete MoO2 VIT and WO2 VIT catalysts bearing different metal loadings, respectively. Homogeneous counterparts, MoO2 VIN and WO2 VIN, as well as randomly ligandgrafted heterogeneous analogues, MoO2 VIG and WO2 VIG, were also prepared for comparison. X-ray absorption fine structure (XAFS), pair distribution function (PDF) and UV–vis data demonstrate that MoO2 VIT and WO2 VIT adopt a more solution-like bis(8-quinolinol) coordination environment than MoO2 VIG and WO2 VIG, respectively. Correspondingly, the templated MoVI and WVI catalysts show superior performances to their randomly grafted counterparts and neat analogues in the epoxidation of cyclooctene. It is found that the representative MoO2 VIT-10% catalyst can be recycled up to five times without significant loss of reactivity, and heterogeneity test confirms the high stability of MoO2 VIT-10% catalyst against leaching of active species into solution. The homogeneity of the discrete bis(8-quinolinol) metal spheres templated on SBA-15 should be responsible for the superior performances.

  8. Structural and optical characterization of metal tungstates (MWO4; M=Ni, Ba, Bi) synthesized by a sucrose-templated method

    PubMed Central

    2013-01-01

    Background Metal tungstates have attracted much attention due to their interesting structural and photoluminescence properties. Depending on the size of the bivalent cation present, the metal tungstates will adopt structures with different phases. In this work, three different phases of metal tungstates MWO4 (M= Ba, Ni and Bi) were synthesized via the sucrose templated method. Results The powders of BaWO4 (tetragonal), NiWO4 (monoclinic) and Bi2WO6 (orthorhombic) formed after calcination temperatures of 750, 650 and 600°C for 4 h respectively are found to be crystalline and exist in their pure phase. Based on Scherrer estimation, their crystallite size are of nanosized. BET results showed NiWO4 has the highest surface area. BaWO4 exhibited less Raman vibrations than the NiWO4 because of the increased lattice symmetry but Bi2WO6 showed almost the same Raman vibrations as BaWO4. From the UV-vis spectra, the band gap transition of the metal tungstates are of the order of BaWO4 > Bi2WO6 > NiWO4. Broad blue-green emission peaks were detected in photoluminescence spectra and the results showed the great dependence on morphology, crystallinity and size of the metal tungstates. Conclusion Three different phases of metal tungstates of BaWO4 (scheelite), NiWO4 (wolframite) and Bi2WO6 (perovskite layer) in their pure phase were successfully prepared by the simple and economical sucrose-templated method. The highest surface area is exhibited by NiWO4 while largest band gap is shown by BaWO4. These materials showed promising optical properties. PMID:23634962

  9. Insertion of unsaturated organic electrophiles into molybdenumbond-alkoxide and rheniumbond-alkoxide bonds of neutral, stable carbonyl complexes.

    PubMed

    Hevia, Eva; Pérez, Julio; Riera, Lucía; Riera, Víctor; Del Río, Ignacio; García-Granda, Santiago; Miguel, Daniel

    2002-10-01

    Alkoxo complexes [Re(OR)(CO)(3)(N-N)] (R=Me, Et, tBu; N-N=2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'bipyridine (bipy'), 1,10-phenanthroline (phen)) and [M(OMe)(eta(3)-allyl)(CO)(2)(phen)] (M=Mo, W) have been synthesized in good yields and using mild conditions by the reaction of sodium alkoxides with [Re(OTf)(CO)(3)(N-N)] and [MCl(eta(3)-allyl)(CO)(2)(phen)] precursors. These have been characterized by IR and NMR spectroscopy as well as by X-ray diffraction for [W(OMe)(eta(3)-allyl)(CO)(2)(phen)] (10). The reactions of the molybdenum and rhenium alkoxo complexes with isocyanates, R'NCO, yield [L(n)M[N(R')C(O)OR

  10. On-line spectroscopic studies of group IV alkoxides and their interactions with organic additives during the sol-gel process

    SciTech Connect

    Wettling, D.; Truchet, S.; Guilment, J.; Poncelet, O.

    1996-12-31

    The potential of vibrational spectroscopy for the study of group 4 alkoxides M(OR){sub 4} has been demonstrated in several papers, but only a few of these papers have presented results from online measurements. The monitoring of different reactions such as the stabilization of the alkoxides with organic additives, the exchange processes between different metal alkoxides (R exchange or M exchange) and the hydrolysis process can be of great importance for the development of new synthetic routes leading to materials which are easier to process. NIR spectroscopy is a very versatile technique but lacks specificity while IR and Raman give more interpretive results but are not always easy during processing. The authors used both techniques along with chemometric tools to extract relevant information on their processes. The 2D correlation allowed benefits from the specificity of IR and Raman to develop robust NIR methods which are able to be used on line to monitor the different steps of the sol-gel process.

  11. Cubic nitride templates

    DOEpatents

    Burrell, Anthony K; McCleskey, Thomas Mark; Jia, Quanxi; Mueller, Alexander H; Luo, Hongmei

    2013-04-30

    A polymer-assisted deposition process for deposition of epitaxial cubic metal nitride films and the like is presented. The process includes solutions of one or more metal precursor and soluble polymers having binding properties for the one or more metal precursor. After a coating operation, the resultant coating is heated at high temperatures under a suitable atmosphere to yield metal nitride films and the like. Such films can be used as templates for the development of high quality cubic GaN based electronic devices.

  12. Synthesis and thermolytic behavior of mixed-valence homo- and heterometallic group 14 alkoxides

    SciTech Connect

    Teff, D.J.; Minear, C.D.; Baxter, D.V.; Caulton, K.G.

    1998-05-18

    The mixed-valence molecule Sn{sup II}Sn{sup IV} (OPr){sub 6} is conveniently synthesized and is shown to exchange bridging and terminal alkoxides in solution in its Sn({micro}-OPr){sub 3}Sn(OPr){sub 3} structure. Pb{sub 3}SnO(POr){sub 8} is synthesized and shown to undergo an intramolecular fluxional process in solution. Both molecules are sufficiently volatile for CVD study, and comparison of CVD behaviors of these and of M(OPr){sub 2} (M = Sn, Pb), Sn(POr){sub 4}, SnZr(OPr){sub 6}, and Pb{sub 3}-ZrO(OPr){sub 8} shows the reducing capacity of the isopropoxide moiety dominates the thermolytic behavior of all these species, giving metallic Sn or Pb in all cases. Only Zr, when it is present, forms ZrO{sub 2}. The oxide in Pb{sub 3}SnO(POr){sub 8}yields PbO (and 2 Pb{sup 0} and 1 Sn{sup 0}), in contrast to the relative electropositivity of Sn and Pb, a fact attributed to kinetic control of CVD behavior.

  13. The first organically templated open-framework metal-sulfites with layered and three-dimensional diamondoid structures.

    PubMed

    Tiwari, Ranjay K; Kumar, Jitendra; Behera, J N

    2016-01-21

    The crystallographic signatures and characterization data of two novel organically templated open-framework zinc-sulfites (NH3CH2CH2NH3)[Zn3(SO3)4], 1, and (CN3H6)2[Zn(SO3)2], 2, are reported for the first time, synthesized under hydrothermal conditions using different amines, namely, ethylenediamine and guanidine, to generate 2D (for 1) and 3D (for 2) assemblies with 4-, 6-, 8- and 12-membered rings. PMID:26615884

  14. Small angle x-ray scattering: Instrument development and studies of protein aggregation, cellulose hydrolysis, and the production of nanoporous metals using surfactact templates

    NASA Astrophysics Data System (ADS)

    Banuelos, Jose Leobardo

    explored using surfactant-templated metal systems. In this, as with many materials for possible energy storage applications, chemically stable systems with good mechanical strength, high temperature resistance, and high surface areas are desirable. Time- dependent SAXS measurements were used to study the templating of Pt and Pd metals onto a surfactant structure. The reduction of these metals was carried out using two methods, reduction with ascorbate and using hydrogen-nitrogen gas mixtures.

  15. Syntheses of rare-earth metal oxide nanotubes by the sol-gel method assisted with porous anodic aluminum oxide templates

    SciTech Connect

    Kuang Qin; Lin Zhiwei; Lian Wei; Jiang Zhiyuan; Xie Zhaoxiong Huang Rongbin; Zheng Lansun

    2007-04-15

    In this paper, we report a versatile synthetic method of ordered rare-earth metal (RE) oxide nanotubes. RE (RE=Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) oxide nanotubes were successfully prepared from corresponding RE nitrate solution via the sol-gel method assisted with porous anodic aluminum oxide (AAO) templates. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction (XRD) have been employed to characterize the morphology and composition of the as-prepared nanotubes. It is found that as-prepared RE oxides evolve into bamboo-like nanotubes and entirely hollow nanotubes. A new possible formation mechanism of RE oxide nanotubes in the AAO channels is proposed. These high-quantity RE oxide nanotubes are expected to have promising applications in many areas such as luminescent materials, catalysts, magnets, etc. - Graphical abstract: A versatile synthetic method for the preparation of ordered rare-earth (RE) oxide nanotubes is reported, by which RE (RE=Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) oxide nanotubes were successfully prepared from corresponding RE nitrate solution via the sol-gel method assisted with porous anodic aluminum oxide (AAO) templates.

  16. Template-Free 3D Microprinting of Metals Using a Force-Controlled Nanopipette for Layer-by-Layer Electrodeposition.

    PubMed

    Hirt, Luca; Ihle, Stephan; Pan, Zhijian; Dorwling-Carter, Livie; Reiser, Alain; Wheeler, Jeffrey M; Spolenak, Ralph; Vörös, János; Zambelli, Tomaso

    2016-03-23

    A novel 3D printing method for voxel-by-voxel metal printing is presented. Hollow atomic force microscopy (AFM) cantilevers are used to locally supply metal ions in an electrochemical cell, enabling a localized electroplating reaction. By exploiting the deflection feedback of these probes, electrochemical 3D metal printing is, for the first time, demonstrated in a layer-by-layer fashion, enabling the fabrication of arbitrary-shaped geometries. PMID:26783090

  17. Self-formation of highly aligned metallic, semiconducting and single chiral single-walled carbon nanotubes assemblies via a crystal template method

    SciTech Connect

    Kawai, Hideki; Hasegawa, Kai; Yanagi, Kazuhiro; Oyane, Ayako; Naitoh, Yasuhisa

    2014-09-01

    The fabrication of an aligned array of single-walled carbon nanotubes (SWCNTs) with a single chiral state has been a significant challenge for SWCNT applications as well as for basic science research. Here, we developed a simple, unique technique to produce assemblies in which metallic, semiconducting, and single chiral state SWCNTs were densely and highly aligned. We utilized a crystal of surfactant as a template on which mono-dispersed SWCNTs in solution self-assembled. Micro-Raman measurements and scanning electron microscopy measurements clearly showed that the SWCNTs were highly and densely aligned parallel to the crystal axis, indicating that approximately 70% of the SWCNTs were within 7° of being parallel. Moreover, the assemblies exhibited good field effect transistor characteristics with an on/off ratio of 1.3 × 10{sup 5}.

  18. Carbonaceous spheres—an unusual template for solid metal oxide mesoscale spheres: Application to ZnO spheres

    SciTech Connect

    Patrinoiu, Greta; Calderón-Moreno, Jose Maria; Culita, Daniela C.; Birjega, Ruxandra; Ene, Ramona; Carp, Oana

    2013-06-15

    A green template route for the synthesis of mesoscale solid ZnO spheres was ascertained. The protocol involves a double coating of the carbonaceous spheres with successive layers of zinc-containing species by alternating a non-ultrasound and ultrasound-assisted deposition, followed by calcination treatments. The composites were characterized by FTIR spectroscopy, thermal analysis, scanning electron microscopy while the obtained ZnO spheres by X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, N{sub 2} adsorption–desorption isotherms and photoluminescence investigations. A growth mechanism of the solid spheres is advanced based on these results. While the spheres' diameters and the mean size values of ZnO are independent on deposition order, the surface area and the external porosity are fairly dependent. The photoluminescence measurements showed interesting emission features, with emission bands in the violet to orange region. The spheres present high photocatalytical activity towards the degradation of phenol under UV irradiation, the main reaction being its mineralization. - Graphical abstract: A novel and eco-friendly methodology for the synthesis of mesoscale solid ZnO spheres was developed. The protocol involves a double coating of the starch-derived carbonaceous spheres with successive layers of zinc-containing species by alternating a non-ultrasound and ultrasound-assisted deposition, followed by calcination treatments. - Highlights: • ZnO solid spheres are obtained via a template route using carbonaceous spheres. • Two-step coatings of interchangeable order are used as deposition procedure. • The coating procedure influences the porosity and surface area. • ZnO spheres exhibited interesting visible photoluminescence properties. • Solid spheres showed photocatalytical activity in degradation of phenol.

  19. Tin(II) alkoxide hydrolysis products for use as base catalysts

    DOEpatents

    Boyle, Timothy J.

    2002-01-01

    Tin alkoxide compounds are provided with accessible electrons. The compounds are a polymeric tin alkoxide, [Sn(OCH.sub.2 C(CH.sub.3).sub.3).sub.2 ].sub.n, and the hydrolysis products Sn.sub.6 O.sub.4 (OCH.sub.2 C(CH.sub.3).sub.3).sub.4 and Sn.sub.5 O.sub.2 (OCH.sub.2 C(CH.sub.3).sub.3).sub.6. The hydrolysis products are formed by hydrolyzing the [Sn(OCH.sub.2 C(CH.sub.3).sub.3).sub.2 ].sub.n in a solvent with controlled amounts of water, between 0.1 and 2 moles of water per mole of the polymeric tin alkoxide.

  20. Dioximate- and Bis(salicylaldiminate)-Bridged Titanium and Zirconium Alkoxides: Structure Elucidation by Mass Spectrometry

    PubMed Central

    Maurer, Christian; Pittenauer, Ernst; Puchberger, Michael; Allmaier, Günter; Schubert, Ulrich

    2013-01-01

    The treatment of titanium alkoxides with 1,5-pentanedioxime or 2,5-hexanedioxime resulted in the formation of complexes [{TiL(OR)2}2] in which the dioximate ligands (L) bridge a dimeric Ti2(μ2-OR)2 unit. The structures of the complexes were determined by single-crystal structure analysis, ESI mass spectrometry, and 1D and 2D solution NMR spectroscopy. In contrast, the treatment of titanium alkoxides with dioximes bearing cyclic linkers, such as cyclohexyl or aryl groups, resulted in insoluble polymeric compounds. The treatment of various bis(salicylaldiminates) with titanium and zirconium alkoxides resulted in compounds with the same composition [{TiL(OR)2}2], in which, however, two monomeric Ti(OR)2 units are bridged by the ligands L. The two structural possibilities can be distinguished by low-energy collision-induced dissociation owing to their different fragmentation patterns. PMID:23795338

  1. Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands.

    PubMed

    Carter, Shawn M; Lee, Jonghyuk; Hixson, Christopher Adam; Powell, Douglas R; Wheeler, Ralph A; Shaw, Michael J; Richter-Addo, George B

    2006-03-14

    We have examined the redox behavior of the osmium and ruthenium compounds (OEP)M(NO)(OEt) and (OEP)M(NO)(SEt) (OEP = octaethylporphyrinato dianion; M = Os, Ru) by cyclic voltammetry and infrared spectroelectrochemistry. The compound (OEP)Os(NO)(OEt) undergoes a single reversible oxidation process in dichloromethane. In contrast, the thiolate compound (OEP)Os(NO)(SEt) undergoes a net irreversible oxidation resulting in formal loss of the SEt ligand. Extended Hückel calculations on crystal structures of these two compounds provide insight into the nature of their HOMOs. In the case of the alkoxide compound, the HOMO is largely metal centered, with 70% of the charge located in the metal's orbital and approximately 25% on the porphyrin ring. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal dxz orbital and the px orbital on the sulfur, and a pi antibonding interaction between the metal d orbital and a pi* orbital on NO. The redox behavior of the Ru analogues have been determined, and are compared with those of the Os compounds. PMID:16505913

  2. Room temperature perovskite production from bimetallic alkoxides by ketone assisted oxo supplementation (KAOS)

    SciTech Connect

    Gaskins, B.C.; Lannutti, J.J.

    1996-08-01

    Barium titanate has been prepared at room temperature from a well-characterized crystalline barium titanium oxo alkoxide by reaction with acetone. An aldol condensation apparently supplies oxygen to condensing oxo alkoxide clusters. Transmission electron microscopy confirms that the crystallites so formed are dense and perfect with an average size of approximately 85 A. Characterization of reactants and products provides a tentative understanding of structural evolution and the intermediates of the transformation. Crystalline SrTiO{sub 3} and BaZrO{sub 3} were also formed at room temperature by this same method. {copyright} {ital 1996 Materials Research Society.}

  3. In Situ Observation of Directed Nanoparticle Aggregation During the Synthesis of Ordered Nanoporous Metal in Soft Templates

    SciTech Connect

    Parent, Lucas R.; Robinson, David B.; Cappillino, Patrick J.; Hartnett, Ryan J.; Abellan Baeza, Patricia; Evans, James E.; Browning, Nigel D.; Arslan, Ilke

    2014-02-11

    The prevalent approach to developing new nanomaterials is a trial and error process of iteratively altering synthesis procedures and then characterizing the resulting nanostructures. This is fundamentally limited in that the growth processes that occur during synthesis can only be inferred from the final synthetic structure. Directly observing real-time nanomaterial growth provides unprecedented insight into the relationship between synthesis conditions and product evolution, and facilitates a mechanistic approach to nanomaterial development. Here we use in situ liquid stage scanning transmission electron microscopy to observe the growth of mesoporous palladium in a solvated block copolymer (BCP) template under various synthesis conditions, and ultimately determine a refined synthesis procedure that yields ordered pores. We find that at low organic solvent (tetrahydrofuran, THF) content, the BCP assembles into a rigid, cylindrical micelle array with a high degree of short-range order, but poor long-range order. Upon slowing the THF evaporation rate using a solvent-vapor anneal step, the long-range order is greatly improved. The electron beam induces nucleation of small particles in the aqueous phase around the micelles. The small particles then flocculate and grow into denser structures that surround the micelles, forming an ordered mesoporous structure. The microscope observations revealed that template disorder can be addressed prior to reaction, and is not invariably induced by the growth process itself, allowing us to more quickly optimize the synthetic method. This work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy under contract DE-AC05-76RL01830. This research

  4. Metal@COFs: covalent organic frameworks as templates for Pd nanoparticles and hydrogen storage properties of Pd@COF-102 hybrid material.

    PubMed

    Kalidindi, Suresh Babu; Oh, Hyunchul; Hirscher, Michael; Esken, Daniel; Wiktor, Christian; Turner, Stuart; Van Tendeloo, Gustaaf; Fischer, Roland A

    2012-08-27

    Three-dimensional covalent organic frameworks (COFs) have been demonstrated as a new class of templates for nanoparticles. Photodecomposition of the [Pd(η(3)-C(3) H(5))(η(5)-C(5)H(5))]@COF-102 inclusion compound (synthesized by a gas-phase infiltration method) led to the formation of the Pd@COF-102 hybrid material. Advanced electron microscopy techniques (including high-angle annular dark-field scanning transmission electron microscopy and electron tomography) along with other conventional characterization techniques unambiguously showed that highly monodisperse Pd nanoparticles ((2.4±0.5) nm) were evenly distributed inside the COF-102 framework. The Pd@COF-102 hybrid material is a rare example of a metal-nanoparticle-loaded porous crystalline material with a very narrow size distribution without any larger agglomerates even at high loadings (30 wt %). Two samples with moderate Pd content (3.5 and 9.5 wt %) were used to study the hydrogen storage properties of the metal-decorated COF surface. The uptakes at room temperature from these samples were higher than those of similar systems such as Pd@metal-organic frameworks (MOFs). The studies show that the H(2) capacities were enhanced by a factor of 2-3 through Pd impregnation on COF-102 at room temperature and 20 bar. This remarkable enhancement is not just due to Pd hydride formation and can be mainly ascribed to hydrogenation of residual organic compounds, such as bicyclopentadiene. The significantly higher reversible hydrogen storage capacity that comes from decomposed products of the employed organometallic Pd precursor suggests that this discovery may be relevant to the discussion of the spillover phenomenon in metal/MOFs and related systems. PMID:22886887

  5. Two Dawson-templated three-dimensional metal-organic frameworks based on oxalate-bridged binuclear cobalt(II)/Nickel(II) SBUs and Bpy linkers.

    PubMed

    Zhao, Xinyu; Liang, Dadong; Liu, Shuxia; Sun, Chunyan; Cao, Ruige; Gao, Chaoying; Ren, Yuanhang; Su, Zhongmin

    2008-08-18

    The Dawson anion P 2W 18O 62 (6-) has been used as a noncoordinating polyoxoanion template for the construction of two metal-organic frameworks, namely, [M 2(bpy) 3(H 2O) 2(ox)][P 2W 18O 62]2(H 2-bpy). nH 2O (M = Co(II), n = 3 ( 1); M = Ni(II), n = 2 ( 2)) (bpy = 4,4'-bipyridine; ox = C 2O 4 (2-)). Single-crystal X-ray analysis reveals that both of the structures exhibit 3D host frameworks constructed from the oxalate-bridged binuclear superoctahedron secondary building units (SBUs) and bpy linkers and the voids of which are occupied by Dawson anions, guest bpy, and water molecules. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the transition-metal centers in compounds 1 and 2. Furthermore, a compound 1-modified carbon paste electrode ( 1-CPE) displays good electrocatalytic activity toward the reduction of nitrite. PMID:18620386

  6. Laser-ignited frontal polymerization of shape-controllable poly(VI-co-AM) hydrogels based on 3D templates toward adsorption of heavy metal ions

    NASA Astrophysics Data System (ADS)

    Fan, Suzhen; Liu, Sisi; Wang, Xiao-Qiao; Wang, Cai-Feng; Chen, Su

    2016-06-01

    Given the increasing heavy metal pollution issue, fast preparation of polymeric hydrogels with excellent adsorption property toward heavy metal ions is very attractive. In this work, a series of poly( N-vinylimidazole-co-acrylamide) (poly(VI-co-AM)) hydrogels were synthesized via laser-ignited frontal polymerization (LIFP) for the first time. The dependence of frontal velocity and temperature on two factors monomer ratios and initiator concentrations was systematically investigated. Poly(VI-co-AM) hydrogels with any self-supporting shapes can be synthesized by a one-step LIFP in seconds through the application of 3D templates. These shape-persistent hydrogels are pH-responsive and exhibit excellent adsorption/desorption characteristics toward Mn(II), Zn(II), Cd(II), Ni(II), Cu(II) and Co(II) ions, and the adsorption conformed to the pseudo-second-order kinetic model. The reusability of the hydrogels toward mental ions adsorption was further researched, which suggested that the hydrogels can be reused without serious decrease in adsorption capacity. This work might open a promising strategy to facilely prepare shape-controllable hydrogels and expand the application of LIFP.

  7. Metal-assisted exfoliation (MAE): green process for transferring graphene to flexible substrates and templating of sub-nanometer plasmonic gaps (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Zaretski, Aliaksandr V.; Marin, Brandon C.; Moetazedi, Herad; Dill, Tyler J.; Jibril, Liban; Kong, Casey; Tao, Andrea R.; Lipomi, Darren J.

    2015-09-01

    This paper describes a new technique, termed "metal-assisted exfoliation," for the scalable transfer of graphene from catalytic copper foils to flexible polymeric supports. The process is amenable to roll-to-roll manufacturing, and the copper substrate can be recycled. We then demonstrate the use of single-layer graphene as a template for the formation of sub-nanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a sub-nanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming sub-nanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

  8. Template Catalysis by Metal-Ligand Cooperation. C-C Bond Formation via Conjugate Addition of Non-activated Nitriles under Mild, Base-free Conditions Catalyzed by a Manganese Pincer Complex.

    PubMed

    Nerush, Alexander; Vogt, Matthias; Gellrich, Urs; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David

    2016-06-01

    The first example of a catalytic Michael addition reaction of non-activated aliphatic nitriles to α,β-unsaturated carbonyl compounds under mild, neutral conditions is reported. A new de-aromatized pyridine-based PNP pincer complex of the Earth-abundant, first-row transition metal manganese serves as the catalyst. The reaction tolerates a variety of nitriles and Michael acceptors with different steric features and acceptor strengths. Mechanistic investigations including temperature-dependent NMR spectroscopy and DFT calculations reveal that the cooperative activation of alkyl nitriles, which leads to the generation of metalated nitrile nucleophile species (α-cyano carbanion analogues), is a key step of the mechanism. The metal center is not directly involved in the catalytic bond formation but rather serves, cooperatively with the ligand, as a template for the substrate activation. This approach of "template catalysis" expands the scope of potential donors for conjugate addition reactions. PMID:27164437

  9. Vertical Carbon Nanotube Device in Nanoporous Templates

    NASA Technical Reports Server (NTRS)

    Maschmann, Matthew Ralph (Inventor); Fisher, Timothy Scott (Inventor); Sands, Timothy (Inventor); Bashir, Rashid (Inventor)

    2014-01-01

    A modified porous anodic alumina template (PAA) containing a thin CNT catalyst layer directly embedded into the pore walls. CNT synthesis using the template selectively catalyzes SWNTs and DWNTs from the embedded catalyst layer to the top PAA surface, creating a vertical CNT channel within the pores. Subsequent processing allows for easy contact metallization and adaptable functionalization of the CNTs and template for a myriad of applications.

  10. Template-assisted synthesis of III-nitride and metal-oxide nano-heterostructures using low-temperature atomic layer deposition for energy, sensing, and catalysis applications (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Biyikli, Necmi; Ozgit-Akgun, Cagla; Eren, Hamit; Haider, Ali; Uyar, Tamer; Kayaci, Fatma; Guler, Mustafa Ozgur; Garifullin, Ruslan; Okyay, Ali K.; Ulusoy, Gamze M.; Goldenberg, Eda

    2015-08-01

    Recent experimental research efforts on developing functional nanostructured III-nitride and metal-oxide materials via low-temperature atomic layer deposition (ALD) will be reviewed. Ultimate conformality, a unique propoerty of ALD process, is utilized to fabricate core-shell and hollow tubular nanostructures on various nano-templates including electrospun nanofibrous polymers, self-assembled peptide nanofibers, metallic nanowires, and multi-wall carbon nanotubes (MWCNTs). III-nitride and metal-oxide coatings were deposited on these nano-templates via thermal and plasma-enhanced ALD processes with thickness values ranging from a few mono-layers to 40 nm. Metal-oxide materials studied include ZnO, TiO2, HfO2, ZrO2, and Al2O3. Standard ALD growth recipes were modified so that precursor molecules have enough time to diffuse and penetrate within the layers/pores of the nano-template material. As a result, uniform and conformal coatings on high-surface area nano-templates were demonstrated. Substrate temperatures were kept below 200C and within the self-limiting ALD window, so that temperature-sensitive template materials preserved their integrity III-nitride coatings were applied to similar nano-templates via plasma-enhanced ALD (PEALD) technique. AlN, GaN, and InN thin-film coating recipes were optimized to achieve self-limiting growth with deposition temperatures as low as 100C. BN growth took place only for >350C, in which precursor decomposition occured and therefore growth proceeded in CVD regime. III-nitride core-shell and hollow tubular single and multi-layered nanostructures were fabricated. The resulting metal-oxide and III-nitride core-shell and hollow nano-tubular structures were used for photocatalysis, dye sensitized solar cell (DSSC), energy storage and chemical sensing applications. Significantly enhanced catalysis, solar efficiency, charge capacity and sensitivity performance are reported. Moreover, core-shell metal-oxide and III-nitride materials

  11. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold.

    PubMed

    Baksi, Ananya; Pradeep, T

    2013-12-21

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd(+) in the gas phase. While a lysozyme-Au adduct forms Au18(+), Au25(+), Au38(+) and Au102(+) ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag(+), Pt(2+), Pd(2+), Cu(2+), Fe(2+), Ni(2+) and Cr(3+)) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38(+). While other metal ions like Cu(2+) help forming Au25(+) selectively, Fe(2+) catalyzes the formation of Au25(+) over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution. PMID:24146135

  12. Porphyrins as Templates for Site-Selective Atomic Layer Deposition: Vapor Metalation and in Situ Monitoring of Island Growth.

    PubMed

    Avila, Jason R; Emery, Jonathan D; Pellin, Michael J; Martinson, Alex B F; Farha, Omar K; Hupp, Joseph T

    2016-08-10

    Examinations of enzymatic catalysts suggest one key to efficient catalytic activity is discrete size metallo clusters. Mimicking enzymatic cluster systems is synthetically challenging because conventional solution methods are prone to aggregation or require capping of the cluster, thereby limiting its catalytic activity. We introduce site-selective atomic layer deposition (ALD) on porphyrins as an alternative approach to grow isolated metal oxide islands that are spatially separated. Surface-bound tetra-acid free base porphyrins (H2TCPP) may be metalated with Mn using conventional ALD precursor exposure to induce homogeneous hydroxide synthetic handles which acts as a nucleation point for subsequent ALD MnO island growth. Analytical fitting of in situ QCM mass uptake reveals island growth to be hemispherical with a convergence radius of 1.74 nm. This growth mode is confirmed with synchrotron grazing-incidence small-angle X-ray scattering (GISAXS) measurements. Finally, we extend this approach to other ALD chemistries to demonstrate the generality of this route to discrete metallo island materials. PMID:27454741

  13. Synthesis and application of a macroporous boronate affinity monolithic column using a metal-organic gel as a porogenic template for the specific capture of glycoproteins.

    PubMed

    Yang, Fan; Lin, Zian; He, Xiwen; Chen, Langxing; Zhang, Yukui

    2011-12-23

    A macroporous boronate affinity monolithic column was prepared and applied to specifically capture glycoproteins using metal-organic gels (MOGs) as a porogenic template. This newly explored application of MOGs has proven to be a more convenient method for the formation of macropores in contrast to traditional porogenic methods. The poly (3-acrylamidophenylboronic acid-co-ethylene dimethacrylate) monolithic columns were synthesized in stainless columns by in situ polymerization. To fabricate the macroporous formation with a uniformed open-channel network, the preparation conditions, such as reaction temperature, the concentration of the MOGs and the ratio of monomers were systematically investigated. The prepared macroporous monoliths were characterized by scanning electron microscope (SEM) and mercury intrusion porosimetry. Furthermore, horseradish peroxidase (HRP) and transferrin (TF) were chosen as test glycoproteins, and the chromatographic analysis demonstrated that the macroporous boronate affinity monoliths exhibited a higher selectivity and better dynamic binding capacity toward glycoproteins compared with non-glycoproteins. The resulted affinity monolithic column was successfully employed to specifically capture TF from a bovine serum sample. PMID:22078233

  14. A template and catalyst-free metal-etching-oxidation method to synthesize aligned oxide nanowire arrays: NiO as an example.

    PubMed

    Wei, Zhi Peng; Arredondo, Miryam; Peng, Hai Yang; Zhang, Zhou; Guo, Dong Lai; Xing, Guo Zhong; Li, Yong Feng; Wong, Lai Mun; Wang, Shi Jie; Valanoor, Nagarajan; Wu, Tom

    2010-08-24

    Although NiO is one of the canonical functional binary oxides, there has been no report so far on the effective fabrication of aligned single crystalline NiO nanowire arrays. Here we report a novel vapor-based metal-etching-oxidation method to synthesize high-quality NiO nanowire arrays with good vertical alignment and morphology control. In this method, Ni foils are used as both the substrates and the nickel source; NiCl(2) powder serves as the additional Ni source and provides Cl(2) to initiate mild etching. No template is deliberately employed; instead a nanograined NiO scale formed on the NiO foil guides the vapor infiltration and assists the self-assembled growth of NiO nanowires via a novel process comprising simultaneous Cl(2) etching and gentle oxidation. Furthermore, using CoO nanowires and Co-doped NiO as examples, we show that this general method can be employed to produce nanowires of other oxides as well as the doped counterparts. PMID:20614899

  15. Noble metal alloy clusters in the gas phase derived from protein templates: unusual recognition of palladium by gold

    NASA Astrophysics Data System (ADS)

    Baksi, Ananya; Pradeep, T.

    2013-11-01

    Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster formation occurs from protein adducts where Au is in the 1+ state while Pd is in the 2+ state. The creation of alloys in the gas phase is not affected whether a physical mixture of Au and Pd adducts or a Au and Pd co-adduct is used as the precursor. The formation of Au cores and AuPd alloy cores of the kind comparable to monolayer protected clusters implies that naked clusters themselves may be nucleated in solution.Matrix assisted laser desorption ionization of a mixture of gold and palladium adducts of the protein lysozyme (Lyz) produces naked alloy clusters of the type Au24Pd+ in the gas phase. While a lysozyme-Au adduct forms Au18+, Au25+, Au38+ and Au102+ ions in the gas phase, lysozyme-Pd alone does not form any analogous cluster. Addition of various transition metal ions (Ag+, Pt2+, Pd2+, Cu2+, Fe2+, Ni2+ and Cr3+) in the adducts contributes to drastic changes in the mass spectrum, but only palladium forms alloys in the gas phase. Besides alloy formation, palladium enhances the formation of specific single component clusters such as Au38+. While other metal ions like Cu2+ help forming Au25+ selectively, Fe2+ catalyzes the formation of Au25+ over all other clusters. Gas phase cluster

  16. Rapid enrichment of rare-earth metals by carboxymethyl cellulose-based open-cellular hydrogel adsorbent from HIPEs template.

    PubMed

    Zhu, Yongfeng; Wang, Wenbo; Zheng, Yian; Wang, Feng; Wang, Aiqin

    2016-04-20

    A series of monolithic open-cellular hydrogel adsorbents based on carboxymethylcellulose (CMC) were prepared through high internal phase emulsions (HIPEs) and used to enrich the rare-earth metals La(3+) and Ce(3+). The changes of pore structure, and the effects of pH, contact time, initial concentration on the adsorption performance were systematically studied. The results show that the as-prepared monolithic hydrogel adsorbents possess good open-cellular framework structure and have fast adsorption kinetics and high adsorption capacity for La(3+) and Ce(3+). The involved adsorption system can reach equilibrium within 30min and the maximal adsorption capacity is determined to be 384.62mg/g for La(3+) and 333.33mg/g for Ce(3+). Moreover, these porous hydrogel adsorbents show an excellent adsorptive reusability for La(3+) and Ce(3+) through five adsorption-desorption cycles. Such a pore hierarchy structure makes this monolithic open-cellular hydrogel adsorbent be an effective adsorbent for effective enrichment of La(3+) and Ce(3+) from aqueous solution. PMID:26876827

  17. Metal-organic framework-templated synthesis of magnetic nanoporous carbon as an efficient absorbent for enrichment of phenylurea herbicides.

    PubMed

    Liu, Xingli; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2015-04-22

    Nanoporous carbon with a high specific surface area and unique porous structure represents an attractive material as an adsorbent in analytical chemistry. In this study, a magnetic nanoporous carbon (MNC) was fabricated by direct carbonization of Co-based metal-organic framework in nitrogen atmosphere without using any additional carbon precursors. The MNC was used as an effective magnetic adsorbent for the extraction and enrichment of some phenylurea herbicides (monuron, isoproturon, diuron and buturon) in grape and bitter gourd samples prior to their determination by high performance liquid chromatography with ultraviolet detection. Several important experimental parameters that could influence the extraction efficiency were investigated and optimized. Under the optimum conditions, a good linearity was achieved in the concentration range of 1.0-100.0 ng g(-1) for monuron, diuron and buturon and 1.5-100.0 ng g(-1) for isoproturon with the correlation coefficients (r) larger than 0.9964. The limits of detection (S/N=3) of the method were in the range from 0.17 to 0.46 ng g(-1). The results indicated that the MNC material was stable and efficient adsorbent for the magnetic solid-phase extraction of phenylurea herbicides and would have a great application potential for the extraction and preconcentration of more organic pollutants from real samples. PMID:25819788

  18. Identifying the Atomic-Level Effects of Metal Composition on the Structure and Catalytic Activity of Peptide-Templated Materials.

    PubMed

    Merrill, Nicholas A; McKee, Erik M; Merino, Kyle C; Drummy, Lawrence F; Lee, Sungsik; Reinhart, Benjamin; Ren, Yang; Frenkel, Anatoly I; Naik, Rajesh R; Bedford, Nicholas M; Knecht, Marc R

    2015-12-22

    Bioinspired approaches for the formation of metallic nanomaterials have been extensively employed for a diverse range of applications including diagnostics and catalysis. These materials can often be used under sustainable conditions; however, it is challenging to control the material size, morphology, and composition simultaneously. Here we have employed the R5 peptide, which forms a 3D scaffold to direct the size and linear shape of bimetallic PdAu nanomaterials for catalysis. The materials were prepared at varying Pd:Au ratios to probe optimal compositions to achieve maximal catalytic efficiency. These materials were extensively characterized at the atomic level using transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, and atomic pair distribution function analysis derived from high-energy X-ray diffraction patterns to provide highly resolved structural information. The results confirmed PdAu alloy formation, but also demonstrated that significant surface structural disorder was present. The catalytic activity of the materials was studied for olefin hydrogenation, which demonstrated enhanced reactivity from the bimetallic structures. These results present a pathway to the bioinspired production of multimetallic materials with enhanced properties, which can be assessed via a suite of characterization methods to fully ascertain structure/function relationships. PMID:26497843

  19. Photoinduced Formation of Colloidal Silver in Nitrocellulose Solutions Containing Titanium Alkoxides

    NASA Astrophysics Data System (ADS)

    Kulak, A. I.; Branitsky, G. A.

    2016-07-01

    The study shows the possibility of photo-induced reduction of silver nitrate and formation of stable colloidal silver particles in an isopropanol-N,N-dimethylacetamide solution of titanium alkoxide (polybutyl titanate) stabilized by nitrocellulose. It is established that titanium alkoxide and the products of its partial hydrolysis in the liquid composition play the role of a photocatalyst for the reduction of silver ions; the introduction of nitric or acetic acid additives to the composition significantly increases its photosensitivity. The films deposited from the liquid composition, previously irradiated with visible or UV light, consist of hydrated titanium dioxide and nitrocellulose with incorporated colloidal silver. Thermal treatment of the films at 150-245°C leads to the decomposition of nitrocellulose and an increase in the absorption by silver particles.

  20. Method for extracting metals from aqueous waste streams for long term storage

    DOEpatents

    Chaiko, D.J.

    1993-01-01

    A liquid-liquid extraction method for removing metals and hydrous metal colloids from waste streams is provided wherein said waste streams are contacted with a solvent system containing a water-in-oil microemulsion wherein the inverted micelles contain the extracted metal. A silicon alkoxide, either alone or in combination with other metal alkoxide compounds is added to the water-in-oil microemulsion, thereby allowing encapsulation of the extracted metal within a silicon oxide network. Lastly, the now-encapsulated metal is precipitated from the water-in-oil microemulsion phase to yield aggregates of metal-silicate particles having average. individual particle sizes of approximately 40 manometers.

  1. Method for extracting metals from aqueous waste streams for long term storage

    DOEpatents

    Chaiko, D.J.

    1995-03-07

    A liquid-liquid extraction method for removing metals and hydrous metal colloids from waste streams is provided wherein said waste streams are contacted with a solvent system containing a water-in-oil microemulsion wherein the inverted micelles contain the extracted metal. A silicon alkoxide, either alone or in combination with other metal alkoxide compounds is added to the water-in-oil microemulsion, thereby allowing encapsulation of the extracted metal within a silicon oxide network. Lastly, the now-encapsulated metal is precipitated from the water-in-oil microemulsion phase to yield aggregates of metal-silicate particles having average individual particle sizes of approximately 40 nanometers. 2 figs.

  2. Method for extracting metals from aqueous waste streams for long term storage

    DOEpatents

    Chaiko, David J.

    1995-01-01

    A liquid--liquid extraction method for removing metals and hydrous metal colloids from waste streams is provided wherein said waste streams are contacted with a solvent system containing a water-in-oil microemulsion wherein the inverted micelles contain the extracted metal. A silicon alkoxide, either alone or in combination with other metal alkoxide compounds is added to the water-in-oil microemulsion, thereby allowing encapsulation of the extracted metal within a silicon oxide network. Lastly, the now-encapsulated metal is precipitated from the water-in-oil microemulsion phase to yield aggregates of metal-silicate particles having average individual particle sizes of approximately 40 nanometers.

  3. Synchronously Achieving Plasmonic Bi Metal Deposition and I(-) Doping by Utilizing BiOIO3 as the Self-Sacrificing Template for High-Performance Multifunctional Applications.

    PubMed

    Yu, Shixin; Huang, Hongwei; Dong, Fan; Li, Min; Tian, Na; Zhang, Tierui; Zhang, Yihe

    2015-12-23

    Herein, we uncover simultaneously achieving plasmonic Bi metal deposition and I(-) doping by employing wide-band-gap BiOIO3 as the self-sacrificing template. It was synthesized via a facile NaBH4-assisted in situ reduction route under ambient conditions. The reducing extent as well as photocatalytic levels can be easily modulated by controlling the concentration of NaBH4 solution. It is interesting that the band gap of BiOIO3 can be continuously narrowed by the modification, and the photoresponse range is drastically extended to cover the whole visible region. Bi/I(-) codecorated BiOIO3 not only exhibits profoundly upgraded photoreactivity in comparison with pristine BiOIO3 but also shows universally strong photooxidation properties toward decomposition of multiple industrial contaminants and pharmaceutical, including phenol, 2,4-Dichlorophenol (2,4-DCP), bisphenol A (BPA), dye model Rhodamine (RhB), tetracycline hydrochloride, and gaseous NO under visible light (λ ≥ 420 nm) or simulated solar light irradiation. It also outperforms the well-known and important photocatalysts C3N4, BiOBr, and Bi2WO6 for NO removal. The cooperative effects from Bi SPR and I(-) doping endow BiOIO3 with a narrowed band gap and highly boosted separation of charge carriers, thus responsible for the outstanding catalytic activity. The present study provides an absorbing candidate for practical environmental applications and also furthers our understanding of developing high-performance photocatalysts by manipulating manifold strategies in a facile way. PMID:26605639

  4. Meerwein-Ponndorf-Verley alkynylation of aldehydes: essential modification of aluminium alkoxides for rate acceleration and asymmetric synthesis.

    PubMed

    Ooi, Takashi; Miura, Tomoya; Ohmatsu, Kohsuke; Saito, Akira; Maruoka, Keiji

    2004-11-21

    A novel carbonyl alkynylation has been accomplished based on utilization of the Meerwein-Ponndorf-Verley (MPV) reaction system. The success of the MPV alkynylation crucially depends on the discovery of the remarkable ligand acceleration effect of 2,2'-biphenol. For example, the alkynylation of chloral (2c) with the aluminium alkoxide 6(R = Ph), prepared in situ from Me(3)Al, 2,2'-biphenol and 2-methyl-4-phenyl-3-butyn-2-ol (1a) as an alkynyl source, proceeded smoothly in CH(2)Cl(2) at room temperature to give the desired propargyl alcohol 3ca in almost quantitative yield after 5 h stirring. The characteristic feature of this new transformation involving no metal alkynides can be visualized by the fact that the alkynyl group bearing keto carbonyl was transferred successfully to aldehyde carbonyl without any side reactions on keto carbonyl. Although the use of (S)-1,1[prime or minute]-bi-2-naphthol and its simple analogues was found to be unsuitable for inducing asymmetry in this reaction, design of new chiral biphenols bearing a certain flexibility of the biphenyl axis led to satisfactory results in terms of enantioselectivity as well as reactivity. PMID:15534709

  5. Stereoselective synthesis of biphenolate/binaphtolate titanate and zirconate alkoxide species: structural characterization and use in the controlled ROP of lactide.

    PubMed

    Azor, Laurine; Bailly, Corinne; Brelot, Lydia; Henry, Marc; Mobian, Pierre; Dagorne, Samuel

    2012-10-15

    Well-defined biphenol/binaphtolate group 4 alkoxide salt species [(Ph-Biphen-O)(2)M(O(i)Pr)]Li(THF) (2a, M = Ti; 4a, M = Zr) and [(Ph-binapht-O)(2)M(O(i)Pr)]Li(THF) (2b, M = Ti; 4b, M = Zr) were found to be readily accessible in good yields via alcohol elimination routes and/or substitution reactions from the corresponding pro-ligands Ph-Biphen-OH (1a) and rac-Ph-Binapht-OH (1b). As established via X-ray crystallographic analysis, the molecular structures of the Ti derivatives 2a and 2b consist of Li(+) salts of anionic Ti-O(i)Pr moieties in which the Ti center adopts a distorted tbp geometry and is effectively chelated by two biphenolate/binaphtolate units. Remarkably, the solution and solid state data for salt species 2a,b agree with the sole presence of one diastereomer (with a (Δ, aS, aS)/(Λ, aR, aR) configuration), thus indicating that formation of the Ti and Zr alkoxide complexes 2a,b/4a,b proceeds stereoselectively. In contrast, the neutral biphenolate/binaphtolate Zr complexes (Ph-biphen-O)(2)Zr(THF)(2) (3a) and (Ph-binapht-O)(2)Zr(THF)(2) (3b) were both isolated and X-ray characterized as stereomers in a heterochiral configuration (Δ, aR, aS)/(Λ, aS, aR). The Ti and Zr alkoxide anionic chelates were found to initiate the ROP of rac-lactide in a controlled manner for production of narrowly disperse and ester-end group PLA, as deduced from SEC, kinetic, and MALDI-TOF data. The Zr-O(i)Pr derivatives 4a,b exhibit superior performance to their Ti counterparts (whether regarding activity, polymerization control, or stereoselectivity) to produce narrowly disperse and heterotactically enriched PLA (P(r) = 0.67, PDI < 1.15). The significantly decreased Lewis acidity of the Zr metal center in anions 4a,b (versus neutral analogues) due to the anionic charge and a likely substantial electronic π donation of the four Zr-O(ArO) oxygens to the Zr metal center may rationalize the moderate polymerization activity. Control experiments suggest that the nature of the

  6. Facile Conversion of Hydroxy Double Salts to Metal-Organic Frameworks Using Metal Oxide Particles and Atomic Layer Deposition Thin-Film Templates.

    PubMed

    Zhao, Junjie; Nunn, William T; Lemaire, Paul C; Lin, Yiliang; Dickey, Michael D; Oldham, Christopher J; Walls, Howard J; Peterson, Gregory W; Losego, Mark D; Parsons, Gregory N

    2015-11-01

    Rapid room-temperature synthesis of metal-organic frameworks (MOFs) is highly desired for industrial implementation and commercialization. Here we find that a (Zn,Cu) hydroxy double salt (HDS) intermediate formed in situ from ZnO particles or thin films enables rapid growth (<1 min) of HKUST-1 (Cu3(BTC)2) at room temperature. The space-time-yield reaches >3 × 10(4) kg·m(-3)·d(-1), at least 1 order of magnitude greater than any prior report. The high anion exchange rate of (Zn,Cu) hydroxy nitrate HDS drives the ultrafast MOF formation. Similarly, we obtained Cu-BDC, ZIF-8, and IRMOF-3 structures from HDSs, demonstrating synthetic generality. Using ZnO thin films deposited via atomic layer deposition, MOF patterns are obtained on pre-patterned surfaces, and dense HKUST-1 coatings are grown onto various form factors, including polymer spheres, silicon wafers, and fibers. Breakthrough tests show that the MOF-functionalized fibers have high adsorption capacity for toxic gases. This rapid synthesis route is also promising for new MOF-based composite materials and applications. PMID:26456471

  7. Templating Influence of Molecular Precursors on Pr(OH)3 Nanostructures.

    PubMed

    Hemmer, Eva; Cavelius, Christian; Huch, Volker; Mathur, Sanjay

    2015-07-01

    Four new praseodymium alkoxo and amido compounds ([Pr3(μ3-OtBu)2(μ2-OtBu)3(OtBu)4(HOtBu)2] (1), [Pr{OC(tBu)3}3(THF)] (2), [PrCl{N(SiMe3)2}2(THF)]2 (3), and [PrCl{OC(tBu)3}2(THF)]2 (4)) were synthesized and structurally characterized by single-crystal X-ray diffraction analysis. Application of these compounds in solvothermal synthesis of praseodymium oxide/hydroxide nanostructures showed their templating influence on the morphology and phase composition of the resulting solid-state materials. Differential reactivity of the chosen alkoxide ligands toward water and the different arrangements of metal-oxygen units in the studied precursor compounds strongly influenced the kinetics of hydrolysis and cross-condensation reactions as manifested in the morphological changes and phase composition of the final products. Thermal decomposition studies of 1-4 confirmed their conversion into the corresponding oxide phases. Activation of compounds 1, 2, and 4 by either a base or a stoichiometric amount of water showed the distinct influence of their chemical configuration on the obtained nanopowders: whereas 1 solely produced nanorods of Pr(OH)3, 2 predominantly formed a mixture of rod-shaped and spherical particles. The solvothermal decomposition of 4 resulted in Pr(OH)2Cl or PrOCl due to the presence of Cl ligands in the molecular precursor. The resultant materials were thoroughly characterized to demonstrate the relationship between precursor chemistry and the processing parameters that are clearly manifested in the morphology and phase of the final ceramics. PMID:26068779

  8. A metal-assisted templating route (S(0)M(+)I(-)) for fabricating thin-layer CoO covered on the channel of nanospherical-HMS with improved catalytic properties.

    PubMed

    Yang, Fu; Zhou, Shijian; Wang, Haiqing; Long, Saifu; Liu, Xianfeng; Kong, Yan

    2016-04-12

    Nanospherical hexagonal mesoporous silica (HMS) with a functional mesochannel covered with thin-layer-dispersed cobalt oxide species was directly fabricated via a novel metal-assisted templating method (S(0)M(+)I(-)). In this special method, cobalt ions would be enriched on the surface of the pore wall by physicochemical interactions among the surfactant, cobalt ions and silica. Typically, a metallomicelle template (S(0)M(+)) formed from the coordinative assembly of metal cations (Co(2+), M(+)) with neutral surfactant dodecyl amine (DDA, S(0)) would match with negatively charged silicate oligomers (I(-)) by counter-ion interactions to assemble into the Co-modified HMS nanosphere. The metallization of DDA micelles and the role of cobalt ions in the assembly process can be demonstrated. Interestingly, the addition of amounts of cobalt apparently affects the size of the HMS nanosphere. Additionally, the coverage of CoO species on the mesochannel is increased with cobalt ions coordinated on the micelles. Finally, the functional Co-HMS with dispersed catalytic active phase and improved structure exhibits a special catalytic activity (yield of ca. 65%) for direct oxidation of phenol to p-benzoquinone with the assistance of a sulfate radical stimulated from cobalt in the presence of peroxymonosulfate. PMID:26777344

  9. The template update problem.

    PubMed

    Matthews, Iain; Ishikawa, Takahiro; Baker, Simon

    2004-06-01

    Template tracking dates back to the 1981 Lucas-Kanade algorithm. One question that has received very little attention, however, is how to update the template so that it remains a good model of the tracked object. We propose a template update algorithm that avoids the "drifting" inherent in the naive algorithm. PMID:18579941

  10. Allylic and Allenic Halide Synthesis via NbCl5- and NbBr5-Mediated Alkoxide Rearrangements

    PubMed Central

    Ravikumar, P. C.; Yao, Lihua; Fleming, Fraser F.

    2009-01-01

    Addition of NbCl5, or NbBr5, to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metalla-halo-[3,3] rearrangement although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure E-allylic or allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. PMID:19739606

  11. Allylic and allenic halide synthesis via NbCl(5)- and NbBr(5)-mediated alkoxide rearrangements.

    PubMed

    Ravikumar, P C; Yao, Lihua; Fleming, Fraser F

    2009-10-01

    Addition of NbCl(5) or NbBr(5) to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metalla-halo-[3,3] rearrangement, although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure (E)-allylic or -allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. PMID:19739606

  12. DNA Templating of Au Nanowires

    NASA Astrophysics Data System (ADS)

    Wood, David; Braun, Gary; Inagaki, Katsuhiko

    2005-03-01

    We have developed a process for fabricating nanoscale wires using DNA templates. The templates were subsequently decorated with gold nanoparticles to make metallic wires. We have successfully deposited linear, straight sections of random (λ-phage) and regular-repeat sequences of DNA, of various lengths, on oxidized silicon substrates. We have also successfully deposited thiolated DNA on gold electrodes, allowing the DNA to electrically bridge gaps between electrode pairs. Electrode gaps ranged from 50 nm to 300 nm, fabricated using electron beam lithography. We decorated the DNA with gold nanoparticles with diameters in the range of 1-13 nm, and have used the nanoparticles as nucleation sites for the growth of continuous gold wires. We have performed AFM characterization of all surfaces and structures. In addition, we have performed current-voltage measurements on the undecorated DNA, the nanoparticle-decorated DNA, and the gold nanowires.

  13. Programmable imprint lithography template

    DOEpatents

    Cardinale, Gregory F.; Talin, Albert A.

    2006-10-31

    A template for imprint lithography (IL) that reduces significantly template production costs by allowing the same template to be re-used for several technology generations. The template is composed of an array of spaced-apart moveable and individually addressable rods or plungers. Thus, the template can be configured to provide a desired pattern by programming the array of plungers such that certain of the plungers are in an "up" or actuated configuration. This arrangement of "up" and "down" plungers forms a pattern composed of protruding and recessed features which can then be impressed onto a polymer film coated substrate by applying a pressure to the template impressing the programmed configuration into the polymer film. The pattern impressed into the polymer film will be reproduced on the substrate by subsequent processing.

  14. Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Chen (Inventor)

    1999-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a percursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  15. Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    1999-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate-solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  16. Kinetics and Mechanism of Calcium Hydroxide Conversion into Calcium Alkoxides: Implications in Heritage Conservation Using Nanolimes.

    PubMed

    Rodriguez-Navarro, Carlos; Vettori, Irene; Ruiz-Agudo, Encarnacion

    2016-05-24

    Nanolimes are alcohol dispersions of Ca(OH)2 nanoparticles used in the conservation of cultural heritage. Although it was believed that Ca(OH)2 particles were inert when dispersed in short-chain alcohols, it has been recently shown that they can undergo transformation into calcium alkoxides. Little is known, however, about the mechanism and kinetics of such a phase transformation as well as its effect on the performance of nanolimes. Here we show that Ca(OH)2 particles formed after lime slaking react with ethanol and isopropanol and partially transform (fractional conversion, α up to 0.08) into calcium ethoxide and isopropoxide, respectively. The transformation shows Arrhenius behavior, with apparent activation energy Ea of 29 ± 4 and 37 ± 6 kJ mol(-1) for Ca-ethoxide and Ca-isopropoxide conversion, respectively. High resolution transmission electron microscopy analyses of reactant and product phases show that the alkoxides replace the crystalline structure of Ca(OH)2 along specific [hkl] directions, preserving the external hexagonal (platelike) morphology of the parent phase. Textural and kinetic results reveal that this pseudomorphic replacement involves a 3D diffusion-controlled deceleratory advancement of the reaction front. The results are consistent with an interface-coupled dissolution-precipitation replacement mechanism. Analysis of the carbonation of Ca(OH)2 particles with different degree of conversion into Ca-ethoxide (α up to 0.08) and Ca-isopropoxide (α up to 0.04) exposed to air (20 °C, 80% relative humidity) reveals that Ca-alkoxides significantly reduce the rate of transformation into cementing CaCO3 and induce the formation of metastable vaterite, as opposed to stable calcite which forms in untransformed Ca(OH)2 samples. Similar effects are obtained when a commercial nanolime partially transformed into Ca-ethoxide is subjected to carbonation. Such effects may hamper/delay the strengthening or consolidation effects of nanolimes, thus having

  17. Method for making monolithic metal oxide aerogels

    DOEpatents

    Droege, Michael W.; Coronado, Paul R.; Hair, Lucy M.

    1995-01-01

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels.

  18. Method for making monolithic metal oxide aerogels

    DOEpatents

    Droege, M.W.; Coronado, P.R.; Hair, L.M.

    1995-03-07

    Transparent, monolithic metal oxide aerogels of varying densities are produced using a method in which a metal alkoxide solution and a catalyst solution are prepared separately and reacted. The resulting hydrolyzed-condensed colloidal solution is gelled, and the wet gel is contained within a sealed, but gas permeable, containment vessel during supercritical extraction of the solvent. The present invention is especially advantageous for making metal oxides other than silica that are prone to forming opaque, cracked aerogels. 6 figs.

  19. A silica sol-gel design strategy for nanostructured metallic materials

    NASA Astrophysics Data System (ADS)

    Warren, Scott C.; Perkins, Matthew R.; Adams, Ashley M.; Kamperman, Marleen; Burns, Andrew A.; Arora, Hitesh; Herz, Erik; Suteewong, Teeraporn; Sai, Hiroaki; Li, Zihui; Werner, Jörg; Song, Juho; Werner-Zwanziger, Ulrike; Zwanziger, Josef W.; Grätzel, Michael; Disalvo, Francis J.; Wiesner, Ulrich

    2012-05-01

    Batteries, fuel cells and solar cells, among many other high-current-density devices, could benefit from the precise meso- to macroscopic structure control afforded by the silica sol-gel process. The porous materials made by silica sol-gel chemistry are typically insulators, however, which has restricted their application. Here we present a simple, yet highly versatile silica sol-gel process built around a multifunctional sol-gel precursor that is derived from the following: amino acids, hydroxy acids or peptides; a silicon alkoxide; and a metal acetate. This approach allows a wide range of biological functionalities and metals—including noble metals—to be combined into a library of sol-gel materials with a high degree of control over composition and structure. We demonstrate that the sol-gel process based on these precursors is compatible with block-copolymer self-assembly, colloidal crystal templating and the Stöber process. As a result of the exceptionally high metal content, these materials can be thermally processed to make porous nanocomposites with metallic percolation networks that have an electrical conductivity of over 1,000 S cm-1. This improves the electrical conductivity of porous silica sol-gel nanocomposites by three orders of magnitude over existing approaches, opening applications to high-current-density devices.

  20. Synthesis of Industrially Relevant Carbamates towards Isocyanates using Carbon Dioxide and Organotin(IV) Alkoxides.

    PubMed

    Germain, Nicolas; Müller, Imke; Hanauer, Matthias; Paciello, Rocco A; Baumann, Robert; Trapp, Oliver; Schaub, Thomas

    2016-07-01

    A straightforward phosgene-free synthesis of aromatic isocyanates and diisocyanates is disclosed. Theoretical investigations suggested that the insertion of carbon dioxide (CO2 ) by dialkyltin(IV) dialkoxides could be used to convert aromatic amines into aromatic mono- and dicarbamates. Here we show, that methyl phenylcarbamate (MPC) from aniline using organotin(IV) dimethoxide and CO2 can be formed in high yield of up to 92 %, experimentally corroborating the predictions of density functional theory (DFT) calculations. MPC was then separated from the tin oxide residues and converted into phenyl isocyanate. Furthermore, organotin(IV) alkoxides could be regenerated from the tin oxide residues and reused, paving the way for a continuous industrial process. Extension of the scope to the synthesis of diurethanes from toluene 2,4-diamine and 4,4'-methylenedianiline could potentially allow the efficient production of industrially relevant diisocyanates. PMID:27319978

  1. Role of tetraalkyl(benzyl)ammonium alkoxides in the catalysis of the alkaline dehydrochlorination reaction

    SciTech Connect

    Shavanov, S.S.; Tolstikov, G.A.; Shutenkova, T.V.; Viktorov, G.A.

    1988-01-10

    The reaction was conducted by the action of aqueous NaOH taken as a 50% solution at a molar ratio to dichloroethane of 2:1 at 50-55 C in the 1% of catalyst on the dichloroethane. The results of the experiments indicated the rising activity of the tetra-alkyl(benzyl) ammonium alkoxides as the lipophilicity of the anion increased, which proceeds in the organic phase. Reaction was effected through a complex formed by the association of quaternary ammonium salts with a hydroxyl-containing compound, the solvation of the associated species with the organochlorine substrate, and coordination with NaOH. The reaction goes in the organic phase and on the interphase surface.

  2. Templates, Numbers & Watercolors.

    ERIC Educational Resources Information Center

    Clemesha, David J.

    1990-01-01

    Describes how a second-grade class used large templates to draw and paint five-digit numbers. The lesson integrated artistic knowledge and vocabulary with their mathematics lesson in place value. Students learned how draftspeople use templates, and they studied number paintings by Charles Demuth and Jasper Johns. (KM)

  3. Templates for Deposition of Microscopic Pointed Structures

    NASA Technical Reports Server (NTRS)

    Pugel, Diane E.

    2008-01-01

    Templates for fabricating sharply pointed microscopic peaks arranged in nearly regular planar arrays can be fabricated by a relatively inexpensive technique that has recently been demonstrated. Depending on the intended application, a semiconducting, insulating, or metallic film could be deposited on such a template by sputtering, thermal evaporation, pulsed laser deposition, or any other suitable conventional deposition technique. Pointed structures fabricated by use of these techniques may prove useful as photocathodes or field emitters in plasma television screens. Selected peaks could be removed from such structures and used individually as scanning tips in atomic force microscopy or mechanical surface profiling.

  4. STAR Grantee 101 template

    EPA Science Inventory

    The presentation covers the standard Terms and Conditions, from reporting, to Human Subject research, to publication disclaimers, and offers some resources to find helpful information. Some slides are intended as a template, where project officers can enter specific information (...

  5. Plug and drill template

    NASA Technical Reports Server (NTRS)

    Orella, S.

    1979-01-01

    Device installs plugs and then drills them after sandwich face sheets are in place. Template guides drill bit into center of each concealed plug thereby saving considerable time and fostering weight reduction with usage of smaller plugs.

  6. LiOOt-Bu as a terminal oxidant in a titanium alkoxide-mediated [2+2+2] reaction cascade☆

    PubMed Central

    Kim, Wan Shin; Aquino, Claudio; Mizoguchi, Haruki; Micalizio, Glenn C.

    2015-01-01

    LiOOt-Bu is an effective oxidant for converting the penultimate organometallic intermediate generated in a titanium alkoxide-mediated [2+2+2] reaction cascade to an allylic alcohol. Oxidation of the presumed allylic titanium species is highly regioselective, providing direct access to substituted hydroindanes containing a primary allylic alcohol. In addition to demonstrating the feasibility of this oxidation process, we document the ability to convert the primary allylic alcohol products to angularly substituted cis-fused hydroindanes. PMID:26097265

  7. Ice-templated synthesis of multifunctional three dimensional graphene/noble metal nanocomposites and their mechanical, electrical, catalytic, and electromagnetic shielding properties.

    PubMed

    Sahoo, P K; Aepuru, Radhamanohar; Panda, Himanshu Sekhar; Bahadur, D

    2015-01-01

    In-situ homogeneous dispersion of noble metals in three-dimensional graphene sheets is a key tactic for producing macroscopic architecture, which is desirable for practical applications, such as electromagnetic interference shielding and catalyst. We report a one-step greener approach for developing porous architecture of 3D-graphene/noble metal (Pt and Ag) nanocomposite monoliths. The resulting graphene/noble metal nanocomposites exhibit a combination of ultralow density, excellent elasticity, and good electrical conductivity. Moreover, in order to illuminate the advantages of the 3D-graphene/noble metal nanocomposites, their electromagnetic interference (EMI) shielding and electrocatalytic performance are further investigated. The as-synthesized 3D-graphene/noble metal nanocomposites exhibit excellent EMI shielding effectiveness when compared to bare graphene; the effectiveness has an average of 28 dB in the 8.2-12.4 GHz X-band range. In the electro-oxidation of methanol, the 3D-graphene/Pt nanocomposite also exhibits significantly enhanced electrocatalytic performance and stability than compared to reduced graphene oxide/Pt and commercial Pt/C. PMID:26638827

  8. Ice-templated synthesis of multifunctional three dimensional graphene/noble metal nanocomposites and their mechanical, electrical, catalytic, and electromagnetic shielding properties

    NASA Astrophysics Data System (ADS)

    Sahoo, P. K.; Aepuru, Radhamanohar; Panda, Himanshu Sekhar; Bahadur, D.

    2015-12-01

    In-situ homogeneous dispersion of noble metals in three-dimensional graphene sheets is a key tactic for producing macroscopic architecture, which is desirable for practical applications, such as electromagnetic interference shielding and catalyst. We report a one-step greener approach for developing porous architecture of 3D-graphene/noble metal (Pt and Ag) nanocomposite monoliths. The resulting graphene/noble metal nanocomposites exhibit a combination of ultralow density, excellent elasticity, and good electrical conductivity. Moreover, in order to illuminate the advantages of the 3D-graphene/noble metal nanocomposites, their electromagnetic interference (EMI) shielding and electrocatalytic performance are further investigated. The as-synthesized 3D-graphene/noble metal nanocomposites exhibit excellent EMI shielding effectiveness when compared to bare graphene; the effectiveness has an average of 28 dB in the 8.2-12.4 GHz X-band range. In the electro-oxidation of methanol, the 3D-graphene/Pt nanocomposite also exhibits significantly enhanced electrocatalytic performance and stability than compared to reduced graphene oxide/Pt and commercial Pt/C.

  9. Ice-templated synthesis of multifunctional three dimensional graphene/noble metal nanocomposites and their mechanical, electrical, catalytic, and electromagnetic shielding properties

    PubMed Central

    Sahoo, P. K.; Aepuru, Radhamanohar; Panda, Himanshu Sekhar; Bahadur, D.

    2015-01-01

    In-situ homogeneous dispersion of noble metals in three-dimensional graphene sheets is a key tactic for producing macroscopic architecture, which is desirable for practical applications, such as electromagnetic interference shielding and catalyst. We report a one-step greener approach for developing porous architecture of 3D-graphene/noble metal (Pt and Ag) nanocomposite monoliths. The resulting graphene/noble metal nanocomposites exhibit a combination of ultralow density, excellent elasticity, and good electrical conductivity. Moreover, in order to illuminate the advantages of the 3D-graphene/noble metal nanocomposites, their electromagnetic interference (EMI) shielding and electrocatalytic performance are further investigated. The as-synthesized 3D-graphene/noble metal nanocomposites exhibit excellent EMI shielding effectiveness when compared to bare graphene; the effectiveness has an average of 28 dB in the 8.2–12.4 GHz X-band range. In the electro-oxidation of methanol, the 3D-graphene/Pt nanocomposite also exhibits significantly enhanced electrocatalytic performance and stability than compared to reduced graphene oxide/Pt and commercial Pt/C. PMID:26638827

  10. Geometries, thermodynamic properties and reactions of methylzinc alkoxide clusters studied by density functional theory calculations.

    PubMed

    Steudel, Ralf; Steudel, Yana

    2006-07-20

    Methylzinc alkoxide complexes are precursors for the preparation of nanosized zinc oxide particles, which in turn are catalysts or reagents in important industrial processes such as methanol synthesis and rubber vulcanization. We report for the first time the structures, energies, atomic charges, dipole moments, and vibrational spectra of more than 20 species of the type [(MeZnOR')n] with R' = H, Me, tBu and n = 1-6, calculated by density functional theory methods, mostly at the B3LYP/6-31+G* level of theory. For R' = Me, the global minimum structure of the tetramer (n = 4) is a highly symmetrical heterocubane but a ladder-type isomer is by only 70.9 kJ mol(-1) less stable. The corresponding trimer is most stable as a rooflike structure; a planar six-membered ring of relative energy 13.5 kJ mol(-1) corresponds to a saddle point connecting two equivalent rooflike trimer structures. All dimers form planar four-membered Zn2O2 rings whereas the monomer has a planar CZnOC backbone. A hexameric drumlike structure represents the global minimum on the potential energy hypersurface of [(MeZnOMe)6]. The enthalpies and Gibbs energies of the related dissociation reactions hexamer --> tetramer --> trimer --> dimer --> monomer as well as of a number of isomerization reactions have been calculated. The complexes [(MeZnOMe)n] (n = 1-3) form adducts with Lewis bases such as tetrahydrofuran (thf) and pyridine (py). The binding energy of py to the zinc atoms is about 65% larger than that of thf but is not large enough to break up the larger clusters. The bimolecular disproportionation of [(MeZnOMe)4] with formation of the dicubane [Zn{(MeZn)3(OMe)4}2] and Me2Zn is less endothermic than any isomerization or dissociation reaction of the heterocubane, but for steric reasons this reaction is not possible if R' = tBu. A novel reaction mechanism for the reported interconversion, disproportionation and ligand exchange reactions of zinc alkoxide complexes is proposed. PMID:16836455

  11. Molecular Level Coating of Metal Oxide Particles

    NASA Technical Reports Server (NTRS)

    McDaniel, Patricia R. (Inventor); St.Clair, Terry L. (Inventor)

    2002-01-01

    Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar osmotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing, synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper. making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

  12. Molecular Level Coating for Metal Oxide Particles

    NASA Technical Reports Server (NTRS)

    McDaniel, Patricia R. (Inventor); Saint Clair, Terry L. (Inventor)

    2000-01-01

    Polymer encapsulated metal oxide particles are prepared by combining a polyamide acid in a polar aprotic solvent with a metal alkoxide solution. The polymer was imidized and the metal oxide formed simultaneously in a refluxing organic solvent. The resulting polymer-metal oxide is an intimately mixed commingled blend, possessing synergistic properties of both the polymer and preceramic metal oxide. The encapsulated metal oxide particles have multiple uses including, being useful in the production of skin lubricating creams, weather resistant paints, as a filler for paper, making ultraviolet light stable filled printing ink, being extruded into fibers or ribbons, and coatings for fibers used in the production of composite structural panels.

  13. Electrochemical synthesis, structural characterization, and decomposition of rhenium oxoethoxide, Re4O4(OEt)12. Ligand influence on the structure and bonding in the high-valent tetranuclear planar rhenium alkoxide clusters.

    PubMed

    Nikonova, Olesya A; Jansson, Kjell; Kessler, Vadim G; Sundberg, Margareta; Baranov, Alexei I; Shevelkov, Andrei V; Drobot, Dmitrii V; Seisenbaeva, Gulaim A

    2008-02-18

    Anodic oxidation of rhenium in ethanol in the presence of LiCl as a conductive additive results with high yield in formation of a new oxoethoxide cluster, Re(4)O(4)(OEt)(12). The structure of the planar centrosymmetric metal-oxygen core of this molecule is composed of four edge-sharing Re(V)O(6) octahedra. Eight electrons are available for the formation of metal-metal bonds indicated by five relatively short Re-Re distances within the Re 4-rhombus, a "planar butterfly" type cluster. The theoretical calculations are indicating relatively low contribution of metal-metal bonding in the stability of the core. The stability of the +V-oxidation state, unusual for rhenium alkoxides can be at least partially attributed to the size effects in the packing of ligands. The X-ray powder study indicates that treatment of Re(4)O(4)(OEt)(12). in ambient atmosphere rapidly transforms it into a mixed-valence derivative Re(4)O(6)(OEt)(10) with a structure related to the earlier investigated cluster Re(4)O(6)(O(i)Pr)(10). Thermal decomposition of the latter rhenium oxoethoxide results in reduction to rhenium metal at as low temperatures as 380 degrees C, producing aggregates of metal nanoparticles with the average size of 3 nm. PMID:18220343

  14. Metal-Organic Framework Templated Synthesis of Copper Azide as the Primary Explosive with Low Electrostatic Sensitivity and Excellent Initiation Ability.

    PubMed

    Wang, Qianyou; Feng, Xiao; Wang, Shan; Song, Naimeng; Chen, Yifa; Tong, Wenchao; Han, Yuzhen; Yang, Li; Wang, Bo

    2016-07-01

    A powerful yet safe primary explosive, embedded in a conductive carbon scaffold, is prepared by using a metal-organic framework as precursor. It simultaneously possesses low electrostatic sensitivity, good flame sensitivity, and excellent initiation ability. This method is simple, scalable, and provides a new platform for the development of energetic materials especially those employed in miniaturized explosive systems. PMID:27159056

  15. Metal-organic framework templated synthesis of Co3O4 nanoparticles for direct glucose and H2O2 detection.

    PubMed

    Hou, Chuantao; Xu, Qin; Yin, Lina; Hu, Xiaoya

    2012-12-21

    Co(3)O(4) nanoparticles (NPs) with an average diameter of about 20 nm were synthesized by using MOFs as a template. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize the as-prepared Co(3)O(4) NPs. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were used to confirm the structure of the Co(3)O(4) NPs. Then the Co(3)O(4) NPs were modified on a glassy carbon electrode (GCE) to obtain a non-enzymatic glucose and H(2)O(2) sensor. The NPs show electrocatalytic activity toward oxidation of glucose and H(2)O(2) in alkaline medium. For glucose detection, the developed sensor shows a short response time (less than 6 s), a high sensitivity of 520.7 μA mM(-1) cm(-2), a detection limit of 0.13 μM (S/N = 3), and good selectivity. The high concentration of NaCl does not poison the electrode. Its application for the detection of glucose in a human blood serum sample shows good agreement with the results obtained from the hospital. Furthermore, the proposed sensor was used for the detection of H(2)O(2). The results indicate that the detection limit and sensitivity for H(2)O(2) are 0.81 μM and 107.4 μA mM(-1) cm(-2), respectively. Determination of H(2)O(2) concentration in a disinfectant sample by the proposed biosensor also showed satisfactory result. The high sensitivity and low detection limit can be attributed to the excellent electrocatalytic performance of the as-prepared Co(3)O(4) NPs. These results demonstrate that the as-prepared Co(3)O(4) NPs have great potential applications in the development of sensors for enzyme-free detection of glucose and H(2)O(2). PMID:23095860

  16. Three-Dimensional Macroporous Polypyrrole-Derived Graphene Electrode Prepared by the Hydrogen Bubble Dynamic Template for Supercapacitors and Metal-Free Catalysts.

    PubMed

    Yang, Xiaoqing; Liu, Anran; Zhao, Yuewu; Lu, Huijia; Zhang, Yuanjian; Wei, Wei; Li, Ying; Liu, Songqin

    2015-10-28

    We report a general method for the fabrication of three-dimensional (3D) macroporous graphene/conducting polymer modified electrode and nitrogen-doped graphene modified electrode. This method involves three consecutive steps. First, the 3D macroporous graphene (3D MG) electrode was fabricated electrochemically by reducing graphene oxide dispersion on different conducting substrates and used hydrogen bubbles as the dynamic template. The morphology and pore size of 3D MG could be governed by the use of surfactants and the dynamics of bubble generation and departure. Second, 3D macroporous graphene/polypyrrole (MGPPy) composites were constructed via directly electropolymerizing pyrrole monomer onto the networks of 3D MG. Due to the benefit of the good conductivity of 3D MG and pseudocapacitance of PPy, the composites manifest outstanding area specific capacitance of 196 mF cm(-2) at a current density of 1 mA cm(-2). The symmetric supercapacitor device assembled by the composite materials had a good capacity property. Finally, the nitrogen-doped MGPPy (N-MGPPy or MGPPy-X) with 3D macroporous nanostructure and well-regulated nitrogen doping was prepared via thermal treatment of the composites. The resultant N-MGPPy electrode was explored as a good electrocatalyst for the oxygen reduction reaction (ORR) with the current density value of 5.56 mA cm(-2) (-0.132 V vs Ag/AgCl). Moreover, the fuel tolerance and durability under the electrochemical environment of the N-MGPPy catalyst were found to be superior to the Pt/C catalyst. PMID:26457969

  17. Synthesis and thermal evolution of structure in alkoxide-derived niobium pentoxide gels

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.

    1993-01-01

    Niobium pentoxide gels in the form of transparent monoliths and powder have been synthesized from the controlled hydrolysis and polycondensation of niobium pentaethoxide under different experimental conditions using various mole ratios of Nb(OC2H5)5:H2O:C2H5OH:HCl. Alcohol acted as the mutual solvent and HCl as the deflocculating agent. In the absence of HCl, precipitation of colloidal particles was encountered on the addition of any water to the alkoxide. The gels were subjected to various thermal treatments and characterized by differential thermal analysis, thermogravimetric analysis, x-ray diffraction, and infrared spectroscopy. After drying at 400 C, the gels were amorphous to x-rays. The amorphous powder crystallized into the low-temperature orthorhombic form of Nb2O5 at approximately 500 C, which transformed irreversibly into the high-temperature monoclinic alpha-Nb2O5 between 900 to 1000 C. The kinetics of crystallization of the amorphous niobium pentoxide have been investigated by non-isothermal differential scanning calorimetry. The crystallization activation energy was determined to be 399 kJ/mol.

  18. Templated blue phases.

    PubMed

    Ravnik, Miha; Fukuda, Jun-ichi

    2015-11-21

    Cholesteric blue phases of a chiral liquid crystal are interesting examples of self-organised three-dimensional nanostructures formed by soft matter. Recently it was demonstrated that a polymer matrix introduced by photopolymerization inside a bulk blue phase not only stabilises the host blue phase significantly, but also serves as a template for blue phase ordering. We show with numerical modelling that the transfer of the orientational order of the blue phase to the surfaces of the polymer matrix, together with the resulting surface anchoring, can account for the templating behaviour of the polymer matrix inducing the blue phase ordering of an achiral nematic liquid crystal. Furthermore, tailoring the anchoring conditions of the polymer matrix surfaces can bring about orientational ordering different from those of bulk blue phases, including an intertwined complex of the polymer matrix and topological line defects of orientational order. Optical Kerr response of templated blue phases is explored, finding large Kerr constants in the range of K = 2-10 × 10(-9) m V(-2) and notable dependence on the surface anchoring strength. More generally, the presented numerical approach is aimed to clarify the role and actions of templating polymer matrices in complex chiral nematic fluids, and further to help design novel template-based materials from chiral liquid crystals. PMID:26412643

  19. Double Emulsion Templated Celloidosomes

    NASA Astrophysics Data System (ADS)

    Arriaga, Laura R.; Marquez, Samantha M.; Kim, Shin-Hyun; Chang, Connie; Wilking, Jim; Monroy, Francisco; Marquez, Manuel; Weitz, David A.

    2012-02-01

    We present a novel approach for fabricating celloidosomes, which represent a hollow and spherical three-dimensional self-assembly of living cells encapsulating an aqueous core. Glass- capillary microfluidics is used to generate monodisperse water-in-oil-in-water double emulsion templates using lipids as stabilizers. Such templates allow for obtaining single but also double concentric celloidosomes. In addition, after a solvent removal step the double emulsion templates turn into monodisperse lipid vesicles, whose membrane spontaneously phase separates when choosing the adequate lipid composition, providing the adequate scaffold for fabricating Janus-celloidosomes. These structures may find applications in the development of bioreactors in which the synergistic effects of two different types of cells selectively adsorbed on one of the vesicle hemispheres may be exploited.

  20. Dual-template synthesis of N-doped macro/mesoporous carbon with an open-pore structure as a metal-free catalyst for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Li, Longjun; Wang, Chih-Liang; Liao, Jin-Yun; Manthiram, Arumugam

    2015-12-01

    Dye-sensitized solar cells (DSSCs) have attracted world-wide attention due to their low cost, high conversion efficiency, and environmental friendliness. Pt catalyst is usually used as the catalyst in the counter electrode of DSSCs due to its high electrochemical catalytic activity toward tri-iodide reduction. However, the high cost and scarcity of Pt prevent its large-scale application in DSSCs. It is highly desirable to replace Pt with low-cost catalysts made from earth-abundant elements. Here, we report a dual-template synthesis of N-doped macro/mesoporous carbon (macro/meso-NC) with an open-pore structure as the catalyst in the counter electrode of DSSCs. The catalytic activity of macro/meso-NC toward tri-iodide reduction has been tested by cyclic voltammetry (CV) and photocurrent-voltage (J-V) curves. It is found that the macro/meso-NC possesses excellent electrochemical catalytic activity with higher open-circuit voltage and cell efficiency than Pt. A high energy conversion efficiency of 7.27% has been achieved based on the metal-free macro/meso-NC, demonstrating as a promising catalyst for low-cost DSSCs.

  1. Large Area Nano-transfer Printing of Sub-50-nm Metal Nanostructures Using Low-cost Semi-flexible Hybrid Templates.

    PubMed

    Nagel, Robin D; Haeberle, Tobias; Schmidt, Morten; Lugli, Paolo; Scarpa, Giuseppe

    2016-12-01

    In this work, we present a method for printing metal micro- and nanopatterns down to sub-50-nm feature sizes using replicated, defect-tolerant stamps made out of OrmoStamp®; material. The relevant parameters for a successful transfer over large areas were investigated and yields above 99 % have been achieved. Comparing our results to conventional nano-transfer printing using PDMS stamps, we find that the more rigid hybrid polymer used here prevents unintended transfer from interspaces between structures of large distance due to roof collapse and deformation of nano-sized structures due to lateral collapse. Yet, our stamps are flexible enough to ensure intimate contact with the underlying substrate over large areas even in the presence of defect particles. Additionally, the presented patterning technique is resist-, solvent-, and chemical-free and is therefore ideally suited for applications in organic nanoelectronics where standard nanostructuring methods can harm or destroy the organic material. PMID:26976429

  2. Large Area Nano-transfer Printing of Sub-50-nm Metal Nanostructures Using Low-cost Semi-flexible Hybrid Templates

    NASA Astrophysics Data System (ADS)

    Nagel, Robin D.; Haeberle, Tobias; Schmidt, Morten; Lugli, Paolo; Scarpa, Giuseppe

    2016-03-01

    In this work, we present a method for printing metal micro- and nanopatterns down to sub-50-nm feature sizes using replicated, defect-tolerant stamps made out of OrmoStamp®; material. The relevant parameters for a successful transfer over large areas were investigated and yields above 99 % have been achieved. Comparing our results to conventional nano-transfer printing using PDMS stamps, we find that the more rigid hybrid polymer used here prevents unintended transfer from interspaces between structures of large distance due to roof collapse and deformation of nano-sized structures due to lateral collapse. Yet, our stamps are flexible enough to ensure intimate contact with the underlying substrate over large areas even in the presence of defect particles. Additionally, the presented patterning technique is resist-, solvent-, and chemical-free and is therefore ideally suited for applications in organic nanoelectronics where standard nanostructuring methods can harm or destroy the organic material.

  3. Macrocyclic Dizinc(II) Alkyl and Alkoxide Complexes: Reversible CO2 Uptake and Polymerization Catalysis Testing.

    PubMed

    Romain, Charles; Bennington, Michael S; White, Andrew J P; Williams, Charlotte K; Brooker, Sally

    2015-12-21

    The synthesis of three new dizinc(II) complexes bearing a macrocyclic [2 + 2] Schiff base ligand is reported. The bis(anilido)tetraimine macrocycle reacts with diethylzinc to form a bis(ethyl)dizinc(II) complex, [L(Et)Zn2Et2] (1). The reaction of complex 1 with isopropyl alcohol is reported, forming a bis(isopropyl alkoxide)dizinc complex, [L(Et)Zn2((i)PrO)2] (2). Furthermore, complex 1, with 2 equiv of alcohol, is applied as an initiator for racemic lactide ring-opening polymerization. It shows moderately high activity, resulting in a pseudo-first-order rate coefficient of 9.8 × 10(-3) min(-1), with [LA] = 1 M and [initiator] = 5 mM at 25 °C and in a tetrahydrofuran solvent. Polymerization occurs with good control, as evidenced by the linear fit to a plot of molecular weight versus conversion, the narrow dispersities, and the limited transesterification. The same initiating system is inactive for the ring-opening copolymerization of carbon dioxide (CO2) and cyclohexene oxide at 80 °C and 1 bar of CO2 pressure. However, stoichiometric reactions between complex 2 and CO2, at 1 bar pressure, result in the reversible formation of new dizinc carbonate species, [L(Et)Zn2((i)PrO)((i)PrOCO2)] (3a) and [L(Et)Zn2((i)PrOCO2)2] (3b), and the reaction was studied using density functional theory calculations. All of the new complexes, 1-3b, are fully characterized, including NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. PMID:26624788

  4. Synthesis of High Surface Area Alumina Aerogels without the Use of Alkoxide Precursors

    SciTech Connect

    Baumann, T F; Gash, A E; Chinn, S C; Sawvel, A M; Maxwell, R S; Satcher Jr., J H

    2004-06-25

    Alumina aerogels were prepared through the addition of propylene oxide to aqueous or ethanolic solutions of hydrated aluminum salts, AlCl{sub 3} {center_dot} 6H{sub 2}O or Al(NO{sub 3}){sub 3} {center_dot} 9H{sub 2}O, followed by drying with supercritical CO{sub 2}. This technique affords low-density (60-130 kg/m{sup 3}), high surface area (600-700 m{sup 2}/g) alumina aerogel monoliths without the use of alkoxide precursors. The dried alumina aerogels were characterized using elemental analysis, high-resolution transmission electron microscopy, powder X-ray diffraction, solid state NMR, acoustic measurements and nitrogen adsorption/desorption analysis. Powder X-ray diffraction and TEM analysis indicated that the aerogel prepared from hydrated AlCl{sub 3} in water or ethanol possessed microstructures containing highly reticulated networks of pseudoboehmite fibers, 2-5 nm in diameter and of varying lengths, while the aerogels prepared from hydrated Al(NO{sub 3}){sub 3} in ethanol were amorphous with microstructures comprised of interconnected spherical particles with diameters in the 5-15 nm range. The difference in microstructure resulted in each type of aerogel displaying distinct physical and mechanical properties. In particular, the alumina aerogels with the weblike microstructure were far more mechanically robust than those with the colloidal network, based on acoustic measurements. Both types of alumina aerogels can be transformed to {gamma}-Al{sub 2}O{sub 3} through calcination at 800 C without a significant loss in surface area or monolithicity.

  5. Heterometallic alkoxides of zirconium with tin(II) or lead(II)

    SciTech Connect

    Teff, D.J.; Huffman, J.C.; Caulton, K.G.

    1996-05-08

    Syntheses of SnZr(OR){sub 6} (R = {sup i}Pr, {sup t}Bu) and PbZr(O{sup t}Bu){sub 6} are described. With Pb and the smaller ligand O{sup i}Pr, no 1:1 compound forms, but instead Pb{sub 4}Zr{sub 2}(O{sup i}Pr){sub 16} and Pb{sub 2}Zr{sub 4}(O{sup i}Pr){sub 20} are isolated. The latter two compounds are shown to have serpentine (not closo) structures with six-coordinate Zr and three- and four-coordinate Pb. Spectroscopic studies show fluxionality (including Pb site exchange) and retention of structure in aromatic solvents. Synthetic interconversions are effected with addition of the appropriate alkoxide (Pb(O{sup i}Pr){sub 2} or Zr(O{sup i}Pr){sub 4}) with the correct stoichiometry. Titanium forms no analogous compounds. Crystallographic data (both P2{sub 1}/c at {minus}174{degrees}C) for Pb{sub 4}Zr{sub 2}(O{sup i}Pr){sub 16}, a = 12.190(6) {angstrom}, b = 14.701(7) {angstrom}, c = 19.978(13) {angstrom}, and {beta} = 105.57(3){degrees} with Z = 2; for Pb{sub 2}Zr{sub 4}(O{sup i}Pr){sub 20}, {alpha} = 16.996(6) {angstrom}, b = 10.014(3) {angstrom}, c = 24.924(9) {angstrom}, and {beta} = 105.86(1){degrees} with Z = 2.

  6. Biometric template revocation

    NASA Astrophysics Data System (ADS)

    Arndt, Craig M.

    2004-08-01

    Biometric are a powerful technology for identifying humans both locally and at a distance. In order to perform identification or verification biometric systems capture an image of some biometric of a user or subject. The image is then converted mathematical to representation of the person call a template. Since we know that every human in the world is different each human will have different biometric images (different fingerprints, or faces, etc.). This is what makes biometrics useful for identification. However unlike a credit card number or a password to can be given to a person and later revoked if it is compromised and biometric is with the person for life. The problem then is to develop biometric templates witch can be easily revoked and reissued which are also unique to the user and can be easily used for identification and verification. In this paper we develop and present a method to generate a set of templates which are fully unique to the individual and also revocable. By using bases set compression algorithms in an n-dimensional orthogonal space we can represent a give biometric image in an infinite number of equally valued and unique ways. The verification and biometric matching system would be presented with a given template and revocation code. The code will then representing where in the sequence of n-dimensional vectors to start the recognition.

  7. Subsea well template levelling system

    SciTech Connect

    Regan, M.; Matsuda, E.S.

    1987-06-23

    A template levelling system is described for levelling a template on piles implanted in the floor of a body of water. The template has receptacles, comprising in combination: a pile receptacle carried in each template receptacle on a gimbal, the pile receptacle having a lower flange extending outwardly from and below the template receptacle; slip means located within each of the pile receptacles for gripping one of the piles to prevent downward movement of the template with respect to the piles; and hydraulic jack means for gripping the pile receptacle and pulling it and the slip means upwardly, causing the flange to contact the lower side of the template receptacle to lift the template to a level position.

  8. Cyclodextrin-Templated Porphyrin Nanorings**

    PubMed Central

    Liu, Pengpeng; Neuhaus, Patrik; Kondratuk, Dmitry V; Balaban, T Silviu; Anderson, Harry L

    2014-01-01

    α- and β-Cyclodextrins have been used as scaffolds for the synthesis of six- and seven-legged templates by functionalizing every primary CH2OH with a 4-pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α-cyclodextrin-based template within the six-porphyrin nanoring (74 m) is almost as high as for the previously studied rigid hexadentate template (180 m). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template-directed synthesis of larger macrocycles. PMID:24916813

  9. Cyclodextrin-templated porphyrin nanorings.

    PubMed

    Liu, Pengpeng; Neuhaus, Patrik; Kondratuk, Dmitry V; Balaban, T Silviu; Anderson, Harry L

    2014-07-21

    α- and β-cyclodextrins have been used as scaffolds for the synthesis of six- and seven-legged templates by functionalizing every primary CH2OH with a 4-pyridyl moiety. Although these templates are flexible, they are very effective for directing the synthesis of macrocyclic porphyrin oligomers consisting of six or seven porphyrin units. The transfer of chirality from the cyclodextrin templates to their nanoring hosts is evident from NMR and circular dichroism spectroscopy. Surprisingly, the mean effective molarity for binding the flexible α-cyclodextrin-based template within the six-porphyrin nanoring (74 M) is almost as high as for the previously studied rigid hexadentate template (180 M). The discovery that flexible templates are effective in this system, and the availability of a template with a prime number of binding sites, open up many possibilities for the template-directed synthesis of larger macrocycles. PMID:24916813

  10. Synthesis, Radical Reactivity, and Thermochemistry of Monomeric Cu(II) Alkoxide Complexes Relevant to Cu/Radical Alcohol Oxidation Catalysis.

    PubMed

    Porter, Thomas R; Capitao, Dany; Kaminsky, Werner; Qian, Zhaoshen; Mayer, James M

    2016-06-01

    Two new monomeric Cu(II) alkoxide complexes were prepared and fully characterized as models for intermediates in copper/radical mediated alcohol oxidation catalysis: Tp(tBuR)Cu(II)OCH2CF3 with Tp(tBu) = hydro-tris(3-tert-butyl-pyrazol-1-yl)borate 1 or Tp(tBuMe) = hydro-tris(3-tert-butyl-5-methyl-pyrazol-1-yl)borate 2. These complexes were made as models for potential intermediates in enzymatic and synthetic catalytic cycles for alcohol oxidation. However, the alkoxide ligands are not readily oxidized by loss of H; instead, these complexes were found to be hydrogen atom acceptors. They oxidize the hydroxylamine TEMPOH, 2,4,6-tri-t-butylphenol, and 1,4-cyclohexadiene to the nitroxyl radical, phenoxyl radical, and benzene, with formation of HOCH2CF3 (TFE) and the Cu(I) complexes Tp(tBuR)Cu(I)-MeCN in dichloromethane/1% MeCN or 1/2 [Tp(tBuR)Cu(I)]2 in toluene. On the basis of thermodynamics and kinetics arguments, these reactions likely proceed through concerted proton-electron transfer mechanisms. Thermochemical analyses give lower limits for the "effective bond dissociation free energies (BDFE)" of the O-H bonds in 1/2[Tp(tBuR)Cu(I)]2 + TFE and upper limits for the free energies associated with alkoxide oxidations via hydrogen atom transfer (effective alkoxide α-C-H BDFEs). These values are summations of the free energies of multiple chemical steps, which include the energetically favorable formation of 1/2[Tp(tBuR)Cu(I)]2. The effective alkoxide α-C-H bonds are very weak, BDFE ≤ 38 ± 4 kcal mol(-1) for 1 and ≤44 ± 5 kcal mol(-1) for 2 (gas-phase estimates), because C-H homolysis is thermodynamically coupled to one electron transfer to Cu(II) as well as the favorable formation of the 1/2[Tp(tBuR)Cu(I)]2 dimer. Treating 1 with the H atom acceptor (t)Bu3ArO(•) did not result in the expected alkoxide oxidation to an aldehyde, but rather net 2,2,2-trifluoroethoxyl radical transfer occurred to generate an unusual 2-substituted dienone-ether product. Treating 2