Morphology Control for Fully Printable Organic-Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer.

PubMed

Kato, Takehito; Oinuma, Chihiro; Otsuka, Munechika; Hagiwara, Naoki

2017-01-10

The photoactive layer of a typical organic thin-film bulk-heterojunction (BHJ) solar cell commonly uses fullerene derivatives as the electron-accepting material. However, fullerene derivatives are air-sensitive; therefore, air-stable material is needed as an alternative. In the present study, we propose and describe the properties of Ti-alkoxide as an alternative electron-accepting material to fullerene derivatives to create highly air-stable BHJ solar cells. It is well-known that controlling the morphology in the photoactive layer, which is constructed with fullerene derivatives as the electron acceptor, is important for obtaining a high overall efficiency through the solvent method. The conventional solvent method is useful for high-solubility materials, such as fullerene derivatives. However, for Ti-alkoxides, the conventional solvent method is insufficient, because they only dissolve in specific solvents. Here, we demonstrate a new approach to morphology control that uses the molecular bulkiness of Ti-alkoxides without the conventional solvent method. That is, this method is one approach to obtain highly efficient, air-stable, organic-inorganic bulk-heterojunction solar cells.

Mass spectrometry in the characterization of reactive metal alkoxides.

PubMed

Peruzzo, Valentina; Chiurato, Matteo Andrea; Favaro, Monica; Tomasin, Patrizia

2018-01-01

Metal alkoxides are metal-organic compounds characterized by the presence of MOC bonds (M = metal). Their chemistry seems to be, in principle, relatively simple but the number of possible reactant species arising as a consequence of their behavior is very remarkable. The physico-chemical properties of metal alkoxides are determined by many different parameters, the most important ones being the electronegativity of the metal, the ramification of the ligand, and the acidity of the corresponding alcohol. Their reactivity makes them suitable and versatile candidates for many applications, including homogeneous catalysis, synthesis of new ceramic materials through the sol-gel process and, recently, also for Cultural Heritage. Metal alkoxides are characterized by a strong tendency to give clusters and/or oligomers through oxo-bridges. Mass spectrometry has been successfully employed for the characterization of metal alkoxides in the gas-phase. Electron ionization (EI) allowed the assessment of the molecular weight and of the most relevant decomposition pathways giving information on the relative bond strength of differently substituted molecules. On the other hand, information on the reactivity in solution of these molecules have been obtained by electrospray ionization (ESI)-matrix assisted laser desorption ionization (MALDI) experiments performed on their reaction products. These data were relevant to investigate the sol-gel process. In this review, these aspects are described and the results obtained are critically evaluated. © 2016 Wiley Periodicals, Inc. Mass Spec Rev. © 2016 Wiley Periodicals, Inc.

Proceedings of the International Symposium on Integrated Ferroelectrics (ISIF) (3rd)

DTIC Science & Technology

1991-04-05

containing Ba, Sr, Ti, Ni, Mn, and Ce as metal alkoxides, metal carboxylates , and metal acetylacetonates dissolved in butanol were deposited by spin...alkoxides, M(OR)x; (ii) metal carboxylates , M(OOCR)x; and (iii) metal acetylacetonates, M(C5H702)x; where R is an alkyl group, and x is the valence of the

Methods for treating a metathesis feedstock with metal alkoxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cohen, Steven A.; Anderson, Donde R.; Wang, Zhe

Various methods are provided for treating and reacting a metathesis feedstock. In one embodiment, the method includes providing a feedstock comprising a natural oil, chemically treating the feedstock with a metal alkoxide under conditions sufficient to diminish catalyst poisons in the feedstock, and, following the treating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

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 for producing of thin coats on ceramics and metallic surfaces.

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.

Different mechanisms at different temperatures for the ring-opening polymerization of lactide catalyzed by binuclear magnesium and zinc alkoxides.

PubMed

Sun, Yangyang; Cui, Yaqin; Xiong, Jiao; Dai, Zhongran; Tang, Ning; Wu, Jincai

2015-10-07

Two binuclear magnesium and zinc alkoxides supported by a bis-salalen type dinucleating heptadentate Schiff base ligand were synthesized and fully characterized. The two complexes are efficient initiators for the ring-opening polymerization (ROP) of L-lactide, affording polymers with narrow polydispersities and desirable molecular weights. Interestingly, the mechanisms for the ROP of lactide are different at different temperatures. At a high temperature of 130 °C, a coordination-insertion mechanism is reasonable for the bulk melt polymerization of lactide. At a low temperature, the alkoxide cannot initiate the ROP reaction; however, upon the addition of external benzyl alcohol into the system, the ROP of lactide can smoothly proceed via an "activated monomer" mechanism. In addition, these complexes display slight stereo-selectivity for the ring-opening polymerization of rac-lactide, affording partially isotactic polylactide in toluene with a Pm value of 0.59.

Chemical Processing of Structural Ceramics and Composites

DTIC Science & Technology

1988-09-01

aluminum isopropoxide (Eq. 2). Silicon alkoxide was purchased (Alfa Products) since it is relatively stable. Mg + 2C2 H 5OH ---> Mg(OC 2H5 )2 + 1/2H 2...hydrolysis of mullite precursor mixed alkoxides (TEOS and aluminum isopropoxide ) were studied. The effect of pH on hydrolysis was significant due to the...followed by IR measurements. A stoichiometric amount of TEOS was added to aluminum isopropoxide , refluxed for 48 hours, then the excess isopropyl

Synthesis and Microstructure of Highly Oriented PbTiO3 Thin Films Prepared by a Sol-Gel Method

DTIC Science & Technology

1989-06-01

lead acetate with titanium isopropoxide * in 2-methoxyethanol,* in a method similar to that reported by Gurkovitch and Blum." The resulting yellow-gold...orientation by a sol-gel processing method. EXPERIMENTAL Precursor Solution Preparation Stock solutions of complex Pb-Ti alkoxide were prepared by reacting... solution had an equivalent PbTiO 3 concentration of approximately 66 wt%. The alkoxide solutions were handled as moisture-sensitive reagents and, as

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.

Titanium alkoxide compound

DOEpatents

Boyle, Timothy J [Albuquerque, NM

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.

Role of the NH2 functionality and solvent in terdentate CNN alkoxide ruthenium complexes for the fast transfer hydrogenation of ketones in 2-propanol.

PubMed

Baratta, Walter; Ballico, Maurizio; Esposito, Gennaro; Rigo, Pierluigi

2008-01-01

The reaction of [RuCl(CNN)(dppb)] (1; HCNN=6-(4-methylphenyl)-2-pyridylmethylamine) with NaOiPr in 2-propanol/C6D6 affords the alcohol adduct alkoxide [Ru(OiPr)(CNN)(dppb)].n iPrOH (5), containing the Ru-NH2 linkage. The alkoxide [Ru(OiPr)(CNN)(dppb)] (4) is formed by treatment of the hydride [Ru(H)(CNN)(dppb)] (2) with acetone in C6D6. Complex 5 in 2-propanol/C6D6 equilibrates quickly with hydride 2 and acetone with an exchange rate of (5.4+/-0.2) s(-1) at 25 degrees C, higher than that found between 4 and 2 ((2.9+/-0.4) s(-1)). This fast process, involving a beta-hydrogen elimination versus ketone insertion into the Ru-H bond, occurs within a hydrogen-bonding network favored by the Ru-NH2 motif. The cationic alcohol complex [Ru(CNN)(dppb)(iPrOH)](BAr(f)4) (6; Ar(f)=3,5-C6H3(CF3)2), obtained from 1, Na[BAr(f)4], and 2-propanol, reacts with NaOiPr to afford 5. Complex 5 reacts with either 4,4'-difluorobenzophenone through hydride 2 or with 4,4'-difluorobenzhydrol through protonation, affording the alkoxide [Ru(OCH(4-C6H4F)2)(CNN)(dppb)] (7) in 90 and 85 % yield of the isolated product. The chiral CNN-ruthenium compound [RuCl(CNN)((S,S)-Skewphos)] (8), obtained by the reaction of [RuCl2(PPh3)3] with (S,S)-Skewphos and orthometalation of HCNN in the presence of NEt3, is a highly active catalyst for the enantioselective transfer hydrogenation of methylaryl ketones (turnover frequencies (TOFs) of up to 1.4 x 10(6) h(-1) at reflux were obtained) with up to 89% ee. Also the ketone CF3CO(4-C6H4F), containing the strong electron-withdrawing CF3 group, is reduced to the R alcohol with 64% ee and a TOF of 1.5 x 10(4) h(-1). The chiral alkoxide [Ru(OiPr)(CNN)((S,S)-Skewphos)]n iPrOH (9), obtained from 8 and NaOiPr in the presence of 2-propanol, reacts with CF3CO(4-C6H4F) to afford a mixture of the diastereomer alkoxides [Ru(OCH(CF3)(4-C6H4F))(CNN)((S,S)-Skewphos)] (10/11; 74% yield) with 67% de. This value is very close to the enantiomeric excess of the alcohol (R)-CF3CH(OH)(4-C6H4F) formed in catalysis, thus suggesting that diastereoisomeric alkoxides with the Ru-NH2 linkage are key species in the catalytic asymmetric transfer hydrogenation reaction.

Improving halide-containing magnesium-ion electrolyte performance via sterically hindered alkoxide ligands

NASA Astrophysics Data System (ADS)

Nist-Lund, Carl A.; Herb, Jake T.; Arnold, Craig B.

2017-09-01

While homoleptic magnesium dialkoxides (MgR2, R = alkoxide) have shown promise as precursors for magnesium-ion electrolytes, the effect of ligand steric bulk on the performance of electrolytes based on these compounds is not fully understood. Increasing steric hindrance, studied via R groups with additional phenyl moieties, produces electrolytes with sequentially lower deposition overpotentials (less than -90 mV), higher purity Mg deposits (ca. 100% Mg), and lower overall cell impedances. The two largest alkoxide ligands show consistent cycling behavior and low stripping and plating overpotentials over 200 constant-current plating/stripping cycles. A deep-red visual change and the presence of large solubilized magnesium particulates above 450 nm in size is observed in an electrolyte containing magnesium bis(triphenylmethoxide) and aluminum chloride in contact with an abraded magnesium anode. Further morphological and impedance characterization show that this electrolyte system rapidly activates the magnesium metal anode surface to produce low overpotentials and, as such, is a candidate for further investigation.

Gallium hydride complexes stabilised by multidentate alkoxide ligands: precursors to thin films of Ga2O3 at low temperatures.

PubMed

Pugh, David; Bloor, Leanne G; Parkin, Ivan P; Carmalt, Claire J

2012-05-07

The donor-functionalised alkoxides {Me(3-x)N(CH(2)CH(2)O)(x)} (L(x); x = 1, 2) have been used to form gallium hydride complexes [{GaH(2)(L(1))}(2)] and [{GaH(L(2))}(2)] that are stable and isolable at room temperature. Along with a heteroleptic gallium tris(alkoxide) complex [Ga(L(1))(3)] and the dimeric complex [{GaMe(L(2))}(2)], these compounds have been used as single-source precursors for the deposition of Ga(2)O(3) by aerosol-assisted chemical vapour deposition (AACVD) with toluene as solvent. The resulting films were mostly transparent, indicating low levels of carbon contamination, and they were also mainly amorphous. However, [Ga(L(1))(3)] did contain visibly crystalline material deposited at a substrate temperature of 450 °C, by far the lowest ever observed for the CVD of gallium oxide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Offermans, Willem K; Bizzarri, Claudia; Leitner, Walter; Müller, Thomas E

2015-01-01

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)Co(III)(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.

O2 Activation and Double C-H Oxidation by a Mononuclear Manganese(II) Complex.

PubMed

Deville, Claire; Padamati, Sandeep K; Sundberg, Jonas; McKee, Vickie; Browne, Wesley R; McKenzie, Christine J

2016-01-11

A Mn(II) complex, [Mn(dpeo)2](2+) (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn(III) complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn(II) complex of the final ketone ligand, cis-[MnBr2(hidpe)2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H2(18)O and (18)O2 labeling experiments suggest that the inserted O atoms originate from two different O2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkoxide-based magnesium electrolyte compositions for magnesium batteries

DOEpatents

Dai, Sheng; Sun, Xiao-Guang; Liao, Chen; Guo, Bingkun

2018-01-30

Alkoxide magnesium halide compounds having the formula: RO--Mg--X (1) wherein R is a saturated or unsaturated hydrocarbon group that is unsubstituted, or alternatively, substituted with one or more heteroatom linkers and/or one or more heteroatom-containing groups comprising at least one heteroatom selected from fluorine, nitrogen, oxygen, sulfur, and silicon; and X is a halide atom. Also described are electrolyte compositions containing a compound of Formula (1) in a suitable polar aprotic or ionic solvent, as well as magnesium batteries in which such electrolytes are incorporated.

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.

Negative Hyperconjugation versus Electronegativity: Vibrational Spectra of Free Fluorinated Alkoxide Ions in the Gas Phase.

PubMed

Oomens, Jos; Berden, Giel; Morton, Thomas Hellman

2015-06-22

CO stretching frequencies of free, gaseous, fluorinated alkoxide ions shift substantially to the blue, relative to those of corresponding alcohols complexed with ammonia. Free α-fluorinated ions, pentafluoroethoxide and heptafluoroisopropoxide anions, display further blue shifts relative to cases with only β-fluorination, providing experimental evidence for fluorine negative hyperconjugation. DFT analysis with the atoms in molecules (AIM) method confirms an increase in CO bond order for the α-fluorinated ions, demonstrating an increase in carbonyl character for the free ions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Better Ceramics Through Chemistry 4. Symposium Held in San Francisco, California on April 16 - 20, 1990. Volume 180

DTIC Science & Technology

1990-04-20

metal alkoxide precursors. For example, we only recently obtained the first X - ray crystallographic data on bismuth alkoxides, Bi(OR)3 (R = C(CH 3)3...OCMe3)6(u.O2CMe)4(J14-O2CMe)2. Complex I was fully characterized by single crystal X - ray crystallography. The six copper atoms are linked by six...hydrolyzed samples of 3 revealed stacks of plate-like particles with sizes up to 20 x 50 microns (Figure 3). X - ray analysis of these plates showed

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.

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.

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.

Solvothermal crystallization of nanocrystals of metal oxides

NASA Astrophysics Data System (ADS)

Furukawa, S.; Amino, H.; Iwamoto, S.; Inoue, M.

2008-07-01

Solvothermal crystallization of the hydroxide gels obtained by hydrolysis of alkoxides (Zr, Ta, Nb, ln, Sn, Ti and Al) was examined. Nanocrystals having high surface areas (SBET > 170 m2 g-1) were obtained except for the product derived from indium isopropoxide. The effect of water in organic solvent upon the crystallinity of the product was investigated. The increase in the activity of water by using high concentration of alkoxide or intentional addition of water to the solvothermal medium led to crystal growth of the products. In contrast, decrease in activity of water by adding ethylene glycol before solvothermal treatment caused a decrease in crystallinity of the product.

Homogeneity of gels and gel-derived glasses

NASA Technical Reports Server (NTRS)

Mukherjee, S. P.

1984-01-01

The significance and implications of gel preparation procedures in controlling the homogeneity of multicomponent oxide gels are discussed. The role of physicochemical factors such as the structure and chemical reactivities of alkoxides, the formation of double-metal alkoxides, and the nature of solvent(s) are critically analyzed in the context of homogeneity of gels during gelation. Three procedures for preparing gels in the SiO2-B2O3-Na2O system are examined in the context of cation distribution. Light scattering results for glasses in the SiO2-B2O3-Na2O system prepared by both the gel technique and the conventional technique are examined.

Antireflective graded index silica coating, method for making

DOEpatents

Yoldas, Bulent E.; Partlow, Deborah P.

1985-01-01

Antireflective silica coating for vitreous material is substantially non-reflecting over a wide band of radiations. This is achieved by providing the coating with a graded degree of porosity which grades the index of refraction between that of air and the vitreous material of the substrate. To prepare the coating, there is first prepared a silicon-alkoxide-based coating solution of particular polymer structure produced by a controlled proportion of water to alkoxide and a controlled concentration of alkoxide to solution, along with a small amount of catalyst. The primary solvent is alcohol and the solution is polymerized and hydrolized under controlled conditions prior to use. The prepared solution is applied as a film to the vitreous substrate and rapidly dried. It is thereafter heated under controlled conditions to volatilize the hydroxyl radicals and organics therefrom and then to produce a suitable pore morphology in the residual porous silica layer. The silica layer is then etched in order to enlarge the pores in a graded fashion, with the largest of the pores remaining being sufficiently small that radiations to be passed through the substrate are not significantly scattered. For use with quartz substrates, extremely durable coatings which display only 0.1% reflectivity have been prepared.

Organically Modified Silicas on Metal Nanowires

PubMed Central

2010-01-01

Organically modified silica coatings were prepared on metal nanowires using a variety of silicon alkoxides with different functional groups (i.e., carboxyl groups, polyethylene oxide, cyano, dihydroimidazole, and hexyl linkers). Organically modified silicas were deposited onto the surface of 6-μm-long, ∼300-nm-wide, cylindrical metal nanowires in suspension by the hydrolysis and polycondensation of silicon alkoxides. Syntheses were performed at several ratios of tetraethoxysilane to an organically modified silicon alkoxide to incorporate desired functional groups into thin organosilica shells on the nanowires. These coatings were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. All of the organically modified silicas prepared here were sufficiently porous to allow the removal of the metal nanowire cores by acid etching to form organically modified silica nanotubes. Additional functionality provided to the modified silicas as compared to unmodified silica prepared using only tetraethoxysilane precursors was demonstrated by chromate adsorption on imidazole-containing silicas and resistance to protein adsorption on polyethyleneoxide-containing silicas. Organically modified silica coatings on nanowires and other nano- and microparticles have potential application in fields such as biosensing or nanoscale therapeutics due to the enhanced properties of the silica coatings, for example, the prevention of biofouling. PMID:20715881

Inorganic-polymer-derived dielectric films

DOEpatents

Brinker, C. Jeffrey; Keefer, Keith D.; Lenahan, Patrick M.

1987-01-01

A method of coating a substrate with a thin film of a polymer of predetermined porosity comprises depositing the thin film on the substrate from a non-gelled solution comprising at least one hydrolyzable metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base, prior to depositing the film, controlling the structure of the polymer for a given composition of the solution exclusive of the acid or base component and the water component, (a) by adjusting each of the water content, the pH, and the temperature to obtain the desired concentration of alkoxide, and then adjusting the time of standing of the solution prior to lowering the temperature of the solution, and (b) lowering the temperature of the solution after the time of standing to about 15 degrees C. or lower to trap the solution in a state in which, after the depositing step, a coating of the desired porosity will be obtained, and curing the deposited film at a temperature effective for curing whereby there is obtained a thin film of a polymer of a predetermined porosity and corresponding pore size on the substrate.

Heterobimetallic dinuclear lanthanide alkoxide complexes as acid-base difunctional catalysts for transesterification.

PubMed

Zeng, Ruijie; Sheng, Hongting; Zhang, Yongcang; Feng, Yan; Chen, Zhi; Wang, Junfeng; Chen, Man; Zhu, Manzhou; Guo, Qingxiang

2014-10-03

A practical lanthanide(III)-catalyzed transesterification of carboxylic esters, weakly reactive carbonates, and much less-reactive ethyl silicate with primary and secondary alcohols was developed. Heterobimetallic dinuclear lanthanide alkoxide complexes [Ln2Na8{(OCH2CH2NMe2)}12(OH)2] (Ln = Nd (I), Sm (II), and Yb (III)) were used as highly active catalysts for this reaction. The mild reaction conditions enabled the transesterification of various substrates to proceed in good to high yield. Efficient activation of transesterification may be endowed by the above complexes as cooperative acid-base difunctional catalysts, which is proposed to be responsible for the higher reactivity in comparison with simple acid/base catalysts.

Toward compositional design of reticular type porous films by mixing and coating titania-based frameworks with silica

NASA Astrophysics Data System (ADS)

Kimura, T.

2015-12-01

A recently developed reticular type porous structure, which can be fabricated as the film through the soft colloidal block copolymer (e.g., PS-b-PEO) templating, is very promising as the porous platform showing high-performance based on its high surface area as well as high diffusivity of targeted organic molecules and effective accommodation of bulky molecules, but the compositional design of oxide frameworks has not been developed so enough to date. Here, I report reliable synthetic methods of the reticular type porous structure toward simple compositional variations. Due to the reproducibility of reticular type porous titania films from titanium alkoxide (e.g., TTIP; titanium tetraisopropoxide), a titania-silica film having similar porous structure was obtained by mixing silicon alkoxide (e.g., tetraethoxysilane) and TTIP followed by their pre-hydrolysis, and the mixing ratio of Ti to Si composition was easily reached to 1.0. For further compositional design, a concept of surface coating was widely applicable; the reticular type porous titania surfaces can be coated with other oxides such as silica. Here, a silica coating was successfully achieved by the simple chemical vapor deposition of silicon alkoxide (e.g., tetramethoxysilane) without water (with water at the humidity level), which was also utilized for pore filling with silica by the similar process with water.

Synthesis and characterization of heteroleptic titanium MOCVD precursors for TiO2 thin films.

PubMed

Kim, Euk Hyun; Lim, Min Hyuk; Lah, Myoung Soo; Koo, Sang Man

2018-02-13

Heteroleptic titanium alkoxides with three different ligands, i.e., [Ti(O i Pr)(X)(Y)] (X = tridentate, Y = bidentate ligands), were synthesized to find efficient metal organic chemical vapor deposition (MOCVD) precursors for TiO 2 thin films. Acetylacetone (acacH) or 2,2,6,6-tetramethyl-3,5-heptanedione (thdH) was employed as a bidentate ligand, while N-methyldiethanolamine (MDEA) was employed as a tridentate ligand. It was expected that the oxygen and moisture susceptibility of titanium alkoxides, as well as their tendency to form oligomers, would be greatly reduced by placing multidentate and bulky ligands around the center Ti atom. The synthesized heteroleptic titanium alkoxides were characterized both physicochemically and crystallographically, and their thermal behaviors were also investigated. [Ti(O i Pr)(MDEA)(thd)] was found to be monomeric and stable against moisture; it also showed good volatility in the temperature window between volatilization and decomposition. This material was used as a single-source precursor during MOCVD to generate TiO 2 thin films on silicon wafers. The high thermal stability of [Ti(O i Pr)(MDEA)(thd)] enabled the fabrication of TiO 2 films over a wide temperature range, with steady growth rates between 500 and 800 °C.

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 important implications in the conservation of cultural heritage.

The low temperature synthesis, characterization and properties of ferroelectrics

NASA Astrophysics Data System (ADS)

Xu, Jie

2000-10-01

PZT 50:50 xerogels prepared by two different sol-gel routes crystallized in a similar fashion to give a mixture of tetragonal and rhombohedral at high temperature (1000°C). Both the diffraction and EXAFS data suggest that the compositional inhomogeneity of the samples prepared by the two routes is similar. The crystallization of CZT gels is complicated. Crystalline CaCO 3 was always detected in the dry gels regardless of the sample composition and preparation methods. At intermediate temperatures a fluorite related phase was always formed and it transformed to perovskite at higher temperatures. The EXAFS data suggest that perovskite CZT samples prepared using alkoxide sol-gel chemistry may not be random solid solutions. All the solution processed ZrTiO4 materials crystallized in the range 600--700°C. The KTN samples prepared using a conventional alkoxide sol-gel route crystallized completely to perovskite at lower temperatures than those prepared using prehydrolyzed precursors. The EXAFS data for the KTN samples prepared using a conventional alkoxide sol-gel route are consistent with a random distribution of tantalum and niobium in the solid solution. However, materials prepared using the inhomogeneous sol-gel route and by the direct reaction of mixed oxides were shown to be compositionally inhomogeneous. The heterogeneity could not be removed by regrinding and heating the mixed oxide samples several times. K2Ta4-xNbxO11 (x = 0, 2, 4) samples were prepared using alkoxide sol-gel chemistry and their crystallization was examined by powder X-ray diffraction. A Rietveld structure analysis of the pyrochlore formed from a gel with bulk composition K2Ta 2Nb2O11 indicated that it was rich in potassium relative to the bulk sample. On heating to high temperatures tetragonal tungsten bronzes were formed. A Rietveld analysis was also performed for K2Ta 2Nb2O11 with tetragonal tungsten bronze structure. The defect pyrochlores "AgTaO3" and GaTaO 3 were synthesized by ion-exchange using pyrochlore KTaO3 as a starting material. The structures of the pyrochlores were examined using the Rietveld method. The pyrochlore-to-perovskite transformations were also explored.

Method to synthesize metal chalcogenide monolayer nanomaterials

DOEpatents

Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

2016-12-13

Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

Swollen poly(dimethylsiloxane) (PDMS) as a template for inorganic morphologies.

PubMed

Brennan, Daniel P; Dobley, Arthur; Sideris, Paul J; Oliver, Scott R J

2005-12-06

We report a series of silica, titania, and zirconia microstructures synthesized within swollen poly(dimethylsiloxane) (PDMS). Voids created by solvent-swelling the polymer are used to template the product. The inorganic morphologies range from spheres to networks, depending upon the nature of the polymer, its degree of swelling, and the synthetic conditions. Organic solvents as well as pure metal alkoxide liquids have been used to swell the polymer. Once the alkoxide precursor is inside the swollen polymer, water is introduced to bring about hydrolysis and condensation polymerization. The product is a textured metal oxide within a PDMS matrix. Scanning electron microscopy (SEM), optical microscopy, nuclear magnetic resonance (NMR), and powder X-ray diffraction (PXRD) were used to characterize the products. Microstructures formed in this manner have potential use as an inexpensive route to catalysts, fillers, capsules, or membranes for separations.

Sol-gel derived sorbents

DOEpatents

Sigman, Michael E.; Dindal, Amy B.

2003-11-11

Described is a method for producing copolymerized sol-gel derived sorbent particles for the production of copolymerized sol-gel derived sorbent material. The method for producing copolymerized sol-gel derived sorbent particles comprises adding a basic solution to an aqueous metal alkoxide mixture for a pH.ltoreq.8 to hydrolyze the metal alkoxides. Then, allowing the mixture to react at room temperature for a precalculated period of time for the mixture to undergo an increased in viscosity to obtain a desired pore size and surface area. The copolymerized mixture is then added to an immiscible, nonpolar solvent that has been heated to a sufficient temperature wherein the copolymerized mixture forms a solid upon the addition. The solid is recovered from the mixture, and is ready for use in an active sampling trap or activated for use in a passive sampling trap.

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.

Study of phase transformation and microstructure of alcohol washed titania nanoparticles for thermal stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Manpreet, E-mail: manpreet.kaur@thapar.edu; Singh, Gaganjot; Bimbraw, Keshav

Nanostructured titania have been successfully synthesized by hydrolysis of alkoxide at calcination temperatures 500 °C, 600 °C and 700 °C. As the calcination temperature increases, alcohol washed samples show lesser rutile content as compared to water washed samples. Morphology and Particle sizes was determined by field emission scanning electron microscopy (FESEM), while thermogravimetric-differential scanning calorimetry (TG-DSC) was used to determine thermal stability. Alcohol washed samples undergo 30% weight loss whereas 16% in water washed samples was observed. The mean particle sizes were found to be increase from 37 nm to 100.9 nm and 35.3 nm to 55.2 nm for water and alcohol washed samplesmore » respectively. Hydrolysis of alkoxide was shown to be an effective means to prepare thermally stable titania by using alcohol washed samples as a precursor.« less

A Boron Protecting Group Strategy for 1,2-Azaborines.

PubMed

Baggett, Andrew W; Liu, Shih-Yuan

2017-10-25

Upon reaction with either molecular oxygen or di-tert-butylperoxide in the presence of a simple copper(I) salt and an alcohol, a range of 1,2-azaborines readily exchange B-alkyl or B-aryl moieties for B-alkoxide fragments. This transformation allows alkyl and aryl groups to serve for the first time as removable protecting groups for the boron position of 1,2-azaborines during reactions that are not compatible with the easily modifiable B-alkoxide moiety. This reaction can be applied to synthesize a previously inaccessible BN isostere of ethylbenzene, a compound of interest in biomedical research. A sequence of epoxide ring opening using N-deprotonated 1,2-azaborines followed by an intramolecular version of the boron deprotection reaction can be applied to access the first examples of BN isosteres of dihydrobenzofurans and benzofurans, classes of compounds that are important to medicinal chemistry and natural product synthesis.

New insights into the formation mechanism of Ag, Au and AgAu nanoparticles in aqueous alkaline media: alkoxides from alcohols, aldehydes and ketones as universal reducing agents.

PubMed

Gomes, Janaina F; Garcia, Amanda C; Ferreira, Eduardo B; Pires, Cleiton; Oliveira, Vanessa L; Tremiliosi-Filho, Germano; Gasparotto, Luiz H S

2015-09-07

In this report we present new insights into the formation mechanism of Ag, Au and AgAu nanoparticles with alcohols, aldehydes and ketones in alkaline medium at room temperature. We selected methanol, ethanol, glycerol, formaldehyde, acetaldehyde and acetone to demonstrate their capability of reducing gold and silver ions under the above-mentioned conditions. We showed that the particles are also formed with potassium tert-butoxide in the absence of hydroxides. Our results strongly suggest that alkoxides, formed from any molecule containing a hydroxyl or a functional group capable of generating them in alkaline medium, are the actual and universal reducing agent of silver and gold ions, in opposition to the currently accepted mechanisms. The universality of the reaction mechanism proposed in this work may impact on the production of noble nanoparticles with simple chemicals normally found in standard laboratories.

Enantiopure pseudo-C3-symmetric titanium alkoxide with propeller-like chirality.

PubMed

Axe, Philip; Bull, Steven D; Davidson, Matthew G; Gilfillan, Carly J; Jones, Matthew D; Robinson, Diane E J E; Turner, Luke E; Mitchell, William L

2007-01-18

An enantiopure amine tris(phenolate) ligand containing a single stereogenic center has been used to control the propeller-like chirality of a derived pseudo-C3-symmetric titanium isopropoxide complex with excellent levels of diastereocontrol. [structure: see text].

Theoretical insights into the sites and mechanisms for base catalyzed esterification and aldol condensation reactions over Cu.

PubMed

Neurock, Matthew; Tao, Zhiyuan; Chemburkar, Ashwin; Hibbitts, David D; Iglesia, Enrique

2017-04-28

Condensation and esterification are important catalytic routes in the conversion of polyols and oxygenates derived from biomass to fuels and chemical intermediates. Previous experimental studies show that alkanal, alkanol and hydrogen mixtures equilibrate over Cu/SiO 2 and form surface alkoxides and alkanals that subsequently promote condensation and esterification reactions. First-principle density functional theory (DFT) calculations were carried out herein to elucidate the elementary paths and the corresponding energetics for the interconversion of propanal + H 2 to propanol and the subsequent C-C and C-O bond formation paths involved in aldol condensation and esterification of these mixtures over model Cu surfaces. Propanal and hydrogen readily equilibrate with propanol via C-H and O-H addition steps to form surface propoxide intermediates and equilibrated propanal/propanol mixtures. Surface propoxides readily form via low energy paths involving a hydrogen addition to the electrophilic carbon center of the carbonyl of propanal or via a proton transfer from an adsorbed propanol to a vicinal propanal. The resulting propoxide withdraws electron density from the surface and behaves as a base catalyzing the activation of propanal and subsequent esterification and condensation reactions. These basic propoxides can readily abstract the acidic C α -H of propanal to produce the CH 3 CH (-) CH 2 O* enolate, thus initiating aldol condensation. The enolate can subsequently react with a second adsorbed propanal to form a C-C bond and a β-alkoxide alkanal intermediate. The β-alkoxide alkanal can subsequently undergo facile hydride transfer to form the 2-formyl-3-pentanone intermediate that decarbonylates to give the 3-pentanone product. Cu is unique in that it rapidly catalyzes the decarbonylation of the C 2n intermediates to form C 2n-1 3-pentanone as the major product with very small yields of C 2n products. This is likely due to the absence of Brønsted acid sites, present on metal oxide catalysts, that rapidly catalyze dehydration of the hemiacetal or hemiacetalate over decarbonylation. The basic surface propoxide that forms on Cu can also attack the carbonyl of a surface propanal to form propyl propionate. Theoretical results indicate that the rates for both aldol condensation and esterification are controlled by reactions between surface propoxide and propanal intermediates. In the condensation reaction, the alkoxide abstracts the weakly acidic hydrogen of the C α -H of the adsorbed alkanal to form the surface enolate whereas in the esterification reaction the alkoxide nucleophilically attacks the carbonyl group of a vicinal bound alkanal. As both condensation and esterification involve reactions between the same two species in the rate-limiting step, they result in the same rate expression which is consistent with experimental results. The theoretical results indicate that the barriers between condensation and esterification are within 3 kJ mol -1 of one another with esterification being slightly more favored. Experimental results also report small differences in the activation barriers but suggest that condensation is slightly preferred.

CNN pincer ruthenium catalysts for hydrogenation and transfer hydrogenation of ketones: experimental and computational studies.

PubMed

Baratta, Walter; Baldino, Salvatore; Calhorda, Maria José; Costa, Paulo J; Esposito, Gennaro; Herdtweck, Eberhardt; Magnolia, Santo; Mealli, Carlo; Messaoudi, Abdelatif; Mason, Sax A; Veiros, Luis F

2014-10-13

Reaction of [RuCl(CNN)(dppb)] (1-Cl) (HCNN=2-aminomethyl-6-(4-methylphenyl)pyridine; dppb=Ph2 P(CH2 )4 PPh2 ) with NaOCH2 CF3 leads to the amine-alkoxide [Ru(CNN)(OCH2 CF3 )(dppb)] (1-OCH2 CF3 ), whose neutron diffraction study reveals a short RuO⋅⋅⋅HN bond length. Treatment of 1-Cl with NaOEt and EtOH affords the alkoxide [Ru(CNN)(OEt)(dppb)]⋅(EtOH)n (1-OEt⋅n EtOH), which equilibrates with the hydride [RuH(CNN)(dppb)] (1-H) and acetaldehyde. Compound 1-OEt⋅n EtOH reacts reversibly with H2 leading to 1-H and EtOH through dihydrogen splitting. NMR spectroscopic studies on 1-OEt⋅n EtOH and 1-H reveal hydrogen bond interactions and exchange processes. The chloride 1-Cl catalyzes the hydrogenation (5 atm of H2 ) of ketones to alcohols (turnover frequency (TOF) up to 6.5×10(4) h(-1) , 40 °C). DFT calculations were performed on the reaction of [RuH(CNN')(dmpb)] (2-H) (HCNN'=2-aminomethyl-6-(phenyl)pyridine; dmpb=Me2 P(CH2 )4 PMe2 ) with acetone and with one molecule of 2-propanol, in alcohol, with the alkoxide complex being the most stable species. In the first step, the Ru-hydride transfers one hydrogen atom to the carbon of the ketone, whereas the second hydrogen transfer from NH2 is mediated by the alcohol and leads to the key "amide" intermediate. Regeneration of the hydride complex may occur by reaction with 2-propanol or with H2 ; both pathways have low barriers and are alcohol assisted. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kleinlein, Claudia; Zheng, Shao-Liang; Betley, Theodore A.

Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type ( ArL)FeX 2 [ ArL = 1,9-(2,4,6-Ph 3C 6H 2) 2-5-mesityldipyrromethene] with X = Cl or tBuO were prepared and found to be high-spin (S = 5/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and 57Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined. While each ferric complex displays reversible reduction and oxidation events, each alkoxide for chloride substitution resultsmore » in a nearly 600 mV cathodic shift of the Fe III/II couple. The oxidation event remains largely unaffected by the ancillary ligand substitution and is likely dipyrrin-centered. While the alkoxide substituted ferric species largely retain the color of their ferrous precursors, characteristic of dipyrrin-based ligand-to-ligand charge transfer (LLCT), the dichloride ferric complex loses the prominent dipyrrin chromophore, taking on a deep green color. Time-dependent density functional theory analyses indicate the weaker-field chloride ligands allow substantial configuration mixing of ligand-to-metal charge transfer into the LLCT bands, giving rise to the color changes observed. Furthermore, the higher degree of covalency between the alkoxide ferric centers is manifest in the observed reactivity. Delocalization of spin density onto the tert-butoxide ligand in ( ArL)FeCl(O tBu) is evidenced by hydrogen atom abstraction to yield ( ArL)FeCl and HOtBu in the presence of substrates containing weak C–H bonds, whereas the chloride ( ArL)FeCl 2 analogue does not react under these conditions.« less

Production and characterization of europium doped sol-gel yttrium oxide

NASA Astrophysics Data System (ADS)

Krebs, J. K.; Hobson, Christopher; Silversmith, Ann

2004-03-01

Sol-gel produced materials have recently gained attention for their use in producing nanoscale dielectric materials for confinement studies. Lanthanide impurities in the dielectric enable experimenters to optically probe the structure and dynamic properties of the nanoparticle hosts. We report on an alkoxide sol-gel production method used to produce trivalent europium doped yttrium oxide. Our process follows the standard hydrolysis of an alkoxide precursor with water containing the lanthanide ions. The sol is then aged and calcined at 800 ^oC to produce the powder samples. X-ray diffraction confirms the structure of the powder is that of Y_2O_3. The emission and excitation of the europium impurities is consistent with that of europium doped single crystal yttrium oxide, where it is known that the europium ions substitute for yttrium in the lattice. We therefore conclude that the sol-gel process enables the incorporation of europium ions into the yttrium oxide structure at temperatures far below the melting temperature. The results of preliminary dynamics measurements will also be discussed.

Enzyme-like catalysis via ternary complex mechanism: alkoxy-bridged dinuclear cobalt complex mediates chemoselective O-esterification over N-amidation.

PubMed

Hayashi, Yukiko; Santoro, Stefano; Azuma, Yuki; Himo, Fahmi; Ohshima, Takashi; Mashima, Kazushi

2013-04-24

Hydroxy group-selective acylation in the presence of more nucleophilic amines was achieved using acetates of first-row late transition metals, such as Mn, Fe, Co, Cu, and Zn. Among them, cobalt(II) acetate was the best catalyst in terms of reactivity and selectivity. The combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (2a: R = CF3, 2b: R = CH3, 2c: R = (t)Bu) with nitrogen-containing ligands, such as 2,2'-bipyridine, provided an efficient catalytic system for transesterification, in which an alkoxide-bridged dinuclear complex, Co2(OCO(t)Bu)2(bpy)2(μ2-OCH2-C6H4-4-CH3)2 (10), was successfully isolated as a key intermediate. Kinetic studies and density functional theory calculations revealed Michaelis-Menten behavior of the complex 10 through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting the formation of alkoxides followed by coordination of the ester.

Metal-oxide-based energetic materials and synthesis thereof

DOEpatents

Tillotson, Thomas M. , Simpson; Randall, L [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2006-01-17

A method of preparing energetic metal-oxide-based energetic materials using sol-gel chemistry has been invented. The wet chemical sol-gel processing provides an improvement in both safety and performance. Essentially, a metal-oxide oxidizer skeletal structure is prepared from hydrolyzable metals (metal salts or metal alkoxides) with fuel added to the sol prior to gelation or synthesized within the porosity metal-oxide gel matrix. With metal salt precursors a proton scavenger is used to destabilize the sol and induce gelation. With metal alkoxide precursors standard well-known sol-gel hydrolysis and condensation reactions are used. Drying is done by standard sol-gel practices, either by a slow evaporation of the liquid residing within the pores to produce a high density solid nanocomposite, or by supercritical extraction to produce a lower density, high porous nanocomposite. Other ingredients may be added to this basic nanostructure to change physical and chemical properties, which include organic constituents for binders or gas generators during reactions, burn rate modifiers, or spectral emitters.

Nucleophilic stabilization of water-based reactive ink for titania-based thin film inkjet printing

NASA Astrophysics Data System (ADS)

Gadea, C.; Marani, D.; Esposito, V.

2017-02-01

Drop on demand deposition (DoD) of titanium oxide thin films (<500 nm) is performed via a novel titanium-alkoxide-based solution that is tailored as a reactive ink for inkjet printing. The ink is developed as water-based solution by a combined use of titanium isopropoxide and n-methyldiethanolamine (MDEA) used as nucleophilic ligand. The function of the ligand is to control the fast hydrolysis/condensation reactions in water for the metal alkoxide before deposition, leading to formation of the TiO2 only after the jet process. The evolution of the titanium-ligand interactions at increasing amount of MDEA is here elucidated in terms of long term stability. The ink printability parameter (Z) is optimized, resulting in a reactive solution with printability, Z, >1, and chemical stability up to 600 h. Thin titanium oxide films (<500 nm) are proved on different substrates. Pure anatase phase is obtained after annealing at low temperature (ca. 400 °C).

Cryogenic Gellant and Fuel Formulation for Metallized Gelled Propellants: Hydrocarbons and Hydrogen with Aluminum

NASA Technical Reports Server (NTRS)

Wong, Wing; Starkovich, John; Adams, Scott; Palaszewski, Bryan; Davison, William; Burt, William; Thridandam, Hareesh; Hu-Peng, Hsiao; Santy, Myrrl J.

1994-01-01

An experimental program to determine the viability of nanoparticulate gellant materials for gelled hydrocarbons and gelled liquid hydrogen was conducted. The gellants included alkoxides (BTMSE and BTMSH) and silica-based materials. Hexane, ethane, propane and hydrogen were gelled with the newly-formulated materials and their rheological properties were determined: shear stress versus shear rate and their attendant viscosities. Metallized hexane with aluminum particles was also rheologically characterized. The propellant and gellant formulations were selected for the very high surface area and relatively-high energy content of the gellants. These new gellants can therefore improve rocket engine specific impulse over that obtained with traditional cryogenic-fuel gellant materials silicon dioxide, frozen methane, or frozen ethane particles. Significant reductions in the total mass of the gellant were enabled in the fuels. In gelled liquid hydrogen, the total mass of gellant was reduced from 10-40 wt percent of frozen hydrocarbon particles to less that 8 wt percent with the alkoxide.

Precursor directed synthesis - ``molecular'' mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures

NASA Astrophysics Data System (ADS)

Seisenbaeva, Gulaim A.; Kessler, Vadim G.

2014-05-01

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials. To Professor David Avnir on his 65th birthday.

Supported Single-Site Ti(IV) on a Metal–Organic Framework for the Hydroboration of Carbonyl Compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Zhiyuan; Liu, Dong; Camacho-Bunquin, Jeffrey

ABSTRACT: A stable and structurally well-defined titanium alkoxide catalyst supported on a metal-organic-framework (MOF) of UiO-67 topology (ANL1-Ti(OiPr)2) was synthesized and fully characterized by a variety of analytical and spectroscopic techniques, including BET, TGA, PXRD, XAS, DRIFT, SEM, and DFT computations. The Ti-functionalized MOF was demonstrated active for the catalytic hydroboration of a wide range of aldehydes and ketones with HBpin as the boron source. Compared to traditional homogeneous and supported hydroboration catalysts, ANL1-Ti(OiPr)2 is completely recyclable and reusable, making it a promising hydroboration catalyst alternative for green and sustainable chemical synthesis. DFT calculations suggest that the catalytic hydroboration proceedsmore » via a (1) hydride transfer between the active Ti-hydride species and a carbonyl moiety (rate determining step), and (2) alkoxide transfer (intramolecular σ-bond metathesis) to generate the boronate ester product.« less

Chemical vapor deposition of aluminum oxide

DOEpatents

Gordon, Roy; Kramer, Keith; Liu, Xinye

2000-01-01

An aluminum oxide film is deposited on a heated substrate by CVD from one or more alkylaluminum alkoxide compounds having composition R.sub.n Al.sub.2 (OR').sub.6-n, wherein R and R' are alkyl groups and n is in the range of 1 to 5.

Synthesis and Processing of Ultra-High Temperature Metal Carbide and Metal Diboride Nanocomposite Materials

DTIC Science & Technology

2008-04-15

cellulose acetate polymers, and diols. Common sol- uble metal/metal oxide-bearing materials are metal alkoxides, metal diketonates, and metal ... carboxylates . Metal-organic compounds are usually subjected to hydrolysis and condensa- tion reactions to produce polymeric or colloidal metal-oxide

Photoinduced manipulation of the molecular assembly in heteroleptic titanium metal alkoxides for use in optical devices

NASA Astrophysics Data System (ADS)

Schneider, Zachary Vernon

The manipulation of molecular structures is an important enabling technology for future advances in nanotechnology. The ability to control the synthesis of nanostructured materials, such as the bond formation and geometry of a molecule is of great significance to nanoscience as nanosystems are constructed from these smaller units. Influencing the assembly of molecular structures at the early stages of material formation can modify the ensuing molecular aggregate structure with the potential for impact in a broad range of optical, chemical, and biological applications. Heteroleptic titanium metal alkoxides (OPy)2Ti(4MP)2 and (OPy)2Ti(TAP)2, where OPy = OC6H 6N, 4MP = OC6H4(SH)-4, and TAP = OC6H 2(CH2N(CH3)2)3-2,4,6 were investigated as precursors for thin film and solution-based synthesis of oxide materials via the photoactivation of intermolecular reactions (e.g. hydrolysis/condensation) at selected ligand sites about the metal center. Manipulation of the molecular structure of these photosensitive metal alkoxides was achieved through the use of optical irradiation parameters, such as the tuning of the excitation wavelength, total optical fluence, and pulse energy intensity. Irradiating these metal alkoxides with UV-light was seen to cause photodisruption in the ligand groups leading to the formation of Ti-O-Ti linking via hydrolysis and condensation reactions. In spin-coated (OPy)2Ti(TAP)2 films, these photoinduced bridge bond formations resulted in an increase in refractive index and film densification as well as produced an insoluble film when rinsed in pyridine. By making use of these photoinduced film properties, the formation of physical relief structures from spin-coated (OPy)2Ti(TAP) 2 films was demonstrated along with the ability to photopattern sub-micron and nanometer features. In addition, the micro- and nanostructure of thin films were optically manipulated through several deposition methods; a novel dip-coated in-situ photodeposition technique was utilized by illuminating at specific distances above the meniscus to further control the early stages of material formation due to changes in the mobility of the reactants from the evaporation and gravitational draining of the solvent. The ability to manipulate molecular development at the on-set of material formation through different deposition techniques and optical parameters allowed for the creation of several thin film optical devices, such as gratings, micro-optic lenslet arrays, and binary "on-off" patterned devices.

THERMALLY STABLE NANOCRYSTALLINE TIO2 PHOTOCATALYSTS SYNTHESIZED VIA SOL-GEL METHODS MODIFIED WITH IONIC LIQUID AND SURFACTANT MOLECULES

EPA Science Inventory

Recently, sol-gel methods employing ionic liquids (ILs) have shown significant implications for the synthesis of well-defined nanostructured inorganic materials. Herein, we synthesized nanocrystalline TiO₂ particles via an alkoxide sol-gel method employing a water-immi...

Effect of Powder Characteristics on Microstructure and Properties in Alkoxide Prepared PZT Ceramics.

DTIC Science & Technology

1984-12-01

Effect of pH of precipitating solution on the pressed and fired densities (9500 C/ h) of PZT (+ 0.25 wt% V2o5 ). * Figure 12. Plot of dielectric...Lectures: a) Electronic Cermics/Dielectrics Properties, b) Glasses and Substrates in Electronics, c) Thick Film Hybrid Circuits; d) Nagnetic Ceramics

Aliphatic imines in titanium-mediated reductive cross-coupling: unique reactivity of Ti(O-i-Pr)4/n-BuLi.

PubMed

Tarselli, Michael A; Micalizio, Glenn C

2009-10-15

A procedure for the coupling of aliphatic imines with allylic and allenic alkoxides is described. The success of these studies was enabled by a unique reactivity profile of Ti(IV) isopropoxide/n-BuLi compared to well-known Ti(IV) isopropoxide/RMgX systems.

Catalysis and Multi-Component Reactions

NASA Astrophysics Data System (ADS)

Shibasaki, Masakatsu; Yus, Miguel; Bremner, Stacy; Comer, Eamon; Shore, Gjergji; Morin, Sylvie; Organ, Michael G.; van der Eycken, Erik; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Ryabukhin, Sergey V.; Ostapchuk, Eugeniy N.; Plaskon, Andrey S.; Volochnyuk, Dmitriy M.; Shivanyuk, Alexander N.; Tolmachev, Andrey A.; Sheibani, Hassan; Babaie, Maryam; Behzadi, Soheila; Dabiri, Minoo; Bahramnejad, Mahboobeh; Bashiribod, Sahareh; Hekmatshoar, Rahim; Sadjadi, Sodeh; Khorasani, Mohammad; Polyakov, Anatoliy I.; Eryomina, Vera A.; Medvedeva, Lidiya A.; Tihonova, Nadezhda I.; Listratova, Anna V.; Voskressensky, Leonid G.; Merkul, Eugen; Dorsch, Dieter; Müller, Thomas J. J.; Sheibani, Hassan; Esfandiarpoor, Zeinab; Behzadi, Soheila; Titova, Julia A.; Fedorova, Olga V.; Ovchinnikova, Irina G.; Valova, Marina S.; Koryakova, Olga V.; Rusinov, Gennady L.; Charushin, Valery N.; Hekmatshoar, Rahim; Sadjadi, Sodeh

We have been studying the development of new asymmetric two-center catalysis using rare earth alkoxides and bifunctional sugar and related ligands. In The Fourth International Conference on Multi-Component Reactions and Related Chemistry (MCR 2009), new catalytic asymmetric reactions using catalysts 1 and 2 and catalytic asymmetric syntheses of ranirestat 3 and tamiflu 4 will be presented.

Inorganic-polymer-derived dielectric films

DOEpatents

Brinker, C.J.; Keefer, K.D.; Lenahan, P.M.

1985-02-25

A method is disclosed for coating a substrate with a thin film of a predetermined porosity. The method comprises: depositing the thin film on the substrate from a non-gelled solution comprising at least one metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base; prior to said depositing step, controlling the porosity and structure of said coating for a given composition of said solution exclusive of the acid or base component and the water component, by adjusting each of the water content, the pH, the temperature and the time of standing of said solution, increasing/descreasing the water content or the pH to increase/decrease the pore size of said coating, and increasing/decreasing the temperature or time of standing of said solution to increase/decrease the pore size of said coating; and curing said deposited film at a temperature effective for curing whereby there is obtained a thin film coating of a predetermined porosity on the substrate.

Development of Alkoxide Precursors-Based Hybrid Coatings on Ti-6Al-4V Alloy for Biomedical Applications: Influence of pH of Sol

NASA Astrophysics Data System (ADS)

Salvador, D. G.; Marcolin, P.; Beltrami, L. V. R.; Brandalise, R. N.; Kunst, S. R.

2018-04-01

The Ti-6Al-4V alloy, widely used in biomedical applications, is associated with cytotoxic effects due to the release of aluminum and vanadium ions in the human body. One of the most effective ways to control the release of cytotoxic ions is through anti-corrosive coatings. Among them, the alkoxysilanes stand out for their good barrier properties and the absence of toxicity. Aiming to improve the clinical success rate of metallic implants, this study sets out to evaluate the influence of the pH of the sol on the physico-chemical, morphological, mechanical and electrochemical characteristics of hybrid films based on 3-(trimethoxysilylpropyl)methacrylate (MAP) and tetraethoxysilane (TEOS) applied to Ti-6Al-4V. The film was prepared by using the sol-gel method for pH values of 3, 4, and 5. The results indicated that maintaining the pH of the sol at 4 favors the hydrolysis rate of alkoxide precursors, which results in a uniform, dense and adherent film with excellent anti-corrosion performance.

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.

Thermoluminescence (TL) of europium-doped ZrO2 obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Rivera, T.; Furetta, C.; Azorín, J.; Barrera, M.; Soto, A. M.

This article reports the preparation and characterization of europium-doped zirconium oxide (ZrO2:Eu3+) formed by homogeneous precipitation from propoxyde of zirconium [Zr(OC3H7)4]. The alkoxide sol gel process is an efficient method to prepare the zirconium oxide matrix by the hydrolysis of alkoxide precursors followed by condensation to yield a polymeric oxo-bridged ZrO2 network. All compounds were characterized by thermal analysis and the X-ray diffractometry method. The thermoluminescence (TL) emission properties of ZrO2:Eu3+ under beta radiation effects are studied. The europium-doped sintered zirconia powder presents a TL glow curve with two peaks (Tmax) centered at around 204 and around 292 °C, respectively. TL response of ZrO2:Eu3+ as a function of beta-absorbed dose was linear from 2 Gy up to 90 Gy. The europium ion (Eu3+)-doped ZrO2 was found to be more sensitive to beta radiation than undoped ZrO2 obtained by the same method and presented a little fading of the TL signal compared with undoped zirconium oxide.

Aliphatic Imines in Titanium-Mediated Reductive Cross-Coupling: Unique Reactivity of Ti(Oi-Pr)4/n-BuLi

PubMed Central

Tarselli, Michael A.; Micalizio, Glenn C.

2009-01-01

A procedure for the coupling of aliphatic imines with allylic and allenic alkoxides is described. The success of these studies was enabled by a unique reactivity profile of Ti(IV) isopropoxide/n-BuLi compared to well-known Ti(IV) isopropoxide/R-MgX systems. PMID:19810765

Sol-Gel deposition of inorganic alkoxides on wood surfaces to enhance their durability under exposure to sunlight and moisture

Treesearch

Mandla A. Tshabalala

2005-01-01

Wood specimens were coated with sol-gel deposits of aluminum isopropoxide, titanium isopropoxide, or zirconium propoxide in the presence of methytrimethoxysilane. Both zirconium propoxide and titanium isopropoxide sol-gel deposits reduced water sorption, whereas aluminum isopropoxide sol-gel deposit increased water sorption, compared with uncoated wood specimens. There...

Preparation of Potassium Alkoxymethyltrifluoroborates and Their Cross-Coupling with Aryl Chlorides

PubMed Central

Canturk, Belgin

2015-01-01

A wide variety of alkoxymethyltrifluoroborate substrates were prepared via SN2 displacement of potassium bromomethyltrifluoroborate with various alkoxides in excellent yields. These alkoxymethyltrifluoroborates were effectively cross-coupled with several aryl chlorides. This method provides a unique dissonant disconnect that allows greater flexibility in the design of new and improved synthetic pathways. PMID:18439019

Multicomponent Oxide Systems for Corrosion Protection.

DTIC Science & Technology

1980-11-15

hydroxides on film growth. New types of mixed oxide coatings deposited from nonaqueous solutions of organometallic compounds were developed. Titanium -aluminum...mixed oxide coatings, deposited from solutions of titanium alkoxides in isopropanol, served as a prototype system for much of this work. It was found...45 13. Coating Steps and Analysis... ...................... 50 14. Auger Depth Profiles of Titanium -Aluminum Mixed Oxide *Coatings Deposited

An unexpected mechanism of hydrosilylation by a silyl hydride complex of molybdenum.

PubMed

Khalimon, Andrey Y; Ignatov, Stanislav K; Simionescu, Razvan; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

2012-01-16

Carbonyl hydrosilylation catalyzed by (ArN)Mo(H)(SiH(2)Ph)(PMe(3))(3) (3) is unusual in that it does not involve the expected Si-O elimination from intermediate (ArN)Mo(SiH(2)Ph)(O(i)Pr)(PMe(3))(2) (7). Instead, 7 reversibly transfers β-CH hydrogen from the alkoxide ligand to metal.

Polyorganometallosiloxane-2- or -4-pyridine coatings

DOEpatents

Sugama, Toshifumi

1997-01-01

A new family of polyorganometallosiloxane-2- or -4-pyridine compounds are provided for corrosion resistant coatings on light metals such as aluminum, magnesium, zinc, steel and their allows. The novel compounds contain backbones modified by metal alkoxides, metallocenes and metallophthalocyanates where the metal is Zr, Ti, Mo, V, Hf, Nb, Si, B and combinations thereof. Methods of making the new compounds are also provided.

Molecules with polymerizable ligands as precursors to porous doped materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hubert-Pfalzgraf, L.G.; Pajot, N.; Papiernik, R.

1996-12-31

Titanium and aluminum alkoxide derivatives with polymerizable ligands such as 2-(methacryloyloxy)ethylacetoacetate (HAAEMA), oleic acid and geraniol (HOGE) have been obtained. The various compounds have been characterized by FT-IR and NMR {sup 1}H. Copolymerization with styrene and divinylbenzene affords porous doped organic materials which have been characterized by scanning electron microscopy (SEM), elemental analysis, density measurements.

Ferroic Materials: Design, Preparation and Characteristics. Ceramic Transactions. Volume 43. Proceedings of International Symposium Held in Honolulu, Hawaii on November 7-10, 1993.

DTIC Science & Technology

1993-11-10

realized. Metal carboxylates are often used as precursors for ceramic oxides since they tend to be air-stable, soluble in organic solvents, and decompose...metalorganic precursors [9] . These include routes based solely on metal alkoxides [9, 101 or metal carboxylates (e.g. the Pechini (or citrate) process

Preparation of uranium compounds

DOEpatents

Kiplinger, Jaqueline L; Montreal, Marisa J; Thomson, Robert K; Cantat, Thibault; Travia, Nicholas E

2013-02-19

UI.sub.3(1,4-dioxane).sub.1.5 and UI.sub.4(1,4-dioxane).sub.2, were synthesized in high yield by reacting turnings of elemental uranium with iodine dissolved in 1,4-dioxane under mild conditions. These molecular compounds of uranium are thermally stable and excellent precursor materials for synthesizing other molecular compounds of uranium including alkoxide, amide, organometallic, and halide compounds.

Atomic layer deposition of zirconium silicate films using zirconium tetrachloride and tetra-n-butyl orthosilicate

NASA Astrophysics Data System (ADS)

Kim, Won-Kyu; Kang, Sang-Woo; Rhee, Shi-Woo; Lee, Nae-In; Lee, Jong-Ho; Kang, Ho-Kyu

2002-11-01

Atomic layer chemical vapor deposition of zirconium silicate films with a precursor combination of ZrCl4 and tetra-n-butyl orthosilicate (TBOS) was studied for high dielectric gate insulators. The effect of deposition conditions, such as deposition temperature, pulse time for purge and precursor injection on the deposition rate per cycle, and composition of the film were studied. At 400 °C, the growth rate saturated to 1.35 Å/cycle above 500 sccm of the argon purge flow rate. The growth rate, composition ratio ((Zr/Zr+Si)), and impurity contents (carbon and chlorine) saturated with the increase of the injection time of ZrCl4 and TBOS and decreased with the increased deposition temperature from 300 to 500 °C. The growth rate, composition ratio, carbon, and chlorine contents of the Zr silicate thin films deposited at 500 °C were 1.05 Å/cycle, 0.23, 1.1 at. %, and 2.1 at. %, respectively. It appeared that by using only zirconium chloride and silicon alkoxide sources, the content of carbon and chlorine impurities could not be lowered below 1%. It was also found that the incorporation rate of metal from halide source was lower than alkoxide source.

Switching on elusive organometallic mechanisms with photoredox catalysis

NASA Astrophysics Data System (ADS)

Terrett, Jack A.; Cuthbertson, James D.; Shurtleff, Valerie W.; MacMillan, David W. C.

2015-08-01

Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to `switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

Switching on elusive organometallic mechanisms with photoredox catalysis.

PubMed

Terrett, Jack A; Cuthbertson, James D; Shurtleff, Valerie W; MacMillan, David W C

2015-08-20

Transition-metal-catalysed cross-coupling reactions have become one of the most used carbon-carbon and carbon-heteroatom bond-forming reactions in chemical synthesis. Recently, nickel catalysis has been shown to participate in a wide variety of C-C bond-forming reactions, most notably Negishi, Suzuki-Miyaura, Stille, Kumada and Hiyama couplings. Despite the tremendous advances in C-C fragment couplings, the ability to forge C-O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C-O bond-forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. Here we demonstrate that visible-light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon-oxygen coupling reaction using abundant alcohols and aryl bromides. More notably, we have developed a general strategy to 'switch on' important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron-transfer catalysts.

Polyorganometallosiloxane-2- or -4-pyridine coatings

DOEpatents

Sugama, T.

1997-12-30

A new family of polyorganometallosiloxane-2- or -4-pyridine compounds are provided for corrosion resistant coatings on light metals such as aluminum, magnesium, zinc, steel and their alloys. The novel compounds contain backbones modified by metal alkoxides, metallocenes and metallophthalocyanates where the metal is Zr, Ti, Mo, V, Hf, Nb, Si, B and combinations thereof. Methods of making the new compounds are also provided. 13 figs.

Dimethylalkoxygallane incorporating a donor-functionalised alkoxide: the monomeric gas-phase structure.

PubMed

Knapp, Caroline E; Carmalt, Claire J; McMillan, Paul F; Wann, Derek A; Robertson, Heather E; Rankin, David W H

2008-12-28

The structure of the vapour produced upon heating the dimethylalkoxygallane [Me(2)GaOCH(2)CH(2)NMe(2)](2) has been studied by gas-phase electron diffraction and ab initio molecular orbital calculations; only the monomeric form [Me(2)GaOCH(2)CH(2)NMe(2)] is observed in the vapour, with the nitrogen atom forming a dative bond with the metal centre.

Nanodesigning of Hierarchical Multifunctional Ceramics

DTIC Science & Technology

1993-09-28

transformations were determined by XRD. As in previous studies, the final particle size of BaTiO 3, obtair-0 trom either the titanium isopropoxide ...conditions by reacting nanosized titanium oxide or titanium alkoxides with a solution of barium hydroxide. The powders produced by this approach range in...optical ceramic-polymer composites using colloidal dispersion techniques. In our experiments, we used either a high purity titania sood or titanium

Controlled Ring-Opening Metathesis Polymerization by Molybdenum and Tungsten Alkylidene Complexes

DTIC Science & Technology

1988-07-29

weights and low polydispersities (as low as 1.03) consistent with a living catalyst system employing 50, 100, 200, and 400 eq of monomer. The reactions are...secondary metathesis of polymer chains Bulky alkoxide ligands Wittig-like reaction Ring-opening metathesis polymerization (ROMP) Feast monomer Cyclic...olefins Retro Diels-Alder reaction Norbornene (NBE) Low temperature column chromatography Endo-,endo-5,6-dicarbomethoxynorbornene Discrete, soluble

Catalytic asymmetric Meerwein-Ponndorf-Verley reduction of glyoxylates induced by a chiral N,N'-dioxide/Y(OTf)3 complex.

PubMed

Wu, Wangbin; Zou, Sijia; Lin, Lili; Ji, Jie; Zhang, Yuheng; Ma, Baiwei; Liu, Xiaohua; Feng, Xiaoming

2017-03-18

An asymmetric Meerwein-Ponndorf-Verley (MPV) reduction of glyoxylates was for the first time accomplished via an N,N'-dioxide/Y(OTf) 3 complex with aluminium alkoxide and molecular sieves (MSs) as crucial additives. A variety of optically active α-hydroxyesters were obtained with excellent results. A possible reaction mechanism was proposed based on the experiments.

A Catalytic Method for the Conversion of Silanes to Stannanes

DTIC Science & Technology

1994-10-08

tributyltin )oxide in tetrahydrofuran. The stannanes are isolated in -quantitative yields after removal of the volatile bis(trimethylsilyl)oxide in vacuc...conditions, and the resulting anion would react with bis( tributyltin )oxide. This reaction would generate a new alkoxide, and the cycle would be...This reaction utilizes inexpensive bis( tributyltin )oxide rather than the more costly and moisture-sensitive tributyltin chloride.5 The reaction allows

Metal Alkoxides - Models for Metal Oxides.

DTIC Science & Technology

1982-07-29

molybdenum, tungsten, pi-donor ligands, carbon-monoxide, hydride, alkyne, catalysis V 20. ABSTRACT (Continue an reverve side it neceser mnd identify by... heterobimetallic activation of small but "tough" molecules such as CO has gained much attention in homogeneous organometallic chemistry within the last...34Organometallic Mechanisms and Catalysis " Academic Press: New York, 1974. 3. Catalytic Activation of Carbon Monoxide, ACS Sym. Ser. 1981, 152. Ford, P.C

Iron on mixed zirconia-titania substrate Fischer-Tropsch catalyst and method of making same

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

F-T process using an iron on mixed zirconia-titania supported catalyst

DOEpatents

Dyer, Paul N.; Nordquist, Andrew F.; Pierantozzi, Ronald

1987-01-01

A Fischer-Tropsch catalyst comprising iron co-deposited with or deposited on particles comprising a mixture of zirconia and titania, preferably formed by co-precipitation of compounds convertible to zirconia and titania, such as zirconium and titanium alkoxide. The invention also comprises the method of making this catalyst and an improved Fischer-Tropsch reaction process in which the catalyst is utilized.

Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

PubMed

Heshmat, Mojgan; Privalov, Timofei

2017-07-06

By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation of carbon-hydrogen bonds and dihydrogen by 1,2-CH-addition across metal-heteroatom bonds.

PubMed

Webb, Joanna R; Burgess, Samantha A; Cundari, Thomas R; Gunnoe, T Brent

2013-12-28

The controlled conversion of hydrocarbons to functionalized products requires selective C-H bond cleavage. This perspective provides an overview of 1,2-CH-addition of hydrocarbons across d(0) transition metal imido complexes and compares and contrasts these to examples of analogous reactions that involve later transition metal amide, hydroxide and alkoxide complexes with d(6) and d(8) metals.

Preparation of glass-forming materials from granulated blast furnace slag

NASA Astrophysics Data System (ADS)

Alonso, M.; Sáinz, E.; Lopez, F. A.

1996-10-01

Glass precursor materials, to be used for the vitrification of hazardous wastes, have been prepared from blast furnace slag powder through a sol-gel route. The slag is initially reacted with a mixture of alcohol (ethanol or methanol) and mineral acid (HNO3 or H2SO4) to give a sol principally consisting of Si, Ca, Al, and Mg alkoxides. Gelation is carried out with variable amounts of either ammonia or water. The gelation rate can be made as fast as desired by adding excess hydrolizing agent or else by distilling the excess alcohol out of the alkoxide solution. The resulting gel is first dried at low temperature and ground. The powder thus obtained is then heat treated at several temperatures. The intermediate and final materials are characterized by thermal analysis, infrared (IR) spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and chemical analysis. From the results, the operating conditions yielding a variety of glass precursors differing in their composition are established. The method, in comparison with direct vitrification of slag, presents a number of advantages: (1) the glass precursor obtained devitrifies at higher temperatures; (2) it enables the adjustment, to a certain extent, of the chemical composition of the glass precursor; and (3) it permits recovering marketable materials at different stages of the process.

Linking Precursor Alterations to Nanoscale Structure and Optical Transparency in Polymer Assisted Fast-Rate Dip-Coating of Vanadium Oxide Thin Films

PubMed Central

Glynn, Colm; Creedon, Donal; Geaney, Hugh; Armstrong, Eileen; Collins, Timothy; Morris, Michael A.; Dwyer, Colm O’

2015-01-01

Solution processed metal oxide thin films are important for modern optoelectronic devices ranging from thin film transistors to photovoltaics and for functional optical coatings. Solution processed techniques such as dip-coating, allow thin films to be rapidly deposited over a large range of surfaces including curved, flexible or plastic substrates without extensive processing of comparative vapour or physical deposition methods. To increase the effectiveness and versatility of dip-coated thin films, alterations to commonly used precursors can be made that facilitate controlled thin film deposition. The effects of polymer assisted deposition and changes in solvent-alkoxide dilution on the morphology, structure, optoelectronic properties and crystallinity of vanadium pentoxide thin films was studied using a dip-coating method using a substrate withdrawal speed within the fast-rate draining regime. The formation of sub-100 nm thin films could be achieved rapidly from dilute alkoxide based precursor solutions with high optical transmission in the visible, linked to the phase and film structure. The effects of the polymer addition was shown to change the crystallized vanadium pentoxide thin films from a granular surface structure to a polycrystalline structure composed of a high density of smaller in-plane grains, resulting in a uniform surface morphology with lower thickness and roughness. PMID:26123117

Grafting strategy to develop single site titanium on an amorphous silica surface.

PubMed

Capel-Sanchez, M C; Blanco-Brieva, G; Campos-Martin, J M; de Frutos, M P; Wen, W; Rodriguez, J A; Fierro, J L G

2009-06-16

Titanium/silica systems were prepared by grafting a titanium alkoxide (titanium isopropoxide and titanium (triethanolaminate) isopropoxide) precursor onto amorphous silica. The grafting process, which consisted of the hydrolysis of the Ti precursor by the hydroxyl groups on the silica surface, yielded samples containing Ti-loadings of 1-1.6 wt %. The as synthesized and calcined TiO(2)-SiO(2) samples were characterized by UV-vis, FTIR, XPS, and XANES spectroscopic techniques. These systems were tested in the liquid-phase epoxidation of oct-1-ene with hydrogen peroxide reaction. Spectroscopic data indicated that titanium anchoring takes place by reaction between the alkoxide precursor and surface OH groups of the silica substrate. The nature of surface titanium species generated by chemical grafting depends largely on the titanium precursor employed. Thus, the titanium isopropoxide precursor yields tetrahedrally coordinated polymeric titanium species, which give rise to a low-efficiency catalyst. However, if an atrane precursor (titanium (triethanolaminate) isopropoxide) is employed, isolated titanium species are obtained. The fact that these species remain isolated even after calcination is due to the protective effect of the triethanolaminate ligand that avoids titanium polymerization. These differences in the titanium environment have a pivotal role in the performance of these systems in the epoxidation of alkenes with hydrogen peroxide.

Grafting Strategy to Develop Single Site Titanium on an Amorphous Silica Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capel-Sanchez, M.; Blanco-Brieva, G; Campos-Martin, J

2009-01-01

Titanium/silica systems were prepared by grafting a titanium alkoxide (titanium isopropoxide and titanium (triethanolaminate) isopropoxide) precursor onto amorphous silica. The grafting process, which consisted of the hydrolysis of the Ti precursor by the hydroxyl groups on the silica surface, yielded samples containing Ti-loadings of 1-1.6 wt %. The as synthesized and calcined TiO2-SiO2 samples were characterized by UV-vis, FTIR, XPS, and XANES spectroscopic techniques. These systems were tested in the liquid-phase epoxidation of oct-1-ene with hydrogen peroxide reaction. Spectroscopic data indicated that titanium anchoring takes place by reaction between the alkoxide precursor and surface OH groups of the silica substrate.more » The nature of surface titanium species generated by chemical grafting depends largely on the titanium precursor employed. Thus, the titanium isopropoxide precursor yields tetrahedrally coordinated polymeric titanium species, which give rise to a low-efficiency catalyst. However, if an atrane precursor (titanium (triethanolaminate) isopropoxide) is employed, isolated titanium species are obtained. The fact that these species remain isolated even after calcination is due to the protective effect of the triethanolaminate ligand that avoids titanium polymerization. These differences in the titanium environment have a pivotal role in the performance of these systems in the epoxidation of alkenes with hydrogen peroxide.« less

Sol-gel-derived TiO(2)-SiO (2) implant coatings for direct tissue attachment. Part I: design, preparation and characterization.

PubMed

Aäritalo, Virpi; Areva, Sami; Jokinen, Mika; Lindén, Mika; Peltola, Timo

2007-09-01

A series of sol-gel derived TiO(2)-SiO(2) mixed oxide coatings were prepared by carefully controlling the process parameters to obtain silica-releasing coatings consisting of nanoparticles. These features are of paramount importance for enhanced cell adhesion and activation. To achieve both these goals the Ti-alkoxide and Si-alkoxide were first separately hydrolysed and the titania-silica mixed sol was further reacted before the dipping process to obtain the desired particle sizes resulting to the biologically favourable topographical features. Silica release was observed from all the prepared coatings and it was dependent on SiO(2) amount added to the sols, i.e., the higher the added amount the higher the release. In addition, calcium phosphate was able to nucleate on the coatings. From the obtained SiO(2) dissolution data, together with the detailed XPS peak analysis, the mixed oxide coatings are concluded to be chemically heterogeneous, consisting of TiO(2) and SiO(2) species most likely linked together by Ti-O-Si bonds. TiO(2) is chemically stable making long-term implant coating possible and the desired nanoscale dimensions were well preserved although the composition was changed as a consequence of SiO(2) dissolution under in vitro conditions.

Switching on Elusive Organometallic Mechanisms with Photoredox Catalysis

PubMed Central

Terrett, Jack A.; Cuthbertson, James D.; Shurtleff, Valerie W.; MacMillan, David W. C.

2015-01-01

Transition metal-catalyzed cross-coupling reactions have become one of the most utilized carbon–carbon and carbon–heteroatom bond-forming reactions in chemical synthesis. More recently, nickel catalysis has been shown to participate in a wide variety of C–C bond forming reactions, most notably Negishi, Suzuki–Miyaura, Stille, Kumada, and Hiyama couplings1,2. Despite the tremendous advances in C–C fragment couplings, the ability to forge C–O bonds in a general fashion via nickel catalysis has been largely unsuccessful. The challenge for nickel-mediated alcohol couplings has been the mechanistic requirement for the critical C–O bond forming step (formally known as the reductive elimination step) to occur via a Ni(III) alkoxide intermediate. In this manuscript, we demonstrate that visible light-excited photoredox catalysts can modulate the preferred oxidation states of nickel alkoxides in an operative catalytic cycle, thereby providing transient access to Ni(III) species that readily participate in reductive elimination. Using this synergistic merger of photoredox and nickel catalysis, we have developed a highly efficient and general carbon–oxygen coupling reaction using abundant alcohols and aryl bromides. More significantly, we have developed a general strategy to “switch on” important yet elusive organometallic mechanisms via oxidation state modulations using only weak light and single-electron transfer (SET) catalysts. PMID:26266976

Effect of Ligand Field Tuning on the SMM Behavior for Three Related Alkoxide-Bridged Dysprosium Dimers.

PubMed

Peng, Yan; Mereacre, Valeriu; Baniodeh, Amer; Lan, Yanhua; Schlageter, Martin; Kostakis, George E; Powell, Annie K

2016-01-04

The synthesis and characterization of three Dy2 compounds, [Dy2(HL1)2(NO3)4] (1), [Dy2(L2)2(NO3)4] (2), and [Dy2(HL3)2(NO3)4] (3), formed using related tripodal ligands with a central tertiary amine bearing picolyl and alkoxy arms, 2-[(2-hydroxy-ethyl)-pyridin-2-ylmethylamino]-ethanol (H2L1), 2-(bis-pyridin-2-ylmethylamino)-ethanol (HL2), and 2-(bis-pyridin-2-ylmethylamino)-propane-1,3-diol (H2L3), are reported. The compounds are rare examples of alkoxide-bridged {Dy2} complexes and display capped square antiprism coordination geometry around each Dy(III) ion. Changes in the ligand field environment around the Dy(III) ions brought about through variations in the ligand donors can be gauged from the magnetic properties, with compounds 1 and 2 showing antiparallel coupling between the Dy(III) ions and 3 showing parallel coupling. Furthermore, slow relaxation of the magnetization typical of SMM behavior could be observed for compounds 2 and 3, suggesting that small variations in the ligand field can have a significant influence on the slow relaxation processes responsible for SMM behavior of Dy(III)-based systems.

Ultrastructure Processing of Advanced Materials.

DTIC Science & Technology

1992-11-01

alkoxide) involving the sodium and the other metal [e.g., NaZr 2(OR)9]. The use of anhydrous ammonia usually solves this problem. MCIX + xNH 3 + xROH - M...the formation of pentacoordinate silicic acid complexes with hydroxide and fluoride ions, as well as neutral adducts with hydrogen fluoride, ammonia ...stable than that for any other small neutral adduct such as water, ammonia , and hydrogen chloride. Elimination of water is much easier by internal

Low temperature process for obtaining thin glass films

DOEpatents

Brinker, C. Jeffrey; Reed, Scott T.

1984-01-01

A method for coating a substrate with a glass-like film comprises, applying to the substrate an aqueous alcoholic solution containing a polymeric network of partially hydrolyzed metal alkoxide into which network there is incorporated finely powdered glass, whereby there is achieved on the substrate a coherent and adherent initial film; and heating said film to a temperature sufficient to melt said powdered glass component, thereby converting said initial film to a final densified film.

Low temperature process for obtaining thin glass films

DOEpatents

Brinker, C.J.; Reed, S.T.

A method for coating a substrate with a glass-like film comprises, applying to the substrate an aqueous alcoholic solution containing a polymeric network of partially hydrolyzed metal alkoxide into which network there is incorporated finely powdered glass, whereby there is achieved on the substrate a coherent and adherent initial film; and heating said film to a temperature sufficient to melt said powdered glass component, thereby converting said initial film to a final densified film.

Preparation and Stoichiometry Effects on Microstructure and Properties of High Purity BaTiO3.

DTIC Science & Technology

1986-03-27

oxalate , citrate) salt solutions, from mixed alkoxide precursors or from hydrothermal solutions. Typical starting materials and reaction sequences...decomposition and calcination reactions to form the BaTiO compound. Both the oxalate and 3 hydrothermal processes show commnercial promise and are briefly...thermal decomposition of oxalates and by hydrothermal synthesis. As-received lots of mixed oxide and oxalate -derived powders had Ba:TI ratios of 0.997 and

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.

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.

Transition-Metal-Free Alkynylation of Aryl Chlorides

PubMed Central

Truong, Thanh; Daugulis, Olafs

2011-01-01

Two sets of conditions have been developed for a base-mediated, transition-metal-free alkynylation of aryl chlorides that proceeds via benzyne intermediates. The first set of conditions involves the use of TMPLi base in a pentane/THF mixture at 25 °C. The second set involves use of a metal alkoxide base in dioxane at elevated temperature. Reasonable functional group tolerance has been observed. Fluoro, trifluoromethyl, silyl, cyano, and alcohol functionalities are compatible with the reaction conditions. PMID:21786825

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeTuri, V.F.; Ervin, K.M.

Energy-resolved competitive collision-induced dissociation methods are used to measure the gas-phase acidities of a series of alcohols (methanol, ethanol, 2-propanol, and 2-methyl-2-propanol). The competitive dissociation reactions of fluoride-alcohol, [F{sup {minus}}{center{underscore}dot}HOR], alkoxide-water, [RO{sup {minus}}{center{underscore}dot}HOH], and alkoxide-methanol [RO{+-}{center{underscore}dot}HOCH{sub 3}] proton-bound complexes are studied using a guided ion beam tandem mass spectrometer. The reaction cross sections and product branching fractions to the two proton transfer channels are measured as a function of collision energy. The enthalpy difference between the two product channels is found by modeling the reaction cross sections near threshold using RRKM theory to account for the energy-dependent product branching ratiomore » and kinetic shift. From the enthalpy difference, the alcohol gas-phase acidities are determined relative to the well-known values of HF and H{sub 2}O. The measured gas-phase acidities are {Delta}{sub acid}H{sub 298}(CH{sub 3}OH) = 1599 {+-} 3 kJ/mol, {Delta}{sub acid}H{sub 298}(CH{sub 3}CH{sub 2}OH) = 1586 {+-} 5 kJ/mol, {Delta}{sub acid}H{sub 298}((CH{sub 3}){sub 2}CHOH) = 1576 {+-} 4 kJ/mol, and {Delta}{sub acid}H{sub 298}((CH{sub 3}){sub 3}COH) = 1573 {+-} 3 kJ/mol.« less

The sol-gel route: A versatile process for up-scaling the fabrication of gas-tight thin electrolyte layers

NASA Astrophysics Data System (ADS)

Viazzi, Céline; Rouessac, Vincent; Lenormand, Pascal; Julbe, Anne; Ansart, Florence; Guizard, Christian

2011-03-01

Sol-gel routes are often investigated and adapted to prepare, by suitable chemical modifications, submicronic powders and derived materials with controlled morphology, which cannot be obtained by conventional solid state chemistry paths. Wet chemistry methods provide attractive alternative routes because mixing of species occurs at the atomic scale. In this paper, ultrafine powders were prepared by a novel synthesis method based on the sol-gel process and were dispersed into suspensions before processing. This paper presents new developments for the preparation of functional materials like yttria-stabilized-zirconia (YSZ, 8% Y2O3) used as electrolyte for solid oxide fuel cells. YSZ thick films were coated onto porous Ni-YSZ substrates using a suspension with an optimized formulation deposited by either a dip-coating or a spin-coating process. The suspension composition is based on YSZ particles encapsulated by a zirconium alkoxide which was added with an alkoxide derived colloidal sol. The in situ growth of these colloids increases significantly the layer density after an appropriated heat treatment. The derived films were continuous, homogeneous and around 20 μm thick. The possible up-scaling of this process has been also considered and the suitable processing parameters were defined in order to obtain, at an industrial scale, homogeneous, crack-free, thick and adherent films after heat treatment at 1400 °C.

Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands.

PubMed

Carroll, Gerard M; Limpens, Rens; Neale, Nathan R

2018-05-09

The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups-alkyls, amides, and alkoxides-on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative to alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands-not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals-are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. These results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.

Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands

DOE PAGES

Carroll, Gerard M.; Limpens, Rens; Neale, Nathan R.

2018-04-16

The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups - alkyls, amides, and alkoxides - on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative tomore » alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands - not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals - are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. Furthermore, these results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.« less

Effect of Chelating Agents on the Stability of Nano-TiO2 Sol Particles for Sol-Gel Coating.

PubMed

Maeng, Wan Young; Yoo, Mi

2015-11-01

Agglomeration of sol particles in a titanium alkoxide (tetrabutyl orthotitanate (TBOT), > 97%) solution during the hydrolysis and condensation steps makes the sol solution difficult to use for synthesizing homogeneous sol-gel coating. Here, we have investigated the effect of stabilizing agents (acetic acid and ethyl acetoacetate (EAcAc)) on the agglomeration of Ti alkoxide particles during hydrolysis and condensation in order to determine the optimized conditions for controlling the precipitation of TiO2 particles. The study was conducted at R(AC) ([acetic acid]/[TBOT]) = 0.1-5 and R(EAcAc)([EAcAc]/[TBOT]) = 0.05-0.65. We also studied the effects of a basic catalyst ethanolamine (ETA), water, and HCl on sol stability. The chelating ligands in the precursor sol were analyzed with FT-IR. The coating properties were examined by focused ion beam. The stabilizing agents (acetic acid and EAcAc) significantly influenced the agglomeration and precipitation of TBOT precursor particles during hydrolysis. As R(AC) and R(EAcAc) increased, the agglomeration remarkably decreased. The stability of the sol with acetic acid and EAcAc arises from the coordination of the chelating ligand to TBOT that hinders hydrolysis and condensation. A uniform fine coating (thickness: 30 nm) on stainless steel was obtained by using an optimized sol with R(AC) = 0.5 and R(EAcAc) = 0.65.

Synthesis and coordination chemistry of TpC*MI complexes where M=Mg, Ca, Sr, Ba and Zn and TpC*=tris[3-(2-methoxy-1,1-dimethyl)pyrazolyl]hydroborate.

PubMed

Chisholm, Malcolm H; Gallucci, Judith C; Yaman, Gulsah

2009-01-14

Reactions involving MI2 where M=Mg, Ca, Sr, Ba or Zn and M'TpC* where M'=Na or Tl and TpC*=tris[3-methoxy-1,1-dimethyl)pyrazolyl]hydroborate in tetrahydrofuran are described leading to the isolation and characterization of the complexes TpC*MgI, , TpC*CaI, , TpC*SrI, , TpC*SrI(THF), , TpC*BaI, , TpC*BaI(pz*H), , where pz*H=3-(2-methoxyl-1,1-dimethyl)pyrazole, TpC*BaI.1/2toluene, and TpC*ZnI, . The compounds , , , , and have been characterized by single-crystal X-ray crystallography. Compounds and are isostructural and are salt-like containing kappa6-TpM+ cations and I- anions. In all other structures, the iodide is bound to the metal and TpC* is kappa6 bonded to the group 2 M(2+) ions. Reactions involving TpC*CaI, , and sodium or lithium alkoxides or amides failed to yield the amide or alkoxide calcium TpC* derivative, though related reactions involving TpC*ZnI, , and KOSiMe3 proceeded quantitatively to yield kappa3TpC*ZnOSiMe3, , which was also structurally characterized and shown to have the kappa3-TpC* bound ligand.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neale, Nathan R; Carroll, Gerard; Limpens, Rens

The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups - alkyls, amides, and alkoxides - on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative tomore » alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands - not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals - are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. These results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.« less

Nonaqueous solution synthesis process for preparing oxide powders of lead zirconate titanate and related materials

DOEpatents

Voigt, J.A.; Sipola, D.L.; Tuttle, B.A.; Anderson, M.T.

1999-06-01

A process is disclosed for producing powders of perovskite-type compounds which comprises mixing a metal alkoxide solution with a lead acetate solution to form a homogeneous, clear metal solution, adding an oxalic acid/n-propanol solution to this metal solution to form an easily filterable, free-flowing precursor powder and then calcining this powder. This process provides fine perovskite-phase powders with ferroelectric properties which are particularly useful in a variety of electronic applications. 4 figs.

Nonaqueous solution synthesis process for preparing oxide powders of lead zirconate titanate and related materials

DOEpatents

Voigt, James A.; Sipola, Diana L.; Tuttle, Bruce A.; Anderson, Mark T.

1999-01-01

A process for producing powders of perovskite-type compounds which comprises mixing a metal alkoxide solution with a lead acetate solution to form a homogeneous, clear metal solution, adding an oxalic acid/n-propanol solution to this metal solution to form an easily filterable, free-flowing precursor powder and then calcining this powder. This process provides fine perovskite-phase powders with ferroelectric properties which are particularly useful in a variety of electronic applications.

Molten carbonate fuel cell cathode with mixed oxide coating

DOEpatents

Hilmi, Abdelkader; Yuh, Chao-Yi

2013-05-07

A molten carbonate fuel cell cathode having a cathode body and a coating of a mixed oxygen ion conductor materials. The mixed oxygen ion conductor materials are formed from ceria or doped ceria, such as gadolinium doped ceria or yttrium doped ceria. The coating is deposited on the cathode body using a sol-gel process, which utilizes as precursors organometallic compounds, organic and inorganic salts, hydroxides or alkoxides and which uses as the solvent water, organic solvent or a mixture of same.

Lithium-promoted hydrogenation of carbon dioxide to formates by heterobimetallic hydridozinc alkoxide clusters.

PubMed

Merz, Klaus; Moreno, Mariluna; Löffler, Elke; Khodeir, Lamy; Rittermeier, Andre; Fink, Karin; Kotsis, Konstantinos; Muhler, Martin; Driess, Matthias

2008-01-07

The remarkably distinct reactivity of hydridozinc heterobimetallic cubanes [(HZnOtBu)4-n(thf LiOtBu)n] 1a-1d towards CO2 is reported--the hydride transfer from Zn-H to CO2 is drastically accelerated in the presence of Li ions in 1b-1d which led to the respective metal formate hydrates; the systems are inspiring models for the selective conversion of water gas into formates on lithium-promoted ZnO supports.

Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism.

PubMed

Schön, Eva; Zhang, Xiangyang; Zhou, Zhiping; Chisholm, Malcolm H; Chen, Peter

2004-11-15

The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

Exploring the relative reactivities of the hydroxyl groups of monosaccharides by molecular modeling and molecular mechanics

NASA Astrophysics Data System (ADS)

Box, V. G. S.; Evans-Lora, T.

2000-01-01

The molecular modeling program STR3DI.EXE, and its molecular mechanics module, QVBMM, were used to simulate, and evaluate, the stereo-electronic effects in the mono-alkoxides of the 4,6- O-ethylideneglycopyranosides of allose, mannose, galactose and glucose. This study has confirmed the ability of these molecular modeling tools to predict the regiochemistry and reactivity of these sugar derivatives, and holds considerable implications for unraveling the chemistry of the rare monosaccharides.

Structural studies of gels and gel-glasses in the SiO2-GeO2 system using vibrational spectroscopy

NASA Technical Reports Server (NTRS)

Mukherjee, Shyama P.; Sharma, Shiv K.

1986-01-01

GeO2 gel and gels in the SiO2-GeO2 system synthesized by the hydrolytic polycondensation of metal alkoxides have been studied by infrared and Raman spectroscopic techniques. The molecular structures, hydroxyl contents, and crystallinity of gels and gel-glasses in relation to the thermal history and GeO2 concentration were investigated. The binary compositions having up to 70 mol percent GeO2 were examined.

Formyl-ended heterobifunctional poly(ethylene oxide): synthesis of poly(ethylene oxide) with a formyl group at one end and a hydroxyl group at the other end.

PubMed

Nagasaki, Y; Kutsuna, T; Iijima, M; Kato, M; Kataoka, K; Kitano, S; Kadoma, Y

1995-01-01

Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

JPRS Report Science & Technology Japan

DTIC Science & Technology

1989-03-02

Oxychlorides MOCln_2 (Organic Metal Salts) Alkoxides M(OR)n Acetylacetonate M(C5H702)n Acetates M(C2H302)n Oxalates M(C204)n/2 2.2 Hydrolysis and Gel...more deeply understanding hydrothermal dynamics during not only a major rupture LOCA but also a minor rupture LOCA and clarifying the combination of... hydrothermal dynamics of the coolant from the beginning of LOCA to its end, using a scale model of PWR (pressurized water reactor). Under the ROSA-III Plan

Precursor directed synthesis--"molecular" mechanisms in the Soft Chemistry approaches and their use for template-free synthesis of metal, metal oxide and metal chalcogenide nanoparticles and nanostructures.

PubMed

Seisenbaeva, Gulaim A; Kessler, Vadim G

2014-06-21

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.

The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-01-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R + R'-OH --> - CH2-CO2-R' + R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'-OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic cations at their transition states. These compensating effects from electrostatic stabilization depend on how similar the charge density in these organic cations is to that in the proton removed. Cations with more localized charge favor strong electrostatic interactions with anions and form more stable ionic structures than do cations with more diffuse charges. Ion-pairs at elimination transition states contain cations with higher local charge density at the sp(2) carbon than for isomerization transition states; as a result, these ion-pairs recover a larger fraction of the deprotonation energy, and, consequently, their reactions become less sensitive to acid strength. These concepts lead us to conclude that the energetic difficulty of a catalytic reaction, imposed by gas-phase reactant proton affinities in transition state analogues, does not determine its sensitivity to the acid strength of solid catalysts.

Glass former composition and method for immobilizing nuclear waste using the same

DOEpatents

Cadoff, Laurence H.; Smith-Magowan, David B.

1988-01-01

An alkoxide glass former composition has silica-containing constituents present as solid particulates of a particle size of 0.1 to 0.7 micrometers in diameter in a liquid carrier phase substantially free of dissolved silica. The glass former slurry is resistant to coagulation and may contain other glass former metal constituents. The immobilization of nuclear waste employs the described glass former by heating the same to reduce the volume, mixing the same with the waste, and melting the resultant mixture to encapsulate the waste in the resultant glass.

Aqueous silicates in biological sol-gel applications: new perspectives for old precursors.

PubMed

Coradin, Thibaud; Livage, Jacques

2007-09-01

Identification of silica sol-gel chemistry with silicon alkoxide hydrolysis and condensation processes is common in modern materials science. However, aqueous silicates exhibit several features indicating that they may be more suitable precursors for specific fields of research and applications related to biology and medicine. In this Account, we illustrate the potentialities of such aqueous precursors for biomimetic studies, bio-hybrid material design, and bioencapsulation routes. We emphasize that the natural relevance, the biocompatibility, and the low ecological impact of silicate chemistry may balance its lack of diversity, flexibility, and processability.

Metal-Metal Bonds and Metal Carbon Bonds in the Chemistry of Molybdenum and Tungsten Alkoxides.

DTIC Science & Technology

1983-02-07

properties. For example, the lanthanide elements and aluminum form an extensive series of isopropoxides of formula MAI3 (OPr i)12 which are volatile solids or...coordination is imposed. !E 2 RO RO RO-_ 0 1_-OR ROe MV’*’ I ’%OR RO RRO (2) The ethoxides and methoxides of titanium (+4) adopt a tetrameric structure in the...solid state, II, whereby each metal atom achieves an octahedral environment. In benzene solution, the titanium ethoxide dissoci- ates to trimers, while

Preparation of 3,5-disubstituted pyrazoles and isoxazoles from terminal alkynes, aldehydes, hydrazines, and hydroxylamine.

PubMed

Harigae, Ryo; Moriyama, Katsuhiko; Togo, Hideo

2014-03-07

The reaction of terminal alkynes with n-BuLi, and then with aldehydes, followed by the treatment with molecular iodine, and subsequently hydrazines or hydroxylamine provided the corresponding 3,5-disubstituted pyrazoles or isoxazoles in good yields with high regioselectivity, through the formations of propargyl secondary alkoxides and α-alkynyl ketones. The present reactions are one-pot preparation of 3,5-disubstituted pyrazoles from terminal alkynes, aldehydes, molecular iodine, and hydrazines, and 3,5-disubstituted isoxazoles from terminal alkynes, aldehydes, molecular iodine, and hydroxylamine.

Metal oxide porous ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1992-01-01

A method is disclosed for the production of metal oxide ceramic membranes of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Metal oxide porous ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1991-01-01

A method is disclosed for the production of metal oxide ceramic membranes of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Exchange Reactions of Organotin and Organosilicon Compounds with Mild Fluorinating Agents

DTIC Science & Technology

1992-03-01

methylphosphonic difluoride, boron trifluoride etherate, and perfluoroisobutene all react with both organosilicon and organotin. alkoxides to give...inlet tube, was charged with tributyltin cyanide (53.30 gm, 0.1686 mol) in a dry glove bag under an inert atmosphere and 500 ml of dry xylene was then...Chem. Vol. 29, p 471 (1985). 6. Tyuleneva, V.V., Rozov, L.A., Zeifman, Yu.V. and I. L. Knuny- ants,"Exchange of Fluorine by Chlorine in Perfluoro-isobutene," Tzv.Akad.Nauk. SSSR. Ser. Khim No. 5, p 1136 (1975). 17

Selective Methylmagnesium Chloride Mediated Acetylations of Isosorbide: A Route to Powerful Nitric Oxide Donor Furoxans.

PubMed

Kielty, Patrick; Smith, Dennis A; Cannon, Peter; Carty, Michael P; Kennedy, Michael; McArdle, Patrick; Singer, Richard J; Aldabbagh, Fawaz

2018-04-26

Isosorbide was functionalized with furoxan for the first time to give adducts that release nitric oxide up to 7.5 times faster than the commercial vasodilator, isosorbide-5-mononitrate (Is5N). The synthesis was facilitated by MeMgCl-mediated selective acetylation of isosorbide or selective deacetylation of isosorbide-2,5-diacetate, which was rationalized in terms of a more stable 5-alkoxide magnesium salt using DFT. Isosorbide-furoxans are safer to handle than Is5N due to greater thermal stability.

New Synthetic Methods. A. Lithiation of Methoxypyridines and N-Methylindoles Directed by a-Amino Alkoxides. B. Synthetic Methods Using N-Acyliminium Ions and 1-Acylpyridinium Salts

DTIC Science & Technology

1990-01-01

32) Kompis , I.; Mueller, W.; Boehni, E.; Then, R.; Montavon, M. Eur. J. Med. Chem.-Chim. Ther. 1977, 12, 531. (33) Gilgow, H.M.; Burton, D.E. J. Org...23 H), 2.70-2.80 (m, 1 H), 4.85-5.70 (m, 3 H), 5.50-5.70 (m, 1 H), 7.05-7.45 (m, 5 H). 118 IV. REFERENCES (1) (a) Zaugg, H.E.; Martin , W.B. Org. React

Liquid phase low temperature method for production of methanol from synthesis gas and catalyst formulations therefor

DOEpatents

Mahajan, Devinder

2005-07-26

The invention provides a homogenous catalyst for the production of methanol from purified synthesis gas at low temperature and low pressure which includes a transition metal capable of forming transition metal complexes with coordinating ligands and an alkoxide, the catalyst dissolved in a methanol solvent system, provided the transition metal complex is not transition metal carbonyl. The coordinating ligands can be selected from the group consisting of N-donor ligands, P-donor ligands, O-donor ligands, C-donor ligands, halogens and mixtures thereof.

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2016-03-22

A process for synthesizing 4-amino-2,4-dioxobutanoic acid involves reacting diethyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding ethyl cyanoacetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoic acid.

Synthesis of zirconia monoliths for chromatographic separations.

PubMed

Randon, Jérôme; Huguet, Samuel; Piram, Anne; Puy, Guillaume; Demesmay, Claire; Rocca, Jean-Louis

2006-03-17

The aim of this work is to join the advantages of two different kinds of stationary phases: monolithic columns and zirconia-based supports. On the one hand, silica monolithic columns allow a higher efficiency with a lower back-pressure than traditional packed columns. On the other hand, chromatographic stationary phases based on zirconia have a higher thermal and chemical stability and specific surface properties. Combining these advantages, a zirconia monolith with a macroporous framework could be a real improvement in separation sciences. Two main strategies can be used in order to obtain a zirconia surface on a monolithic skeleton: coating or direct synthesis. The coverage by a zirconia layer of the surface of a silica-based monolith can be performed using the chemical properties of the silanol surface groups. We realized this coverage using zirconium alkoxide and we further grafted n-dodecyl groups using phosphate derivatives. Any loss of efficiency was observed and fast separations have been achieved. The main advance reported in this paper is related to the preparation of zirconia monoliths by a sol-gel process starting from zirconium alkoxide. The synthesis parameters (hydrolysis ratio, porogen type, precursor concentration, drying step, etc.) were defined in order to produce a macroporous zirconia monoliths usable in separation techniques. We produced various homogeneous structures: zirconia rod 2 cm long with a diameter of 2.3 mm, and zirconia monolith inside fused silica capillaries with a 75 microm I.D. These monoliths have a skeleton size of 2 microm and have an average through pore size of 6 microm. Several separations have been reported.

Erratum to "The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase" : [Int. J. Mass Spectrom. Ion Process. 172 (1998) 25

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-02-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R+R'-OH-->-CH2-CO2-R'+R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'--OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Chiral nematic porous germania and germanium/carbon films

NASA Astrophysics Data System (ADS)

Xu, Jing; Nguyen, Thanh-Dinh; Xie, Kai; Hamad, Wadood Y.; MacLachlan, Mark J.

2015-07-01

We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering.We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering. Electronic supplementary information (ESI) available: TGA, IR, Raman, TEM, SEM, BET. See DOI: 10.1039/c5nr02520f

Importance of a serine proximal to the C(4a) and N(5) flavin atoms for hydride transfer in choline oxidase.

PubMed

Yuan, Hongling; Gadda, Giovanni

2011-02-08

Choline oxidase catalyzes the flavin-dependent, two-step oxidation of choline to glycine betaine with the formation of an aldehyde intermediate. In the first oxidation reaction, the alcohol substrate is initially activated to its alkoxide via proton abstraction. The substrate is oxidized via transfer of a hydride from the alkoxide α-carbon to the N(5) atom of the enzyme-bound flavin. In the wild-type enzyme, proton and hydride transfers are mechanistically and kinetically uncoupled. In this study, we have mutagenized an active site serine proximal to the C(4a) and N(5) atoms of the flavin and investigated the reactions of proton and hydride transfers by using substrate and solvent kinetic isotope effects. Replacement of Ser101 with threonine, alanine, cysteine, or valine resulted in biphasic traces in anaerobic reductions of the flavin with choline investigated in a stopped-flow spectrophotometer. Kinetic isotope effects established that the kinetic phases correspond to the proton and hydride transfer reactions catalyzed by the enzyme. Upon removal of Ser101, there is an at least 15-fold decrease in the rate constants for proton abstraction, irrespective of whether threonine, alanine, valine, or cysteine is present in the mutant enzyme. A logarithmic decrease spanning 4 orders of magnitude is seen in the rate constants for hydride transfer with increasing hydrophobicity of the side chain at position 101. This study shows that the hydrophilic character of a serine residue proximal to the C(4a) and N(5) flavin atoms is important for efficient hydride transfer.

Direct observation of macrostructure formation of hierarchically structured meso-macroporous aluminosilicates with 3D interconnectivity by optical microscope.

PubMed

Lemaire, Arnaud; Rooke, Joanna Claire; Chen, Li-Hua; Su, Bao-Lian

2011-03-15

Hierarchically structured spongy meso-macroporous aluminosilicates with high tetrahedral aluminum content were synthesized from a mixture of single molecular alkoxide precursor, (sec-BuO)2-Al-O-Si(OEt)3, already containing Si-O-Al bonds, and a silica coreactant, tetramethoxysilane (TMOS). The spontaneous byproduct templated macroporous structure formation has been directly visualized using in situ high-resolution optical microscopy (OM), allowing the crucial observation of a microbubble dispersion which is directly correlated to the macrostructure observed by electronic microscopies (SEM and TEM). This discovery leads to a comparative study with meso-macroporous pure metal oxide and to a proposal of the formation mechanism of meso-macroporous aluminosilicates with 3D interconnectivity. The aluminosilicate phase/microbubbles emulsion is produced by a phase separation process occurring between the aluminosilicate nanoparticles and the liquid hydrolysis-condensation reaction byproducts (water, methanol, ethanol, and butanol). The use of alkoxysilane improves the heterocondensation rates between the highly reactive aluminum alkoxide part of the single precursor and added silica species but, above all, leads to the spontaneous generation of an unusual meso-macroporosity in alkaline media. The particles obtained at pH = 13.0 featured regular micrometer-sized macrospheres separated by very thin mesoporous walls and connected by submicrometric openings, providing a 3D interconnectivity. The slight increase in pH value to 13.5 induced significant modifications in morphology and textural properties due to the slower gelification process of the aluminosilicate phase, resulting in the formation of an aluminosilicate material constituted of 1-2 µm large independent hollow mesoporous spheres.

Mesoporous titanium dioxide (TiO2) with hierarchically 3D dendrimeric architectures: formation mechanism and highly enhanced photocatalytic activity.

PubMed

Li, Xiao-Yun; Chen, Li-Hua; Rooke, Joanna Claire; Deng, Zhao; Hu, Zhi-Yi; Wang, Shao-Zhuan; Wang, Li; Li, Yu; Krief, Alain; Su, Bao-Lian

2013-03-15

Mesoporous TiO(2) with a hierarchically 3D dendrimeric nanostructure comprised of nanoribbon building units has been synthesized via a spontaneous self-formation process from various titanium alkoxides. These hierarchically 3D dendrimeric architectures can be obtained by a very facile, template-free method, by simply dropping a titanium butoxide precursor into methanol solution. The novel configuration of the mesoporous TiO(2) nanostructure in nanoribbon building units yields a high surface area. The calcined samples show significantly enhanced photocatalytic activity and degradation rates owing to the mesoporosity and their improved crystallinity after calcination. Furthermore, the 3D dendrimeric architectures can be preserved after phase transformation from amorphous TiO(2) to anatase or rutile, which occurs during calcination. In addition, the spontaneous self-formation process of mesoporous TiO(2) with hierarchically 3D dendrimeric architectures from the hydrolysis and condensation reaction of titanium butoxide in methanol has been followed by in situ optical microscopy (OM), revealing the secret on the formation of hierarchically 3D dendrimeric nanostructures. Moreover, mesoporous TiO(2) nanostructures with similar hierarchically 3D dendrimeric architectures can also be obtained using other titanium alkoxides. The porosities and nanostructures of the resultant products were characterized by SEM, TEM, XRD, and N(2) adsorption-desorption measurements. The present work provides a facile and reproducible method for the synthesis of novel mesoporous TiO(2) nanoarchitectures, which in turn could herald the fabrication of more efficient photocatalysts. Copyright © 2012 Elsevier Inc. All rights reserved.

Engineered, Solid-State Processes for Enhanced Biosolar Hydrogen Production and Exploitation of Solar Energy with Tailored Light-Harvesting Systems

DTIC Science & Technology

2012-09-30

PEG200, and  betaine . It was found that  Synechocystis sp. PCC 6803 is highly sensitive to an initial stress presented by exposure to all these...detrimental to long  term viability, while  betaine  had  little impact. Figure 3 illustrates  stable quantum efficiency of PSII  in both alkoxide and aqueous

Remote Central-to-Axial Chirality Conversion: Direct Atroposelective Ester to Biaryl Transformation.

PubMed

Link, Achim; Sparr, Christof

2018-05-16

A strategy for the remote central-to-axial chirality conversion by simultaneous planarization of an encoding and a transient stereocenter is presented. Based on a diastereoselective double addition of a chiral 1,5-bifunctional organomagnesium alkoxide reagent to a broad range of aryl ester substrates, axially chiral biaryls are directly obtained upon in situ reduction. Various structurally distinct atropisomeric biaryl silanes that serve as valuable chiral biaryl anion surrogates are accessible in one step with e.r. values of up to 98:2. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ceramic membranes with enhanced thermal stability

DOEpatents

Anderson, Marc A.; Xu, Qunyin; Bischoff, Brian L.

1993-01-01

A method of creating a ceramic membrane with enhanced thermal stability is disclosed. The method involves combining quantities of a first metal alkoxide with a second metal, the quantities selected to give a preselected metal ratio in the resultant membrane. A limited amount of water and acid is added to the combination and stirred until a colloidal suspension is formed. The colloid is dried to a gel, and the gel is fired at a temperature greater than approximately 400.degree. C. The porosity and surface area of ceramic membranes formed by this method are not adversely affected by this high temperature firing.

Method of making metal oxide ceramic membranes with small pore sizes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1992-01-01

A method for the production of metal oxide ceramic membranes is composed of very small pore size. The process is particularly useful in the creation of titanium and other transition metal oxide membranes. The method utilizes a sol-gel process in which the rate of particle formation is controlled by substituting a relatively large alcohol in the metal alkoxide and by limiting the available water. Stable, transparent metal oxide ceramic membranes are created having a narrow distribution of pore size, with the pore diameter being manipulable in the range of 5 to 40 Angstroms.

Preparation of hydrophobic coatings

DOEpatents

Branson, Eric D [Albuquerque, NM; Shah, Pratik B [Albuquerque, NM; Singh, Seema [Rio Rancho, NM; Brinker, C Jeffrey [Albuquerque, NM

2009-02-03

A method for preparing a hydrophobic coating by preparing a precursor sol comprising a metal alkoxide, a solvent, a basic catalyst, a fluoroalkyl compound and water, depositing the precursor sol as a film onto a surface, such as a substrate or a pipe, heating, the film and exposing the film to a hydrophobic silane compound to form a hydrophobic coating with a contact angle greater than approximately 150.degree.. The contact angle of the film can be controlled by exposure to ultraviolet radiation to reduce the contact angle and subsequent exposure to a hydrophobic silane compound to increase the contact angle.

Fischer-Tropsch process

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch process utilizing a product selective and stable catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Better Ceramics Through Chemistry IV. Materials Research Society Sumposium Proceedings. Volume 180

DTIC Science & Technology

1991-03-31

GELS 117 L.F. Nazar, D.G. Napier, D. Lapham, and E. Epperson SMALL ANGLE X - RAY SCATTERING STUDIES Or POLYMERIC ZIRCONIUM SPECIES IN AQUEOUS SOLUTION...recently obtained the first X - ray crystallographic data on bismuth alkoxides, Bi(OR) 3 (R = C(CH3) 3 and C6 H4 (CH 3 )2 -2,6) [8]. These data showed that...d8, ppm): 12.5 (O2CMe), 9.6 (OCMe3). The complex was identified by X - ray crystallography. 1 crystallizes in space group P21/n with a = 13.149(2) A, b

An easy access to nanocrystalline alkaline earth metal fluorides - just by shaking

NASA Astrophysics Data System (ADS)

Dreger, M.; Scholz, G.; Kemnitz, E.

2012-04-01

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF2 (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH4F as fluorinating agent. Even very simple manual shaking experiments between NH4F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Dan; Yang, Ping, E-mail: mse_yangp@ujn.edu.cn; Huang, Baibiao

Graphical abstract: The iron alkoxide precursors are calcined into α-Fe{sub 2}O{sub 3}, Fe{sub 3}O{sub 4} microstructures with different morphologies by changing calcination atmosphere, reaction time of precursors and calcination temperature simply. The Fe{sub 2}O{sub 3}/Ag hybrid composites prepared through aqueous synthesis and light irradiation. - Highlights: • α-Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} microstructures with different morphologies were created. • Solvents play an important role for the solvothermal treatment of precursors. • The α-Fe{sub 2}O{sub 3} microstructures show excellent adsorption properties. • Fe{sub 2}O{sub 3}/Ag hybrid composites were prepared to improve their properties. - Abstract: The flower-like precursors ofmore » Fe alkoxide constructed by the self-assembly of nanoflakes were prepared. Time-dependent experiments confirmed the formation mechanism of flower-like precursors. After calcination, α-Fe{sub 2}O{sub 3} and Fe{sub 3}O{sub 4} nanostructures with different morphologies were created. Fe{sub 3}O{sub 4} nanostructures containing blocks with a truncated octahedron structure were obtained under N{sub 2} protection. α-Fe{sub 2}O{sub 3} nanostructures were prepared in an air atmosphere. The values of maximum adsorption capacity of α-Fe{sub 2}O{sub 3} nanostructures for Cr{sup 6+} ions were much higher than that of commercial bulk α-Fe{sub 2}O{sub 3}. Ag NPs were deposited on α-Fe{sub 2}O{sub 3} nanostructures through an aqueous synthesis and light irradiation using L-cysteine as a linker. Such procedure is utilizable for the preparation of the composites of noble metals and magnetic materials.« less

Sol-gel chemistry-based Ucon-coated columns for capillary electrophoresis.

PubMed

Hayes, J D; Malik, A

1997-07-18

A sol-gel chemistry-based novel approach for the preparation of a Ucon-coated fused-silica capillary column in capillary electrophoresis is presented. In this approach the sol-gel process is carried out inside 25 microm I.D. fused-silica capillaries. The sol solution contained appropriate quantities of an alkoxide-based sol-gel precursor, a polymeric coating material (Ucon), a crosslinking reagent, a surface derivatizing reagent, controlled amounts of water and a catalyst dissolved in a suitable solvent system. The coating procedure involves filling a capillary with the sol solution and allowing the sol-gel process to proceed for an optimum period. Hydrolysis of the alkoxide precursor and polycondensation of the hydrolyzed products with the surface silanol groups and the hydroxy-terminated Ucon molecules lead to the formation of a surface-bonded sol-gel coating on the inner walls of the capillary. The thickness of the coated film can be controlled by varying the reaction time, coating solution composition and experimental conditions. Commercial availability of high purity sol-gel precursors (e.g., TEOS 99.999%), the ease of coating, run-to-run and column-to-column reproducibility, and long column lifetimes make sol-gel coating chemistry very much suitable for being applied in analytical microseparations column technology. Test samples of basic proteins and nucleotides were used to evaluate the column performance. These results show that the sol-gel coating scheme has allowed for the generation of bio-compatible surfaces characterized by high separation efficiencies in CE. For different types of solutes, the sol-gel coated Ucon column consistently provided migration time R.S.D. values of the order of 0.5%.

Exploring encapsulation mechanism of DNA and mononucleotides in sol-gel derived silica.

PubMed

Kapusuz, Derya; Durucan, Caner

2017-07-01

The encapsulation mechanism of DNA in sol-gel derived silica has been explored in order to elucidate the effect of DNA conformation on encapsulation and to identify the nature of chemical/physical interaction of DNA with silica during and after sol-gel transition. In this respect, double stranded DNA and dAMP (2'-deoxyadenosine 5'-monophosphate) were encapsulated in silica using an alkoxide-based sol-gel route. Biomolecule-encapsulating gels have been characterized using UV-Vis, 29 Si NMR, FTIR spectroscopy and gas adsorption (BET) to investigate chemical interactions of biomolecules with the porous silica network and to examine the extent of sol-gel reactions upon encapsulation. Ethidium bromide intercalation and leach out tests showed that helix conformation of DNA was preserved after encapsulation. For both biomolecules, high water-to-alkoxide ratio promoted water-producing condensation and prevented alcoholic denaturation. NMR and FTIR analyses confirmed high hydraulic reactivity (water adsorption) for more silanol groups-containing DNA and dAMP encapsulated gels than plain silica gel. No chemical binding/interaction occurred between biomolecules and silica network. DNA and dAMP encapsulated silica gelled faster than plain silica due to basic nature of DNA or dAMP containing buffer solutions. DNA was not released from silica gels to aqueous environment up to 9 days. The chemical association between DNA/dAMP and silica host was through phosphate groups and molecular water attached to silanols, acting as a barrier around biomolecules. The helix morphology was found not to be essential for such interaction. BET analyses showed that interconnected, inkbottle-shaped mesoporous silica network was condensed around DNA and dAMP molecules.

The Role of MgCl 2 as a Lewis Base in ROMgCl-MgCl 2 Electrolytes for Magnesium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Baofei; Huang, Jinhua; He, Meinan

2016-02-04

A series of strong Lewis acid-free alkoxide/siloxide-based Mg electrolytes were deliberately developed with remarkable oxidative stability up to 3.5 V (vs. Mg/Mg2+). Despite the perception of ROMgCl (R=alkyl, silyl) as a strong base, ROMgCl acts like Lewis acid, whereas the role of MgCl2 in was unambiguously demonstrated as a Lewis base through the identification of the key intermediate using single crystal X-ray crystallography. This Lewis-acid-free strategy should provide a prototype system for further investigation of Mg-ion batteries.

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.

Numerical simulation of magnetic interactions in polycrystalline YFeO 3

NASA Astrophysics Data System (ADS)

Lima, E.; Martins, T. B.; Rechenberg, H. R.; Goya, G. F.; Cavelius, C.; Rapalaviciute, R.; Hao, S.; Mathur, S.

The magnetic behavior of polycrystalline yttrium orthoferrite was studied from the experimental and theoretical points of view. Magnetization measurements up to 170 kOe were carried out on a single-phase YFeO 3 sample synthesized from heterobimetallic alkoxides. The complex interplay between weak-ferromagnetic and antiferromagnetic interactions, observed in the experimental M( H) curves, was successfully simulated by locally minimizing the magnetic energy of two interacting Fe sublattices. The resulting values of exchange field ( HE=5590 kOe), anisotropy field ( HA=0.5 kOe) and Dzyaloshinsky-Moriya antisymmetric field ( HD=149 kOe) are in good agreement with previous reports on this system.

Research study for gel precursors as glass and ceramic starting materials for space processing applications research

NASA Technical Reports Server (NTRS)

Downs, R. L.; Miller, W. J.

1983-01-01

The development of techniques for the preparation of glass and ceramic starting materials that will result in homogeneous glasses or ceramic products when melted and cooled in a containerless environment is described. Metal-organic starting materials were used to make compounds or mixtures which were then decomposed by hydrolysis reactions to the corresponding oxides. The sodium tungstate system was chosen as a model for a glass with a relatively low melting temperature. The alkoxide tungstates also have interesting optical properties. For all the compositions studied, comparison samples were prepared from inorganic starting materials and submitted to the same analyses.

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.

Inorganic-organic nanocomposites for optical coatings

NASA Astrophysics Data System (ADS)

Schmidt, Helmut K.; Krug, Herbert; Sepeur-Zeitz, Bernhard; Geiter, Elisabeth

1997-10-01

The fabrication of nanoparticles by the sol-gel process and their use in polymeric or sol-gel-derived inorganic-organic composite matrices opens up interesting possibilities for designing new optical materials. Two different routes have been chosen for preparing optical nanocomposites: The first is the so-called 'in situ route,' where the nanoparticles are synthesized in a liquid mixture from Zr-alkoxides in a polymerizable system and diffractive gratings were produced by embossing uncured film. The second is the 'separate' preparation route, where a sterically stabilized dry nanoboehmite powder was completely redispersed in an epoxy group-containing matrix and hard coatings with optical quality on polycarbonate were prepared.

A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis

DOE PAGES

Michaelos, Thoe K.; Shopov, Dimitar Y.; Sinha, Shashi Bhushan; ...

2017-03-08

Here, water-oxidation catalysis is a critical bottleneck in the direct generation of solar fuels by artificial photosynthesis. Catalytic oxidation of difficult substrates such as water requires harsh conditions, so that the ligand must be designed both to stabilize high oxidation states of the metal center and to strenuously resist ligand degradation. Typical ligand choices either lack sufficient electron donor power or fail to stand up to the oxidizing conditions. This research on Ir-based water-oxidation catalysts (WOCs) has led us to identify a ligand, 2-(2'-pyridyl)-2-propanoate or “pyalk” that fulfills these requirements.

Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal Propargyl Alcohols.

PubMed

Lee, Kui Fun; Bai, Wei; Sung, Herman H Y; Williams, Ian D; Lin, Zhenyang; Jia, Guochen

2018-06-07

The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm) 3 ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph 2, C(OH)Me 2 , C(OH)HPh, C(OH)H 2 ) produced the vinylidene complexes ReI(=C=CHR)(dppm) 2 with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm) 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supported fischer-tropsch catalyst and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald; Withers, Howard P.

1987-01-01

A Fischer-Tropsch catalyst and a method of making the catalyst for a Fischer-Tropsch process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas, is selectively converted to higher hydrocarbons of relatively narrow carbon number range is disclosed. In general, the selective and notably stable catalyst, consist of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of a Fischer-Tropsch metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2016-03-22

A process for synthesizing 4-amino-2,4-dioxobutanoate involves reacting a dialkyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding an alkyl cyano acetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoate. The 4-amino-2,4-dioxobutanoate may be acidified into 4-amino-2,4-dioxobutanoic acid.

Colloidal synthesis of silicon nanoparticles in molten salts.

PubMed

Shavel, A; Guerrini, L; Alvarez-Puebla, R A

2017-06-22

Silicon nanoparticles are unique materials with applications in a variety of fields, from electronics to catalysis and biomedical uses. Despite technological advancements in nanofabrication, the development of a simple and inexpensive route for the synthesis of homogeneous silicon nanoparticles remains highly challenging. Herein, we describe a new, simple and inexpensive colloidal synthetic method for the preparation, under normal pressure and mild temperature conditions, of relatively homogeneous spherical silicon nanoparticles of either ca. 4 or 6 nm diameter. The key features of this method are the selection of a eutectic salt mixture as a solvent, the identification of appropriate silicon alkoxide precursors, and the unconventional use of alkali earth metals as shape-controlling agents.

Reactions of Metal-Metal Multiple Bonds. 14. Synthesis and Characterization of Triangulo-W3 and Mo2W-oxo Capped Alkoxide Clusters. Comproportionation of M-M Triple Bonds, sigma(2)pi(4) and d(o) Metal-oxo Groups: M Triple Bond M + M Triple Bond O Yields M3(micron 3-O).

DTIC Science & Technology

1984-05-02

the syntheses of dinuclear and trinuclear complexes employing metal -alkylidyne or -alkylidene fragments.8 Reaction 1 also has a parallel with the...1 0 which was previously examined. The mixed metal complex is undoubtedly disordered with respect to the disposition of molybdenum and tungsten atoms...than for the analogous Mo3 complex suggests greater metal - metal overlap and possibly stronger bonding interactions in the W3 complex which would not

Concentration-independent pH detection with a luminescent dimetallic Eu(III)-based probe.

PubMed

Moore, Jeremiah D; Lord, Richard L; Cisneros, G Andrés; Allen, Matthew J

2012-10-24

A pH-responsive, luminescent, dimetallic Eu(III)-containing complex has been synthesized and exhibits a unique mechanism of response. The luminescence-decay rate of the complex is slow, due to a lack of water molecules coordinated to the Eu(III) ions. However, the luminescence-decay rate decreases with increasing pH over a biologically relevant range of 4-8. Physical characterization and computational analysis suggest that the pH response is due to protonation of a bridging alkoxide at lower pH values. Modulation of the luminescence-decay rate is independent from the concentration of Eu(III), which we expect to be useful in the non-invasive imaging of in vivo pH.

Mechanical Property and Thermal Endurance of Room Temperature Vulcanizing Silicone Compound with Reduced Environmental Impact

NASA Astrophysics Data System (ADS)

Cho, Hiroaki; Ashida, Yasunori; Nakamura, Shuhei; Shimizu, Wataru; Murakami, Yasushi

Room temperature vulcanizing (RTV) elastic silicone usually employs organic tin compounds as a hardener. It is well known that they are strong biohazardous. Thus, European Union is going to regulate the use of organic tin compounds and to exclude them from industrial products till 2015. Authors have succeeded in making a substitute of organic tin compounds as a hardener for RTV elastic silicone by using titanium alkoxide and a carboxylate ester as a hardener and a promoter, respectively. In this paper, composites of RTV elastic silicone made with silica particles and a silane coupling agent are studied based on the mechanical, heat-resistive and adhesive properties.

Catalyst for selective conversion of synthesis gas and method of making the catalyst

DOEpatents

Dyer, Paul N.; Pierantozzi, Ronald

1986-01-01

A Fischer-Tropsch (F-T) catalyst, a method of making the catalyst and an F-T process utilizing the catalyst by which synthesis gas, particularly carbon-monoxide rich synthesis gas is selectively converted to higher hydrocarbons of relatively narrow carbon number range. In general, the selective and notably stable catalyst, consists of an inert carrier first treated with a Group IV B metal compound (such as zirconium or titanium), preferably an alkoxide compound, and subsequently treated with an organic compound of an F-T metal catalyst, such as cobalt, iron or ruthenium carbonyl. Reactions with air and water and calcination are specifically avoided in the catalyst preparation procedure.

Preparation and Characterization of Ferroelectric BaTi0.91(Hf0.5, Zr0.5)0.09O3 Thin Films by Sol-Gel Process Using Titanium and Zirconium Alkoxides

NASA Astrophysics Data System (ADS)

Thongrueng, Jirawat; Nishio, Keishi; Nagata, Kunihiro; Tsuchiya, Toshio

2000-09-01

Sol-gel-derived BaTi0.91(Hf0.5, Zr0.5)0.09O3 (BTHZ-9) thin films have been successfully prepared on Pt and Pt(111)/Ti/SiO2/Si(100) substrates by spin-coating and sintering from 550 to 900°C for 2 h in oxygen ambient. X-ray diffraction measurement indicated that the single perovskite phase of the BTHZ-9 thin films was obtained at heat treatment above 650°C. The formation temperature of the double-alkoxy-derived BTHZ-9 thin films was lower by at least 80°C than that of the films prepared from only titanium alkoxide. The microstructure of the films was observed by atomic force microscopy and scanning electron microscopy. The grain size of the films increased from 70 to 200 nm with increasing sintering temperature ranging from 650 to 850°C. The maximum peak for the dielectric constant, corresponding to the Curie point (87°C), was broad and lower in magnitude compared with that of the BTHZ-9 bulk ceramics. Tensile stresses resulting from the differences between thermal expansion coefficients of the substrate and the film caused poor electrical properties. BTHZ-9 thin films exhibited a well-saturated polarization-electric field hysteresis loop. The polarization and coercive field for the 850-nm-thick BTHZ-9 thin film prepared on Pt/Ti/SiO2/Si substrate at 750°C were determined to be 8 μC/cm2 and 15 kV/cm, respectively. Those of the BTHZ-9 thin film prepared on Pt substrate at 850°C were found to be 9 μC/cm2 and 18 kV/cm, respectively.

Effect of annealing temperature on titania nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manikandan, K., E-mail: sanjaymani367@gmail.com; Arumugam, S., E-mail: sanjaymani367@gmail.com; Chandrasekaran, G.

2014-04-24

Titania polycrystalline samples are prepared by using sol-gel route hydrolyzing a alkoxide titanium precursor under acidic conditions. The as prepared samples are treated with different calcination temperatures. The anatase phase of titania forms when treated below 600°C, above that temperature the anatase phase tends to transform into the rutile phase of titania. The experimental determination of average grain size, phase formation, lattice parameters and the crystal structures of titania samples at different calcinations is done using X-ray diffraction (XRD). Fourier Transform Infra-red Spectroscopy (FTIR), UV-vis-NIR spectroscopy and Scanning Electron Microscopy (SEM) and Energy Dispersive Analysis X-ray are used to characterizemore » the samples to bring impact on the respective properties.« less

Photodegradation of surfactants on the nanosized TiO2 prepared by hydrolysis of the alkoxide titanium.

PubMed

Zhang, Rubing; Gao, Lian; Zhang, Qinghong

2004-01-01

Nanosized TiO(2) was synthesized by hydrolysis of titanium tetraisopropoxide in the nanodroplets of microemulsions. The microemulsion provided by functionalized surfactants derived from the mixture of the commercially available sodium dodecylbenzensulfonate (DBS) and sodium dodecyl sulfate (DS). The resulting TiO(2) nanoparticles were characterized by transmission electron microscopy, X-ray diffraction, and differential thermal analysis. Nanosized TiO(2) of anatase was found to show good photocatalytic properties in the photodegradation of DBS and DS surfactants. The cleavage of the aromatic moiety, the intermediate products and ultimate mineralization to CO(2) were examined in the process of photodegradation. A mechanism is also proposed on the basis of these experimental results.

Synthesis of TiO2 nanoparticles by hydrolysis and peptization of titanium isopropoxide solution

NASA Astrophysics Data System (ADS)

Mahata, S.; Mahato, S. S.; Nandi, M. M.; Mondal, B.

2012-07-01

Here we report the synthesis and characterization of a stable suspension of modified titania nanoparticles. Phase-pure TiO2 nanocrystallites with narrow particle-size distributions were selectively prepared by hydrolysis-peptization of modified alkoxide followed by hydrothermal treatment. Autoclaving modified TiO2 in the presence of HNO3 as cooperative catalysts led to the formation of crystalline TiO2 with narrow-sized distribution. Following the hydrothermal treatment at 150°C, X-ray diffraction shows the particles to be exclusively anatase. Synthesized powder is characterized by FT-IR, scanning electron microscopy (FESEM) and transmission electron microscopy (HRTEM). The photocatalytic activity in the degradation of orange-II is quite comparable to good anatase and rutile nanocrystallites.

Organo-metallic elements for associative information processing

NASA Astrophysics Data System (ADS)

Potember, Richard S.; Poehler, Theodore O.

1989-01-01

In the three years of the program we have: (1) built and tested a 4 bit element matrix device for possible use in high density content-addressable memories systems; (2) established a test and evaluation laboratory to examine optical materials for nonlinear effects, saturable absorption, harmonic generation and photochromism; (3) successfully designed, constructed and operated a codeposition processing system that enables organic materials to be deposited on a variety of substrates to produce optical grade coatings and films. This system is also compatible with other traditional microelectronic techniques; (4) used the sol-gel process with colloidal AgTCNQ to fabricate high speed photochromic switches; (5) develop and applied for patent coverage to make VO2 optical switching materials via the sol-gel processing using vanadium (IV) alkoxide compounds.

Magnetic epoxy nanocomposites reinforced with hierarchical α-Fe2O3 nanoflowers: a study of mechanical properties

NASA Astrophysics Data System (ADS)

Balguri, Praveen Kumar; Harris Samuel, D. G.; Thumu, Udayabhaskararao

2017-09-01

In this work, we presented the potentiality of monodispersed 3D hierarchical α-Fe2O3 nanoflowers (α-Fe2O3) as reinforcement for epoxy polymer. α-Fe2O3 are synthesized through the thermal decomposition of iron alkoxide precursor in ethylene glycol. α-Fe2O3/epoxy nanocomposites (0.1 wt% of α-Fe2O3) show 109%, 59%, 13%, and 15% enhancement in impact (un-notched), impact (notched), flexural and tensile properties, respectively. The uniformly embedded α- Fe2O3 nanoflowers in epoxy polymer not only provide mechanical strength but also induced magnetic nature to the nanocomposite as observed from the Scanning electron microscopy and vibrating sample magnetometer.

Double Reformatsky reaction: divergent synthesis of δ-hydroxy-β-ketoesters.

PubMed

Mineno, Masahiro; Sawai, Yasuhiro; Kanno, Kazuaki; Sawada, Naotaka; Mizufune, Hideya

2013-06-21

The double Reformatsky reaction, tandem addition of two molecules of zinc alkanoate to a carbonyl compound, and its synthetic application to a series of δ-hydroxy-β-ketoesters has been developed. The key to accelerate the double Reformatsky reaction is considered to be a complex-induced proximity effect of the in situ generated zinc alkoxide coordinated with the pyridyl group of the substrate or bidentate amines. A noteworthy feature of the reaction system is its high tolerance of functional groups due to the moderate nucleophilicity of organozinc reagents and the mild reaction conditions. Moreover, spectroscopic and crystallographic analyses of the zinc complex of the double Reformatsky product support the proposed mechanism of reaction site discrimination for ketones, aldehydes, nitriles, carboxylic acid anhydrides, and esters.

Variation of the shape and morphological properties of silica and metal oxide powders by electro homogeneous precipitation

DOEpatents

Harris, M.T.; Basaran, O.A.; Sisson, W.G.; Brunson, R.R.

1997-02-18

The present invention provides a method for preparing irreversible linear aggregates (fibrils) of metal oxide powders by utilizing static or pulsed DC electrical fields across a relatively non-conducting liquid solvent in which organometal compounds or silicon alkoxides have been dissolved. The electric field is applied to the relatively non-conducting solution throughout the particle formation and growth process promoting the formation of either linear aggregates (fibrils) or spherical shaped particles as desired. Thus the present invention provides a physical method for altering the size, shape and porosity of precursor hydrous metal oxide or hydrous silicon oxide powders for the development of advanced ceramics with improved strength and insulating capacity. 3 figs.

Ultrapure glass optical waveguide development in microgravity by the sol-gel process

NASA Technical Reports Server (NTRS)

Mukherjee, S. P.; Holman, R. A.

1981-01-01

Multicomponent, homogeneous, noncrystalline oxide gels can be prepared by the sol-gel process and these gels are promising starting materials for melting glasses in the space environment. The sol-gel process referred to here is based on the polymerization reaction of alkoxysilane with other metal alkoxy compounds or suitable metal salts. Many of the alkoxysilanes or other metal alkoxides are liquids and thus can be purified by distillation. The use of gels offers several advantages such as high purity and lower melting times and temperatures. The sol-gel process is studied for utilization in the preparation of multicomponent ultrapure glass batches for subsequent containerless melting of the batches in space to prepare glass blanks for optical waveguides.

Supported Tetrahedral Oxo-Sn Catalyst: Single Site, Two Modes of Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beletskiy, Evgeny V.; Hou, Xianliang; Shen, Zhongliang

2016-03-17

Mild calcination in ozone of a (POSS)-Sn- (POSS) complex grafted on silica generated a heterogenized catalyst that mostly retained the tetrahedral coordination of its homogeneous precursor, as evidenced by spectroscopic characterizations using EXAFS, NMR, UV-vis, and DRIFT. The Sn centers are accessible and uniform and can be quantified by stoichiometric pyridine poisoning. This Sn-catalyst is active in hydride transfer reactions as a typical solid Lewis acid. However, the Sn centers can also create Brønsted acidity with alcohol by binding the alcohol strongly as alkoxide and transferring the hydroxyl H to the neighboring Sn-O-Si bond. The resulting acidic silanol is activemore » in epoxide ring opening and acetalization reactions.« less

Redox and Lewis acid relay catalysis: a titanocene/zinc catalytic platform in the development of multicomponent coupling reactions.

PubMed

Gianino, Joseph B; Campos, Catherine A; Lepore, Antonio J; Pinkerton, David M; Ashfeld, Brandon L

2014-12-19

A titanocene-catalyzed multicomponent coupling is described herein. Using catalytic titanocene, phosphine, and zinc dust, zinc acetylides can be generated from the corresponding iodoalkynes to affect sequential nucleophilic additions to aromatic aldehydes. The intermediate propargylic alkoxides are trapped in situ with acetic anhydride, which are susceptible to a second nucleophilic displacement upon treatment with a variety of electron-rich species, including acetylides, allyl silanes, electron-rich aromatics, silyl enol ethers, and silyl ketene acetals. Additionally, employing cyclopropane carboxaldehydes led to ring-opened products resulting from iodine incorporation. Taken together, these results form the basis for a new mode of three-component coupling reactions, which allows for rapid access to value added products in a single synthetic operation.

Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

DOEpatents

Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

2011-12-13

Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

Continuous supercritical synthesis and dielectric behaviour of the whole BST solid solution.

PubMed

Reverón, H; Elissalde, C; Aymonier, C; Bousquet, C; Maglione, M; Cansell, F

2006-07-28

In this study we show that pure and well crystallized nanoparticles of Ba(x)Sr(1-x)TiO(3) (BST) can be synthesized over the entire range of composition through the hydrolysis and further crystallization of alkoxide precursors under supercritical conditions. To our knowledge, this is the first time that the whole ferroelectric solid solution has been produced in a continuous way, using the same experimental conditions. The composition of the powder can be easily controlled by adjusting the feed solution composition. The powders consist of soft-aggregated monocrystalline nanoparticles with an average particle size ranging from approximately 20 to 40 nm. Ferroelectric ceramics with accurately adjustable Curie temperature (100-390 K) can thus be obtained by sintering.

Supercritical fluid route for synthesizing crystalline Barium Strontium Titanate nanoparticles.

PubMed

Reverón, H; Elissalde, C; Aymonier, C; Bidault, O; Maglione, M; Cansell, F

2005-10-01

Pure and well-crystallized Barium Strontium Titanate (BST) nanoparticles with controlled Ba/Sr ratio have been successfully synthesized under supercritical conditions using a continuous-flow reactor in the temperature range of 150-380 degrees C at 26 MPa. To synthesize the Ba0.6Sr0.4TiO3 composition, alkoxides, ethanol and water were used. The resulting nanopowder consists of fine particles with an average particle size of 23 nm. The results show that the Ba/Sr ratio of this powder can be accurately controlled from the composition of precursor. The characterization of the as-synthesized Ba0.6Sr0.4TiO3 solid-solution and the dielectric properties of the sintered ceramics are here reported.

Green and scalable production of colloidal perovskite nanocrystals and transparent sols by a controlled self-collection process

NASA Astrophysics Data System (ADS)

Liu, Shuangyi; Huang, Limin; Li, Wanlu; Liu, Xiaohua; Jing, Shui; Li, Jackie; O'Brien, Stephen

2015-07-01

Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity.Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02351c

Transformation of bulk alloys to oxide nanowires

NASA Astrophysics Data System (ADS)

Lei, Danni; Benson, Jim; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2017-01-01

One dimensional (1D) nanostructures offer prospects for enhancing the electrical, thermal, and mechanical properties of a broad range of functional materials and composites, but their synthesis methods are typically elaborate and expensive. We demonstrate a direct transformation of bulk materials into nanowires under ambient conditions without the use of catalysts or any external stimuli. The nanowires form via minimization of strain energy at the boundary of a chemical reaction front. We show the transformation of multimicrometer-sized particles of aluminum or magnesium alloys into alkoxide nanowires of tunable dimensions, which are converted into oxide nanowires upon heating in air. Fabricated separators based on aluminum oxide nanowires enhanced the safety and rate capabilities of lithium-ion batteries. The reported approach allows ultralow-cost scalable synthesis of 1D materials and membranes.

A new powder production route for transparent spinel windows: powder synthesis and window properties

NASA Astrophysics Data System (ADS)

Cook, Ronald; Kochis, Michael; Reimanis, Ivar; Kleebe, Hans-Joachim

2005-05-01

Spinel powders for the production of transparent polycrystalline ceramic windows have been produced using a number of traditional ceramic and sol-gel methods. We have demonstrated that magnesium aluminate spinel powders produced from the reaction of organo-magnesium compounds with surface modified boehmite precursors can be used to produce high quality transparent spinel parts. The new powder production method allows fine control over the starting particle size, size distribution, purity and stoichiometry. The new process involves formation of a boehmite sol-gel from the hydrolysis of aluminum alkoxides followed by surface modification of the boehmite nanoparticles using carboxylic acids. The resulting surface modified boehmite nanoparticles can then be metal exchanged at room temperature with magnesium acetylacetonate to make a precursor powder that is readily transformed into pure phase spinel.

Synthesis of TiO{sub 2} nanoparticles by hydrolysis and peptization of titanium isopropoxide solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahata, S.; Mahato, S. S.; Nandi, M. M.

2012-07-23

Here we report the synthesis and characterization of a stable suspension of modified titania nanoparticles. Phase-pure TiO{sub 2} nanocrystallites with narrow particle-size distributions were selectively prepared by hydrolysis-peptization of modified alkoxide followed by hydrothermal treatment. Autoclaving modified TiO{sub 2} in the presence of HNO3 as cooperative catalysts led to the formation of crystalline TiO{sub 2} with narrow-sized distribution. Following the hydrothermal treatment at 150 Degree-Sign C, X-ray diffraction shows the particles to be exclusively anatase. Synthesized powder is characterized by FT-IR, scanning electron microscopy (FESEM) and transmission electron microscopy (HRTEM). The photocatalytic activity in the degradation of orange-II is quitemore » comparable to good anatase and rutile nanocrystallites.« less

The formation of titanium dioxide crystallite nanoparticles during activation of PAN nanofibers containing titanium isopropoxide

NASA Astrophysics Data System (ADS)

Mehrpouya, Fahimeh; Tavanai, Hossein; Morshed, Mohammad; Ghiaci, Mehran

2012-08-01

Activated carbon (AC) can act as an important carrier for TiO2 nanoparticles. TiO2 nanoparticle can be fabricated by the hydrolysis and condensation of titanium alkoxides like titanium isopropoxide. This study showed that the formation of titanium dioxide crystallite nanoparticle during activation of PAN nanofibers containing titanium isopropoxide leads to the formation of mainly anatase crystal TiO2 nanoparticle in AC nanofibers, with a good dispersion in both the longitude and cross section of nanofibers. The TiO2 crystallite size lies in the range of 7.3-11.3 nm. The dispersion of TiO2 nanoparticles in the matrix of AC nanofibers is far superior to the direct mixing of TiO2 nanoparticles in the original electrospinning solution.

Preparation of fullerene/glass composites

DOEpatents

Mattes, Benjamin R.; McBranch, Duncan W.; Robinson, Jeanne M.; Koskelo, Aaron C.; Love, Steven P.

1995-01-01

Synthesis of fullerene/glass composites. A direct method for preparing solid solutions of C.sub.60 in silicon dioxide (SiO.sub.2) glass matrices by means of sol-gel chemistry is described. In order to produce highly concentrated fullerene-sol-gel-composites it is necessary to increase the solubility of these "guests" in a delivery solvent which is compatible with the starter sol (receiving solvent). Sonication results in aggregate disruption by treatment with high frequency sound waves, thereby accelerating the rate of hydrolysis of the alkoxide precursor, and the solution process for the C.sub.60. Depending upon the preparative procedure, C.sub.60 dispersed within the glass matrix as microcrystalline domains, or dispersed as true molecular solutions of C.sub.60 in a solid glass matrix, is generated by the present method.

Preparation of fullerene/glass composites

DOEpatents

Mattes, B.R.; McBranch, D.W.; Robinson, J.M.; Koskelo, A.C.; Love, S.P.

1995-05-30

Synthesis of fullerene/glass composites is described. A direct method for preparing solid solutions of C{sub 60} in silicon dioxide (SiO{sub 2}) glass matrices by means of sol-gel chemistry is described. In order to produce highly concentrated fullerene-sol-gel-composites it is necessary to increase the solubility of these ``guests`` in a delivery solvent which is compatible with the starter sol (receiving solvent). Sonication results in aggregate disruption by treatment with high frequency sound waves, thereby accelerating the rate of hydrolysis of the alkoxide precursor, and the solution process for the C{sub 60}. Depending upon the preparative procedure, C{sub 60} dispersed within the glass matrix as microcrystalline domains, or dispersed as true molecular solutions of C{sub 60} in a solid glass matrix, is generated by the present method.

Method for synthesizing thin film electrodes

DOEpatents

Boyle, Timothy J [Albuquerque, NM

2007-03-13

A method for making a thin-film electrode, either an anode or a cathode, by preparing a precursor solution using an alkoxide reactant, depositing multiple thin film layers with each layer approximately 500 1000 .ANG. in thickness, and heating the layers to above 600.degree. C. to achieve a material with electrochemical properties suitable for use in a thin film battery. The preparation of the anode precursor solution uses Sn(OCH.sub.2C(CH.sub.3).sub.3).sub.2 dissolved in a solvent in the presence of HO.sub.2CCH.sub.3 and the cathode precursor solution is formed by dissolving a mixture of (Li(OCH.sub.2C(CH.sub.3).sub.3)).sub.8 and Co(O.sub.2CCH.sub.3).H.sub.2O in at least one polar solvent.

Direct nanopatterning of 100 nm metal oxide periodic structures by Deep-UV immersion lithography.

PubMed

Stehlin, Fabrice; Bourgin, Yannick; Spangenberg, Arnaud; Jourlin, Yves; Parriaux, Olivier; Reynaud, Stéphanie; Wieder, Fernand; Soppera, Olivier

2012-11-15

Deep-UV lithography using high-efficiency phase mask has been developed to print 100 nm period grating on sol-gel based thin layer. High efficiency phase mask has been designed to produce a high-contrast interferogram (periodic fringes) under water immersion conditions for 244 nm laser. The demonstration has been applied to a new developed immersion-compatible sol-gel layer. A sol-gel photoresist prepared from zirconium alkoxides caped with methacrylic acids was developed to achieve 50 nm resolution in a single step exposure. The nanostructures can be thermally annealed into ZrO(2). Such route considerably simplifies the process for elaborating nanopatterned surfaces of transition metal oxides, and opens new routes for integrating materials of interest for applications in the field of photocatalysis, photovoltaic, optics, photonics or microelectronics.

Characterization of the Sol-Gel Transition for Zirconia-Toughened Alumina Precursors

NASA Technical Reports Server (NTRS)

Moeti, I.; Karikari, E.; Chen, J.

1998-01-01

High purity ZTA ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and theological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. In all experimental cases a-alumina and tetragonal zirconia phases were confirmed even in the absence of yttria.

Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst.

PubMed

Shimizu, Wataru; Nakamura, Satoshi; Sato, Takaaki; Murakami, Yasushi

2012-08-21

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.

Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis.

PubMed

Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David W C

2018-05-04

The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atomic insights into nanoparticle formation of hydroxyfluorinated anatase featuring titanium vacancies

DOE PAGES

Li, Wei; Body, Monique; Legein, Christophe; ...

2016-06-28

Anatase TiO 2 with exposed highly reactive (001) surface is commonly prepared using solution-based synthesis in the presence of a fluorinating agent acting as a structure directing agent. Here, the solvothermal reaction of titanium tetraisopropoxide in the presence of aqueous HF has resulted in the stabilization of an oxyhydroxyfluorinated anatase phase featuring cationic vacancies. In the present work, we have studied its formation mechanism, revealing a solid-state transformation of a highly defective anatase phase having a hydroxyfluoride composition that subsequently evolves through an oxolation reaction into an oxyhydroxyfluoride phase. Importantly, this work confirms that titanium alkoxide precursors can react withmore » HF via a fluorolysis process yielding fluorinated molecular precursors, which further condense to produce new composition and structural features deviating from a well ordered anatase network.« less

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1991-02-12

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Homogeneous catalyst formulations for methanol production

DOEpatents

Mahajan, Devinder; Sapienza, Richard S.; Slegeir, William A.; O'Hare, Thomas E.

1990-01-01

There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Homogeneous and Supported Niobium Catalysts as Lewis Acid and Radical Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wayne Tikkanen

2006-12-31

The synthesis of tetrachlorotetraphenylcyclopentadienyl group 5 metal complexes has been accomplished through two routes, one a salt metathesis with lithiumtetraphenylcyclopentadiende and the other, reaction with trimethyltintetraphenylcyclopentadiene. The reactants and products have been characterized by {sup 1}H and {sup 13}C({sup 1}H) NMR spectroscopy. The niobium complex promotes the silylcyanation of butyraldehyde. The grafting of metal complexes to silica gel surfaces has been accomplished using tetrakisdimethylamidozirconium as the metal precursor. The most homogeneous binding as determined by CP-MAS {sup 13}C NMR and infrared spectroscopy was obtained with drying at 500 C at 3 mtorr vacuum. The remaining amido groups can be replacedmore » by reaction with alcohols to generate surface bound metal alkoxides. These bound catalysts promote silylcyanation of aryl aldehydes and can be reused three times with no loss of activity.« less

High temperature stability of anatase in titania-alumina semiconductors with enhanced photodegradation of 2, 4-dichlorophenoxyacetic acid.

PubMed

López-Granada, G; Barceinas-Sánchez, J D O; López, R; Gómez, R

2013-12-15

The incorporation of aluminum acetylacetonate as alumina source during the gelation of titanium alkoxide reduces the nucleation sites for the formation of large rutile crystals on temperatures ranging from 400 to 800°C. As a result, the aggregation of anatase crystals is prevented at high temperature. A relationship among the specific surface area, pore size, energy band gap, crystalline structure and crystallite size as the most relevant parameters are evaluated and discussed. According to the results for the photocatalytic degradation of 2,4-dichlorophenoxyacetic acid, the specific surface area, pore size, Eg band gap are not determinant in the photocatalytic properties. It was found that the anatase crystallite size is the mores important parameter affecting the degradation efficiency. Copyright © 2013 Elsevier B.V. All rights reserved.

Transformation of bulk alloys to oxide nanowires.

PubMed

Lei, Danni; Benson, Jim; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2017-01-20

One dimensional (1D) nanostructures offer prospects for enhancing the electrical, thermal, and mechanical properties of a broad range of functional materials and composites, but their synthesis methods are typically elaborate and expensive. We demonstrate a direct transformation of bulk materials into nanowires under ambient conditions without the use of catalysts or any external stimuli. The nanowires form via minimization of strain energy at the boundary of a chemical reaction front. We show the transformation of multimicrometer-sized particles of aluminum or magnesium alloys into alkoxide nanowires of tunable dimensions, which are converted into oxide nanowires upon heating in air. Fabricated separators based on aluminum oxide nanowires enhanced the safety and rate capabilities of lithium-ion batteries. The reported approach allows ultralow-cost scalable synthesis of 1D materials and membranes. Copyright © 2017, American Association for the Advancement of Science.

Metallized Gelled Propellants Combustion Experiments in a Pulse Detonation Engine

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan; Jurns, John; Breisacher, Kevin; Kearns, Kim

2006-01-01

A series of combustion tests were performed with metallized gelled JP 8/aluminum fuels in a Pulse Detonation Engine (PDE). Nanoparticles of aluminum were used in the 60 to 100 nanometer diameter. Gellants were also of a nanoparticulate type composed of hydrocarbon alkoxide materials. Using simulated air (a nitrogen-oxygen mixture), the ignition potential of metallized gelled fuels with nanoparticle aluminum was investigated. Ignition of the JP 8/aluminum was possible with less than or equal to a 23-wt% oxygen loading in the simulated air. JP 8 fuel alone was unable to ignite with less than 30 percent oxygen loaded simulated air. The tests were single shot tests of the metallized gelled fuel to demonstrate the capability of the fuel to improve fuel detonability. The tests were conducted at ambient temperatures and with maximal detonation pressures of 1340 psia.

MgCl 2 : The Key Ingredient to Improve Chloride Containing Electrolytes for Rechargeable Magnesium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Baofei; Huang, Jinhua; Sa, Niya

The effect of MgCl2 on a series of chloride containing magnesium electrolytes was investigated. In the presence of extra MgCl2, the electrochemical properties of Grignard reagents (RMgCl, R = Ph, Et, iPr) were significantly improved, and the advance of MgCl2 was further demonstrated in Mg-Mo6S8 rechargeable batteries with improved capacities and much smaller over-potentials. MgCl2 was then further proven to be powerful reagent to improve the performance of well-established strong Lewis acid derived magnesium electrolytes including the “all-phenyl” complex (APC) and alkoxide-based magnesium electrolytes. The results suggest that MgCl2 salt is a very important species to benefit all chloride containingmore » electrolytes for rechargeable magnesium-ion batteries.« less

Ultrapure glass optical waveguide development in microgravity by the sol-gel process

NASA Technical Reports Server (NTRS)

1982-01-01

Containerless melting of glasses in space for the preparation of ultrapure homogeneous glass for optical waveguides is discussed. The homogenization of the glass using conventional raw materials is normally achieved on Earth either by the gravity induced convection currents or by the mechanical stirring of the melt. Because of the absence of gravity induced convection currents, the homogenization of glass using convectional raw materials is difficult in the space environment. Multicomponent, homogeneous, noncrystalline oxide gels can be prepared by the sol-gel process and these gels are promising starting materials for melting glasses in the space environment. The sol-gel process is based on the polymerization reaction of alkoxysilane with other metal alkoxy compounds or suitable metal salts. Many of the alkoxysilanes or other metal alkoxides are liquids and thus can be purified by distillation.

Supported inorganic membranes

DOEpatents

Sehgal, Rakesh; Brinker, Charles Jeffrey

1998-01-01

Supported inorganic membranes capable of molecular sieving, and methods for their production, are provided. The subject membranes exhibit high flux and high selectivity. The subject membranes are substantially defect free and less than about 100 nm thick. The pores of the subject membranes have an average critical pore radius of less than about 5 .ANG., and have a narrow pore size distribution. The subject membranes are prepared by coating a porous substrate with a polymeric sol, preferably under conditions of low relative pressure of the liquid constituents of the sol. The coated substrate is dried and calcined to produce the subject supported membrane. Also provided are methods of derivatizing the surface of supported inorganic membranes with metal alkoxides. The subject membranes find use in a variety of applications, such as the separation of constituents of gaseous streams, as catalysts and catalyst supports, and the like.

Magnetic relaxation pathways in lanthanide single-molecule magnets.

PubMed

Blagg, Robin J; Ungur, Liviu; Tuna, Floriana; Speak, James; Comar, Priyanka; Collison, David; Wernsdorfer, Wolfgang; McInnes, Eric J L; Chibotaru, Liviu F; Winpenny, Richard E P

2013-08-01

Single-molecule magnets are compounds that exhibit magnetic bistability caused by an energy barrier for the reversal of magnetization (relaxation). Lanthanide compounds are proving promising as single-molecule magnets: recent studies show that terbium phthalocyanine complexes possess large energy barriers, and dysprosium and terbium complexes bridged by an N2(3-) radical ligand exhibit magnetic hysteresis up to 13 K. Magnetic relaxation is typically controlled by single-ion factors rather than magnetic exchange (whether one or more 4f ions are present) and proceeds through thermal relaxation of the lowest excited states. Here we report polylanthanide alkoxide cage complexes, and their doped diamagnetic yttrium analogues, in which competing relaxation pathways are observed and relaxation through the first excited state can be quenched. This leads to energy barriers for relaxation of magnetization that exceed 800 K. We investigated the factors at the lanthanide sites that govern this behaviour.

Solution-derived sodalite made with Si- and Ge-ethoxide precursors for immobilizing electrorefiner salt

NASA Astrophysics Data System (ADS)

Riley, Brian J.; Lepry, William C.; Crum, Jarrod V.

2016-01-01

Chlorosodalite has the general form of Na8(AlSiO4)6Cl2 and this paper describes experiments conducted to synthesize sodalite with a solution-based approach to immobilize a simulated spent electrorefiner salt solution containing a mixture of alkali, alkaline earth, and lanthanide chlorides. The reactants used were the salt solution, NaAlO2, and either Si(OC2H5)4 or Ge(OC2H5)4. Additionally, seven different glass sintering aids (at loadings of 5 mass%) were evaluated as sintering aids for consolidating the as-made powders using a cold-press-and-sinter technique. This process of using alkoxide additives for the Group IV component can be used to produce large quantities of sodalite at near-room temperature as compared to a method where colloidal silica was used as the silica source. However, the small particle sizes inhibited densification during heat treatments.

Optimization of mechanical strength of titania fibers fabricated by direct drawing

NASA Astrophysics Data System (ADS)

Hanschmidt, Kelli; Tätte, Tanel; Hussainova, Irina; Part, Marko; Mändar, Hugo; Roosalu, Kaspar; Chasiotis, Ioannis

2013-11-01

Nanostructured polycrystalline titania (TiO2) microfibers were produced by direct drawing from visco-elastic alkoxide precursors. The fiber crystallinity and grain size were shown to depend on post-treatment calcination temperature. Tensile tests with individual fibers showed strong sensitivity of the elastic modulus and the tensile strength to microstructural details of the fibers. The elastic modulus of as-fabricated fibers increased about 10 times after calcination at 700 ∘C, while the strain at failure remained almost the same at ˜1.4 %. The highest tensile strength of more than 800 MPa was exhibited by nanoscale grained fibers with a bimodal grain size distribution consisting of rutile grains embedded into an anatase matrix. This structure is believed to have reduced the critical defect size, and thus increased the tensile strength. The resultant fibers showed properties that were appropriate for reinforcement of different matrixes.

Improved modification for the density-functional theory calculation of thermodynamic properties for C-H-O composite compounds.

PubMed

Liu, Min Hsien; Chen, Cheng; Hong, Yaw Shun

2005-02-08

A three-parametric modification equation and the least-squares approach are adopted to calibrating hybrid density-functional theory energies of C(1)-C(10) straight-chain aldehydes, alcohols, and alkoxides to accurate enthalpies of formation DeltaH(f) and Gibbs free energies of formation DeltaG(f), respectively. All calculated energies of the C-H-O composite compounds were obtained based on B3LYP6-311++G(3df,2pd) single-point energies and the related thermal corrections of B3LYP6-31G(d,p) optimized geometries. This investigation revealed that all compounds had 0.05% average absolute relative error (ARE) for the atomization energies, with mean value of absolute error (MAE) of just 2.1 kJ/mol (0.5 kcal/mol) for the DeltaH(f) and 2.4 kJ/mol (0.6 kcal/mol) for the DeltaG(f) of formation.

Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents.

PubMed

López-Maya, Elena; Montoro, Carmen; Rodríguez-Albelo, L Marleny; Aznar Cervantes, Salvador D; Lozano-Pérez, A Abel; Cenís, José Luis; Barea, Elisa; Navarro, Jorge A R

2015-06-01

The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A first-principles study of methyl lactate adsorption on the chiral Cu (643) surface

NASA Astrophysics Data System (ADS)

Yuk, Simuck F.; Asthagiri, Aravind

2014-11-01

We used dispersion-corrected density function theory (DFT) to investigate the enantiospecific adsorption of R- and S-methyl lactate on the chiral Cu (643)R surface. Initial study of methyl lactate adsorbed on the Cu (111) surface revealed that the most strongly bound states are associated with interaction of the hydroxyl and alkoxide group with the surface. Using dispersion-corrected DFT-derived pre-factors and desorption energies within the Redhead analysis predicts peak temperatures that are in relatively good agreement with experimental values for molecular methyl lactate desorption from both the Cu (111) and Cu (643)R surface. The global minimum of S-methyl lactate is more firmly bound by 9.5 kJ/mol over its enantiomer on the Cu (643)R surface, with a peak temperature difference of 25 K versus an experimental value of 12 K.

Roles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rios, Daniel; Schoendorff, George E.; Van Stipdonk, Michael J.

2012-12-03

Combined collision-induced dissociation mass-spectrometry experiments and DFT calculations were employed to elucidate the molecular structure of "hypercoordinated" species and the energetics of water-elimination reactions of uranyl acetone complexes observed in earlier work (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). It is shown that the "hypercoordinated" species contain diacetone alcohol ligands bonded in either bidentate or monodentate fashion, which are indistinguishable from (acetone)2 in mass spectrometry. Calculations confirm that four diacetone ligands can form stable complexes, but that the effective number of atoms coordinating with uranium in the equatorial plane doesmore » not exceed five. Diacetone alcohol ligands are shown to form mesityl oxide ligands and alkoxide species through the elimination of water, providing an explanation for the observed water-elimination reactions.« less

Method for producing metal oxide aerogels

DOEpatents

Tillotson, Thomas M.; Poco, John F.; Hrubesh, Lawrence W.; Thomas, Ian M.

1995-01-01

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm.sup.3 and greater than 0.27g/cm.sup.3. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.

Development of thermally stable phosphonitrile elastomers for advanced aerospace structures

NASA Technical Reports Server (NTRS)

Reynard, K. A.; Rose, S. H.

1972-01-01

Attempts to prepare low molecular weight, curable poly-(fluoroalkoxyphosphazenes) have been successful. Derivatization of /Cl2PN/n polymer with alkoxides gave functionally reactive terpolymers. These terpolymers could be crosslinked with polyisocyanates at room temperature. Attempts to control molecular weight have not been as successful. The effects of (Cl2PN)3 monomer purity, use of (Cl2PN)3,4 mixture, and early termination of the bulk polymerization of (Cl2PN)3 were studied briefly. Both low and high molecular weight polymers were obtained. Reaction of NH4Cl with PCl5 with subsequent heating to give chain extension gave either gels of oils with molecular weights of several thousand. The stabilization of poly-(fluoroalkoxyphosphazene) was investigated. The results generally were inconclusive, but acids were found to be deleterious while bases had little discernible effect. Improvements in stability by modification of end groups was inconclusive.

Sol-gel precursors and products thereof

DOEpatents

Warren, Scott C.; DiSalvo, Jr., Francis J.; Weisner, Ulrich B.

2017-02-14

The present invention provides a generalizable single-source sol-gel precursor capable of introducing a wide range of functionalities to metal oxides such as silica. The sol-gel precursor facilitates a one-molecule, one-step approach to the synthesis of metal-silica hybrids with combinations of biological, catalytic, magnetic, and optical functionalities. The single-source precursor also provides a flexible route for simultaneously incorporating functional species of many different types. The ligands employed for functionalizing the metal oxides are derived from a library of amino acids, hydroxy acids, or peptides and a silicon alkoxide, allowing many biological functionalities to be built into silica hybrids. The ligands can coordinate with a wide range of metals via a carboxylic acid, thereby allowing direct incorporation of inorganic functionalities from across the periodic table. Using the single-source precursor a wide range of functionalized nanostructures such as monolith structures, mesostructures, multiple metal gradient mesostructures and Stober-type nanoparticles can be synthesized. ##STR00001##

Effect of Agitation in Alkalization Process on the Characteristics of Sodium Carboxymethyl Sago and Cassava Starches

NASA Astrophysics Data System (ADS)

Titi, C. S.; Fachrudin, R.; Ruriani, E.; Yuliasih, I.

2018-05-01

Sodium carboxymethyl starch (Sodium CMS) is a modified starch prepared by two successive processes, alkalization and etherification. Alkalization will change the activated hydroxyl group of starch to more reactive alkoxide (St-O-), and then carboxymethyl group will substitute the hydroxyl group into sodium CMS. This research investigated the effect of agitation (1000 rpm of stirring and 4000 rpm of homogenization) in alkalization process to the modification of native starch into sodium CMS. Cassava and sago starches were mixed with sodium hydroxide (1.8 and 1.9 moles per mole anhydrous glucose units). The combination of NaOH and homogenizing gave the highest degrees of substitution for cassava (DS 0.73) and sago (DS 0.55) starches. The sodium CMS characteristics (paste clarity, water and oil absorption capacities, solubility, swelling power) were a function of mixing method but not on the amount of NaOH used.

Ferro- and piezoelectric properties of polar-axis-oriented CaBi4Ti4O15 films

NASA Astrophysics Data System (ADS)

Kato, Kazumi; Fu, Desheng; Suzuki, Kazuyuki; Tanaka, Kiyotaka; Nishizawa, Kaori; Miki, Takeshi

2004-05-01

Polar-axis-oriented CaBi4Ti4O15 (CBTi144) films were fabricated on Pt foils using a complex metal alkoxide solution. The 500-nm-thick film showed the columnar structure and consisted of well-developed grains. The a/b-axis orientation of the ferroelectric films is considered to be associated with the preferred orientation of Pt foil. The film showed good ferro- and piezoelectric properties. The Pr and Ec were 25 μC/cm2 and 306 kV/cm, respectively, at an applied voltage of 115 V. The d33 was characterized as 30 pm/V by piezoresponse force microscopy. The values were twice as large as those of the CBTi144 thin film with random orientation. The polar-axis-oriented CBTi144 films would open up possibilities for devices as Pb-free piezoelectric materials.

Chitosan bio-based organic-inorganic hybrid aerogel microspheres.

PubMed

El Kadib, Abdelkrim; Bousmina, Mosto

2012-07-02

Recently, organic-inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface-reactive organic-inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self-standing microspheres. Nanocasting of sol-gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO(2) supercritical drying provide high-surface-area organic-inorganic hybrid materials. Examples including chitosan-SiO(2), chitosan-TiO(2), chitosan-redox-clusters and chitosan-clay-aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, T.M.; Poco, J.F.; Hrubesh, L.W.; Thomas, I.M.

1995-04-25

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm{sup 3} and greater than 0.27g/cm{sup 3}. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods. 8 figs.

Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

PubMed

Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

2016-02-01

Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

Chemical processing of glasses

NASA Astrophysics Data System (ADS)

Laine, Richard M.

1990-11-01

The development of chemical processing methods for the fabrication of glass and ceramic shapes for photonic applications is frequently Edisonian in nature. In part, this is because the numerous variables that must be optimized to obtain a given material with a specific shape and particular properties cannot be readily defined based on fundamental principles. In part, the problems arise because the basic chemistry of common chemical processing systems has not been fully delineated. The prupose of this paper is to provide an overview of the basic chemical problems associated with chemical processing. The emphasis will be on sol-gel processing, a major subset pf chemical processing. Two alternate approaches to chemical processing of glasses are also briefly discussed. One approach concerns the use of bimetallic alkoxide oligomers and polymers as potential precursors to mulimetallic glasses. The second approach describes the utility of metal carboxylate precursors to multimetallic glasses.

Chemically Derived Dense Alumina-Zirconia Composites for Improved Mechanical and Wear Erosion Properties

NASA Technical Reports Server (NTRS)

1998-01-01

As a result of this funded project high purity Zirconia-Toughened Alumina (ZTA) ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and rheological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. This improved materials should have enhanced properties such strength, toughness, and wear resistance for advanced structural applications, for example engine components in high technology aerospace applications.

Microstructural evolutions and stress studies of titania films derived by "spin-deposition" methods

NASA Astrophysics Data System (ADS)

Eun, Tai Hee

Titania (TiO2) films were fabricated by a "spin-deposition" process. Titanium alkoxides react with moisture in the air, leading to the formation of metal hydroxides which subsequently form an oxide network during deposition. The microstructure of film is easily controlled by the selection of titanium alkoxides and solvents. Films from titanium n-butoxide (Ti(OC 4H9n)4) in toluene exhibited a dense microstructure devoid of cracks. In contrast, films produced from titanium isopropoxide (Ti(OC3H7i)4) in the toluene regularly contained micro-cracks. Titanium isopropoxide in either isopropanol or n-propanol produces highly porous films. After annealing at 300°C, the film derived from titanium n-butoxide in toluene possessed 2˜3 nm nanocrystallites of titanium monoxide (TiO, cubic) in amorphous matrices. TEM and FTIR investigations indicate that the intermediates formed from the oligomers of titanium n-butoxide lead to the formation of the TiO. By annealing at 400°C, the TiO nanoparticles transformed to the TiO2 (anatase). At annealing higher than 450°C, the film was completely crystallized into a polycrystalline of ˜5 nm anatase. In water-rich environments, all amorphous titania films crystallized within 24 hours at 100°C. The crystallization of films is confirmed by XRD and FTIR studies. Amorphous titania films have remnant bridging and terminal hydroxy groups. Removal of these hydroxy groups is promoted by water vapor, which induces the crystallization of amorphous titania to anatase. The mechanism of crystallization in a water-rich environment was proposed based on the FTIR study. Stress evolution in titania films spin-deposited on silicon with solutions of titanium n-butoxide in toluene was investigated by an in-situ wafer curvature method. Tensile stresses were induced due to the densification by removal of water molecules attached to Ti-O-Ti linkages from 200°C to 300°C. The effect of crystallization on stress in the film was studied by comparing results of oxygen and nitrogen anneals. Compositional stress in anatase (a non-stoichiometric oxide) was measured by cyclic reduction-oxidation experiments performed at 700°C. The state of stress observed under reduction conditions was tensile in nature while compressive stresses evolved under oxidizing conditions. The measured value of the compositional stress of the film is 29.6 MPa.

Synthesis and characterization of a family of structurally characterized dysprosium alkoxides for improved fatigue-resistance characteristics of PDyZT thin films.

PubMed

Boyle, Timothy J; Bunge, Scott D; Clem, Paul G; Richardson, Jacob; Dawley, Jeffrey T; Ottley, Leigh Anna M; Rodriguez, Mark A; Tuttle, Bruce A; Avilucea, Gabriel R; Tissot, Ralph G

2005-03-07

Using either an ammoniacal route, the reaction between DyCl3, Na0, and HOR in liquid ammonia, or preferentially reacting Dy(N(SiMe3)2)3 with HOR in a solvent, we isolated a family of dysprosium alkoxides as [Dy(mu-ONep)2(ONep)]4 (1), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(THF)]2(mu-ONep) (2), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(py)]2(mu-ONep) (3), [Dy3(mu3-OBut)2(mu-OBut3(OBut)4(HOBut)2] (4), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(THF)2] (5), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(py)2] (6), (DMP)Dy(mu-DMP)4[Dy(DMP)2(NH3)]2 (7), [Dy(eta6-DMP)(DMP)2]2 (8), Dy(DMP)3(THF)3 (9), Dy(DMP)3(py)3 (10), Dy(DIP)3(NH3)2 (11), [Dy(eta6-DIP)(DIP)2]2 (12), Dy(DIP)3(THF)2 (13), Dy(DIP)3(py)3 (14), Dy(DBP)3(NH3) (15), Dy(DBP)3 (16), Dy(DBP)3(THF) (17), Dy(DBP)3(py)2 (18), [Dy(mu-TPS)(TPS2]2 (19), Dy(TPS)3(THF)3 (20), and Dy(TPS)3(py)3 (21), where ONep = OCH2CMe3, OBut) = OCMe3, DMP = OC6H3(Me)(2)-2,6, DIP = OC6H3(CHMe2)(2)-2,6, DBP = OC6H3(CMe3)(2)-2,6, TPS = OSi(C6H5)3, tol = toluene, THF = tetrahydrofuran, and py = pyridine. We were not able to obtain X-ray quality crystals of compounds 2, 8, and 9. The structures observed and data collected for the Dy compounds are consistent with those reported for its other congeners. A number of these precursors were used as Dy dopants in Pb(Zr0.3Ti0.7)O3 (PZT 30/70) thin films, with compound 12 yielding the highest-quality films. The resulting Pb0.94Dy0.04(Zr0.3Ti0.7)O3 [PDyZT (4/30/70)] had similar properties to PZT (30/70), but showed substantial resistance to polarization reversal fatigue.

Mechanism of epoxide hydrolysis in microsolvated nucleotide bases adenine, guanine and cytosine: a DFT study.

PubMed

Vijayalakshmi, Kunduchi P; Mohan, Neetha; Ajitha, Manjaly J; Suresh, Cherumuttathu H

2011-07-21

Six water molecules have been used for microsolvation to outline a hydrogen bonded network around complexes of ethylene epoxide with nucleotide bases adenine (EAw), guanine (EGw) and cytosine (ECw). These models have been developed with the MPWB1K-PCM/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) level of DFT method and calculated S(N)2 type ring opening of the epoxide due to amino group of the nucleotide bases, viz. the N6 position of adenine, N2 position of guanine and N4 position of cytosine. Activation energy (E(act)) for the ring opening was found to be 28.06, 28.64, and 28.37 kcal mol(-1) respectively for EAw, EGw and ECw. If water molecules were not used, the reactions occurred at considerably high value of E(act), viz. 53.51 kcal mol(-1) for EA, 55.76 kcal mol(-1) for EG and 56.93 kcal mol(-1) for EC. The ring opening led to accumulation of negative charge on the developing alkoxide moiety and the water molecules around the charge localized regions showed strong hydrogen bond interactions to provide stability to the intermediate systems EAw-1, EGw-1 and ECw-1. This led to an easy migration of a proton from an activated water molecule to the alkoxide moiety to generate a hydroxide. Almost simultaneously, a proton transfer chain reaction occurred through the hydrogen bonded network of water molecules and resulted in the rupture of one of the N-H bonds of the quaternized amino group. The highest value of E(act) for the proton transfer step of the reaction was 2.17 kcal mol(-1) for EAw, 2.93 kcal mol(-1) for EGw and 0.02 kcal mol(-1) for ECw. Further, the overall reaction was exothermic by 17.99, 22.49 and 13.18 kcal mol(-1) for EAw, EGw and ECw, respectively, suggesting that the reaction is irreversible. Based on geometric features of the epoxide-nucleotide base complexes and the energetics, the highest reactivity is assigned for adenine followed by cytosine and guanine. Epoxide-mediated damage of DNA is reported in the literature and the present results suggest that hydrated DNA bases become highly S(N)2 active on epoxide systems and the occurrence of such reactions can inflict permanent damage to the DNA.

Titanium (IV) sol-gel chemistry in varied gravity environments

NASA Astrophysics Data System (ADS)

Hales, Matthew; Martens, Wayde; Steinberg, Theodore

Sol-gel synthesis in reduced gravity is a relatively new topic in the literature and further inves-tigation is essential to realise its potential and application to other sol-gel systems. The sol-gel technique has been successfully applied to the synthesis of silica systems of varying porosity for many diverse applications [1-5]. It is proposed that current methods for the synthesis of silica sol-gels in reduced gravity may be applied to titanium sol-gel processing in order to enhance desirable physical and chemical characteristics of the final materials. The physical and chemical formation mechanisms for titanium alkoxide based sol-gels, to date, is not fully understood. However, various authors [6-9] have described potential methods to control the hydrolysis and condensation reactions of titanium alkoxides through the use of chemical inhibitors. A preliminary study of the reaction kinetics of titanium alkoxide sol-gel reaction in normal gravity was undertaken in order to determine reactant mixtures suitable for further testing under varied gravity conditions of limited duration. Through the use of 1H Nuclear Magnetic Resonance spectroscopy (NMR) for structural analysis of precursor materials, Ultra-Violet-Visible spectroscopy (UV-VIS) and viscosity measurements, it was demonstrated that not only could the rate of the chemical reaction could be controlled, but directed linear chain growth within the resulting gel structure was achievable through the use of increased inhibitor concentrations. Two unique test systems have been fabricated to study the effects of varied gravity (reduced, normal, high) on the formation of titanium sol-gels. Whilst the first system is to be used in conjunction with the recently commissioned drop tower facility at Queensland University of Technology in Brisbane, Australia to produce reduced gravity conditions. The second system is a centrifuge capable of providing high gravity environments of up to 70 G's for extended periods of time. The test systems and experimental results obtained will be presented. 1. Okubo, T., Tsuchida, A., Okuda, T., Fujitsuna, K., Ishikawa, M., Morita, T., Tada, T. , Kinetic Analyses of Colloidal Crystallization in Microgravity -Aircraft Experiments. . Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1999. 153: p. 515-524. 2. Okubo, T., Tsuchida, A., Kobayashi, K., Kuno, A., Morita, T., Fujishima, M., Kohno, Y., Kinetic Study of the Formation Reaction of Colloidal Silica Spheres in Microgravity Using Aircraft. Colloid Polymer Science, 1999. 277(5): p. 474-478. 3. Pienaar, C.L., Chiffoleau, G. J. A., Follens, L. R. A., Martens, J. A., Kirschhock, C. E. A., Steinberg, T. A., Effect of Gravity on the Gelation of Silica Sols. Chem. Mater., 2007. 19(4): p. 660-664. 4. Smith, D.D., et al., Effect of Microgravity on the Growth of Silica Nanostructures. Langmuir, 2000. 16(26): p. 10055-10060. 5. Zhang, X., Johnson, D.P., Manerbino, A.R., Moore, J.J., Schowengerdt, F. , Recent Mi-crogravity Results in the Synthesis of Porous Materials. AIP Conference Proceedings (Space Technology and Applications International Forum-1999, Pt. 1), 1999. 458: p. 88-93. 6. Dunbar, P.B., Bendzko, N.J.,, 1H and 13C NMR observation of the reaction of acetic acid with titanium isopropoxide. Materials Chemistry and Physics, 1999. 59: p. 26-35. 7. Krunks, M., Oja, I., T˜nsuaadu, K., Es-Souni, M., Gruselle, M., Niinistü,. L, Thermoanalytical study of acetylacetonate-modified titanium (iv) isopropoxide as precursor for TiO2 films. Journal of Thermal Analysis and Calorimetry, 2005: p. 483-488. 8. Moran, P.D., Bowmaker, G. A., Cooney, R. P., Vibrational Spectra and Molecular Associa-tion of Titanium Tetraisopropoxide. Inorg. Chem., 1998. 37(1): p. 2741-2748. 9. Somogyvari, A., Serpone, N.,, Evidence for five-coordination in titanium(1V) complexes. A nuclear magnetic resonance investigation. Canadian Journal of Chemistry, 1977. 56: p. 316-319.

Block copolymers for biomimetic composites

NASA Astrophysics Data System (ADS)

Calvert, Paul D.; Oner, Mualla; Burdon, Jeremy; Rieke, Peter C.; Farmer, Kelly

1993-07-01

Mineralized biological tissues can be regarded as composites where a fine reinforcement is laid down in a very controlled fashion within a tough polymeric matrix. Such materials include bone, antler, tooth enamel, mollusc shell, and crustacean shell. We have been exploring ways of forming similar structures by synthetic routes involving precipitation of reinforcing particles directly into a polymeric matrix. Part of this biomimetic approach requires polymer matrices which can exert a high degree of control over the mineralization process. Polymer gels have been formed from cross-linked methacrylates with various types of functionality within the gel. By incorporating calcium binding groups we have been producing gels which lead to preferential mineralization of the gel when it is incubated in a supersaturated solution of calcium oxalate or calcium carbonate. Similarly we have been incorporating silane groups within the gel in order to promote the deposition of silica in a gel body when it is immersed in a metastable solution of partly hydrolysed silicon alkoxides.

Optical and morphological properties of sol gel derived titanium dioxide films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, A. B.; Sharma, S. K.; M, Vishwas

2015-08-28

Titanium oxide (Titania) thin films were synthesized on different substrates via the sol-gel dip-coating method using alkoxide solution. Some selected samples were also prepared with different percentage of Lead (Pb). The influence of Pb addition in precursor sol on the optical properties of titanium dioxide thin films was studied. The optical transmittance in the visible region has increased with increase in weight percentage of lead. The refractive index was slightly decreased with Pb addition. Crystallization of these coatings was achieved through thermal annealing at temperatures above 400 °C. The structural properties and surface morphology of the crystallized coatings were studiedmore » by Scanning Electron Microscopy. Increase in average grain size from 250 nm to 350 nm with increase in Pb concentration is observed. Films were appeared to more coarse with increase in Pb addition. An increase in Pb addition resulted increase in average roughness from 12 nm to 25 nm.« less

Macroporous ceramics by colloidal templating

NASA Astrophysics Data System (ADS)

Subramaniam, G.; Pine, David J.

2000-04-01

We describe a novel method of fabricating macroporous ceramics employing colloidal dispersion of ultrafine ceramic particles with latex particles as the templates. The colloidal particles form a particulate gel on drying and fill the voids of the ordered latex templates. Subsequent removal of the template by calcination results in the formation of an ordered macroporous ceramic. The process has significant advantages over the traditional sol-gel process employing alkoxide precursors. Most importantly, the much lower shrinkage compared to the sol-gel process enabled us to produce larger pieces of the sample. The larger shrinkage involved in the sol-gel process often results in small and fragile pieces of the macroporous material which has to be subsequently heat treated to induce crystallization. The ability to choose crystalline colloidal particles in our method obviates the need for heat treatment to achieve crystallinity. We have synthesized a variety of materials such as macroporous silica, titania, alumina and recently have also extended the approach to macroporous silicon which is not amenable to the sol-gel process.

Manganite perovskite ceramics, their precursors and methods for forming

DOEpatents

Payne, David Alan; Clothier, Brent Allen

2015-03-10

Disclosed are a variety of ceramics having the formula Ln.sub.1-xM.sub.xMnO.sub.3, where 0.Itoreq.x.Itoreq.1 and where Ln is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or Y; M is Ca, Sr, Ba, Cd, or Pb; manganite precursors for preparing the ceramics; a method for preparing the precursors; and a method for transforming the precursors into uniform, defect-free ceramics having magnetoresistance properties. The manganite precursors contain a sol and are derived from the metal alkoxides: Ln(OR).sub.3, M(OR).sub.2 and Mn(OR).sub.2, where R is C.sub.2 to C.sub.6 alkyl or C.sub.3 to C.sub.9 alkoxyalkyl, or C.sub.6 to C.sub.9 aryl. The preferred ceramics are films prepared by a spin coating method and are particularly suited for incorporation into a device such as an integrated circuit device.

Photoluminescence and cathodoluminescence of Tb-doped Al 2O 3-ZrO 2 nanostructures obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Zawadzki, M.; Hreniak, D.; Wrzyszcz, J.; Miśta, W.; Grabowska, H.; Malta, O. L.; Stręk, W.

2003-07-01

Terbium-doped Al 2O 3-ZrO 2 mixed oxides of 10 wt% zirconia content were prepared by the alkoxide sol-gel method. The obtained samples were characterized by XRD, SEM, thermal analysis, textural and TPR studies. The effect of thermal treatment of Tb-doped Al 2O 3-ZrO 2 samples on photo- and cathodoluminescence spectra was investigated. It was found that the photoluminescence spectrum induced by UV excitation was characterized by a green luminescence pattern arising from the 5D 4 → 7F J ( J=6-0) transitions of the Tb 3+ ion. This photoluminescence became almost completely damped for the samples sintered at 1200 °C. However, these samples have demonstrated an intense cathodoluminescence under high electron accelerating potential (60 kV). Moreover, it was observed that apart of the green luminescence, the blue emission lines arising from 5D 3 → 7F J transitions of Tb 3+ were observed. The nature of such behavior is discussed.

Hybrid aerogel rigid ceramic fiber insulation and method of producing same

NASA Technical Reports Server (NTRS)

Barney, Andrea O. (Inventor); Heng, Vann (Inventor); Oka, Kris Shigeko (Inventor); Santos, Maryann (Inventor); Zinn, Alfred A. (Inventor); Droege, Michael (Inventor)

2004-01-01

A hybrid insulation material comprises of porous ceramic substrate material impregnated with nanoporous material and method of making the same is the topic of this invention. The porous substrate material has bulk density ranging from 6 to 20 lb/ft.sup.3 and is composed of about 60 to 80 wt % silica (SiO.sub.2) 20 to 40 wt % alumina (Al.sub.2 O.sub.3) fibers, and with about 0.1 to 1.0 wt % boron-containing constituent as the sintering agent. The nanoporous material has density ranging from 1.0 to 10 lb/ft.sup.3 and is either fully or partially impregnated into the substrate to block the pores, resulting in substantial reduction in conduction via radiation and convention. The nanoporous material used to impregnate the fiber substrate is preferably formed from a precursor of alkoxysilane, alcohol, water, and an acid or base catalyst for silica aerogels, and from a precursor of aluminum alkoxide, alcohol, water, and an acid or base catalyst for alumina aerogels.

Silicification of wood adopted for barrel production using pure silicon alkoxides in gas phase to avoid microbial colonisation.

PubMed

Guzzon, Raffaele; Widmann, Giacomo; Bertoldi, Daniela; Nardin, Tiziana; Callone, Emanuela; Nicolini, Giorgio; Larcher, Roberto

2015-02-01

The paper presents a new approach, covering wood with silica-based material in order to protect it from spoilage due to microbial colonisation and avoiding the loss of the natural features of the wood. Wood specimens derived from wine barrels were treated with methyltriethoxysilane in gas phase, leading to the deposition of a silica nanofilm on the surface. (29)Si and (13)C solid state Nuclear Magnetic Resonance and Scanning Electron Microscope-Energy Dispersive X-ray analysis observations showed the formation of a silica polymeric film on the wood samples, directly bonding with the wood constituents. Inductively Coupled Plasma-Mass Spectroscopy quantification of Si showed a direct correlation between the treatment time and silica deposition on the surface of the wood. The silica-coated wood counteracted colonisation by the main wine spoilage microorganisms, without altering the migration from wood to wine of 21 simple phenols measured using a HPLC-Electrochemical Coulometric Detection. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ferroelectric properties of PZT/BFO multilayer thin films prepared using the sol-gel method.

PubMed

Jo, Seo-Hyeon; Lee, Sung-Gap; Lee, Young-Hie

2012-01-05

In this study, Pb(Zr0.52Ti0.48)O3/BiFeO3 [PZT/BFO] multilayer thin films were fabricated using the spin-coating method on a Pt(200 nm)/Ti(10 nm)/SiO2(100 nm)/p-Si(100) substrate alternately using BFO and PZT metal alkoxide solutions. The coating-and-heating procedure was repeated several times to form the multilayer thin films. All PZT/BFO multilayer thin films show a void-free, uniform grain structure without the presence of rosette structures. The relative dielectric constant and dielectric loss of the six-coated PZT/BFO [PZT/BFO-6] thin film were approximately 405 and 0.03%, respectively. As the number of coatings increased, the remanent polarization and coercive field increased. The values for the BFO-6 multilayer thin film were 41.3 C/cm2 and 15.1 MV/cm, respectively. The leakage current density of the BFO-6 multilayer thin film at 5 V was 2.52 × 10-7 A/cm2.

Preparation of Carboxylato-Coordinated Titanium Alkoxides from Carboxylic Anhydrides: Alkoxido Group Transfer from Metal Atom to Carbonyl Group.

PubMed

Czakler, Matthias; Artner, Christine; Schubert, Ulrich

2012-07-01

Reaction of titanium(IV) isopropoxide, Ti(O i Pr) 4 , with an equimolar amount of phthalic anhydride resulted in the transfer of an isopropoxido group from the metal atom to one carbonyl group of the anhydride and coordination of the thus formed monoester to the titanium atom. One monoester ligand in Ti 2 (O i Pr) 6 (μ 2 -OOC-C 6 H 4 -COO i Pr)(η 1 -OOC-C 6 H 4 -COO i Pr)( i PrOH) is bridging and the other is η 1 -coordinated. When the reaction is performed in the presence of 1 mol-equiv. of acetic acid, the oxido cluster Ti 6 (μ 3 -O) 6 (O i Pr) 6 (μ 2 -OOC-C 6 H 4 -COO i Pr) 6 was instead obtained. The μ 3 -oxygen groups in the latter compound are due to esterification of acetic acid by the cleaved isopropyl alcohol.

Efficient synthesis of novel dialkyl-3-cyanopropylphosphate derivatives and evaluation of their anticholinesterase activity.

PubMed

Aouani, Iyadh; Sellami, Badreddine; Lahbib, Karima; Cavalier, Jean-François; Touil, Soufiane

2017-06-01

Based on the broad spectrum of biological activities associated with organophosphates, a novel type of this class of compounds was synthesized, bearing a nitrile group, from the sodium alkoxide-catalyzed reaction of dialkylphosphites with γ-ketonitriles at 80°C under solvent-free conditions. A reaction mechanism involving a phospha-Brook type rearrangement is proposed. Eight title compounds were investigated for their in vitro inhibitory potency and selectivity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) using Ellman's spectrophotometric method. The synthesized derivatives exhibited mostly a moderate activity against both cholinesterases. The IC 50 values for BChE were in a smaller concentration range (5.96-23.35µM) compared to those for AChE inhibition (9.61-53.74µM). The diethyl-3-cyano-1-p-tolylpropylphosphate which displayed the higher dual inhibitory potency towards both cholinesterases could be considered as a potential candidate for developing new drugs to treat Alzheimer's disease. Copyright © 2017 Elsevier Inc. All rights reserved.

Sol-gel derived CaCu{sub 3}Ti{sub 4}O{sub 12} ceramics: Synthesis, characterization and electrical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Laijun; Fan Huiqing; Fang Pinyang

2008-07-01

The giant dielectric constant material CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO) has been synthesized by sol-gel method, for the first time, using nitrate and alkoxide precursor. The electrical properties of CCTO ceramics, showing an enormously large dielectric constant {epsilon} {approx} 60,000 (100 Hz at RT), were investigated in the temperature range from 298 to 358 K at 0, 5, 10, 20, and 40 V dc. The phases, microstructures, and impedance properties of final samples were characterized by X-ray diffraction, scanning electron microscopy, and precision impedance analyzer. The dielectric permittivity of CCTO synthesized by sol-gel method is at least three times ofmore » magnitude larger than that synthesized by other low-temperature method and solid-state reaction method. Furthermore, the results support the internal barrier layer capacitor (IBLC) model of Schottky barriers at grain boundaries between semiconducting grains.« less

Nanoparticulate gellants for metallized gelled liquid hydrogen with aluminum

NASA Technical Reports Server (NTRS)

Palaszewski, Bryan; Starkovich, John; Adams, Scott

1996-01-01

Gelled liquid hydrogen was experimentally formulated using sol-gel technology. As a follow-on to work with cryogenic simulants, hydrogen was gelled with an alkoxide material: BTMSE. Initial results demonstrated that gellants with a specific surface area of 1000 m(exp 2)/g could be repeatably fabricated. Gelled hexane and metallized gelled hexane (with 13.8-wt% Al) were produced. Propellant settling testing was conducted for acceleration levels of 2 to 10 times normal gravity and a minimum gellant percentage was determined for stable gelled hexane and metalized gelled hexane. A cryogenic capillary rheometer was also designed, constructed, and used to determine the viscosity of gelled hydrogen. Small volumes of liquid hydrogen were gelled with a 7- to 8-wt% gellant level. The gelled H2 viscosity was 1.5 to 3.7 times that of liquid hydrogen: 0.048 to 0.116 mPa-s versus 0.03 mPa-s for liquid H2 (at 16 K and approximately 1 atm pressure).

Taggants, method for forming a taggant, and a method for detecting an object

DOEpatents

Harrup, Mason K [Idaho Falls, ID; Stewart, Frederick F [Idaho Falls, ID; Stone, Mark L [Idaho Falls, ID

2012-02-28

A taggant comprising at least one perfluorocarbon compound surrounded by a polyphosphazene compound. The polyphosphazene compound has the chemical structure: ##STR00001## wherein G.sub.1 and G.sub.2 are pendant groups having different polarities, m is an integer greater than or equal to 100, and each of A and B is independently selected from hydrogen, an alkyl, an alkene, an alkoxide, a polyether, a polythioether, a siloxane, and --X(CH.sub.2).sub.nY.sup.1(CH.sub.2)p.sub.1Y.sup.2(CH.sub.2)p.sub.2 . . . Y.sup.i(CH.sub.2)p.sub.iCH.sub.3, where n ranges from 1 to 6, X and Y are independently selected from oxygen, sulfur, selenium, tellurium, and polonium, and p.sub.1 through p.sub.i range from 1 to 6. Cyclic polyphosphazene compounds lacking the A and B groups are also disclosed, as are methods of forming the taggant and of detecting an object.

Surface modification of metallic cardiovascular stents by strongly adhering aliphatic polyester coatings.

PubMed

Jérôme, Christine; Aqil, Abdelhafid; Voccia, Samuël; Labaye, David-Emmanuel; Maquet, Véronique; Gautier, Sandrine; Bertrand, Olivier F; Jérôme, Robert

2006-03-01

This article reports on a novel two-step strategy for the coating of cardiovascular stents by strongly adhering biocompatible and biodegradable aliphatic polyesters. First, a precoating of poly(ethylacrylate) (PEA) was electrografted onto the metallic substrate by cathodic reduction of the parent monomer in dimethylformamide (DMF). The electrodeposition of PEA, in a good solvent of it, was confirmed by both Infra-red and Raman spectroscopies. The pendant ester groups of PEA were then chemically reduced into aluminum alkoxides, able to initiate the ring-opening polymerization (ROP) of either D,L-lactide (LA) or epsilon-caprolactone (CL). Growth of biodegradable PLA or PCL coatings from the adhering precoating was confirmed by both Infra-red and Raman spectroscopies, and directly observed by scanning electron microscopy (SEM). This type of coating can act as an anchoring layer for the subsequent casting of drug-loaded polyester films allowing the controlled release of antiproliferative agents for the treatment of in-stent restenosis. (c) 2005 Wiley Periodicals, Inc.

Strategies to indium nitride and gallium nitride nanoparticles: Low-temperature, solution-phase and precursor routes

NASA Astrophysics Data System (ADS)

Dingman, Sean Douglas

I present new strategies to low-temperature solution-phase synthesis of indium and gallium nitride (InN and GaN) ceramic materials. The strategies include: direct conversion of precursor molecules to InN by pyrolysis, solution-phase synthesis of nanostructured InN fibers via molecular precursors and co-reactants, and synthesis of powders through reactions derived from molten-salt chemistry. Indium nitride powders are prepared by pyrolysis of the precursors R 2InN3 (R = t-Bu (1), i-Amyl(2), Et(3), i-Pr( 4)). The precursors are synthesized via azide-alkoxide exchange of R2InOMe with Me3SiN3. The precursors are coordination polymers containing five-coordinate indium centers. Pyrolysis of 1 and 2 under N2 at 400°C yields powders consisting primarily of InN with average crystal sizes of 15--35 nm. 1 yields nanocrystalline InN with average particle sizes of 7 nm at 250°C. 3 and 4 yield primarily In metal from pyrolysis. Refluxing 1 in diisopropylbenzene (203°C) in the presence of primary amines yields InN nanofibers 10--100 nm in length. InN nanofibers of up to 1 mum can be synthesized by treating 1 with 1,1-dimethylhydrazine (DMHy) The DMHy appears to control the fiber length by acting as a secondary source of active nitrogen in order to sustain fiber growth. The resulting fibers are attached to droplets of indium metal implying a solution-liquid-solid growth mechanism. Precursor 4 yields crystalline InN whiskers when reacted with DMHy. Reactions of 4 with reducing agents such as HSnBu3, yield InN nanoparticles with an average crystallite size of 16 nm. Gallium precursors R2GaN3 (R = t-Bu( 5), Me3SiCH2(6) and i-Pr( 7)), synthesized by azide-alkoxide exchange, are found to be inert toward solution decomposition and do not yield GaN. These compounds are molecular dimers and trimers unlike the indium analogs. Compound 6 displays a monomer-dimer equilibrium in benzene solution, but exists as a solid-state trimer. InN powders are also synthesized by reactions of InCl3 and LiNH2 in a molten alkali-halide eutectic, KBr: Liar (60:40), at 400°C. The molten salt acts as an appropriate recrystallization medium for InN. Large InN platelets up to 500 nm could be synthesized. This is a significant step in finding mild reaction conditions that yield large InN crystals.

Synthesis, properties and applications of bio-based materials

NASA Astrophysics Data System (ADS)

Srinivasan, Madhusudhan

Bio-based feedstock have become very significant as they offer a value proposition in terms of carbon balance and also in terms of endowing biodegradability where needed. Thus a lot of attention is being given to the modification such feedstock for different applications. Soybean oil is one such feedstock. The oil is a triglyceride ester composed of different fatty acids, which are common to other plant oils. Thus soybean oil serves as a platform for plant oils, as modifications of this oil, can in theory be extended to cover other plant oils. Methyl oleate was used as a model fatty acid ester, to synthesize hydroxyesters with ethylene glycol via a two stage oxidative cleavage of the double bonds. Ozone was chosen as the oxidant due to its many advantages. The first stage involved oxidation of the double bond to aldehydes, ozonides and acetals, which were subsequently converted to hydroxyesters (hydroxy values of 220 - 270) in near quantitative yield by treatment with Oxone. This method could be extended to soybean oil to make "polyols" which could find applications in resin syntheses. Silylation was employed as another platform to functionalize soybean oil and fatty acid methyl esters with a reactive silane (vinyltrimethoxy silane). This simple modification produced materials that are cured by atmospheric moisture and are useful as coatings. The silylation was controlled by varying the grafting time, cure temperature and the concentration of the silane. Products with gel content as high as 90% could be achieved. The coating exhibited good adhesion to metal, glass, concrete and paper. Steel panels coated with these coatings exhibited good stability against corrosion in high humidity conditions and moderate stability against a salt spray. The silylation was also successfully utilized to improve the tensile strength of the blend of biodegradable polyester, poly (butylene adipate-co-terephthalate) with talc. A reactive extrusion process was employed to graft vinyl silanes on the polyester in short reaction times of 5 minutes. This improved the compatibility with the talc filler. This biodegradable polyester product was characterized by high tensile strength and moderate elongation. The modification method is simple is applicable to a variety of aliphatic biodegradable polyesters. Finally a rapid polymerization of 1, 4-dioxan-2-one in very short times was accomplished with titanium alkoxides as initiators. At low [monomer]/ [initiator] ratios (100:1), nearly all the alkoxide groups initiated polymerization. High conversions up to 90% were achieved even at high ratios (2400:1). The activation energy for polymerization for titanium tetraisopropoxide is the lowest reported (33.5 kJ/mol) for this monomer system.

Simple size control of TiO2 nanoparticles and their electrochemical performance: emphasizing the contribution of the surface area to lithium storage at high-rates

NASA Astrophysics Data System (ADS)

Lim, Joohyun; Um, Ji Hyun; Lee, Kyung Jae; Yu, Seung-Ho; Kim, Young-Jae; Sung, Yung-Eun; Lee, Jin-Kyu

2016-03-01

The particle size effects of TiO2 nanoparticles (TNPs), which are composed of small crystallites, on Li ion storage are a very fundamental and important subject. However, size control of TNPs under 200 nm using a sol-gel method has been limited due to the highly reactive precursor, titanium alkoxide. In this study, TNPs with various sizes even under 100 nm are obtained by controlling the reactant concentrations in a mixed solvent of ethanol and acetonitrile. Among them, three different sizes of TNPs are prepared to compare the Li ion storage capacity, and 60 nm TNPs are found to have the best reversible capacity of 182 mA h g-1 after 50 cycles at 1 C and a remarkable rate performance of 120 mA h g-1 at 10 C. Capacity increase upon cycling is observed in the size-controlled TNPs, and the explanation of this phenomenon is proposed to the lattice volume expansion of TiO2 upon intercalation for enabling further penetration of the electrolyte into the particles' interior. Moreover, the capacity at high rates is more closely related to the surface area from Hg porosimetry analysis than from typical N2 adsorption/desorption analysis.The particle size effects of TiO2 nanoparticles (TNPs), which are composed of small crystallites, on Li ion storage are a very fundamental and important subject. However, size control of TNPs under 200 nm using a sol-gel method has been limited due to the highly reactive precursor, titanium alkoxide. In this study, TNPs with various sizes even under 100 nm are obtained by controlling the reactant concentrations in a mixed solvent of ethanol and acetonitrile. Among them, three different sizes of TNPs are prepared to compare the Li ion storage capacity, and 60 nm TNPs are found to have the best reversible capacity of 182 mA h g-1 after 50 cycles at 1 C and a remarkable rate performance of 120 mA h g-1 at 10 C. Capacity increase upon cycling is observed in the size-controlled TNPs, and the explanation of this phenomenon is proposed to the lattice volume expansion of TiO2 upon intercalation for enabling further penetration of the electrolyte into the particles' interior. Moreover, the capacity at high rates is more closely related to the surface area from Hg porosimetry analysis than from typical N2 adsorption/desorption analysis. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00104a

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

NASA Astrophysics Data System (ADS)

Kelp, G.; Tätte, T.; Pikker, S.; Mändar, H.; Rozhin, A. G.; Rauwel, P.; Vanetsev, A. S.; Gerst, A.; Merisalu, M.; Mäeorg, U.; Natali, M.; Persson, I.; Kessler, V. G.

2016-03-01

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped. Electronic supplementary information (ESI) available: IR spectrum of additives found in the residual butanol layer formed during precursor preparation. See DOI: 10.1039/c5nr07942j

Sol–gel preparation of well-adhered films and long range ordered inverse opal films of BaTiO{sub 3} and Bi{sub 2}Ti{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al-Arjan, Wafa S.; King Faisal University, PO Box 380, Al Hofuf; Algaradah, Mohammed M.F.

Highlights: • Highly adaptable sols are presented for processing of the electroceramic materials BaTiO{sub 3} and Bi{sub 2}Ti{sub 2}O{sub 7}. • High quality thin films are produced by dip coating with good phase control. • Infiltration of cross-linked polystyrene templates led to high quality inverse opals. - Abstract: Barium and bismuth titanate thin films and well-ordered inverse opal films are produced by dip coating from sols containing titanium alkoxides with acetic acid, acetylacetone, methoxyethanol and water. The inverse opal preparations used crosslinked polystyrene opal templates. Heat treatment in air produced tetragonal BaTiO{sub 3} or mixtures of the hexagonal and tetragonalmore » phases, or phase pure Bi{sub 2}Ti{sub 2}O{sub 7}. Good quality films were obtained with a thickness of 5 μm from a single dipping, and the thickness could be increased by dipping multiple times. Inverse opals were well ordered and exhibited opalescence and photonic stop band effects.« less

Better ceramics through chemistry. 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zelinski, B.J.J.; Brinker, C.J.; Clark, D.E.

1990-01-01

At this year's meeting, research into the area of reaction mechanisms and kinetics of silicon species remained strong, while significant advances in the area of structure and properties of modified and unmodified metal alkoxide species were reported. The complementary area of processing in water based systems also received considerable attention with emphasis being placed on the hydrolysis behavior of ions in solution. The nature of particle/aggregate growth was also a major topic of discussion with papers being presented on the role of aggregation in particle growth and on the nature and rheology of concentrated suspensions. Important developments in the areamore » of mechanical properties of aerogels, fibers and films were presented as well as research into techniques for in situ monitoring of films during dip coating. Continued advances in applications which utilize solution derived ceramics were also reported. These applications included GRIN lenses, planar waveguides, optical filters and switches, transpiration cooled windows, dye-polymer composites for nonlinear optics, dielectrics and electro-optic materials including PLZT's and the niobates, and chemical sensors. Finally, one of the meeting highlights was a special evening session on biomimetics: ceramic processing in natural systems.« less

Labeling transplanted mice islet with polyvinylpyrrolidone coated superparamagnetic iron oxide nanoparticles for in vivo detection by magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Huang, Hai; Xie, Qiuping; Kang, Muxing; Zhang, Bo; Zhang, Hui; Chen, Jin; Zhai, Chuanxin; Yang, Deren; Jiang, Biao; Wu, Yulian

2009-09-01

Superparamagnetic iron oxide nanoparticles (SPIO) are emerging as a novel probe for noninvasive cell tracking with magnetic resonance imaging (MRI) and have potential wide usage in medical research. In this study, we have developed a method using high-temperature hydrolysis of chelate metal alkoxide complexes to synthesize polyvinylpyrrolidone coated iron oxide nanoparticles (PVP-SPIO), as a biocompatible magnetic agent that can efficiently label mice islet β-cells. The size, crystal structure and magnetic properties of the as-synthesized nanoparticles have been characterized. The newly synthesized PVP-SPIO with high stability, crystallinity and saturation magnetization can be efficiently internalized into β-cells, without affecting viability and function. The imaging of 100 PVP-SPIO-labeled mice islets in the syngeneic renal subcapsular model of transplantation under a clinical 3.0 T MR imager showed high spatial resolution in vivo. These results indicated the great potential application of the PVP-SPIO as an MRI contrast agent for monitoring transplanted islet grafts in the clinical management of diabetes in the near future.

Atomically designed precursors in optical fiber amplifiers: The thermal stability of the heterobimetallic ErAl3(OPri)12 in a solution-coated silica soot

NASA Astrophysics Data System (ADS)

Engholm, M.; Lashgari, K.; Edvardsson, S.; Westin, G.; Norin, L.

2005-06-01

The thermal stability of the bimetallic alkoxide ErAl3(OPri)12 doped in an unsintered silica (soot) has been investigated. Samples have been heated to different temperatures (up to 1500°C and analyzed by using ultraviolet-visible-near infrared absorption spectroscopy, infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal gravimetric analysis, and powder x-ray diffraction. It is seen that the doped samples heated up to 1000°C show broad glasslike absorption spectra, indicating an amorphous structure, while the high-temperature sample shows an ordered crystallinelike structure with sharp characteristic absorption peaks. X-ray diffraction measurements indicate the formation of an ordered structure at temperatures of 1500°C, revealing a crystal phase of silica and phases of erbium and aluminosilicate. A comparison is also made with a sample doped with aqueous ErCl3 and Al(NO3)3. It is concluded that the local structure of the ErAl3 precursor is not preserved at temperatures above 1000°C. Alternative doping procedures are discussed.

A Phos-tag-based magnetic-bead method for rapid and selective separation of phosphorylated biomolecules.

PubMed

Tsunehiro, Masaya; Meki, Yuma; Matsuoka, Kanako; Kinoshita-Kikuta, Emiko; Kinoshita, Eiji; Koike, Tohru

2013-04-15

A simple and efficient method based on magnetic-bead technology has been developed for the separation of phosphorylated and nonphosphorylated low-molecular-weight biomolecules, such as nucleotides, phosphorylated amino acids, or phosphopeptides. The phosphate-binding site on the bead is an alkoxide-bridged dinuclear zinc(II) complex with 1,3-bis(pyridin-2-ylmethylamino)propan-2-olate (Phos-tag), which is linked to a hydrophilic cross-linked agarose coating on a magnetic core particle. All steps for the phosphate-affinity separation are conducted in buffers of neutral pH with 50 μL of the magnetic beads in a 1.5-mL microtube. The entire separation protocol for phosphomonoester-type compounds, from addition to elution, requires less than 12 min per sample if the buffers and the zinc(II)-bound Phos-tag magnetic beads have been prepared in advance. The phosphate-affinity magnetic beads are reusable at least 15 times without a decrease in their phosphate-binding ability and they are stable for three months in propan-2-ol. Copyright © 2013 Elsevier B.V. All rights reserved.

Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

DOEpatents

Sugama, Toshifumi

1992-01-01

Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR).sub.n (wherein M is Ti, Zr, Ge or Al; R is CH.sub.3, C.sub.2 H.sub.5 or C.sub.3 H.sub.7 ; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., <1000.degree. C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

DOEpatents

Sugama, Toshifumi

1993-01-01

Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR).sub.n (wherein M is Ti, Zr, Ge or Al; R is CH.sub.3, C.sub.2 H.sub.5 or C.sub.3 H.sub.7 ; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., <1000.degree. C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

Solid-gel precursor solutions and methods for the fabrication of polymetallicsiloxane coating films

DOEpatents

Toshifumi Sugama.

1993-04-06

Solutions and preparation methods necessary for the fabrication of metal oxide cross-linked polysiloxane coating films are disclosed. The films are useful in provide heat resistance against oxidation, wear resistance, thermal insulation, and corrosion resistance of substrates. The sol-gel precursor solution comprises a mixture of a monomeric organoalkoxysilane, a metal alkoxide M(OR)[sub n] (wherein M is Ti, Zr, Ge or Al; R is CH[sub 3], C[sub 2]H[sub 5] or C[sub 3]H[sub 7]; and n is 3 or 4), methanol, water, HCl and NaOH. The invention provides a sol-gel solution, and a method of use thereof, which can be applied and processed at low temperatures (i.e., < 1,000 C.). The substrate can be coated by immersing it in the above mentioned solution at ambient temperature. The substrate is then withdrawn from the solution. Next, the coated substrate is heated for a time sufficient and at a temperature sufficient to yield a solid coating. The coated substrate is then heated for a time sufficient, and temperature sufficient to produce a polymetallicsiloxane coating.

Ferroelectric properties of PZT/BFO multilayer thin films prepared using the sol-gel method

PubMed Central

2012-01-01

In this study, Pb(Zr0.52Ti0.48)O3/BiFeO3 [PZT/BFO] multilayer thin films were fabricated using the spin-coating method on a Pt(200 nm)/Ti(10 nm)/SiO2(100 nm)/p-Si(100) substrate alternately using BFO and PZT metal alkoxide solutions. The coating-and-heating procedure was repeated several times to form the multilayer thin films. All PZT/BFO multilayer thin films show a void-free, uniform grain structure without the presence of rosette structures. The relative dielectric constant and dielectric loss of the six-coated PZT/BFO [PZT/BFO-6] thin film were approximately 405 and 0.03%, respectively. As the number of coatings increased, the remanent polarization and coercive field increased. The values for the BFO-6 multilayer thin film were 41.3 C/cm2 and 15.1 MV/cm, respectively. The leakage current density of the BFO-6 multilayer thin film at 5 V was 2.52 × 10-7 A/cm2. PMID:22221519

Diastereoselective addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones

NASA Astrophysics Data System (ADS)

Uteuliyev, Maulen M.; Nguyen, Thien T.; Coltart, Don M.

2015-12-01

The α-alkylation of ketones and their derivatives by the addition of their corresponding enolates to alkyl halides is a fundamental synthetic transformation, but its utility is limited because the key bond-forming step proceeds in a bimolecular nucleophilic substitution fashion. Here we describe how an umpolung strategy that involves the addition of Grignard reagents to α-epoxy N-sulfonyl hydrazones—directed by the alkoxide of the 1-azo-3-alkoxy propenes formed in situ via base-induced ring opening of the epoxide—leads to the syn-selective production of α-alkyl-β-hydroxy N-sulfonyl hydrazones with α-quaternary centres. This transformation is remarkable in its ability to incorporate an unprecedented range of carbon-based substituents, which include primary, secondary and tertiary alkyl, as well as alkenyl, aryl, allenyl and alkynyl groups. Subsequent hydrolysis of the β-hydroxy N-sulfonyl hydrazone products produces the corresponding β-hydroxy ketones. In addition to hydrolysis, the hydrazone products are poised to undergo numerous different known synthetic transformations via well-established chemistry, which would provide access to a wide array of useful structures.

A novel low cost non-aqueous chemical route for giant dielectric constant CaCu3Ti4O12 ceramic

NASA Astrophysics Data System (ADS)

Singh, Laxman; Kim, Ill Won; Woo, Won Seok; Sin, Byung Cheol; Lee, Hyung-il; Lee, Youngil

2015-05-01

This paper reports a simple, fast, low cost and environment-friendly route for preparing a highly crystalline giant dielectric material, CaCu3Ti4O12 (CCTO), through combustion of metal nitrates in non-aqueous precursor solution using inexpensive solid TiO2 powder. The route to producing pure phase CCTO ceramic using stable solid TiO2 is better than other several sol-gel routes reported earlier in which expensive alkoxides, oxynitrates, or chlorides of titanium are used as the titanium sources. X-ray diffraction revealed the formation of cubic perovskite CCTO. Scanning electron microscopy image showed the average grain sizes in the range of 1.5-5 μm. At 10 kHz and room temperature, the best CCTO ceramic exhibited a high dielectric constant, ε‧ ∼43325.24, with low dielectric loss, tan δ ∼0.088. The dielectric relaxation behavior was rationalized from impedance and modulus studies and the presence of a non-Debye type of relaxation was confirmed.

Effects of acid catalyst type on structural, morphological, and optoelectrical properties of spin-coated TiO2 thin film

NASA Astrophysics Data System (ADS)

Golobostanfard, Mohammad Reza; Abdizadeh, Hossein

2013-03-01

The effects of different acid catalysts of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, acetic acid, and citric acid on structural, morphological, and optoelectrical properties of nanocrystalline spin-coated TiO2 thin films synthesized via alkoxide sol-gel route were investigated. It was found that only the sols with HNO3 and HCl are suitable for film preparation. The X-ray diffractometry and Raman analysis showed that crystalline phases could be controlled by the type of acid catalyst. Although the H2SO4 sol shows good stability, it causes extremely different morphology to form due to its different sol nature and high contact angle. Fourier transformed infrared spectra confirmed the presence of acid anion species in all samples even after calcination. Furthermore, it was inferred from UV-visable absorption spectra that although the band gap and thickness of the films are independent of acid catalyst type, the refractive index and porosity of the films are strongly affected by the type of acids.

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate

PubMed Central

Depond, Philip J

2018-01-01

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the deposition mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. The results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials. PMID:29765806

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate.

PubMed

Martin, Aiden A; Depond, Philip J

2018-01-01

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the deposition mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. The results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.

Synthesis and luminescence properties of cinnamide based nanohybrid materials containing Eu (II) ions

NASA Astrophysics Data System (ADS)

Kiran Kumar, A. B. V.; Jayasimhadri, M.; Cha, Hyeongrae; Chen, Kuangcai; Lim, Jae-Min; Lee, Yong-Ill

2011-07-01

In the present work, the cinnamide based organic-inorganic hybrid luminescent materials were prepared by using sol-gel technique, in which both the components are covalently linked via Si-C bonds. The organic precursor N-(3-(triethoxysilyl)propyl)cinnamide (Cn-Si) was synthesized by (3-aminopropyl) triethoxysilane being reacted with cinnamoyal chloride. Finally, novel hybrid materials were prepared successfully through hydrolysis and polycondensation processes between the alkoxide groups of precursors Cn-Si and tetraethylorthosilane (TEOS) in the presence of europium nitrate. We have characterized thoroughly the prepared samples using FT-IR, thermal analysis (TGA/DTA), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS) and photoluminescence (PL) spectroscopy. The results indicate that these materials exhibit the excellent thermal stability up to 350 °C. The X-ray diffraction patterns confirmed the amorphous nature of the developed materials. The rare-earth doped hybrid materials have exhibited an intense green emission at 530 nm with CIE chromaticity coordinates (0.4801, 0.4669). Whereas, the un-doped one gives some remarkable blue emission properties under UV excitation.

Protonation at the aromatic ring vs at the carbonyl group of lanthanide-diaryl ketone dianion species by aryl alcohols. Formation, structural characterization, and reactivity of lanthanide aryloxide, mixed aryloxide/alkoxide, and aryloxide/enolate complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshimura, Takashi; Hou, Z.; Wakatsuki, Yasua

1995-11-01

Reaction of the ytterbium-benzophenone dianion complex (1), which was formed by reaction of Yb metal with benzophenone in THF/HMPA, with 2,6-di-tert-butyl-4-methylphenol, yielded the ytterbium(II) aryloxide complex Yb(OAr){sub 2}(HMPA){sub 2} (2, Ar= C{sub 6}H{sub 2} -{sup t}Bu{sub 2}-2,6-Me-4) as a major product (80%) and the ytterbium(III) enolate complex (3) as a minor one (ca. 5% yield). The mechanisms of these reactions are discussed. X-ray crystallographic studies reveal that 3, 4a, and 7b are isostructural, and so are 5a and 6. The central metal ions in these complexes are all five-coordinated in a trigonal bipyramid form (highly distorted in the case ofmore » 5a and 6) with two HMPA ligands at the apical and three anionic oxygen ligands at the equatorial positions. 25 refs., 7 figs., 7 tabs.« less

The controlled deposition of metal oxides onto carbon nanotubes by atomic layer deposition: examples and a case study on the application of V2O4 coated nanotubes in gas sensing.

PubMed

Willinger, Marc-Georg; Neri, Giovanni; Bonavita, Anna; Micali, Giuseppe; Rauwel, Erwan; Herntrich, Tobias; Pinna, Nicola

2009-05-21

A new atomic layer deposition (ALD) process was applied for the uniform coating of carbon nanotubes with a number of transition-metal oxide thin films (vanadium, titanium, and hafnium oxide). The presented approach is adapted from non-aqueous sol-gel chemistry and utilizes metal alkoxides and carboxylic acids as precursors. It allows the coating of the inner and outer surface of the tubes with a highly conformal film of controllable thickness and hence, the production of high surface area hybrid materials. The morphology and the chemical composition as well as the high purity of the films are evidenced through a combination of electron microscopic and electron-energy-loss spectrometric techniques. Furthermore, in order to highlight a possible application of the obtained hybrids, the electrical and sensing properties of resistive gas sensors based on hybrid vanadium oxide-coated carbon nanotubes (V2O4-CNTs) are reported and the effect of thermal treatment on the gas sensing properties is studied.

Mechanistic Studies of ε-Caprolactone Polymerization by (salen)AlOR Complexes and a Predictive Model for Cyclic Ester Polymerizations

PubMed Central

2016-01-01

Aluminum alkoxide complexes (2) of salen ligands with a three-carbon linker and para substituents having variable electron-withdrawing capabilities (X = NO2, Br, OMe) were prepared, and the kinetics of their ring-opening polymerization (ROP) of ε-caprolactone (CL) were investigated as a function of temperature, with the aim of drawing comparisons to similar systems with two-carbon linkers investigated previously (1). While 1 and 2 exhibit saturation kinetics and similar dependences of their ROP rates on substituents X (invariant Keq, similar Hammett ρ = +1.4(1) and 1.2(1) for k2, respectively), ROP by 2 was significantly faster than for 1. Theoretical calculations confirm that, while the reactant structures differ, the transition state geometries are quite similar, and by analyzing the energetics of the involved distortions accompanying the structural changes, a significant contribution to the basis for the rate differences was identified. Using this knowledge, a simplified computational method for evaluating ligand structural influences on cyclic ester ROP rates is proposed that may have utility for future catalyst design. PMID:26900488

Synthesis and characterization of thick PZT films via sol-gel dip coating method

NASA Astrophysics Data System (ADS)

Shakeri, Amid; Abdizadeh, Hossein; Golobostanfard, Mohammad Reza

2014-09-01

Thick films of lead zirconate titanate (PZT) offer possibilities for micro-electro-mechanical systems such as high frequency ultrasonic transducers. In this paper, crack-free thick films of PZT have been prepared up to 45 μm thickness via modified sol-gel dip coating method. In this procedure, acetic acid-alcoholic based sol is used by applying diethanolamine (DEA) and deionized water as additives. The effects of DEA and water on the crystal structure and surface morphology of the films are investigated. The mechanisms of acetic acid and DEA complexations are introduced by using FTIR spectrometer which illustrates suitable substitution of complexing agents with alkoxide groups. DEA/(Ti + Zr) = 0.5 or water/(Ti + Zr) = 0.5 are determined as the optimum molar ratio of additives, which lead to the formation of almost pure perovskite phase with the tetragonal lattice parameters of ct = 4.16 Ǻ and at = 4.02 Ǻ and a distortion of 2%. Values of remanent polarization and dielectric constant of 7.8 μC cm-2 and 1630 were obtained for 45 μm thick films, respectively.

Thin-film decoupling capacitors for multi-chip modules

NASA Astrophysics Data System (ADS)

Dimos, D.; Lockwood, S. J.; Schwartz, R. W.; Rogers, M. S.

Thin-film decoupling capacitors based on ferroelectric lead lanthanum zirconate titanate (PLZT) films are being developed for use in advanced packages, such as multi-chip modules. These thin-film decoupling capacitors are intended to replace multi-layer ceramic capacitors for certain applications, since they can be more fully integrated into the packaging architecture. The increased integration that can be achieved should lead to decreased package volume and improved high-speed performance, due to a decrease in interconnect inductance. PLZT films are fabricated by spin coating using metal carboxylate/alkoxide solutions. These films exhibit very high dielectric constants ((var epsilon) greater than or equal to 900), low dielectric losses (tan(delta) = 0.01), excellent insulation resistances (rho greater than 10(exp 13) (Omega)-cm at 125 C), and good breakdown field strengths (E(sub B) = 900 kV/cm). For integrated circuit applications, the PLZT dielectric is less than 1 micron thick, which results in a large capacitance/area (8-9 nF/sq mm). The thin-film geometry and processing conditions also make these capacitors suitable for direct incorporation onto integrated circuits and for packages that require embedded components.

Ordered Mesoporous Titania/Carbon Hybrid Monoliths for Lithium-ion Battery Anodes with High Areal and Volumetric Capacity.

PubMed

Dörr, Tobias S; Fleischmann, Simon; Zeiger, Marco; Grobelsek, Ingrid; de Oliveira, Peter W; Presser, Volker

2018-04-25

Free-standing, binder-free, and conductive additive-free mesoporous titanium dioxide/carbon hybrid electrodes were prepared from co-assembly of a poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) block copolymer and a titanium alkoxide. By tailoring an optimized morphology, we prepared macroscopic mechanically stable 300 μm thick monoliths that were directly employed as lithium-ion battery electrodes. High areal mass loading of up to 26.4 mg cm -2 and a high bulk density of 0.88 g cm -3 were obtained. This resulted in a highly increased volumetric capacity of 155 mAh cm -3 , compared to cast thin film electrodes. Further, the areal capacity of 4.5 mAh cm -2 represented a 9-fold increase compared to conventionally cast electrodes. These attractive performance metrics are related to the superior electrolyte transport and shortened diffusion lengths provided by the interconnected mesoporous nature of the monolith material, assuring superior rate handling, even at high cycling rates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure evolution, thermal stability and fractal behavior of water vapor flow assisted in situ growth poly(vinylcarbazole)-titania quantum dots nanocomposites

NASA Astrophysics Data System (ADS)

Mombrú, Dominique; Romero, Mariano; Faccio, Ricardo; Mombrú, Alvaro W.

2017-12-01

Here, we report a novel strategy for the preparation of TiO2 quantum dots fillers prepared from alkoxide precursor via in situ water vapor flow diffusion into poly(N-vinylcarbazole) host. A detailed characterization by means of infrared and Raman spectroscopy, X-ray powder diffraction, small angle X-ray scattering and differential scanning calorimetry is reported. The growth mechanism of both crystallites and particles was mostly governed by the classical coarsening reaction limited growth and the polymer host showed no detectable chemical modifications at the interface or active participation in the growing process. The main relevance of our strategy respect to the typical sol-gel growth in solution is the possibility of the interruption of the reaction by simple stopping the water vapor flow diffusion into the polymer host thus achieving good control in the nanoparticles size. The thermal stability and fractal behavior of our nanocomposites were also studied by differential scanning calorimetry and in situ small angle X-ray scattering versus temperature. Strong correlations between modifications in the fractal behavior and glass transition or fusion processes were observed for these nanocomposites.

A new sol-gel processing routine without chelating agents for preparing highly transparent solutions and nanothin films: engineering the role of chemistry to design the process

NASA Astrophysics Data System (ADS)

Ashiri, Rouholah

2015-01-01

The great sensitivity of titanium alkoxides to hydrolysis makes their sol-gel transformation very fast and thus difficult to control. A method was proposed to alleviate this drawback. Preparation of highly transparent solutions and nanothin films is another objective of the present research. Employing nanoemulsion method and optimizing the processing conditions, a clear solution of well-dispersed nanosized particles was obtained. With the proposed process BaTiO3 precursor sols and nanothin films with enhanced optical transparency towards the visible were prepared. The optimal formulation of the sol consists of acetic acid, barium acetate, 2-propanol, TTIP and deionized water with 6:1:1:1:150 M ratios, respectively. It was found that the reduction of the temperature in the initial stage of mixing of precursors controls the size of the forming species and accordingly improves the stability and transparency of the sol. The results also showed that the applied modifications and optimizations significantly downsize the particles within the sol to the nanometric scale and accordingly result in a significant improvement in the optical response of the products.

Synthesis and characterization of TiC nanopowders via sol-gel and subsequent carbothermal reduction process

NASA Astrophysics Data System (ADS)

Chen, Xu; Fan, Jinglian; Lu, Qiong

2018-06-01

TiC nanocrystalline powders were synthesized by in-situ carbothermic reduction of Ti-O-C precursor under vacuum atmosphere. And the Ti-O-C precursor was formed by sol-gel method from titanium butyrate (TBOT) and sucrose. To obtain stable sol, TBOT was directly added into mixed solution which contains water, sucrose, acetic acid (AcOH) and acetylacetone (ACAC). This procedure is more convenient and economical because it avoids the use of alcohol which is used as solvent in most reports of alkoxide hydrolysis sol-gel method. TG-DSC, XRD, FTIR and SEM/TEM were employed to analyze and characterize the product during the entire process. The phase composition and crystalline structure parameters of powders with different C/Ti molar ratio were investigated by Rietveld refinement method, and elemental quantitative analysis of the samples were performed. Furthermore, the optimal parameters of carbothermal reduction were obtained and the grain growth mechanism was demonstrated. The results show that TiC nanocrystalline powders (C/Ti molar ratio is 3.5 in the precursor) were synthesized at 1300 °C for 2 h, which have near standard lattice parameter, well crystallinity and fine average grain size ( 37.4 nm).

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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) complexesmore » 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.« less

Titania-coated manganite nanoparticles: Synthesis of the shell, characterization and MRI properties

NASA Astrophysics Data System (ADS)

Jirák, Zdeněk; Kuličková, Jarmila; Herynek, Vít; Maryško, Miroslav; Koktan, Jakub; Kaman, Ondřej

2017-04-01

Novel procedure for coating of oxide nanoparticles with titania, employing hydrolysis and polycondensation of titanium alkoxides under high-dilution conditions and cationic surfactants, is developed and applied to magnetic cores of perovskite manganite. Bare particles of the ferromagnetic La0.65Sr0.35MnO3 phase, possessing high magnetization, M10 kOe(4.5 K) = 63.5 emu g-1, and Curie temperature, TC = 355 K, are synthesized by sol-gel procedure and subsequently coated with titania. Further, a comparative silica-coated product is prepared. In order to analyse the morphology, colloidal stability, and surface properties of these two types of coated particles, a detailed study by means of transmission electron microscopy, dynamic light scattering, zeta-potential measurements, and IR spectroscopy is carried out. The experiments on the titania-coated sample reveal a continuous though porous character of the TiO2 shell, the nature of which is amorphous but can be transformed to anatase at higher temperatures. Finally, the relaxometric study at the magnetic field of 0.5 T, performed to quantity the transverse relaxivity and its temperature dependence, reveals important differences between the titania-coated and silica-coated nanoparticles.

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate [Formation Mechanisms of Boron Oxide Fillms Fabricated by Large Area Electron Beam-Induced Deposition of Trimethyl Borate

DOE PAGES

Martin, Aiden A.; Depond, Philip J.

2018-04-24

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the depositionmore » mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. Lastly, the results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.« less

Sol-gel preparation of Ag-silica nanocomposite with high electrical conductivity

NASA Astrophysics Data System (ADS)

Ma, Zhijun; Jiang, Yuwei; Xiao, Huisi; Jiang, Bofan; Zhang, Hao; Peng, Mingying; Dong, Guoping; Yu, Xiang; Yang, Jian

2018-04-01

Sol-gel derived noble-metal-silica nanocomposites are very useful in many applications. Due to relatively low price, higher conductivity, and higher chemical stability of silver (Ag) compared with copper (Cu), Ag-silica has gained much more research interest. However, it remains a significant challenge to realize high loading of Ag content in sol-gel Ag-silica composite with high structural controllability and nanoparticles' dispersity. Different from previous works by using multifunctional silicon alkoxide to anchor metal ions, here we report the synthesis of Ag-silica nanocomposite with high loading of Ag nanoparticles by employing acetonitrile bi-functionally as solvent and metal ions stabilizer. The electrical conductivity of the Ag-silica nanocomposite reached higher than 6800 S/cm. In addition, the Ag-silica nanocomposite could simultaneously possess high electrical conductivity and positive conductivity-temperature coefficient by properly controlling the loading content of Ag. Such behavior is potentially advantageous for high-temperature devices (like phosphoric acid fuel cells) and inhibiting the thermal-induced increase of devices' internal resistance. The strategy proposed here is also compatible with block-copolymer directed self-assembly of mesoporous material, spin-coating of film and electrospinning of nanofiber, making it more charming in various practical applications.

Improvement of bias-stability in amorphous-indium-gallium-zinc-oxide thin-film transistors by using solution-processed Y{sub 2}O{sub 3} passivation

DOE Office of Scientific and Technical Information (OSTI.GOV)

An, Sungjin; Mativenga, Mallory; Kim, Youngoo

2014-08-04

We demonstrate back channel improvement of back-channel-etch amorphous-indium-gallium-zinc-oxide (a-IGZO) thin-film transistors by using solution-processed yttrium oxide (Y{sub 2}O{sub 3}) passivation. Two different solvents, which are acetonitrile (35%) + ethylene glycol (65%), solvent A and deionized water, solvent B are investigated for the spin-on process of the Y{sub 2}O{sub 3} passivation—performed after patterning source/drain (S/D) Mo electrodes by a conventional HNO{sub 3}-based wet-etch process. Both solvents yield devices with good performance but those passivated by using solvent B exhibit better light and bias stability. Presence of yttrium at the a-IGZO back interface, where it occupies metal vacancy sites, is confirmed by X-ray photoelectronmore » spectroscopy. The passivation effect of yttrium is more significant when solvent A is used because of the existence of more metal vacancies, given that the alcohol (65% ethylene glycol) in solvent A may dissolve the metal oxide (a-IGZO) through the formation of alkoxides and water.« less

Unraveling the role of water in the stereoselective step of aqueous proline-catalyzed aldol reactions.

PubMed

Ribas-Arino, Jordi; Carvajal, Maria Angels; Chaumont, Alain; Masia, Marco

2012-12-03

A multiscale computational study was performed with the aim of tracing the source of stereoselectivity and disclosing the role of water in the stereoselective step of propionaldehyde aldol self-condensation catalyzed by proline amide in water, a reaction that serves as a model for aqueous organocatalytic aldol condensations. Solvent mixing and hydration behavior were assessed by classical molecular dynamics simulations, which show that the reaction between propanal and the corresponding enamine takes place in a fully hydrated environment. First-principles molecular dynamics simulations were used to study the free-energy profile of four possible reaction paths, each of which yields a different stereoisomer, and high-level static first-principles calculations were employed to characterize the transition states for microsolvated species. The first solvation shell of the oxygen atom of the electrophilic aldehyde at the transition states contains two water molecules, each of which donates one hydrogen bond to the nascent alkoxide and thereby largely stabilizes its excess electron density. The stereoselectivity originates in an extra hydrogen bond donated by the amido group of proline amide in two reaction paths. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation mechanisms of boron oxide films fabricated by large-area electron beam-induced deposition of trimethyl borate [Formation Mechanisms of Boron Oxide Fillms Fabricated by Large Area Electron Beam-Induced Deposition of Trimethyl Borate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, Aiden A.; Depond, Philip J.

Boron-containing materials are increasingly drawing interest for the use in electronics, optics, laser targets, neutron absorbers, and high-temperature and chemically resistant ceramics. In this article, the first investigation into the deposition of boron-based material via electron beam-induced deposition (EBID) is reported. Thin films were deposited using a novel, large-area EBID system that is shown to deposit material at rates comparable to conventional techniques such as laser-induced chemical vapor deposition. The deposition rate and stoichiometry of boron oxide fabricated by EBID using trimethyl borate (TMB) as precursor is found to be critically dependent on the substrate temperature. By comparing the depositionmore » mechanisms of TMB to the conventional, alkoxide-based precursor tetraethyl orthosilicate it is revealed that ligand chemistry does not precisely predict the pathways leading to deposition of material via EBID. Lastly, the results demonstrate the first boron-containing material deposited by the EBID process and the potential for EBID as a scalable fabrication technique that could have a transformative effect on the athermal deposition of materials.« less

Quantifying accessible sites and reactivity on titania–silica (photo)catalysts: Refining TOF calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eaton, Todd R.; Campos, Michael P.; Gray, Kimberly A.

2014-01-01

It can be difficult to determine the number of active atoms accessible to the fluid phase in mixed oxide catalysts, as required for obtaining true turnover frequencies (TOF). Here, we utilize the selective titration of surface Ti atoms with phenylphosphonic acid (PPA) on TiO 2–SiO 2 materials to estimate the number of reactant-accessible sites. TiO 2–SiO 2 composites were synthesized over a range of Ti loadings from grafting of titanocene dichloride (Cp 2TiCl 2) or tetraethoxy orthotitanate (TEOT) on SiO 2 and sol–gel co-hydrolysis of Si and Ti alkoxides. The materials were characterized by DRUV–vis, XRD, BET, and XANES. Despitemore » the significant morphological and electronic differences, materials prepared by Cp 2TiCl 2 and TEOT yielded a near-constant TOF of 0.14 h -1 (±0.04) across Ti loadings, for benzyl alcohol photooxidation, when normalizing rates by sites titrated by PPA. The fraction of Ti atoms titrated by PPA was strongly dependent on synthesis method and surface density. PPA titration and benzyl alcohol photooxidation may be useful measures of surface accessibility in other supported oxides.« less

Mesoporous zirconium titanium oxides. Part 2: Synthesis, porosity, and adsorption properties of beads.

PubMed

Sizgek, G Devlet; Sizgek, Erden; Griffith, Christopher S; Luca, Vittorio

2008-11-04

Mesoporous zirconium titanium mixed-oxide beads having disordered wormhole textures and mole fractions of Zr (x) ranging from x=0.25 to 0.67 have been prepared. The bead preparation method combined the forced hydrolysis of mixtures of zirconium-titanium alkoxides in the presence of long-chain carboxylates with external gelation. Uniformly sized beads could be produced in the size range 0.5-1.1 mm by varying the droplet size and viscosity of the mixed-oxide sol, thus making them suitable for large-scale column chromatographic applications. The beads exhibited narrow pore size distributions with similar mean pore diameters of around 3.7 nm. The specific surface areas of the beads were linked to the Zr mole fraction in the precursor solution and were generally greater than 350 m2/g for x=0.5. A combination of scanning transmission electron microscopy and X-ray absorption fine structure analysis indicated that the pore walls of the beads were composed of atomically dispersed Zr and Ti to form a continuous network of Zr-O-Ti bonds. Mass transport in the beads was evaluated by monitoring the kinetics of vanadate and vanadyl adsorption at pH 10.5 and 0.87, respectively.

Electro-Caloric Properties of BT/PZT Multilayer Thin Films Prepared by Sol-Gel Method.

PubMed

Kwon, Min-Su; Lee, Sung-Gap; Kim, Kyeong-Min

2018-09-01

In this study, Barium Titanate (BT)/Lead Zirconate Titanate (PZT) multilayer thin films were fabricated by the spin-coating method on Pt (200 nm)/Ti (10 nm) SiO2 (100 nm)/P-Si (100) substrates using BaTiO3 and Pb(Zr0.90Ti0.10)O3 metal alkoxide solutions. The coating and heating procedure was repeated several times to form the multilayer thin films. All of BT/PZT multilayer thin films show X-ray diffraction patterns typical to a polycrystalline perovskite structure and a uniform and void free grain microstructure. The thickness of the BT and PZT film by one-cycle of drying/sintering was approximately 50 nm and all of the films consisted of fine grains with a flat surface morphology. The electrocaloric properties of BT/PZT thin films were investigated by indirect estimation. The results showed that the temperature change ΔT can be calculated as a function of temperature using Maxwell's relation; the temperature change reaches a maximum value of ~1.85 °C at 135 °C under an applied electric field of 260 kV/cm.

Synthesis, characterization and color performance of novel Co²+-doped alumina/titania nanoceramic pigments.

PubMed

Hafez, Hoda S; El-Fadaly, E

2012-09-01

Blue-green nanoceramic pigments from Co(2+)-doped alumina-titania (xCo(2+)-Al(2)O(3)/TiO(2)) have been synthesized by alkoxide sol-gel route from a mixture of titania and boehmite sols that derived from titanium isopropoxide and aluminum nitrate precursors. The composition of the alumina/titania (AT) matrix is 3:1M ratio. A series of xCo(2+):3TiO(2):1Al(2)O(3) mixed oxides with different Co(2+)-dopant ion concentration has been prepared. The molar ratio of the Co(2+)-dopant ion in the Al(2)O(3)/TiO(2) matrix is from x=0 to 0.5M ratio relative to the titania composition. Characterizations of Co(2+)-doped alumina/titania nanocomposites are carried out using reflectance spectroscopy, transmission electron microscope (TEM), scanning electron microscopy (SEM-EDS), thermo-gravimetric analysis (TGA) and X-ray diffractometer (XRD). The experimental results demonstrated that the prepared Co(2+)-doped alumina-titania nanocomposites fulfill the current technological requirements for ceramic pigment applications that exhibit a high physico-chemical and thermal stabilities at high firing temperatures. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermochemical Stability and Friction Properties of Soft Organosilica Networks for Solid Lubrication.

PubMed

Gonzalez Rodriguez, Pablo; Dral, A Petra; van den Nieuwenhuijzen, Karin J H; Lette, Walter; Schipper, Dik J; Ten Elshof, Johan E

2018-01-24

In view of their possible application as high temperature solid lubricants, the tribological and thermochemical properties of several organosilica networks were investigated over a range of temperatures between 25 and 580 °C. Organosilica networks, obtained from monomers with terminal and bridging organic groups, were synthesized by a sol-gel process. The influence of carbon content, crosslink density, rotational freedom of incorporated hydrocarbon groups, and network connectivity on the high temperature friction properties of the polymer was studied for condensed materials from silicon alkoxide precursors with terminating organic groups, i.e., methyltrimethoxysilane, propyltrimethoxysilane, diisopropyldimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and 4-biphenylyltriethoxysilane networks, as well as precursors with organic bridging groups between Si centers, i.e., 1,4-bis(triethoxysilyl)benzene and 4,4'-bis(triethoxysilyl)-1,1'-biphenyl. Pin-on-disc measurements were performed using all selected solid lubricants. It was found that materials obtained from phenyltrimethoxysilane and cyclohexyltrimethoxysilane precursors showed softening above 120 °C and performed best in terms of friction reduction, reaching friction coefficients as low as 0.01. This value is lower than that of graphite films (0.050 ± 0.005), a common bench mark for solid lubricants.

Thermochemical Stability and Friction Properties of Soft Organosilica Networks for Solid Lubrication

PubMed Central

Gonzalez Rodriguez, Pablo; van den Nieuwenhuijzen, Karin J. H.; Lette, Walter; Schipper, Dik J.

2018-01-01

In view of their possible application as high temperature solid lubricants, the tribological and thermochemical properties of several organosilica networks were investigated over a range of temperatures between 25 and 580 °C. Organosilica networks, obtained from monomers with terminal and bridging organic groups, were synthesized by a sol-gel process. The influence of carbon content, crosslink density, rotational freedom of incorporated hydrocarbon groups, and network connectivity on the high temperature friction properties of the polymer was studied for condensed materials from silicon alkoxide precursors with terminating organic groups, i.e., methyltrimethoxysilane, propyltrimethoxysilane, diisopropyldimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane and 4-biphenylyltriethoxysilane networks, as well as precursors with organic bridging groups between Si centers, i.e., 1,4-bis(triethoxysilyl)benzene and 4,4′-bis(triethoxysilyl)-1,1′-biphenyl. Pin-on-disc measurements were performed using all selected solid lubricants. It was found that materials obtained from phenyltrimethoxysilane and cyclohexyltrimethoxysilane precursors showed softening above 120 °C and performed best in terms of friction reduction, reaching friction coefficients as low as 0.01. This value is lower than that of graphite films (0.050 ± 0.005), a common bench mark for solid lubricants. PMID:29364164

Synthesis and characterisation of the hollandite solid solution Ba1.2-xCsxFe2.4-xTi5.6+xO16 for partitioning and conditioning of radiocaesium

NASA Astrophysics Data System (ADS)

Bailey, Daniel J.; Stennett, Martin C.; Mason, Amber R.; Hyatt, Neil C.

2018-05-01

The geological disposal of high level radioactive waste requires careful budgeting of the heat load produced by radiogenic decay. Removal of high-heat generating radionuclides, such as 137Cs, reduces the heat load in the repository allowing the remaining high level waste to be packed closer together therefore reducing demand for repository space and the cost of the disposal of the remaining wastes. Hollandites have been proposed as a possible host matrix for the long-term disposal of Cs separated from HLW raffinate. The incorporation of Cs into the hollandite phase is aided by substitution of cations on the B-site of the hollandite structure, including iron. A range of Cs containing iron hollandites were synthesised via an alkoxide-nitrate route and the structural environment of Fe in the resultant material characterised by Mössbauer and X-ray Absorption Near Edge Spectroscopy. The results of spectroscopic analysis found that Fe was present as octahedrally co-ordinated Fe (III) in all cases and acts as an effective charge compensator over a wide solid solution range.

Sol-gel chemistry by ring-opening polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.

2000-02-07

Sol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. The authors have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits them to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solventmore » is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which they have successfully demonstrated.« less

Artificial photosynthesis of. beta. -ketocarboxylic acids from carbon dioxide and ketones via enolate complexes of aluminum porphyrin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirai, Yasuhiro; Aida, Takuzo; Inoue, Shohei

1989-04-12

Photochemical fixation of carbon dioxide is of much interest in connection with biological photosynthesis by green plants as well as from the viewpoint of carbon resource utilization. One of the important steps in the assimilation of carbon dioxide is the carboxylation of a carbonyl compound into ketocarboxylic acid, where the reaction proceeds via an enolate species as reactive intermediate. For example, in four carbon (C{sub 4}) pathway and Crassulacean acid metabolism (CAM) processes, pyruvate is converted with the aid of ATP into phosphoenolpyruvate, which is subsequently carboxylated to give oxaloacetate by the action of pyruvate carboxylase. In relation to thismore » interesting biological process, some artificial systems have been exploited for the synthesis of {beta}-ketocarboxylic acid derivatives from carbon dioxide and ketones using nucleophiles such as metal carbonates, thiazolates, phenolates, alkoxides, and strong organic as well as inorganic basis, which promote the enolization of ketones in the intermediate step. We wish to report here a novel, visible light-induced fixation of carbon dioxide with the enolate complex of aluminum porphyrin, giving {beta}-ketocarboxylic acid under mild conditions.« less

Zinc complexes supported by methyl salicylato ligands: synthesis, structure, and application in ring-opening polymerization of L-lactide.

PubMed

Petrus, Rafał; Sobota, Piotr

2013-10-14

Two novel zinc alkoxides supported by chelating methyl salicylato (MesalO; MesalOH = methyl salicylate) ligands were successfully synthesized and characterized. Reaction of MesalOH with ZnEt2 (2:1) gives a tetranuclear cluster [Zn(MesalO)2]4 (1), which by addition of pyridine is transformed to the mononuclear compound [Zn(MesalO)2(py)2] (2). Compounds 1 and 2 were characterized by elemental analysis, NMR, IR, and single crystal X-ray diffraction. The catalytic activity of both compounds was tested for the ring-opening polymerization (ROP) of L-lactide (L-LA). It was found that compounds 1 and 2 are efficient initiators of the ROP of L-LA, yielding cyclic PLLA with weight average molecular weights up to 100 kDa for 2. The treatment of 2 with 1 equiv. of BnOH in toluene afforded a dimeric compound [Zn(OBn)(MesalO)(py)]2 (3). The addition of L-LA to a combination of 1 and 4 equiv. of BnOH in THF or 2 and 1 equiv. of BnOH in toluene led to the rapid and efficient generation of PLLA with end-capped BnO groups.

Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions.

PubMed

Filimonov, Valeriy O; Dianova, Lidia N; Galata, Kristina A; Beryozkina, Tetyana V; Novikov, Mikhail S; Berseneva, Vera S; Eltsov, Oleg S; Lebedev, Albert T; Slepukhin, Pavel A; Bakulev, Vasiliy A

2017-04-21

High yield solvent-base-controlled, transition metal-free synthesis of 4,5-functionalized 1,2,3-thiadiazoles and 1,2,3-triazoles from 2-cyanothioacetamides and sulfonyl azides is described. Under diazo transfer conditions in the presence of a base in an aprotic solvent 2-cyanothioacetamides operating as C-C-S building blocks produce 5-amino-4-cyano-1,2,3-thiadiazoles exclusively. The use of alkoxide/alcohol system completely switches the reaction course due to the change of one of the reaction centers in the 2-cyanothioacetamide (C-C-N building block) resulting in the formation of 5-sulfonamido-1,2,3-triazole-4-carbothioamide sodium salts as the only products. The latter serve as good precursors for 5-amino-1,2,3-thiadiazole-4-carboximidamides, the products of Cornforth-type rearrangement occurring in neutral protic medium or under acid conditions. According to DFT calculations (B3LYP/6-311+G(d,p)) the rearrangement proceeds via intermediate formation of a diazo compound, and can be catalyzed by acids via the protonation of oxygen atom of the sulfonamide group.

Tuning surface grafting density of CeO2 nanocrystals with near- and supercritical solvent characteristics.

PubMed

Giroire, B; Slostowski, C; Marre, S; Aymonier, C; Aida, T; Hojo, D; Aoki, N; Takami, S; Adschiri, T

2016-01-21

In this work, the solvent effect on the synthesis of CeO2 nanocrystals synthesized in near- and supercritical alcohols is discussed. The materials prepared displayed a unique morphology of small nanocrystals (<10 nm) aggregated into larger nanospheres (∼100-200 nm). In such syntheses, alcohol molecules directly interact with the nanocrystal surface through alkoxide and carboxylate bondings. The grafting density was quantified from the weight loss measured using thermogravimetric analysis. A direct correlation between the grafting density and the alcohol chain length can be established. It was demonstrated that the shorter the alcohol chain length (i.e. methanol), the higher the surface coverage is. This trend is independent of the synthesis mode (batch or continuous). Additionally, an influence of the grafting density on the resulting nanocrystal size was established. It is suggested that the surface coverage has a high influence on the early stages of the nucleation and growth. Indeed, when high surface coverages are reached, all surface active sites are blocked, limiting the growth step and therefore leading to smaller particles. This effect was noticed with the materials prepared in the continuous mode where shorter reaction time was performed.

Identification on Membrane and Characterization of Phosphoproteins Using an Alkoxide-Bridged Dinuclear Metal Complex as a Phosphate-Binding Tag Molecule

PubMed Central

Nakanishi, Tsuyoshi; Ando, Eiji; Furuta, Masaru; Kinoshita, Eiji; Kinoshita-Kikuta, Emiko; Koike, Tohru; Tsunasawa, Susumu; Nishimura, Osamu

2007-01-01

We have developed a method for on-membrane direct identification of phosphoproteins, which are detected by a phosphate-binding tag (Phos-tag) that has an affinity to phosphate groups with a chelated Zn2+ ion. This rapid profiling approach for phosphoproteins combines chemical inkjet technology for microdispensing of reagents onto a tiny region of target proteins with mass spectrometry for on-membrane digested peptides. Using this method, we analyzed human epidermoid carcinoma cell lysates of A-431 cells stimulated with epidermal growth factor, and identified six proteins with intense signals upon affinity staining with the phosphate-binding tag. It was already known that these proteins are phosphorylated, and our new approach proved to be effective at rapid profiling of phosphoproteins. Furthermore, we tried to determine their phosphorylation sites by MS/MS analysis after in-gel digestion of the corresponding spots on the 2DE gel to the rapid on-membrane identifications. As one example of use of information gained from the rapid-profiling approach, we successfully characterized a phosphorylation site at Ser-113 on prostaglandin E synthase 3. PMID:18166671

Substrate effect on nanoporous structure of silica wires by channel-confined self-assembly of block-copolymer and sol-gel precursors

DOE PAGES

Hu, Michael Z.; Lai, Peng

2015-09-22

Nanoporous silica wires of various wire diameters were developed by space-confined molecular self-assembly of triblock copolymer ethylene/propylene/ethylene (P123) and silica alkoxide precursor (tetraethylorthosilicate, TEOS). Two distinctive hard-templating substrates, anodized aluminum oxide (AAO) and track-etched polycarbonate (EPC), with channel diameters in the range between 10 nm and 200 nm were employed for space-confinement of soft molecular self-assembly driven by the block-copolymer microphase separation. It was observed in the scanning and transmission electron microscope (STEM) studies that the substrate geometry and material characteristics had pronounced effects on the structure and morphology of the silica nanowires. A substrate wall effect was proposed tomore » explain the ordering and orientation of the intra-wire mesostructure. Circular and spiral nanostructures were found only in wires formed in AAO substrate, not in EPC. Pore-size differences and distinctive wall morphologies of the nanowires relating to the substrates were discussed. It was shown that the material and channel wall characteristics of different substrates play key roles in the ordering and morphology of the intra-wire nanostructures.« less

The sol-gel template synthesis of porous TiO2 for a high performance humidity sensor

NASA Astrophysics Data System (ADS)

Wang, Zhuyi; Shi, Liyi; Wu, Fengqing; Yuan, Shuai; Zhao, Yin; Zhang, Meihong

2011-07-01

This research develops a simple template assisted sol-gel process for preparing porous TiO2 for a high performance humidity sensor. Tetraethyl orthosilicate (TEOS) as a template was directly introduced into TiO2 sol formed by the hydrolysis and condensation of titanium alkoxide; the following calcination led to the formation of TiO2-SiO2 composite, and the selective removal of SiO2 by dilute HF solution led to the formation of porous structure in TiO2. The resulting porous TiO2-based sensor exhibits high sensitivity and linear response in the wide relative humidity (RH) range of 11%-95%, with an impedance variation of four orders of magnitude to humidity change. Moreover, it exhibits a rapid and highly reversible response characterized by a very small hysteresis of < 1% RH and a short response-recovery time (5 s for adsorption and 8 s for desorption), and a 30-day stability test also confirms its long-term stability. Compared with pure TiO2 prepared by the conventional sol-gel method, our product shows remarkably improved performance and good prospect for a high performance humidity sensor. The complex impedance spectra were used to elucidate its humidity sensing mechanism in detail.

Modelos estereoquimicos na quimica de coordenacao e organometalica de lantanideos e actinideos: aplicacoes a complexos de torio (iv) com boratos de polipirazolilo (Stereochemical models in lanthanide and actinide coordination and organometallic chemistry: Applications to thorium (IV) complexes with polypyrazolylborates). Doctoral thesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Almeida, J.C.M.

1990-01-01

A detailed analysis is made of two stereochemical models commonly used in lanthanide and actinide coordination and organometallic chemistry. Li Xing-fu's Cone Packing Model and K. N. Raymond's Ionic Model. Corrections are introduced in the first model as a basis to discuss the stability and structure of known complexes. A Steric Coordination Number is defined for the second model, based on the solid angle to correlate metal-ligand distances in complexes with the ionic radii of the elements and to assign effective radii to the ligands, related to the donating power of the coordinating atoms. As an application of the models,more » the syntheses and characterizations of thorium(IV) complexes with polypyrazolylborates. (HBPz3) {sup -1} and (HB(3.5-Me2Pz)3) {sup -1}, and alkoxides, aryloxides, carboxylates, amides, thiolates, alkyls and cyclopentadienyl are described and their stabilities discussed. The geometries of the complexes in the solid and in solution are discussed and a mechanism is proposed to explain the fluxionality in solution of the complexes with (HBPz3) {sup -1}.« less

Splitting a C-O bond in dialkylethers with bis(1,2,4-tri-t-butylcyclopentadienyl) cerium-hydride does not occur by a sigma-bond metathesis pathway: a combined experimental and DFT computational study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werkema, Evan; Yahia, Ahmed; Maron, Laurent

2010-04-06

Addition of diethylether to [1,2,4(Me3C)3C5H2]2CeH, abbreviated Cp'2CeH, gives Cp'2CeOEt and ethane. Similarly, di-n-propyl- or di-n-butylether gives Cp'2Ce(O-n-Pr) and propane or Cp'2Ce(O-n-Bu) and butane, respectively. Using Cp'2CeD, the propane and butane contain deuterium predominantly in their methyl groups. Mechanisms, formulated on the basis of DFT computational studies, show that the reactions begin by an alpha or beta-CH activation with comparable activation barriers but only the beta-CH activation intermediate evolves into the alkoxide product and an olefin. The olefin then inserts into the Ce-H bond forming the alkyl derivative, Cp'2CeR, that eliminates alkane. The alpha-CH activation intermediate is in equilibrium with themore » starting reagents, Cp'2CeH and the ether, which accounts for the deuterium label in the methyl groups of the alkane. The one-step sigma-bond metathesis mechanism has a much higher activation barrier than either of the two-step mechanisms.« less

Structure and Reactivity of Alucone-Coated Films on Si and Li(x)Si(y) Surfaces.

PubMed

Ma, Yuguang; Martinez de la Hoz, Julibeth M; Angarita, Ivette; Berrio-Sanchez, Jose M; Benitez, Laura; Seminario, Jorge M; Son, Seoung-Bum; Lee, Se-Hee; George, Steven M; Ban, Chunmei; Balbuena, Perla B

2015-06-10

Coating silicon particles with a suitable thin film has appeared as a possible solution to accommodate the swelling of silicon upon lithiation and its posterior cracking and pulverization during cycling of Li-ion batteries. In particular, aluminum alkoxide (alucone) films have been recently deposited over Si anodes, and the lithiation and electrochemical behavior of the system have been characterized. However, some questions remain regarding the lithium molecular migration mechanisms through the film and the electronic properties of the alucone film. Here we use density functional theory, ab initio molecular dynamics simulations, and Green's function theory to examine the film formation, lithiation, and reactivity in contact with an electrolyte solution. It is found that the film is composed of Al-O complexes with 3-O or 4-O coordination. During lithiation, Li atoms bind very strongly to the O atoms in the most energetically favorable sites. After the film is irreversibly saturated with Li atoms, it becomes electronically conductive. The ethylene carbonate molecules in liquid phase are found to be reduced at the surface of the Li-saturated alucone film following similar electron transfer mechanisms as found previously for lithiated silicon anodes. The theoretical results are in agreement with those from morphology and electrochemical analyses.

Reflection-mode micro-spherical fiber-optic probes for in vitro real-time and single-cell level pH sensing.

PubMed

Yang, Qingbo; Wang, Hanzheng; Lan, Xinwei; Cheng, Baokai; Chen, Sisi; Shi, Honglan; Xiao, Hai; Ma, Yinfa

2015-02-01

pH sensing at the single-cell level without negatively affecting living cells is very important but still a remaining issue in the biomedical studies. A 70 μm reflection-mode fiber-optic micro-pH sensor was designed and fabricated by dip-coating thin layer of organically modified aerogel onto a tapered spherical probe head. A pH sensitive fluorescent dye 2', 7'-Bis (2-carbonylethyl)-5(6)-carboxyfluorescein (BCECF) was employed and covalently bonded within the aerogel networks. By tuning the alkoxide mixing ratio and adjusting hexamethyldisilazane (HMDS) priming procedure, the sensor can be optimized to have high stability and pH sensing ability. The in vitro real-time sensing capability was then demonstrated in a simple spectroscopic way, and showed linear measurement responses with a pH resolution up to an average of 0.049 pH unit within a narrow, but biological meaningful pH range of 6.12-7.81. Its novel characterizations of high spatial resolution, reflection mode operation, fast response and high stability, great linear response within biological meaningful pH range and high pH resolutions, make this novel pH probe a very cost-effective tool for chemical/biological sensing, especially within the single cell level research field.

Syntheses, structures, and 1H, 13C{ 1H} and 119Sn{ 1H} NMR chemical shifts of a family of trimethyltin alkoxide, amide, halide and cyclopentadienyl compounds

DOE PAGES

Lichtscheidl, Alejandro G.; Janicke, Michael T.; Scott, Brian L.; ...

2015-08-21

The synthesis and full characterization, including Nuclear Magnetic Resonance (NMR) data ( 1H, 13C{ 1H} and 119Sn{ 1H}), for a series of Me 3SnX (X = O-2,6-tBu 2C 6H 3 (1), (Me 3Sn)N(2,6- iPr 2C 6H 3) (3), NH-2,4,6- tBu 3C 6H 2 (4), N(SiMe 3) 2 (5), NEt 2, C 5Me 5 (6), Cl, Br, I, and SnMe 3) compounds in benzene-d 6, toluene-d 8, dichloromethane-d 2, chloroform-d 1, acetonitrile-d 3, and tetrahydrofuran-d 8 are reported. The X-ray crystal structures of Me 3Sn(O-2,6- tBu 2C 6H 3) (1), Me 3Sn(O-2,6- iPr 2C 6H 3) (2), and (Me 3Sn)(NH-2,4,6- tBumore » 3C 6H 2) (4) are also presented. As a result, these compiled data complement existing literature data and ease the characterization of these compounds by routine NMR experiments.« less

High rate capability of a BaTiO3-decorated LiCoO2 cathode prepared via metal organic decomposition

NASA Astrophysics Data System (ADS)

Teranishi, Takashi; Katsuji, Naoto; Yoshikawa, Yumi; Yoneda, Mika; Hayashi, Hidetaka; Kishimoto, Akira; Yoda, Koji; Motobayashi, Hidefumi; Tasaki, Yuzo

2016-10-01

Metal organic decomposition (MOD) using octylic acid salts was applied to synthesize a BaTiO3-LiCoO2 (BT-LC) composite powder. The Ba and Ti octylates were utilized as metal precursors, in an attempt to synthesize homogeneous BT nanoparticles on the LC matrix. The BT-LC composite, having a phase-separated composite structure without any impurity phase, was successfully obtained by optimizing the MOD procedure. The composite prepared using octylate precursors exhibited a sharper distribution and better dispersibility of decorated BT particles. Additionally, the average particle size of the decorated BTs using metal octylate was reduced to 23.3 nm, compared to 44.4 nm from conventional processes using Ba acetate as well as Ti alkoxide as precursors. The composite cathode displayed better cell performance than its conventional counterpart; the discharge capacity of the metal octylate-derived specimen was 55.6 mAh/g at a 50C rate, corresponding to 173% of the capacity of the conventional specimen (32.2 mAh/g). The notable improvement in high rate capability obtained in this study, compared with the conventional route, was attributed to the higher density of the triple junction formed by the BT-LC-electrolyte interface.

Controlled coordination in vanadium(V) dimethylhydrazido compounds.

PubMed

Sakuramoto, Takashi; Moriuchi, Toshiyuki; Hirao, Toshikazu

2016-11-01

The vanadium(V) dimethylhydrazido compounds were structurally characterized to elucidate the effect of the alkoxide ligands in the coordination environment of vanadium(V) hydrazido center. The single-crystal X-ray structure determination of the vanadium(V) dimethylhydrazido compound with isopropoxide ligands revealed a dimeric structure with the V(1)-N(1) distance of 1.680(5)Å, in which each vanadium atom is coordinated in a distorted trigonal-bipyramidal geometry (τ 5 =0.81) with the hydrazido and bridging isopropoxide ligands in the apical positions. On the contrary, nearly tetrahedral arrangement around the vanadium metal center (τ 4 =0.06) with the V(1)-N(1) distance of 1.660(2)Å was observed in the vanadium(V) dimethylhydrazido compound with tert-butoxide ligands. The introduction of the 2,2',2″-nitrilotriethoxide ligand led to a pseudo-trigonal-bipyramidal geometry (τ 5 =0.92) at the vanadium center with the V(1)-N(1) distance of 1.691(5)Å, wherein vanadium atom is pulled out of the plane formed by the nitrilotriethoxide oxygen atoms in the direction of the hydrazido nitrogen. The coordination from the apical ligand in the vanadium(V) dimethylhydrazido compound was found to result in the longer V(1)-N(1) distance. Copyright © 2016 Elsevier Inc. All rights reserved.

Reflection-mode micro-spherical fiber-optic probes for in vitro real-time and single-cell level pH sensing

PubMed Central

Yang, Qingbo; Wang, Hanzheng; Lan, Xinwei; Cheng, Baokai; Chen, Sisi; Shi, Honglan; Xiao, Hai; Ma, Yinfa

2014-01-01

pH sensing at the single-cell level without negatively affecting living cells is very important but still a remaining issue in the biomedical studies. A 70 μm reflection-mode fiber-optic micro-pH sensor was designed and fabricated by dip-coating thin layer of organically modified aerogel onto a tapered spherical probe head. A pH sensitive fluorescent dye 2′, 7′-Bis (2-carbonylethyl)-5(6)-carboxyfluorescein (BCECF) was employed and covalently bonded within the aerogel networks. By tuning the alkoxide mixing ratio and adjusting hexamethyldisilazane (HMDS) priming procedure, the sensor can be optimized to have high stability and pH sensing ability. The in vitro real-time sensing capability was then demonstrated in a simple spectroscopic way, and showed linear measurement responses with a pH resolution up to an average of 0.049 pH unit within a narrow, but biological meaningful pH range of 6.12–7.81. Its novel characterizations of high spatial resolution, reflection mode operation, fast response and high stability, great linear response within biological meaningful pH range and high pH resolutions, make this novel pH probe a very cost-effective tool for chemical/biological sensing, especially within the single cell level research field. PMID:25530670

Inherent substrate-dependent growth initiation and selective-area atomic layer deposition of TiO{sub 2} using “water-free” metal-halide/metal alkoxide reactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atanasov, Sarah E.; Kalanyan, Berç; Parsons, Gregory N., E-mail: gnp@ncsu.edu

2016-01-15

Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, themore » surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.« less

A novel precursor system and its application to produce tin doped indium oxide.

PubMed

Veith, M; Bubel, C; Zimmer, M

2011-06-14

A new type of precursor has been developed by molecular design and synthesised to produce tin doped indium oxide (ITO). The precursor consists of a newly developed bimetallic indium tin alkoxide, Me(2)In(O(t)Bu)(3)Sn (Me = CH(3), O(t)Bu = OC(CH(3))(3)), which is in equilibrium with an excess of Me(2)In(O(t)Bu). This quasi single-source precursor is applied in a sol-gel process to produce powders and coatings of ITO using a one-step heat treatment process under an inert atmosphere. The main advantage of this system is the simple heat treatment that leads to the disproportionation of the bivalent Sn(II) precursor into Sn(IV) and metallic tin, resulting in an overall reduced state of the metal in the final tin doped indium oxide (ITO) material, hence avoiding the usually necessary reduction step. Solid state (119)Sn-NMR measurements of powder samples confirm the appearance of Sn(II) in an amorphous gel state and of metallic tin after annealing under nitrogen. The corresponding preparation of ITO coatings by spin coating on glass leads to transparent conductive layers with a high transmittance of visible light and a low electrical resistivity without the necessity of a reduction step.

Plating and stripping calcium in an organic electrolyte

NASA Astrophysics Data System (ADS)

Wang, Da; Gao, Xiangwen; Chen, Yuhui; Jin, Liyu; Kuss, Christian; Bruce, Peter G.

2018-01-01

There is considerable interest in multivalent cation batteries, such as those based on magnesium, calcium or aluminium. Most attention has focused on magnesium. In all cases the metal anode represents a significant challenge. Recent work has shown that calcium can be plated and stripped, but only at elevated temperatures, 75 to 100 °C, with small capacities, typically 0.165 mAh cm-2, and accompanied by significant side reactions. Here we demonstrate that calcium can be plated and stripped at room temperature with capacities of 1 mAh cm-2 at a rate of 1 mA cm-2, with low polarization (~100 mV) and in excess of 50 cycles. The dominant product is calcium, accompanied by a small amount of CaH2 that forms by reaction between the deposited calcium and the electrolyte, Ca(BH4)2 in tetrahydrofuran (THF). This occurs in preference to the reactions which take place in most electrolyte solutions forming CaCO3, Ca(OH)2 and calcium alkoxides, and normally terminate the electrochemistry. The CaH2 protects the calcium metal at open circuit. Although this work does not solve all the problems of calcium as an anode in calcium-ion batteries, it does demonstrate that significant quantities of calcium can be plated and stripped at room temperature with low polarization.

Encapsulation of biomaterials in porous glass-like matrices prepared via an aqueous colloidal sol-gel process

DOEpatents

Liu, Dean-Mo; Chen, I-Wei

2001-01-01

The present invention provides a process for the encapsulation of biologically important proteins into transparent, porous silica matrices by an alcohol-free, aqueous, colloidal sol-gel process, and to the biological materials encapsulated thereby. The process is exemplified by studies involving encapsulated cytochrome c, catalase, myoglobin, and hemoglobin, although non-proteinaceous biomaterials, such as active DNA or RNA fragments, cells or even tissues, may also be encapsulated in accordance with the present methods. Conformation, and hence activity of the biomaterial, is successfully retained after encapsulation as demonstrated by optical characterization of the molecules, even after long-term storage. The retained conformation of the biomaterial is strongly correlated to both the rate of gelation and the subsequent drying speed of the encapsulatng matrix. Moreover, in accordance with this process, gelation is accelerated by the use of a higher colloidal solid concentration and a lower synthesis pH than conventional methods, thereby enhancing structural stability and retained conformation of the biomaterials. Thus, the invention also provides a remarkable improvement in retaining the biological activity of the encapsulated biomaterial, as compared with those involved in conventional alkoxide-based processes. It further provides new methods for the quantitative and qualitative detection of test substances that are reactive to, or catalyzed by, the active, encapsulated biological materials.

Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation

PubMed Central

Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.

2013-01-01

Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)CuI/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV–visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) “catalyst oxidation” in which CuI and TEMPO–H are oxidized by O2 via a binuclear Cu2O2 intermediate and (2) “substrate oxidation” mediated by CuII and the nitroxyl radical of TEMPO via a CuII-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O2 is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols. PMID:23317450

Stereocontrolled Alkylative Construction of Quaternary Carbon Centers

PubMed Central

Kummer, David A.; Chain, William J.; Morales, Marvin R.; Quiroga, Olga; Myers, Andrew G.

2009-01-01

Protocols for the stereodefined formation of α,α-disubstituted enolates of pseudoephedrine amides are presented followed by the implementation of these in diastereoselective alkylation reactions. Direct alkylation of α,α-disubstituted pseudoephedrine amide substrates is demonstrated to be both efficient and diastereoselective across a range of substrates, as exemplified by alkylation of the diastereomeric pseudoephedrine α-methylbutyramides, where both substrates are found to undergo stereospecific replacement of the α-C-H bond with α-C-alkyl, with retention of stereochemistry. This is shown to arise by sequential stereospecific enolization and alkylation reactions, with the alkyl halide attacking a common π-face of the E- and Z-enolates, proposed to be that opposite the pseudoephedrine alkoxide side-chain. Pseudoephedrine α-phenylbutyramides are found to undergo highly stereoselective but not stereospecific α-alkylation reactions, which evidence suggests is due to facile enolate isomerization. Also, we show that α, α-disubstituted pseudoephedrine amide enolates can be generated in a highly stereocontrolled fashion by conjugate addition of an alkyllithium reagent to the s-cis-conformer of an α-alkyl-α,β-unsaturated pseudoephedrine amide, providing α,α-disubstituted enolate substrates that undergo alkylation in the same sense as those formed by direct deprotonation. Methods are presented to transform the α-quaternary pseudoephedrine amide products into optically active carboxylic acids, ketones, primary alcohols, and aldehydes. PMID:18788739

Guided in Situ Polymerization of MEH-PPV in Mesoporous Titania Photoanodes.

PubMed

Minar, Norma K; Docampo, Pablo; Fattakhova-Rohlfing, Dina; Bein, Thomas

2015-05-20

Incorporation of conjugated polymers into porous metal oxide networks is a challenging task, which is being pursued via many different approaches. We have developed the guided in situ polymerization of poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) in porous titania films by means of surface functionalization. The controlled polymerization via the Gilch route was induced by an alkoxide base and by increasing the temperature. The selected and specially designed surface-functionalizing linker molecules mimic the monomer or its activated form, respectively. In this way, we drastically enhanced the amount of MEH-PPV incorporated into the porous titania phase compared to nonfunctionalized samples by a factor of 6. Additionally, photovoltaic measurements were performed. The devices show shunting or series resistance limitations, depending on the surface functionalization prior to in situ polymerization of MEH-PPV. We suggest that the reason for this behavior can be found in the orientation of the grown polymer chains with respect to the titania surface. Therefore, the geometry of the anchoring via the linker molecules is relevant for exploiting the full electronic potential of the conjugated polymer in the resulting hybrid composite. This observation will help to design future synthesis methods for new hybrid materials from conjugated polymers and n-type semiconductors to take full advantage of favorable electronic interactions between the two phases.

Synthesis of Titania-supported Copper Nanoparticles via Refined Alkoxide Sol-gel Process

NASA Astrophysics Data System (ADS)

Wu, Jeffrey C. S.; Tseng, I.-Hsiang; Chang, Wan-Chen

2001-06-01

Nanoparticles of titania and copper-loaded titania were synthesized by a refined sol-gel method using titanium butoxide. Unlike the conventional sol-gel procedure of adding water directly, the esterification of anhydrous butanol and glacial acetic acid provided the hydrolyzing water. In addition, acetic acid also served as a chelating ligand to stabilize the hydrolysis-condensation process and minimize the agglomeration of titania. Following the hydrolysis, Cu/TiO2 was prepared by adding copper chloride to titania sol. The sol was dried, then calcined at 500°C to remove organics and transformed to anatase titania which was verified by XRD. Cu/TiO2 was further hydrogen-reduced at 300°C. The recovery of Ti was exceeded by an average of 95% from titanium butoxide. TEM micrographs show that the Cu/TiO2 particles are near uniform. The average crystallite sizes are 17-20 nm estimated from the peak broadening of XRD spectra. The bandgaps of TiO2 and reduced Cu/TiO2 range from 2.70 to 3.15 eV estimated from the diffusive reflective UV-Vis spectra. XPS analysis shows that Cu 2p3/2 is 933.4 eV indicating primary Cu2O form on the TiO2 supports. The binding energy of Ti does not exhibit chemical shift suggesting negligible interaction of Cu cluster and TiO2 support.

Bacteria-directed construction of hollow TiO2 micro/nanostructures with enhanced photocatalytic hydrogen evolution activity.

PubMed

Zhou, Han; Fan, Tongxiang; Ding, Jian; Zhang, Di; Guo, Qixin

2012-03-12

A general method has been developed for the synthesis of various hollow TiO2 micro/nanostructures with bacteria as templates to further study the structural effect on photocatalytic hydrogen evolution properties. TiO2 hollow spheres and hollow tubes, served as prototypes, are obtained via a surface sol-gel process using cocci and bacillus as biotemplates, respectively. The formation mechanisms are based on absorption of metal-alkoxide molecules from solution onto functional cell wall surfaces and subsequent hydrolysis to give nanometer-thick oxide layers. The UV-Vis absorption spectrum shows that the porous TiO2 hollow spheres have enhanced light harvesting property compared with the corresponding solid counterpart. This could be attributed to their unique hollow porous micro/nanostructures with microsized hollow cavities and nanovoids which could bring about multiple scattering and rayleigh scattering of light, respectively. The hollow TiO2 structures exhibit superior photocatalytic hydrogen evolution activities under UV and visible light irradiation in the presence of sacrificial reagents. The hydrogen evolution rate of hollow structures is about 3.6 times higher than the solid counterpart and 1.5 times higher than P25-TiO2. This work demonstrates the structural effect on enhancing the photocatalytic hydrogen evolution performance which would pave a new pathway to tailor and improve catalytic properties over a broad range.

High Performance, Low Temperature Solution-Processed Barium and Strontium Doped Oxide Thin Film Transistors.

PubMed

Banger, Kulbinder K; Peterson, Rebecca L; Mori, Kiyotaka; Yamashita, Yoshihisa; Leedham, Timothy; Sirringhaus, Henning

2014-01-28

Amorphous mixed metal oxides are emerging as high performance semiconductors for thin film transistor (TFT) applications, with indium gallium zinc oxide, InGaZnO (IGZO), being one of the most widely studied and best performing systems. Here, we investigate alkaline earth (barium or strontium) doped InBa(Sr)ZnO as alternative, semiconducting channel layers and compare their performance of the electrical stress stability with IGZO. In films fabricated by solution-processing from metal alkoxide precursors and annealed to 450 °C we achieve high field-effect electron mobility up to 26 cm 2 V -1 s -1 . We show that it is possible to solution-process these materials at low process temperature (225-200 °C yielding mobilities up to 4.4 cm 2 V -1 s -1 ) and demonstrate a facile "ink-on-demand" process for these materials which utilizes the alcoholysis reaction of alkyl metal precursors to negate the need for complex synthesis and purification protocols. Electrical bias stress measurements which can serve as a figure of merit for performance stability for a TFT device reveal Sr- and Ba-doped semiconductors to exhibit enhanced electrical stability and reduced threshold voltage shift compared to IGZO irrespective of the process temperature and preparation method. This enhancement in stability can be attributed to the higher Gibbs energy of oxidation of barium and strontium compared to gallium.

Sol-gel derived ceramic electrolyte films on porous substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kueper, T.W.

1992-05-01

A process for the deposition of sol-gel derived thin films on porous substrates has been developed; such films should be useful for solid oxide fuel cells and related applications. Yttria-stabilized zirconia films have been formed from metal alkoxide starting solutions. Dense films have been deposited on metal substrates and ceramic substrates, both dense and porous, through dip-coating and spin-coating techniques, followed by a heat treatment in air. X-ray diffraction has been used to determine the crystalline phases formed and the extent of reactions with various substrates which may be encountered in gas/gas devices. Surface coatings have been successfully applied tomore » porous substrates through the control of substrate pore size and deposition parameters. Wetting of the substrate pores by the coating solution is discussed, and conditions are defined for which films can be deposited over the pores without filling the interiors of the pores. Shrinkage cracking was encountered in films thicker than a critical value, which depended on the sol-gel process parameters and on the substrate characteristics. Local discontinuities were also observed in films which were thinner than a critical value which depended on the substrate pore size. A theoretical discussion of cracking mechanisms is presented for both types of cracking, and the conditions necessary for successful thin formation are defined. The applicability of these film gas/gas devices is discussed.« less

Surface derivatization strategy for combinatorial analysis of cell response to mixtures of protein domains.

PubMed

Chiang, Chunyi; Karuri, Stella W; Kshatriya, Pradnya P; Schwartz, Jeffrey; Schwarzbauer, Jean E; Karuri, Nancy W

2012-01-10

We report a robust strategy for conjugating mixtures of two or more protein domains to nonfouling polyurethane surfaces. In our strategy, the carbamate groups of polyurethane are reacted with zirconium alkoxide from the vapor phase to give a surface-bound oxide that serves as a chemical layer that can be used to bond organics to the polymer substrate. A hydroxyalkylphosphonate monolayer was synthesized on this layer, which was then used to covalently bind primary amine groups in protein domains using chloroformate-derived cross-linking. The effectiveness of this synthesis strategy was gauged by using an ELISA to measure competitive, covalent bonding of cell-binding (III(9-10)) and fibronectin-binding (III(1-2)) domains of the cell adhesion protein fibronectin. Cell adhesion, spreading, and fibronectin matrix assembly were examined on surfaces conjugated with single domains, a 1:1 surface mixture of III(1-2) and III(9-10), and a recombinant protein "duplex" containing both domains in one fusion protein. The mixture performed as well as or better than the other surfaces in these assays. Our surface activation strategy is amenable to a wide range of polymer substrates and free amino group-containing protein fragments. As such, this technique may be used to create biologically specific materials through the immobilization of specific protein groups or mixtures thereof on a substrate surface.

Structural and magnetic properties of pure and Ca-doped LaCoO3 nanopowders obtained by a sol-gel route.

PubMed

Armelao, Lidia; Barreca, Davide; Bottaro, Gregorio; Maragno, Cinzia; Tondello, Eugenio; Caneschi, Andrea; Sangregorio, Claudio; Gialanella, Stefano

2006-04-01

Pure and Ca-doped LaCoO3 nanopowders were prepared by a non-alkoxidic sol-gel route using cobalt(II) acetate, lanthanum(III) nitrate and calcium(II) acetate as oxide precursors. The structural evolution and magnetic properties of the samples were studied as a function of thermal treatments in air up to 1273 K. In particular, the microstructure and composition of the systems were analyzed by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS). Both pure and calcium-doped samples annealing at 973 K resulted in the formation of cubic LaCoO3 (average crystallite size <30 nm). This phase was fully retained in the calcium-doped materials even after annealing at higher temperatures, whereas a transition to the rhomboedral polymorph was detected in the pure samples at 1073 K. The magnetic behavior of the nanopowders was investigated as a function of temperature and applied field using both dynamic and static susceptibility measurements. Pure lanthanum cobaltite samples underwent a transition to an ordered state at 88 K, and their magnetic properties changed as a function of thermal treatments. As concerns calcium-doped samples, they ordered ferromagnetically at 171 and 185 K depending on the annealing temperature and displayed open hysteresis loops with coercive fields as large as 1.75 T at low temperatures.

The crystal structure of halofantrine-ferriprotoporphyrin IX and the mechanism of action of arylmethanol antimalarials.

PubMed

de Villiers, Katherine A; Marques, Helder M; Egan, Timothy J

2008-08-01

The crystal structure of the complex formed between the antimalarial drug halofantrine and ferriprotoporphyrin IX (Fe(III)PPIX) has been determined by single crystal X-ray diffraction. The structure shows that halofantrine coordinates to the Fe(III) center through its alcohol functionality in addition to pi-stacking of the phenanthrene ring over the porphyrin. The length of the Fe(III)-O bond is consistent with an alkoxide and not an alcohol coordinating group. The iron porphyrin is five coordinate and monomeric. Changes in the electronic spectrum of Fe(III)PPIX upon addition of halofantrine base in acetonitrile solution are almost identical to those observed upon addition of quinidine free base in the same solvent. This suggests homologous binding. Molecular mechanics modeling of Fe(III)PPIX complexes of quinidine, quinine, 9-epiquinine and 9-epiquinidine based on this homology suggests that the antimalarially active quinidine and quinine can readily adopt conformations that permit formation of an intramolecular salt bridge between the protonated quinuclidine tertiary amino group and unprotonated heme propionate group, while the inactive epimers 9-epiquinidine and 9-epiquinine have to adopt high energy conformations in order to accommodate such salt bridge formation. We propose that salt bridge formation may interrupt formation of the hemozoin precursor dimer formed during the heme detoxification pathway and so account for the strong activity of the two active isomers.

An orthogonal ferromagnetically coupled tetracopper(II) 2 x 2 homoleptic grid supported by micro-O4 bridges and its DFT study.

PubMed

Roy, Somnath; Mandal, Tarak Nath; Barik, Anil Kumar; Pal, Sachindranath; Butcher, Ray J; El Fallah, Mohamed Salah; Tercero, Javier; Kar, Susanta Kumar

2007-03-28

A pyrazole based ditopic ligand (PzOAP), prepared by the reaction between 5-methylpyrazole-3-carbohydrazide and methyl ester of imino picolinic acid, reacts with Cu(NO3)2.6H2O to form a self-assembled, ferromagnetically coupled, alkoxide bridged tetranuclear homoleptic Cu(II) square grid-complex [Cu4(PzOAP)4(NO3)2] (NO3)2.4H2O (1) with a central Cu4[micro-O4] core, involving four ligand molecules. In the Cu4[micro-O4] core, out of four copper centers, two copper centers are penta-coordinated and the remaining two are hexa-coordinated. In each case of hexa-coordination, the sixth position is occupied by the nitrate ion. The complex 1 has been characterized structurally and magnetically. Although Cu-O-Cu bridge angles are too large (138-141 degrees) and Cu-Cu distances are short (4.043-4.131 A), suitable for propagation of expected antiferromagnetic exchange interactions within the grid, yet intramolecular ferromagnetic exchange (J = 5.38 cm(-1)) is present with S = 4/2 magnetic ground state. This ferromagnetic interaction is quite obvious from the bridging connections (d(x2-y2)) lying almost orthogonally between the metal centers. The exchange pathways parameters have been evaluated from density functional calculations.

Hydride transfer made easy in the oxidation of alcohols catalyzed by choline oxidase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gadda, G.; Orville, A.; Pennati, A.

2008-06-08

Choline oxidase (E.C. 1.1.3.17) catalyzes the two-step, four-electron oxidation of choline to glycine betaine with betaine aldehyde as enzyme-associated intermediate and molecular oxygen as final electron acceptor (Scheme 1). The gem-diol, hydrated species of the aldehyde intermediate of the reaction acts as substrate for aldehyde oxidation, suggesting that the enzyme may use similar strategies for the oxidation of the alcohol substrate and aldehyde intermediate. The determination of the chemical mechanism for alcohol oxidation has emerged from biochemical, mechanistic, mutagenetic, and structural studies. As illustrated in the mechanism of Scheme 2, the alcohol substrate is initially activated in the active sitemore » of the enzyme by removal of the hydroxyl proton. The resulting alkoxide intermediate is then stabilized in the enzyme-substrate complex via electrostatic interactions with active site amino acid residues. Alcohol oxidation then occurs quantum mechanically via the transfer of the hydride ion from the activated substrate to the N(5) flavin locus. An essential requisite for this mechanism of alcohol oxidation is the high degree of preorganization of the activated enzyme-substrate complex, which is achieved through an internal equilibrium of the Michaelis complex occurring prior to, and independently from, the subsequent hydride transfer reaction. The experimental evidence that support the mechanism for alcohol oxidation shown in Scheme 2 is briefly summarized in the Results and Discussion section.« less

Efficient Hydrogenation of Ketones and Aldehydes Catalyzed by Well-Defined Iron(II) PNP Pincer Complexes: Evidence for an Insertion Mechanism

PubMed Central

2014-01-01

We have prepared and structurally characterized a new class of Fe(II) PNP pincer hydride complexes [Fe(PNP-iPr)(H)(CO)(L)]n (L = Br–, CH3CN, pyridine, PMe3, SCN–, CO, BH4–; n = 0, +1) based on the 2,6-diaminopyridine scaffold where the PiPr2 moieties of the PNP ligand are connected to the pyridine ring via NH and/or NMe spacers. Complexes [Fe(PNP-iPr)(H)(CO)(L)]n with labile ligands (L = Br–, CH3CN, BH4–) and NH spacers are efficient catalysts for the hydrogenation of both ketones and aldehydes to alcohols under mild conditions, while those containing inert ligands (L = pyridine, PMe3, SCN–, CO) are catalytically inactive. Interestingly, complex [Fe(PNPMe-iPr)(H)(CO)(Br)], featuring NMe spacers, is an efficient catalyst for the chemoselective hydrogenation of aldehydes. The first type of complexes involves deprotonation of the PNP ligand as well as heterolytic dihydrogen cleavage via metal-alkoxide cooperation, but no reversible aromatization/deprotonation of the PNP ligand. In the case of the N-methylated complex the mechanism remains unclear, but obviously does not allow bifunctional activation of dihydrogen. The experimental results complemented by DFT calculations strongly support an insertion of the C=O bond of the carbonyl compound into the Fe–H bond. PMID:27642211

A DFT Investigation of the Mechanism of Propene Ammoxidation over α-Bismuth Molybdate

DOE PAGES

Licht, Rachel B.; Bell, Alexis T.

2016-11-17

We investigated the mechanisms and energetics for the propene oxidation and ammoxidation occurring on the (010) surface of Bi 2 Mo 3 O 12 using density functional theory (DFT). An energetically feasible sequence of elementary steps for propene oxidation to acrolein, propene ammoxidation to acrylonitrile, and acrolein ammoxidation to acrylonitrile is proposed. Consistent with experimental findings, the rate-limiting step for both propene oxidation and ammoxidation is the initial hydrogen abstraction from the methyl group of propene, which is calculated to have an apparent activation energy of 27.3 kcal/mol. The allyl species produced in this reaction is stabilized as an allylmore » alkoxide, which can then undergo hydrogen abstraction to form acrolein or react with ammonia adsorbed on under-coordinated surface Bi 3+ cations to form allylamine. Dehydrogenation of allylamine is shown to produce acrylonitrile, whereas reaction with additional adsorbed ammonia leads to the formation of acetonitrile and hydrogen cyanide. The dehydrogenation of allyalkoxide species is found to have a significantly higher activation barrier than reaction with adsorbed ammonia, consistent with the observation that very little acrolein is produced when ammonia is present. Finally, we found that rapid reoxidation of the catalyst surface to release wate the driving force for all reactions involving the cleavage of C-H or N-H bonds, because practically all of these steps are endothermic. (Chemical Equation Presented).« less

Mononuclear salen-gallium complexes for iso-selective ring-opening polymerization (ROP) of rac-lactide.

PubMed

Specklin, David; Fliedel, Christophe; Hild, Frédéric; Mameri, Samir; Karmazin, Lydia; Bailly, Corinne; Dagorne, Samuel

2017-10-03

A series of mononuclear salen-supported gallium amido/alkoxide derivatives were prepared and structurally characterized and subsequently used as initiators in rac-lactide ring-opening polymerisation (ROP). The reaction of variously substituted salen ligands (1a-1f) with 0.5 equiv. of Ga 2 (NMe 2 ) 6 allowed the isolation of the corresponding (salen)Ga-NMe 2 chelates (2b-2d, 2f) via an amine elimination route, as poorly soluble compounds in common solvents. The (salen)Ga-OBn derivatives (3a-3e) may be readily accessed by an amine-elimination/alcoholysis sequence and the molecular structures of 3a, 3d and 3e were confirmed through X-ray crystallography diffraction analysis. The present (salen)Ga-X species may effectively mediate the iso-selective ROP of rac-LA in a controlled manner (P m up to 0.77 using a 1/1 2f/BnOH mixture as ROP initiator), with a ROP activity greatly dependent upon steric hindrance and geometrical constraints imposed by the variously substituted salen ligands. Based on the present study, salen ligands with limited steric hindrance and a certain degree of flexibility appear best suited for iso-selective ROP by (salen)Ga chelates. The salen-gallium complex 3a is also effective for the controlled ROP of ε-caprolactone (CL) and the production of PCL-b-PLA copolymers.

Preparation of Water-Repellent Glass by Sol-Gel Process Using Perfluoroalkylsilane and Tetraethoxysilane.

PubMed

Jeong, Hye-Jeong; Kim, Dong-Kwon; Lee, Soo-Bok; Kwon, Soo-Han; Kadono, Kohei

2001-03-01

Coating films on glass substrate were prepared by sol-gel process using alkoxide solutions containing perfluoroalkylsilane (PFAS) and tetraethoxysilane (TEOS). The physical properties of the coating films were characterized by SEM, FT-IR, and XRD. And their surface properties were investigated by measuring contact angles and atomic compositions. Transparent coating films with smooth surface and uniform thickness could be obtained. The contact angles of the coating films for water and methylene iodide are extremely high, at 118 degrees and 97 degrees, respectively, and their surface free energies are about 9.7 dyn/cm. It was found that the water-repellent glass prepared is very hydrophobic and exhibits excellent water-repellency. Hydrophobic perfluoroalkyl groups are preferentially enriched to the outermost layer at the coating film-air interface, and two layers probably exist in the coating film. The upper layer oriented toward the air is composed of mainly perfluoroalkyl groups originating from PFAS, and the lower layer is composed of mainly -OSiO- groups originating from TEOS. The heat treatment after drying step cannot influence the surface enrichment of the perfluoroalkyl group. The hydrolysis reaction should be more completely done before the dip coating step to obtain lower surface free energy. The burning temperature should be less than 300 degrees C because the perfluoroalkyl group begins to decompose from this temperature. Copyright 2001 Academic Press.

Living hybrid materials capable of energy conversion and CO2 assimilation.

PubMed

Meunier, Christophe F; Rooke, Joanna C; Léonard, Alexandre; Xie, Hao; Su, Bao-Lian

2010-06-14

This paper reviews our work on the fabrication of photobiochemical hybrid materials via immobilisation of photosynthetically active entities within silica materials, summarising the viability and productivity of these active entities post encapsulation and evaluating their efficiency as the principal component of a photobioreactor. Immobilisation of thylakoids extracted from spinach leaves as well as whole cells such as A. thaliana, Synechococcus and C. caldarium was carried out in situ using sol-gel methods. In particular, a comprehensive overview is given of the efforts to find the most biocompatible inorganic precursors that can extend the lifetime of the organisms upon encapsulation. The effect of matrix-cell interactions on cell lifetime and the photosynthetic efficiency of the resultant materials are discussed. Precursors based on alkoxides, commonly used in "Chimie Douce" to form porous silica gel, release by-products which are often cytotoxic. However by controlling the formation of gels from aqueous silica precursors and silica nanoparticles acting as "cements" one can significantly enhance the life span of the entrapped organelles and cells. Adapted characteristic techniques have shown survival times of up to 5 months with the photosynthetic production of oxygen recorded as much as 17 weeks post immobilisation. These results constitute a significant advance towards the final goal, long-lasting semi-artificial photobioreactors that can advantageously exploit solar radiation to convert polluting carbon dioxide into useful biofuels, sugars or medical metabolites.

High Performance, Low Temperature Solution-Processed Barium and Strontium Doped Oxide Thin Film Transistors

PubMed Central

2013-01-01

Amorphous mixed metal oxides are emerging as high performance semiconductors for thin film transistor (TFT) applications, with indium gallium zinc oxide, InGaZnO (IGZO), being one of the most widely studied and best performing systems. Here, we investigate alkaline earth (barium or strontium) doped InBa(Sr)ZnO as alternative, semiconducting channel layers and compare their performance of the electrical stress stability with IGZO. In films fabricated by solution-processing from metal alkoxide precursors and annealed to 450 °C we achieve high field-effect electron mobility up to 26 cm2 V–1 s–1. We show that it is possible to solution-process these materials at low process temperature (225–200 °C yielding mobilities up to 4.4 cm2 V–1 s–1) and demonstrate a facile “ink-on-demand” process for these materials which utilizes the alcoholysis reaction of alkyl metal precursors to negate the need for complex synthesis and purification protocols. Electrical bias stress measurements which can serve as a figure of merit for performance stability for a TFT device reveal Sr- and Ba-doped semiconductors to exhibit enhanced electrical stability and reduced threshold voltage shift compared to IGZO irrespective of the process temperature and preparation method. This enhancement in stability can be attributed to the higher Gibbs energy of oxidation of barium and strontium compared to gallium. PMID:24511184

Sol-gel nano-porous silica-titania thin films with liquid fill for optical interferometric sensors

NASA Astrophysics Data System (ADS)

Martin, Andrew J.; Green, Mino

1990-11-01

The production of thin films whose refractive index is measurand specific, for use in an interferometric fiber optic chemical sensor, is discussed. The problem of making such coatings has been tackled by a system we have termed the "guest-host" approach, in which an active liquid whose index varies with measurand, is contained within a porous glass host of fixed index. Suitable porous silica-titania glass films have been produced via the sol-gel process. The use of this system enables the index of the glass to be varied, so that the composite index of the liquid filled film can be tailored to that required by the optical system. The sol-gel method developed is based upon the hydrolysis and polymerisation of metal alkoxides, in an acidic aqueous/alcoholic solution. Thin film slab waveguides were deposited in order to measure the light scattering losses, which were found to be typically ''1dB/cm. The porosity of films was studied using a new technique developed in which water adsorption isotherms are plotted using ellipsometry. The pore size was found to be very small of pore diameter in the nanometer range, and the total porosity -1O%. Both of these factors were increased by the removal of residual organic material, using hydrogen peroxide. Finally the use of pH indicator dyes as a liquid fill is discussed, to produce a pH sensor.

Phase formation of V{sub 2}O{sub 5}.xNb{sub 2}O{sub 5} compounds via gels and freeze-dried precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langbein, Hubert; Mayer-Uhma, Tobias

2009-03-05

An X-ray powder diffraction study of the phase formation in the system V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} is performed. Freeze-dried ammonium vanadate and ammonium oxalato niobate, alkoxide-derived xerogels and a mixture of active oxides are used as precursors to compare the resulting phase composition. Thermal decomposition of the freeze-dried precursor is monitored with DTA/TG and mass spectrometry. In the quasi-binary system V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} metastable VNbO{sub 5}, V{sub 4}Nb{sub 18}O{sub 55}, VNb{sub 9}O{sub 25} and solid solutions of V{sub 2}O{sub 5} in TT-Nb{sub 2}O{sub 5} as also thermodynamically stable VNb{sub 9}O{sub 25} exist. The thermal decomposition of freeze-driedmore » vanadate-oxalatoniobate solution allows the synthesis of all these phases in a relative simple manner. Structural relationships between an intermediate phase and the product, or, in the case of solid-state reactions, between one of the starting oxide and the product, favour the desired reaction. Therefore, the structure of a former phase influences or directs the structure of the product similar to a topotactic reaction.« less

Effect of capping and particle size on Raman laser-induced degradation of {gamma}-Fe{sub 2}O{sub 3} nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varadwaj, K.S.K.; Panigrahi, M.K.; Ghose, J.

2004-11-01

Diol capped {gamma}-Fe{sub 2}O{sub 3} nanoparticles are prepared from ferric nitrate by refluxing in 1,4-butanediol (9.5nm) and 1,5-pentanediol (15nm) and uncapped particles are prepared by refluxing in 1,2-propanediol followed by sintering the alkoxide formed. X-ray diffraction (XRD) shows that all the samples have the spinel phase. Raman spectroscopy shows that the samples prepared in 1,4-butanediol and 1,5-pentanediol and 1,2-propanediol (sintered at 573 and 673K) are {gamma}-Fe{sub 2}O{sub 3} and the 773K-sintered sample is Fe{sub 3}O{sub 4}. Raman laser studies carried out at various laser powers show that all the samples undergo laser-induced degradation to {alpha}-Fe{sub 2}O{sub 3} at higher lasermore » power. The capped samples are however, found more stable to degradation than the uncapped samples. The stability of {gamma}-Fe{sub 2}O{sub 3} sample with large particle size (15.4nm) is more than the sample with small particle size (10.2nm). Fe{sub 3}O{sub 4} having a particle size of 48nm is however less stable than the smaller {gamma}-Fe{sub 2}O{sub 3} nanoparticles.« less

One-pot synthesis and optical properties of Eu3+-doped nanocrystalline TiO2 and ZrO2

NASA Astrophysics Data System (ADS)

Julián, Beatriz; Corberán, Rosa; Cordoncillo, Eloisa; Escribano, Purificación; Viana, Bruno; Sanchez, Clément

2005-11-01

A simple and versatile one-pot sol-gel synthesis of Eu3+-doped nanocrystalline TiO2 and ZrO2 nanomaterials is reported in this paper. It consists of the controlled crystallization of Eu3+-doped TiO2 or ZrO2 nanoparticles from an initial solution containing the metal alkoxide, the lanthanide precursor, a complexing agent and a non-complexing acid. The main interest is that it could be extended to different lanthanide ions and inorganic metal oxides to prepare other multifunctional nanomaterials. The characterization by XRD, HRTEM and SAED techniques showed that the TiO2 and ZrO2 crystallization takes place at very low temperatures (60 °C) and that the crystallite size can be tailored by modifying the synthetic conditions. The optical properties of the resulting materials were studied by emission spectra and decay measurements. Both Eu3+:TiO2 and Eu3+:ZrO2 samples exhibited long lifetime values after removing organic components (τ = 0.7 and 1.3 ms, respectively), but the Eu3+:ZrO2 system is specially promising for photonic applications since its τ value is longer than some reported for other inorganic or hybrid matrices in which Eu3+ ions are complexed. This behaviour has been explained through an effective dispersion of the lanthanide ions within the ZrO2 nanocrystals.

Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

PubMed

Kucheryavy, Pavel; He, Jibao; John, Vijay T; Maharjan, Pawan; Spinu, Leonard; Goloverda, Galina Z; Kolesnichenko, Vladimir L

2013-01-15

Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe(3)O(4) with the same particle size, but their r(1) relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability.

Effective surface passivation of multi-shelled InP quantum dots through a simple complexing with titanium species

NASA Astrophysics Data System (ADS)

Jo, Jung-Ho; Kim, Min-Seok; Han, Chang-Yeol; Jang, Eun-Pyo; Do, Young Rag; Yang, Heesun

2018-01-01

Fluorescent efficiency of various visible quantum dots (QDs) has been incessantly improved to meet industrially high standard mainly through the advance in core/shell heterostructural design, however, their stability against degradable environments appears still lacking. The most viable strategy to cope with this issue was to exploit chemically inert oxide phases to passivate QD surface in the form of either individual overcoating or matrix embedding. Herein, we report a simple but effective means to passivate QD surface by complexing its organic ligands with a metal alkoxide of titanium isopropoxide (Ti(i-PrO)4). For this, highly efficient red-emitting InP QDs with a multi-shell structure of ZnSeS intermediate plus ZnS outer shell are first synthesized and then the surface of resulting InP/ZnSeS/ZnS QDs is in-situ decorated with Ti(i-PrO)4. The presence of Tisbnd O species from Ti(i-PrO)4 on QD surface is verified by x-ray photoelectron and Fourier transform infrared spectroscopic analyses. Two comparative dispersions of pristine versus Ti(i-PrO)4-complexed QDs are exposed for certain periods of time to UV photon and heat and their temporal changes in photoluminescence are monitored, resulting in a huge improvement in QD stability from the latter ones through Ti(i-PrO)4-mediated better surface passivation.

Methods for and products of processing nanostructure nitride, carbonitride and oxycarbonitride electrode power materials by utilizing sol gel technology for supercapacitor applications

DOEpatents

Huang, Yuhong; Wei, Oiang; Chu, Chung-tse; Zheng, Haixing

2001-01-01

Metal nitride, carbonitride, and oxycarbonitride powder with high surface area (up to 150 m.sup.2 /g) is prepared by using sol-gel process. The metal organic precursor, alkoxides or amides, is synthesized firstly. The metal organic precursor is modified by using unhydrolyzable organic ligands or templates. A wet gel is formed then by hydrolysis and condensation process. The solvent in the wet gel is then be removed supercritically to form porous amorphous hydroxide. This porous hydroxide materials is sintered to 725.degree. C. under the ammonia flow and porous nitride powder is formed. The other way to obtain high surface area nitride, carbonitride, and oxycarbonitride powder is to pyrolyze polymerized templated metal amides aerogel in an inert atmosphere. The electrochemical capacitors are prepared by using sol-gel prepared nitride, carbonitride, and oxycarbonitride powder. Two methods are used to assemble the capacitors. Electrode is formed either by pressing the mixture of nitride powder and binder to a foil, or by depositing electrode coating onto metal current collector. The binder or coating is converted into a continuous network of electrode material after thermal treatment to provide enhanced energy and power density. Liquid electrolyte is soaked into porous electrode. The electrochemical capacitor assembly further has a porous separator layer between two electrodes/electrolyte and forming a unit cell.

Nickel-catalyzed cycloadditions of unsaturated hydrocarbons, aldehydes, and ketones.

PubMed

Tekavec, Thomas N; Louie, Janis

2008-04-04

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3,3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon-carbon bond is formed, prior to a competitive beta-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No beta-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C-O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon-carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr).

Nickel-Catalyzed Cycloadditions of Unsaturated Hydrocarbons, Aldehydes, and Ketones

PubMed Central

Tekavec, Thomas N.

2014-01-01

The nickel-catalyzed cycloaddition of unsaturated hydrocarbons and carbonyls is reported. Diynes and enynes were used as coupling partners. Carbonyl substrates include both aldehdyes and ketones. Reactions of diynes and aldehydes afforded the [3, 3] electrocyclic ring-opened tautomers, rather than pyrans, in high yields. The cycloaddition reaction of enynes and aldehydes afforded two distinct products. A new carbon–carbon bond is formed, prior to a competitive β-hydrogen elimination of a nickel alkoxide, between the carbonyl carbon and either one of the carbons of the olefin or the alkyne. The steric hindrance of the enyne greatly affected the chemoselectivity of the cycloaddition of enynes and aldehydes. In some cases, dihydropyran was also formed. The scope of the cycloaddition reaction was expanded to include the coupling of enynes and ketones. No β-hydrogen elimination was observed in cycloaddition reaction of enynes and ketones. Instead, C–O bond-forming reductive elimination occurred exclusively to afford dihydropyrans in excellent yields. In all cases, complete chemoselectivity was observed; only dihydropyrans where the carbonyl carbon forms a carbon–carbon bond with a carbon of the olefin, rather than of the alkyne, were observed. All cycloaddition reactions occur at room temperature and employ nickel catalysts bearing the hindered 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or its saturated analogue, 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene (SIPr). PMID:18318544

Influence of calcinated and non calcinated nanobioglass particles on hardness and bioactivity of sol-gel-derived TiO2-SiO2 nano composite coatings on stainless steel substrates.

PubMed

Dadash, Mohammad Saleh; Karbasi, Saeed; Esfahani, Mojtaba Nasr; Ebrahimi, Mohammad Reza; Vali, Hojatollah

2011-04-01

Thick films of calcinated and non calcinated nanobioglass (NBG)-titania composite coatings were prepared on stainless steel substrates by alkoxide sol-gel process. Dip-coating method was used for the films preparation. The morphology, structure and composition of the nano composite films were evaluated using environmental scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscope. The SEM investigation results showed that prepared thick NBG-titania films are smooth and free of macrocracking, fracture or flaking. The grain size of these films was uniform and nano scale (50-60 nm) which confirmed with TEM. Also FTIR confirmed the presence of Si-O-Si bands on the calcinated NBG-titania films. The hardness of the prepared films (TiO(2)-calcinated NBG and TiO(2)-Non calcinated NBG) was compared by using micro hardness test method. The results verified that the presence of calcinated NBG particles in NBG-titania composite enhanced gradually the mechanical data of the prepared films. The in vitro bioactivity of these films was discussed based on the analysis of the variations of Ca and P concentrations in the simulated body fluid (SBF) and their surface morphologies against immersion time. Surface morphology and Si-O-Si bands were found to be of great importance with respect to the bioactivity of the studied films. The results showed that calcinated NBG-titania films have better bioactivity than non calcinated NBG-titania films.

Development Of HUD Combiner For Automotive Windshield Application

NASA Astrophysics Data System (ADS)

Hattori, Akimasa; Makita, Kensuke; Okabayashi, Shigeru

1989-12-01

The head-up display system (HUM) has been developed for the windshield of Nissan Motor's passenger car, '88 model of Silvia (240SX) and '89 model of Maxima. HUD consists of a projector with high brightness VFT and a combiner which is a light-selective reflective film applied on the surface of ' e windshield. The system provides nice display legibility of speed in a three-digit reap at the position more than one meter far from driver's eye even under the bright sunlight. In this report, we present the optical properties and manufacturing process of the advanced combiner. The combiner has to have high transmittance as well as high reflectance so that a driver can see both foreground object and display reading at the same time. The optical design for the combiner is based on the concepts: (a) Visible light transmittance has to be 70% or more in accordance with a legal requirement, and (b) taking both peak wavelengths of Vim' and sensitivity characteristics of human eyes into consideration, 530nm of wave length is chosen as a reflective light. The combiner consists of a dielectric thin layer of Ti02-Si02 system. Its basic structure is decided by simulation with matrix method of the resultant waves. The coating film is applied on the restricted area of the forth surface of laminated windshield by newly developed solgel printing process using a metal alkoxide solution with a relatively long storage life.

Study on the decomposition mechanism of alkyl carbonate on lithium metal by pyrolysis-gas chromatography-mass spectroscopy

NASA Astrophysics Data System (ADS)

Mogi, Ryo; Inaba, Minoru; Iriyama, Yasutoshi; Abe, Takeshi; Ogumi, Zempachi

The surface films formed on deposited lithium in electrolyte solutions based on ethylene carbonate (EC), diethyl carbonate (DEC), and dimethyl carbonate (DMC) were analyzed by pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS). In 1 M LiClO 4/EC, the main component of the surface film was easily hydrolyzed to give ethylene glycol after exposure to air, and hence was considered to have a chemical structure of ROCH 2CH 2OR', of which OR and OR' are OLi or OCO 2Li. Ethylene oxide, acetaldehyde, and 1,4-dioxane were detected in decomposition products, and they were considered to have been formed by pyrolysis of ROCH 2CH 2OR' in the pyrolyzer. The presence of ethanol in decomposition products confirmed that ring cleavage at the CH 2O bonds of EC occurs by one electron reduction. In addition, the presence of methanol implied the cleavage of the CC bond of EC upon reduction. From the surface films formed in 1 M LiClO 4/DEC and /DMC, ethanol and methanol, respectively, were detected, which suggested that corresponding lithium alkoxides and/or lithium alkyl carbonates were the main components. In 1 M LiClO 4/EC+DEC (1:1), EC dominantly decomposed to form the surface film. The surface film formed in 1 M LiPF 6/EC+DEC (1:1) contained a much smaller amount of organic compounds.

Fluorescent Hydrogel Generated Conveniently from a Perylene Tetracarboxylate Derivative of Titanium(IV) Alkoxide.

PubMed

Zou, Dan-Hong; Wang, Peng; Luo, Wen; Hou, Jin-Le; Zhu, Qin-Yu; Dai, Jie

2018-02-05

Organic gelators and metal-coordination frameworks based on perylene derivatives as functional materials have attracted great attention because of their intense fluorescence emission as well as unique electronic and photonic properties. We report here the structures and properties of a luminescent titanium(IV) coordination compound of a perylene tetracarboxylate (PTC) derivative, [Ti 2 (O i Pr) 6 (L 1 )(phen) 2 ] (1), along with its two naphthalene analogues, [Ti 2 (O i Pr) 6 (L 2 )(phen) 2 ] (2) and [Ti 2 (O i Pr) 6 (L 2 )(bpy) 2 ] (3), where L 1 = 3,9-dicarboxylate-(4,10-diisopropanolcarboxylate)perylene, phen = 1,10-phenanthroline, L 2 = 1,5-dicarboxylate-(2,6-diisopropanolcarboxylate)naphthalene, and bpy = 2,2'-bipyridine. Compound 1 is a rare early-transition-metal PTC coordination compound that can be simply prepared in one pot as crystals by a low-heat synthesis. Unlike those of paramagnetic late-transition-metal PTC compounds, compound 1 showed intense fluorescence emission. More remarkably, the crystals of 1 can be turned immediately to a fluorescent hydrogel just through a simple procedure, putting the crystals in water and then treating with ultrasound. No acid catalyst or pH adjustment is needed. Hydrolysis of the titanium isopropanol group in water and π-π interaction of the perylene and phen play important roles in the gelation process. The film prepared from the gel can be used as a visual fluorescence sensor for aromatic amines and phenols, which are hazards for the human and environment.

Comparative Study of Rhodamine B degradation by Tio2 nanoparticles synthesized from titanium sec butoxide and its chloroacetato derivatves.

PubMed

Ambreen, S; Pandey, N D; Pandey, A

2017-07-31

TiO2 has been well recognized as a proficient photocatalyst. TiO2 nanoparticles have been synthesized from titanium sec butoxide (1) and its monochloroacetate derived compounds. The modifications of Ti(OsBu)4 with monochloroacetic acid in 1:1 and 1:2 molar ratios afforded Ti(OsBu)3(OOCCH2Cl) (2) and Ti(OsBu)2(OOCCH2Cl)2 (3), respectively. The use of monochloroacetic acid as a modifier allows the control of both the degree of condensation and oligomerization of the precursor. The cross linking of the gel and connectivity of the molecular building blocks are lowered in these heteroleptic alkoxides which results in the formation of gels instead of crystalline precipitate. This modification of the precursors leads to the generation of new building blocks which significantly affect the properties of the resulting TiO2. TiO2 powders were prepared via sol-gel method from these precursors and calcined at 400°C and 600°C for 4 h. Phase and morphology of the prepared metal oxide nanoparticles were studied. XRD patterns showed TiO2 in anatase phase. After coating with the surfactant trioctyl phosphinoxide (TOPO), TiO2 particles were dispersed in chloroform to study the particle size and distribution. The optical properties were studied by UV-VIS drs. The photocatalytic activity was studied over the degradation of Rhodamine B under UV radiation.

Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

PubMed

Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

2017-07-21

Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroxyapatite-TiO(2)-based nanocomposites synthesized in supercritical CO(2) for bone tissue engineering: physical and mechanical properties.

PubMed

Salarian, Mehrnaz; Xu, William Z; Wang, Zhiqiang; Sham, Tsun-Kong; Charpentier, Paul A

2014-10-08

Calcium phosphate-based nanocomposites offer a unique solution toward producing scaffolds for orthopedic and dental implants. However, despite attractive bioactivity and biocompatibility, hydroxyapatite (HAp) has been limited in heavy load-bearing applications due to its intrinsically low mechanical strength. In this work, to improve the mechanical properties of HAp, we grew HAp nanoplates from the surface of one-dimensional titania nanorod structures by combining a coprecipitation and sol-gel methodology using supercritical fluid processing with carbon dioxide (scCO2). The effects of metal alkoxide concentration (1.1-1.5 mol/L), reaction temperature (60-80 °C), and pressure (6000-8000 psi) on the morphology, crystallinity, and surface area of the resulting nanostructured composites were examined using scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and Brunauer-Emmet-Teller (BET) method. Chemical composition of the products was characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray absorption near-edge structure (XANES) analyses. HAp nanoplates and HAp-TiO2 nanocomposites were homogeneously mixed within poly(ε-caprolactone) (PCL) to develop scaffolds with enhanced physical and mechanical properties for bone regeneration. Mechanical behavior analysis demonstrated that the Young's and flexural moduli of the PCL/HAp-TiO2 composites were substantially higher than the PCL/HAp composites. Therefore, this new synthesis methodology in scCO2 holds promise for bone tissue engineering with improved mechanical properties.

Sol-gel preparation of silica and titania thin films

NASA Astrophysics Data System (ADS)

Thoř, Tomáš; Václavík, Jan

2016-11-01

Thin films of silicon dioxide (SiO2) and titanium dioxide (TiO2) for application in precision optics prepared via the solgel route are being investigated in this paper. The sol-gel process presents a low cost approach, which is capable of tailoring thin films of various materials in optical grade quality. Both SiO2 and TiO2 are materials well known for their application in the field of anti-reflective and also highly reflective optical coatings. For precision optics purposes, thickness control and high quality of such coatings are of utmost importance. In this work, thin films were deposited on microscope glass slides substrates using the dip-coating technique from a solution based on alkoxide precursors of tetraethyl orthosilicate (TEOS) and titanium isopropoxide (TIP) for SiO2 and TiO2, respectively. As-deposited films were studied using spectroscopic ellipsometry to determine their thickness and refractive index. Using a semi-empirical equation, a relationship between the coating speed and the heat-treated film thickness was described for both SiO2 and TiO2 thin films. This allows us to control the final heat-treated thin film thickness by simply adjusting the coating speed. Furthermore, films' surface was studied using the white-light interferometry. As-prepared films exhibited low surface roughness with the area roughness parameter Sq being on average of 0.799 nm and 0.33 nm for SiO2 and TiO2, respectively.

Development of Advanced Materials for Electro-Ceramic Application Final Report CRADA No. TC-1331-96

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caplan, M.; Olstad, R.; McMillan, L.

The goal of this project was to further develop and characterize the electrochemical methods originating in Russia for producing ultra high purity organometallic compounds utilized as precursors in the production of high quality electro-ceramic materials. Symetrix planned to use electro-ceramic materials with high dielectric constant for microelectronic memory circuit applications. General Atomics planned to use the barium titanate type ceramics with low loss tangent for producing a high power ferroelectric tuner used to match radio frequency power into their Dill-D fusion machine. Phase I of the project was scheduled to have a large number of organometallic (alkoxides) chemical samples producedmore » using various methods. These would be analyzed by LLNL, Soliton and Symetrix independently to determine the level of chemical impurities thus verifying each other's analysis. The goal was to demonstrate a cost-effective production method, which could be implemented in a large commercial facility to produce high purity organometallic compounds. In addition, various compositions of barium-strontium-titanate ceramics were to be produced and analyzed in order to develop an electroceramic capacitor material having the desired characteristics with respect to dielectric constant, loss tangent, temperature characteristics and non-linear behavior under applied voltage. Upon optimizing the barium titanate material, 50 capacitor preforms would be produced from this material demonstrating the ability to produce, in quantity, the pills ultimately required for the ferroelectric tuner (approx 2000-3000 ceramic pills).« less

Facile sonochemical synthesis of amorphous NiFe-(oxy)hydroxide nanoparticles as superior electrocatalysts for oxygen evolution reaction.

PubMed

Lee, Eunjik; Park, Ah-Hyeon; Park, Hyun-Uk; Kwon, Young-Uk

2018-01-01

In this work, we present facile synthesis of amorphous Ni/Fe mixed (oxy)hydroxide (NiFe(H)) nanoparticles (NPs) and their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline media. a-NiFe(H) NPs have received lots of attention as OER electrocatalysts with many desirable properties. By using a simple sonochemical route, we prepared amorphous Ni and Fe-alkoxide (NiFe(A)) NPs whose composition can be controlled in the entire composition range (Ni 100-x Fe x , 0≤x≤1). These samples are composed of extremely small NiFe(A) NPs with Ni and Fe atoms homogeneously distributed. NiFe(A) NPs are readily converted into corresponding electrocatalytically active NiFe(H) NP by a simple electrochemical treatment. Electrochemical analysis data show that the OER activity of amorphous NiFe(H) samples follows the volcano-type trend when plotted against the Fe content. Ni 70 Fe 30 (H) sample showed the lowest overpotential of 292mV at 10mAcm -2 geo and the lowest Tafel slope of 30.4mVdec -1 , outperforming IrO x /C (326mV, 41.7mVdec -1 ). Our samples are highly durable based on the chronopotentiometry data at the current density of 10mAcm -2 geo for 2h which show that Ni 70 Fe 30 sample maintains the steady-state potential, contrary to the time-varying IrO x /C. Copyright © 2017 Elsevier B.V. All rights reserved.

Silica coatings formed on noble dental casting alloy by the sol-gel dipping process.

PubMed

Yoshida, K; Tanagawa, M; Kamada, K; Hatada, R; Baba, K; Inoi, T; Atsuta, M

1999-08-01

The sol-gel dipping process, in which liquid silicon alkoxide is transformed into the solid silicon-oxygen network, can produce a thin film coating of silica (SiO2). The features of this method are high homogeneity and purity of the thin SiO2 film and a low sinter temperature, which are important in preparation of coating films that can protect from metallic ion release from the metal substrate and prevent attachment of dental plaque. We evaluated the surface characteristics of the dental casting silver-palladium-copper-gold (Ag-Pd-Cu-Au) alloy coated with a thin SiO2 film by the sol-gel dipping process. The SiO2 film bonded strongly (over 40 MPa) to Ti-implanted Ag-Pd-Cu-Au alloy substrate as demonstrated by a pull test. Hydrophobilization of Ti-implanted/SiO2-coated surfaces resulted in a significant increase of the contact angle of water (80.5 degrees) compared with that of the noncoated alloy specimens (59.3 degrees). Ti-implanted/SiO2-coated specimens showed the release of many fewer metallic ions (192 ppb/cm2) from the substrate than did noncoated specimens (2,089 ppb/cm2). The formation of a thin SiO2 film by the sol-gel dipping process on the surface of Ti-implanted Ag-Pd-Cu-Au alloy after casting clinically may be useful for minimizing the possibilities of the accumulation of dental plaque and metal allergies caused by intraoral metal restorations.

Probing the Effects of Templating on the UV and Visible Light Photocatalytic Activity of Porous Nitrogen-Modified Titania Monoliths for Dye Removal.

PubMed

Nursam, Natalita M; Wang, Xingdong; Tan, Jeannie Z Y; Caruso, Rachel A

2016-07-13

Porous nitrogen-modified titania (N-titania) monoliths with tailored morphologies were prepared using phase separation and agarose gel templating techniques. The doping and templating process were simultaneously carried out in a one-pot step using alcohol amine-assisted sol-gel chemistry. The amount of polymer used in the monoliths that were prepared using phase separation was shown to affect both the physical and optical properties: higher poly(ethylene glycol) content increased the specific surface area, porosity, and visible light absorption of the final materials. For the agarose-templated monoliths, the infiltration conditions affected the monolith morphology. A porous monolith with high surface area and the least shrinkage was obtained when the N containing alkoxide precursor was infiltrated into the agarose scaffolds at 60 °C. The effect of the diverse porous morphologies on the photocatalytic activity of N-titania was studied for the decomposition of methylene blue (MB) under visible and UV light irradiation. The highest visible light activity was achieved by the agarose-templated N-titania monolith, in part due to higher N incorporation. This sample also showed better UV activity, partly because of the higher specific surface area (up to 112 m(2) g(-1)) compared to the phase separation-induced monoliths (up to 103 m(2) g(-1)). Overall, agarose-templated, porous N-titania monoliths provided better features for effectively removing the MB contaminant.

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

NASA Astrophysics Data System (ADS)

De Michele, Vincenzo; Romanelli, Giovanni; Cupane, Antonio

2018-02-01

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid-liquid transition of supercooled confined water) on a "wet" sample with hydration h 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually "dry" sample at h 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid-liquid transition hypothesis.

Silver-Loaded Aluminosilicate Aerogels As Iodine Sorbents.

PubMed

Riley, Brian J; Kroll, Jared O; Peterson, Jacob A; Matyáš, Josef; Olszta, Matthew J; Li, Xiaohong; Vienna, John D

2017-09-27

In this paper, aluminosilicate aerogels were used as scaffolds for silver nanoparticles to capture I 2 (g). The starting materials for these scaffolds included Na-Al-Si-O and Al-Si-O aerogels, both synthesized from metal alkoxides. The Ag 0 particles were added by soaking the aerogels in aqueous AgNO 3 solutions followed by drying and Ag + reduction under H 2 /Ar to form Ag 0 crystallites within the aerogel matrix. In some cases, aerogels were thiolated with 3-(mercaptopropyl)trimethoxysilane as an alternative method for binding Ag + . During the Ag + -impregnation steps, for the Na-Al-Si-O aerogels, Na was replaced with Ag, and for the Al-Si-O aerogels, Si was replaced with Ag. The Ag-loading of thiolated versus nonthiolated Na-Al-Si-O aerogels was comparable at ∼35 atomic %, whereas the Ag-loading in unthiolated Al-Si-O aerogels was significantly lower at ∼7 atomic % after identical treatment. Iodine loadings in both thiolated and unthiolated Ag 0 -functionalized Na-Al-Si-O aerogels were >0.5 m I m s -1 (denoting the mass of iodine captured per starting mass of the sorbent) showing almost complete utilization of the Ag through chemisorption to form AgI. Iodine loading in the thiolated and Ag 0 -functionalized Al-Si-O aerogel was 0.31 m I m s -1 . The control of Ag uptake over solution residence time and [Ag] demonstrates the ability to customize the Ag-loading in the base sorbent to regulate the loading capacity of iodine.

Changes in the near edge X-ray absorption fine structure of hybrid organic-inorganic resists upon exposure.

PubMed

Fallica, Roberto; Watts, Benjamin; Roesner, Benedikt; Della Giustina, Gioia; Brigo, Laura; Brusatin, Giovanna; Ekinci, Yasin

2018-06-14

We report on the near edge X-ray absorption fine structure (NEXAFS) spectroscopy of hybrid organic-inorganic resists. These materials are nonchemically amplified systems based on Si, Zr, and Ti oxides, synthesized from organically modified precursors and transition metal alkoxides by a sol-gel route and designed for ultraviolet, extreme ultraviolet and electron beam lithography. The experiments were conducted using a scanning transmission X-ray microscope (STXM) which combines high spatial-resolution microscopy and NEXAFS spectroscopy. The absorption spectra were collected in the proximity of the carbon edge (~ 290 eV) before and after in situ exposure, enabling the measurement of a significant photo-induced degradation of the organic group (phenyl or methyl methacrylate, respectively), the degree of which depends on the configuration of the ligand. Photo-induced degradation was more efficient in the resist synthesized with pendant phenyl substituents than it was in the case of systems based on bridging phenyl groups. The degradation of the methyl methacrylate group was relatively efficient, with about half of the initial ligands dissociated upon exposure. Our data reveal that the such dissociation can produce different outcomes, depending on the structural configuration. While all the organic groups were expected to detach and desorb from the resist in their entirety, a sizeable amount of them remain and form undesired byproducts such as alkene chains. In the framework of the materials synthesis and engineering through specific building blocks, these results provide a deeper insight into the photochemistry of resists, in particular for extreme ultraviolet lithography. © 2018 IOP Publishing Ltd.

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

PubMed

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

2015-07-06

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.

Dioxo-Fluoroalkoxide Tungsten(VI) Complexes for Growth of WOx Thin Films by Aerosol-Assisted Chemical Vapor Deposition.

PubMed

Bonsu, Richard O; Kim, Hankook; O'Donohue, Christopher; Korotkov, Roman Y; Abboud, Khalil A; Anderson, Timothy J; McElwee-White, Lisa

2015-08-03

The soluble bis(fluoroalkoxide) dioxo tungsten(VI) complexes WO2(OR)2(DME) [1, R = C(CF3)2CH3; 2, R = C(CF3)3] have been synthesized by alkoxide-chloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WOx. The (1)H NMR and (19)F NMR spectra of 1 and 2 are consistent with an equilibrium between the dimethoxyethane (DME) complexes 1 and 2 and the solvato complexes WO2(OR)2(CD3CN)2 [1b, R = C(CF3)2CH3; 2b, R = C(CF3)3] in acetonitrile-d3 solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and thermolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimerization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 °C and produced both substoichiometric amorphous WOx and a polycrystalline W18O49 monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work function (4.9-5.6 eV), mean optical transmittance (39.1-91.1%), conductivity (0.4-2.3 S/cm), and surface roughness (3.4-7.9 nm) of the WOx films are suitable for charge injection layers in organic electronics.

Imino-Oxy Acetic Acid Dealkylation as Evidence for an Inner-Sphere Alcohol Intermediate in the Reaction Catalyzed by Peptidylglycine α-Hydroxylating Monooxygenase (PHM)

PubMed Central

McIntyre, Neil R.; Lowe, Edward W.; Merkler, David J.

2009-01-01

Peptidylglycine α-hydroxylating monooxygenase (PHM, EC 1.14.17.3) catalyzes the stereospecific hydroxylation of a glycyl α-carbon in a reaction that requires O2 and ascorbate. Subsequent dealkylation of the α-hydroxyglycine by another enzyme, peptidylamidoglycolate lyase (PAL. EC 4.3.2.5), yields a bioactive amide and glyoxylate. PHM is a non-coupled, type II dicopper monooxygenase which activates O2 at only a single copper atom, CuM. In this study, the PHM mechanism was probed using a non-natural substrate, benzaldehyde imino-oxy acetic acid (BIAA). PHM catalyzes the O-oxidative dealkylation of BIAA to benzaldoxime and glyoxylate with no involvement of PAL. The minimal kinetic mechanism for BIAA was shown to be steady-state ordered using primary deuterium kinetic isotope effects. The D(V/K)APPARENT, BIAA decreased from 14.7 ± 1.0 as [O2] → 0 to 1.0 ± 0.2 as [O2] → ∞ suggesting the dissociation rate constant from the PHM·BIAA complex decreases as [O2] increases; thereby, reducing the steady-state concentration of [PHM]free. BIAA was further used to differentiate between potential oxidative Cu/O species using a QM/MM reaction coordinate simulation to determine which species could yield product O-dealkylation that matched our experimental data. The results of this study provided compelling evidence for the presence of a covalently linked CuII-alkoxide intermediate with a quartet spin state responsible BIAA oxidation. PMID:19569683

Preparation of hydroxyapatite-titania hybrid coatings on titanium alloy.

PubMed

Un, Serhat; Durucan, Caner

2009-08-01

Hydroxypapatite-titania hybrid films on Ti6Al4V alloys were prepared by sol-gel technique by incorporating presynthesized hydroxypapatite (Ca(10)(PO(4))(6)(OH)(2) or HAp) powders into a titanium-alkoxide dip coating solution. Titania network was formed by the hydrolysis and condensation of Ti-isopropoxide Ti[OCH(CH(3))(2)](4)-based sols. The effect of titania sol formulation, specifically the effect of organic solvents on the microstructure of the dip coated films calcined at 500 degrees C has been investigated. The coatings exhibit higher tendency for cracking when a high vapor pressure solvent, such as ethanol (C(2)H(5)OH) is used causing development of higher macroscopic stresses during evaporation of the sol. Titania sol formulations replacing the solvent with n-proponal (CH(3)(CH(2))(2)OH) and acetly-acetone (C(5)H(8)O) combinations enhanced the microstructural integrity of the coating during evaporation and calcination treatments. Sol-gel processing parameters, such as multilayer coating application and withdrawal rate, can be employed to change the titania thickness in the range of 0.120-1.1 microm and to control the microstructure of HAp-titania hybrid coatings. A high-calcination temperature in the range of 400-600 degrees C does not cause a distinct change in crystals nature of the titania matrix or HAp, but results in more cracking due to the combined effect of densification originated stresses and thermal stresses upon cooling. Slower withdraw rates and multilayer dip coating lead to coatings more vulnerable to microcracking.

Hydrocarbon-soluble calcium hydride: a "worker-bee" in calcium chemistry.

PubMed

Spielmann, Jan; Harder, Sjoerd

2007-01-01

The reactivity of the hydrocarbon-soluble calcium hydride complex [{CaH(dipp-nacnac)(thf)}(2)] (1; dipp-nacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) with a large variety of substrates has been investigated. Addition of 1 to C=O and C=N functionalities gave easy access to calcium alkoxide and amide complexes. Similarly, reduction of the C[triple chemical bond]N bond in a cyanide or an isocyanide resulted in the first calcium aldimide complexes [Ca{N=C(H)R}(dipp-nacnac)] and [Ca{C(H)=NR}(dipp-nacnac)], respectively. Complexation of 1 with borane or alane Lewis acids gave the borates and alanates as contact ion pairs. In reaction with epoxides, nucleophilic ring-opening is observed as the major reaction. The high reactivity of hydrocarbon-soluble 1 with most functional groups contrasts strongly with that of insoluble CaH(2), which is essentially inert and is used as a common drying agent. Crystal structures of the following products are presented: [{Ca{OC(H)Ph(2)}(dipp-nacnac)}(2)], [{Ca{N=C(H)Ph}(dipp-nacnac)}(2)], [{Ca{C(H)=NC(Me)(2)CH(2)C(Me)(3)}(dipp-nacnac)}(2)], [{Ca{C(H)=NCy}(dipp-nacnac)}(2)], [Ca(dipp-nacnac)(thf)](+)[H(2)BC(8)H(14)](-) and [{Ca(OCy)(dipp-nacnac)}(2)]. The generally smooth and clean conversions of 1 with a variety of substrates and the stability of most intermediates against ligand exchange make 1 a valuable key precursor in the syntheses of a wide variety of beta-diketiminate calcium complexes.

Solution synthesis of germanium nanowires using a Ge+2 alkoxide precursor.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyle, Timothy J.; Tribby, Louis, J; Bunge, Scott D.

2006-02-01

A simple solution synthesis of germanium (Ge{sup 0}) nanowires under mild conditions (<400 C and 1 atm) was demonstrated using germanium 2,6 dibutylphenoxide Ge(DBP){sub 2} (1) as the precursor where DBP = OC{sub 6}H{sub 3}(C(CH{sub 3}){sub 3}){sub 2}-2,6. Compound 1, synthesized from Ge(NR{sub 2}){sub 2} where R = SiMe{sub 3} and two equivalents of DBP-H, was characterized as a mononuclear species by single crystal X-ray diffraction. Dissolution of 1 in oleylamine, followed by rapid injection into a 1-octadecene solution heated to 300 C under an atmosphere of Ar, led to the formation of Ge{sup 0} nanowires. The Ge{sup 0} nanowiresmore » were characterized by transmission electron microscopy (TEM), X-ray diffraction analysis, and Fourier transform infrared spectroscopy. These characterizations revealed that the nanowires are single crystalline in the cubic phase and coated with oleylamine surfactant. We also observed that the nanowire length (0.1 to 10 {micro}m) increases with increasing temperature (285 to 315 C) and time (5 to 60 min). Two growth mechanisms are proposed based on the TEM images intermittently taken during the growth process as a function of time: (1) self-seeding mechanism where one of two overlapping nanowires serves as a seed, while the other continues to grow as a wire and (2) self-assembly mechanism where an aggregate of small rods (< 50 nm in diameter) recrystallize on the tip of a longer wire, extending its length.« less

A SIFT study of the reactions of H2ONO+ ions with several types of organic molecules

NASA Astrophysics Data System (ADS)

Smith, David; Wang, Tianshu; Spanel, Patrik

2003-11-01

A selected ion flow tube (SIFT) study has been carried out of the reactions of hydrated nitrosonium ions, NO+H2O, which theory has equated to protonated nitrous acid ions, H2ONO+. One objective of this study was to investigate if this ion exhibits the properties of both a cluster ion and a protonated acid in their reactions with a variety of organic molecules. The chosen reactant molecules comprise two each of the following types--amines, terpenes, aromatic hydrocarbons, esters, carboxylic acids, ketones, aldehydes and alcohols. The reactant H2ONO+ (NO+H2O) ions are formed in a discharge ion source and injected into helium carrier gas where they are partially vibrationally excited and partially dissociated to NO+ ions. Hence, the reactions of the H2ONO+ ions had to be studies simultaneously with NO+ ions, the reactions of the latter ions readily being studied by selectively injecting NO+ ions into the carrier gas. The results of this study indicate that the H2ONO+ ions undergo a wide variety of reaction processes that depend on the properties of the reactant molecules such as their ionisation energies and proton affinities. These processes include charge transfer with compounds, M, that have low ionisation energies (producing M+), proton transfer with compounds possessing large proton affinities (MH+), hydride ion transfer (M---H+), alkyl radical (M---R+), alkoxide radical transfer (M---OR+), ion-molecule association (NO+H2OM) and ligand switching (NO+M), producing the ions given in parentheses.

In situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion as potential electrode materials for energy applications

NASA Astrophysics Data System (ADS)

Mombrú, Dominique; Romero, Mariano; Faccio, Ricardo; Castiglioni, Jorge; Mombrú, Alvaro W.

2017-06-01

In situ preparation of polyaniline-ceramic nanocomposites has recently demonstrated that the electrical properties are highly improved with respect to the typical ex situ preparations. In this report, we present for the first time, to the best of our knowledge, the in situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion as an easily adaptable route to prepare other ceramic-polymer nanocomposites. The main relevance of this method is the possibility to prepare ceramic quantum dots from alkoxide precursors using water vapor flow into any hydrophobic polymer host and to achieve good homogeneity and size-control. In addition, we perform full characterization by means of high-resolution transmission electron microscopy, X-ray powder diffraction, small angle X-ray scattering, thermogravimetric and calorimetric analyses, confocal Raman microscopy and impedance spectroscopy analyses. The presence of the polymer host and interparticle Coulomb repulsive interactions was evaluated as an influence for the formation of 3-8 nm equally-sized quantum dots independently of the concentration. The polyaniline polaron population showed an increase for the quantum dots diluted regime and the suppression at the concentrated regime, ascribed to the formation of chemical bonds at the interface, which was confirmed by theoretical simulations. In agreement with the previous observation, the in situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion could be very useful as a novel approach to prepare electrode materials for energy conversion and storage applications.

Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate L-lactide polymerization.

PubMed

Gerling, Kimberly A; Rezayee, Nomaan M; Rheingold, Arnold L; Green, David B; Fritsch, Joseph M

2014-11-21

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.

Dehydration of 1-octadecanol over H-BEA: A combined experimental and computational study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Wenji; Liu, Yuanshuai; Barath, Eszter

Liquid phase dehydration of 1-octdecanol, which is intermediately formed during the hydrodeoxygenation of microalgae oil, has been explored in a combined experimental and computational study. The alkyl chain of C18 alcohol interacts with acid sites during diffusion inside the zeolite pores, resulting in an inefficient utilization of the Brønsted acid sites for samples with high acid site concentrations. The parallel intra- and inter- molecular dehydration pathways having different activation energies pass through alternative reaction intermediates. Formation of surface-bound alkoxide species is the rate-limiting step during intramolecular dehydration, whereas intermolecular dehydration proceeds via a bulky dimer intermediate. Octadecene is the primarymore » dehydration product over H-BEA at 533 K. Despite of the main contribution of Brønsted acid sites towards both dehydration pathways, Lewis acid sites are also active in the formation of dioctadecyl ether. The intramolecular dehydration to octadecene and cleavage of the intermediately formed ether, however, require strong BAS. L. Wang, D. Mei and J. A. Lercher, acknowledge the partial support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.« less

Synthesis and structural studies of heterobimetallic alkoxide complexes supported by bis(phenolate) ligands: efficient catalysts for ring-opening polymerization of L-lactide.

PubMed

Chen, Hsuan-Ying; Liu, Mei-Yu; Sutar, Alekha Kumar; Lin, Chu-Chieh

2010-01-18

A series of heterobimetallic titanium(IV) complexes [LTi(O(i)Pr)(mu-O(i)Pr)(2)Li(THF)(2)], [LTi(O(i)Pr)(mu-O(i)Pr)(2)Na(THF)(2)], [LTi(mu-O(i)Pr)(2)Zn(O(i)Pr)(2)], and [LTi(mu-O(i)Pr)(2)Mg(O(i)Pr)(2)] (where L = bidentate bisphenol ligands) have been synthesized and characterized including a structural determination of [L(1)Ti(mu(2)-O(i)Pr)(2)(O(i)Pr)Li(THF)(2)] (1a). These complexes were investigated for their utility in the ring-opening polymerization (ROP) of l-lactide (LA). Polymerization activities have been shown to correlate with the electronic properties of the substituent within the bisphenol ligand. In contrast to monometallic titanium initiator 1e, all the heterobimetallic titanium initiators (Ti-Li, Ti-Na, Ti-Zn, and Ti-Mg) show enhanced catalytic activity toward ring-opening polymerization (ROP) of l-LA. In addition, the use of electron-donating methoxy or methylphenylsulfonyl functional ligands reveals the highest activity. The bisphenol bimetallic complexes give rise to controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number-average molecular weight. The polymerization kinetics using 2c as an initiator were also studied, and the experimental results indicate that the reaction rate is first-order with respect to both monomer and catalyst concentration with a polymerization rate constant, k = 81.64 M(-1) min(-1).

Direct Partial Oxidations Using Molecular Oxygen - Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kemp, Richard

In 2006, Richard A. Kemp (University of New Mexico) and Karen I. Goldberg (University of Washington) formed a team and began to investigate new strategies to accomplish direct selective aerobic oxidations, with a particular emphasis on the epoxidation of propylene and higher olefins. This DOE-BES funded project was renewed twice and concluded after a no-cost extension earlier this year. Multiple novel strategies involving homogeneous catalyst systems were initiated and investigated during the award. Important fundamental understanding and insight concerning requirements for promotion of aerobic olefin epoxidation was generated. During the tenure of this project, new knowledge was generated concerning themore » synthesis, characterization and aerobic reactivity of metal hydrides and hydroxides. Key results describing synthetic strategies and optimization of the preparation of mononuclear late metal hydrides were published. The team reported the first example of O2 insertion into a Pd-H bond, a reaction which had been proposed in the literature but never previously observed. Our experimental investigation of the mechanism was later followed by computational work, and a description of what is now referred to as the Hydrogen Atom Abstraction (HAA) pathway for this reaction has been widely accepted in the community. After investigation of many other late metal hydrides, both experimentally and computationally, the team put together a chapter that included a description of key contributing factors that allow reaction by the HAA mechanism. A brief sampling of other classic papers from our project include hydrogenolysis reactions of late metal hydroxide and alkoxide complexes, the synthesis of nickel-hydrides, and the involvement of hemilabile ligands in promoting new reaction pathways.« less

Silver-Loaded Aluminosilicate Aerogels As Iodine Sorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riley, Brian J.; Kroll, Jared O.; Peterson, Jacob A.

This paper discusses the development of aluminosilicates aerogels as scaffolds for Ag0 nanoparticles used for chemisorption of I2(g). The starting materials for these scaffolds included both Na-Al-Si-O and Al-Si-O aerogels, both synthesized from metal alkoxides. The Ag0 particles are added by soaking the aerogels in AgNO3 followed by drying and flowing under H2/Ar to reduce Ag+ → Ag0. In some cases, samples were soaked in 3-(mercaptopropyl)trimethoxysilane under supercritical CO2 to add –SH tethers to the aerogel surfaces for more effective binding of Ag+. During the Ag+-impregnation steps, for the Na-Al-Si-O aerogels, Na was replaced with Ag, and for the Al-Si-Omore » aerogel, Si was replaced with Ag. The Ag-loading of thiolated versus non-thiolated Na-Al-Si-O aerogels was comparable at ~35 at% whereas the Ag-loading in unthiolated Al-Si-O aerogels was significantly lower at ~ 7 at% after identical treatment. Iodine loadings in both thiolated and unthiolated Ag0-functionalized Na-Al-Si-O aerogels were > 0.5 g g-1 showing almost complete utilization of the Ag through chemisorption to form AgI. Iodine loading in the thiolated Al-Si-O aerogel was 0.31 g g-1. The control of Ag uptake over solution residence time and [AgNO3] demonstrates the ability to customize the Ag-loading in the base sorbent to regulate the capacity of iodine chemisorption. Consolidation experimental results are also presented.« less

Composite Aerogel Multifoil Protective Shielding

NASA Technical Reports Server (NTRS)

Jones, Steven M.

2013-01-01

New technologies are needed to survive the temperatures, radiation, and hypervelocity particles that exploration spacecraft encounter. Multilayer insulations (MLIs) have been used on many spacecraft as thermal insulation. Other materials and composites have been used as micrometeorite shielding or radiation shielding. However, no material composite has been developed and employed as a combined thermal insulation, micrometeorite, and radiation shielding. By replacing the scrims that have been used to separate the foil layers in MLIs with various aerogels, and by using a variety of different metal foils, the overall protective performance of MLIs can be greatly expanded to act as thermal insulation, radiation shielding, and hypervelocity particle shielding. Aerogels are highly porous, low-density solids that are produced by the gelation of metal alkoxides and supercritical drying. Aerogels have been flown in NASA missions as a hypervelocity particle capture medium (Stardust) and as thermal insulation (2003 MER). Composite aerogel multifoil protective shielding would be used to provide thermal insulation, while also shielding spacecraft or components from radiation and hypervelocity particle impacts. Multiple layers of foil separated by aerogel would act as a thermal barrier by preventing the transport of heat energy through the composite. The silica aerogel would act as a convective and conductive thermal barrier, while the titania powder and metal foils would absorb and reflect the radiative heat. It would also capture small hypervelocity particles, such as micrometeorites, since it would be a stuffed, multi-shock Whipple shield. The metal foil layers would slow and break up the impacting particles, while the aerogel layers would convert the kinetic energy of the particles to thermal and mechanical energy and stop the particles.

Facile Synthesis and Proposed Mechanism of α,ω-Oxetanyl-Telechelic Poly(3-nitratomethyl-3-methyl oxetane) by an SN2(i) Nitrato Displacement Method in Basic Media

NASA Astrophysics Data System (ADS)

Desai, Hemant J.; Acheampong, Daniel O.; Hudson, Robert; Lacey, Richard; Stanley, Claire; Turner, Helen; Whitmore, Hannah; Torry, Simon; Golding, Peter; Erothu, Harikrishna; Topham, Paul

2017-01-01

The synthesis of a novel heterocyclic-telechelic polymer, α,ω-oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane), is described. Infrared spectroscopy (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy have been used to confirm the successful synthesis, demonstrating the presence of the telechelic-oxetanyl moieties. Synthesis of the terminal functionalities has been achieved via displacement of nitrato groups, in a manner similar to that employed with other leaving groups such as azido, bromo, and nitro, initiated by nucleophiles. In the present case, displacement occurs on the ends of a nitrato-functionalized polymer driven by the formation of sodium nitrate, which is supported by the polar aprotic solvent N,N-dimethyl formamide. The formation of an alkoxide at the polymer chain ends is favored and allows internal back-biting to the nearest carbon bearing the nitrato group, intrinsically in an SN2(i) reaction, leading to α,ω-oxetanyl functionalization. The telechelic-oxetanyl moieties have the potential to be cross-linked by chemical (e.g., acidic) or radiative (e.g., ultraviolet) curing methods without the use of high temperatures, usually below 100°C. This type of material was designed for future use as a contraband simulant, whereby it would form the predominant constituent of elastomeric composites comprising rubbery polymer with small quantities of solids, typically crystals of contraband substances, such as explosives or narcotics. This method also provides an alternative approach to ring closure and synthesis of heterocycles.

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.

2016-03-04

Here we demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. Our results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order tomore » achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

PubMed

Sad, María E; Neurock, Matthew; Iglesia, Enrique

2011-12-21

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. © 2011 American Chemical Society

Magnetically separable mesoporous Fe{sub 3}O{sub 4}/silica catalysts with very low Fe{sub 3}O{sub 4} content

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grau-Atienza, A.; Serrano, E.; Linares, N.

2016-05-15

Two magnetically separable Fe{sub 3}O{sub 4}/SiO{sub 2} (aerogel and MSU-X) composites with very low Fe{sub 3}O{sub 4} content (<1 wt%) have been successfully prepared at room temperature by co-condensation of MPTES-functionalized Fe{sub 3}O{sub 4} nanoparticles (NPs) with a silicon alkoxide. This procedure yields a homogeneous incorporation of the Fe{sub 3}O{sub 4} NPs on silica supports, leading to magnetic composites that can be easily recovered using an external magnetic field, despite their very low Fe{sub 3}O{sub 4} NPs content (ca. 1 wt%). These novel hybrid Fe{sub 3}O{sub 4}/SiO{sub 2} materials have been tested for the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) withmore » hydrogen peroxide showing an enhancement of the stability of the NPs in the Fe{sub 3}O{sub 4}/silica aerogel as compared to the Fe{sub 3}O{sub 4} NPs alone, even after five catalytic cycles, no leaching or agglomeration of the Fe{sub 3}O{sub 4}/SiO{sub 2} systems. - Graphical abstract: Novel magnetically separable mesoporous silica-based composites with very low magnetite content. - Highlights: • An innovative way to prepare magnetically separable composites with <1 wt% NPs. • The Fe{sub 3}O{sub 4}/silica composites are readily magnetized/demagnetized. • The Fe{sub 3}O{sub 4}/silica composites can be easily recovered using an external magnetic field. • Excellent catalytic performance and recyclability despite the low Fe{sub 3}O{sub 4} NPs content.« less

The adsorption of methyl, acetylide, chlorine and phosphorus trifluoride on zinc oxide: A quantum-chemical study

NASA Astrophysics Data System (ADS)

Rodriguez, JoséA.

1989-11-01

The chemisorptions of methyl (CH 3), acetylide (H-CC), chlorine (Cl) and phosphorus trifluoride (PF 3) on ZnO(0001) and of Cl on ZnO(101¯0) have been examined employing semi-em- pirical quantum-chemical calculations (INDO/S) and neutral clusters of limited size (Zn 13O 13). CH 3, H-CC and Cl appear as strong electron acceptors when adsorbed on Zn sites of ZnO. The chemisorption bonds of these molecules are almost pure σ-bonds and are largely localized on the adsorption site. An increase in the work function of ZnO surfaces upon adsorption of CH 3, H-CC and Cl is predicted. The PF 3 molecule is a very weak acceptor of electrons when adsorbed on a-top sites of ZnO(0001). The bonding mechanism of CH 3, H-CC, Cl and PF 3 on the ZnO(0001) surface involves primarily the HOMO and LUMO of the adsorbate and the Zn(4s,4p) orbitals of the substrate. The effects of chemisorption on the C-H bonds of CH 3 and H-CC, the C-C bond of H-CC, and the P-F bonds of PF 3 are examined. On the basis of these INDO/S results, the possible UPS spectra for CH 3, H-CC and PF 3 adsorbed on ZnO(0001) are discussed and compared with results for adsorption on transition-metal surfaces. A general picture of the chemisorption bond of alkyls, acetylides, alkoxides, carboxylates and halogens on a-top sites of ZnO(0001) is obtained by comparing our results for adsorption of CH 3, H-CC and Cl with those previously reported for adsorption of methoxy, OH and formate.

The substrate oxidation mechanism of pyranose 2-oxidase and other related enzymes in the glucose-methanol-choline superfamily.

PubMed

Wongnate, Thanyaporn; Chaiyen, Pimchai

2013-07-01

Enzymes in the glucose-methanol-choline (GMC) oxidoreductase superfamily catalyze the oxidation of an alcohol moiety to the corresponding aldehyde. In this review, the current understanding of the sugar oxidation mechanism in the reaction of pyranose 2-oxidase (P2O) is highlighted and compared with that of other enzymes in the GMC family for which structural and mechanistic information is available, including glucose oxidase, choline oxidase, cholesterol oxidase, cellobiose dehydrogenase, aryl-alcohol oxidase, and pyridoxine 4-oxidase. Other enzymes in the family that have been newly discovered or for which less information is available are also discussed. A large primary kinetic isotope effect was observed for the flavin reduction when 2-d-D-glucose was used as a substrate, but no solvent kinetic isotope effect was detected for the flavin reduction step. The reaction of P2O is consistent with a hydride transfer mechanism in which there is stepwise formation of d-glucose alkoxide prior to the hydride transfer. Site-directed mutagenesis of P2O and pH-dependence studies indicated that His548 is a catalytic base that facilitates the deprotonation of C2-OH in D-glucose. This finding agrees with the current mechanistic model for aryl-alcohol oxidase, glucose oxidase, cellobiose dehydrogenase, methanol oxidase, and pyridoxine 4-oxidase, but is different from that of cholesterol oxidase and choline oxidase. Although all of the GMC enzymes share similar structural folding and use the hydride transfer mechanism for flavin reduction, they appear to have subtle differences in the fine-tuned details of how they catalyze substrate oxidation. © 2013 The Authors Journal compilation © 2013 FEBS.

A Comparison of Gallium and Indium Alkoxide Complexes as Catalysts for Ring-Opening Polymerization of Lactide.

PubMed

Kremer, Alexandre B; Andrews, Ryan J; Milner, Matthew J; Zhang, Xu R; Ebrahimi, Tannaz; Patrick, Brian O; Diaconescu, Paula L; Mehrkhodavandi, Parisa

2017-02-06

The impact of the metal size and Lewis acidity on the polymerization activity of group 13 metal complexes was studied, and it was shown that, within the same ligand family, indium complexes are far more reactive and selective than their gallium analogues. To this end, gallium and aluminum complexes supported by a tridentate diaminophenolate ligand, as well as gallium complexes supported by N,N'-ethylenebis(salicylimine)(salen) ligands, were synthesized and compared to their indium analogues. Using the tridentate ligand set, it was possible to isolate the gallium chloride complexes 3 and (±)-4 and the aluminum analogues 5 and (±)-6. The alkoxygallium complex (±)-2, supported by a salen ligand, was also prepared and characterized and, along with the three-component system GaCl 3 /BnOH/NEt 3 , was tested for the ring-opening polymerization of lactide and ε-caprolactone. The polymerization rates and selectivities of both systems were significantly lower than those for the indium analogues. The reaction of (±)-2 with 1 equiv of lactide forms the first insertion product, which is stable in solution and can be characterized at room temperature. In order to understand the differences of the reactivity within the group 13 metal complexes, a Lewis acidity study using triethylphosphine oxide (the Gutmann-Beckett method) was undertaken for a series of aluminum, gallium, and indium halide complexes; this study shows that indium halide complexes are less Lewis acidic than their aluminum and gallium analogues. Density functional theory calculations show that the Mulliken charges for the indium complexes are higher than those for the gallium analogues. These data suggest that the impact of ligands on the reactivity is more significant than that of the metal Lewis acidity.

Effect of chain length on thermal conversion of alkoxy-substituted copper phthalocyanine precursors.

PubMed

Fukuda, Takamitsu; Kikukawa, Yuu; Tsuruya, Ryota; Fuyuhiro, Akira; Ishikawa, Naoto; Kobayashi, Nagao

2011-11-21

A series of dialkoxy-substituted copper phthalocyanine (CuPc) precursors (4a-4d) have been prepared by treating phthalonitrile with the corresponding lithium alkoxide under mild conditions. The precursors exhibited high solubilities in common organic solvents, including acetone, toluene, tetrahydrofuran (THF), CH(2)Cl(2), and CHCl(3). Elongation of the alkoxy chains improved the solubilities of the precursors effectively, and accordingly, the butoxy-substituted derivative (4d) showed the highest solubility among 4a-4d. X-ray crystallography clarified that the conjugated skeletons of 4a-4d are all isostructural, and have two alkoxy groups in a syn-conformation fashion, leading to highly bent structures. Thermal conversions of the precursors examined by thermogravimetry (TG) and differential thermal analysis (DTA) demonstrate that 4a was converted into CuPc via two distinct exothermic processes in the 200-250 °C temperature range, while 4d exhibits only one exothermic signal in the DTA. In the field emission scanning electron microscopy (FESEM) images of 4a, the presence of two types of distinct crystal morphology (prismatic and plate-like crystals) can be recognized, implying that the two observed exothermic processes in the DTA can be attributed to the different crystal morphologies of the samples rather than the step-by-step elimination of the alkoxy groups. The thermal formation of CuPc from the precursors has been unambiguously confirmed by X-ray powder diffraction, UV-vis spectroscopy, and elemental analysis. The precursors were converted into CuPc at lower temperature with increasing chain length, presumably because of the increased void volume in the crystals. Thermal conversion performed in the solution phase results in a bright blue-colored solution with prominent absorption bands in the 650-700 nm region, strongly supporting the formation of CuPc.

A new sol-gel synthesis of 45S5 bioactive glass using an organic acid as catalyst.

PubMed

Faure, J; Drevet, R; Lemelle, A; Ben Jaber, N; Tara, A; El Btaouri, H; Benhayoune, H

2015-02-01

In this paper a new sol-gel approach was explored for the synthesis of the 45S5 bioactive glass. We demonstrate that citric acid can be used instead of the usual nitric acid to catalyze the sol-gel reactions. The substitution of nitric acid by citric acid allows to reduce strongly the concentration of the acid solution necessary to catalyze the hydrolysis of silicon and phosphorus alkoxides. Two sol-gel powders with chemical compositions very close to that of the 45S5 were obtained by using either a 2M nitric acid solution or either a 5mM citric acid solution. These powders were characterized and compared to the commercial Bioglass®. The surface properties of the two bioglass powders were assessed by scanning electron microscopy (SEM) and by Brunauer-Emmett-Teller method (BET). The Fourier transformed infrared spectroscopy (FTIR) and the X-ray diffraction (XRD) revealed a partial crystallization associated to the formation of crystalline phases on the two sol-gel powders. The in vitro bioactivity was then studied at the key times during the first hours of immersion into acellular Simulated Body Fluid (SBF). After 4h immersion into SBF we clearly demonstrate that the bioactivity level of the two sol-gel powders is similar and much higher than that of the commercial Bioglass®. This bioactivity improvement is associated to the increase of the porosity and the specific surface area of the powders synthesized by the sol-gel process. Moreover, the nitric acid is efficiently substituted by the citric acid to catalyze the sol-gel reactions without alteration of the bioactivity of the 45S5 bioactive glass. Copyright © 2014 Elsevier B.V. All rights reserved.

Organozinc Precursor-Derived Crystalline ZnO Nanoparticles: Synthesis, Characterization and Their Spectroscopic Properties.

PubMed

Liang, Yucang; Wicker, Susanne; Wang, Xiao; Erichsen, Egil Severin; Fu, Feng

2018-01-04

Crystalline ZnO -ROH and ZnO -OR (R = Me, Et, i Pr, n Bu) nanoparticles (NPs) have been successfully synthesized by the thermal decomposition of in-situ-formed organozinc complexes Zn(OR)₂ deriving from the reaction of Zn[N(SiMe₃)₂]₂ with ROH and of the freshly prepared Zn(OR)₂ under an identical condition, respectively. With increasing carbon chain length of alkyl alcohol, the thermal decomposition temperature and dispersibility of in-situ-formed intermediate zinc alkoxides in oleylamine markedly influenced the particle sizes of ZnO -ROH and its shape (sphere, plate-like aggregations), while a strong diffraction peak-broadening effect is observed with decreasing particle size. For ZnO -OR NPs, different particle sizes and various morphologies (hollow sphere or cuboid-like rod, solid sphere) are also observed. As a comparison, the calcination of the fresh-prepared Zn(OR)₂ generated ZnO -R NPs possessing the particle sizes of 5.4~34.1 nm. All crystalline ZnO nanoparticles are characterized using X-ray diffraction analysis, electron microscopy and solid-state ¹H and 13 C nuclear magnetic resonance (NMR) spectroscopy. The size effect caused by confinement of electrons' movement and the defect centres caused by unpaired electrons on oxygen vacancies or ionized impurity heteroatoms in the crystal lattices are monitored by UV-visible spectroscopy, electron paramagnetic resonance (EPR) and photoluminescent (PL) spectroscopy, respectively. Based on the types of defects determined by EPR signals and correspondingly defect-induced probably appeared PL peak position compared to actual obtained PL spectra, we find that it is difficult to establish a direct relationship between defect types and PL peak position, revealing the complication of the formation of defect types and photoluminescence properties.

Organozinc Precursor-Derived Crystalline ZnO Nanoparticles: Synthesis, Characterization and Their Spectroscopic Properties

PubMed Central

Wicker, Susanne; Wang, Xiao; Erichsen, Egil Severin; Fu, Feng

2018-01-01

Crystalline ZnO-ROH and ZnO-OR (R = Me, Et, iPr, nBu) nanoparticles (NPs) have been successfully synthesized by the thermal decomposition of in-situ-formed organozinc complexes Zn(OR)2 deriving from the reaction of Zn[N(SiMe3)2]2 with ROH and of the freshly prepared Zn(OR)2 under an identical condition, respectively. With increasing carbon chain length of alkyl alcohol, the thermal decomposition temperature and dispersibility of in-situ-formed intermediate zinc alkoxides in oleylamine markedly influenced the particle sizes of ZnO-ROH and its shape (sphere, plate-like aggregations), while a strong diffraction peak-broadening effect is observed with decreasing particle size. For ZnO-OR NPs, different particle sizes and various morphologies (hollow sphere or cuboid-like rod, solid sphere) are also observed. As a comparison, the calcination of the fresh-prepared Zn(OR)2 generated ZnO-R NPs possessing the particle sizes of 5.4~34.1 nm. All crystalline ZnO nanoparticles are characterized using X-ray diffraction analysis, electron microscopy and solid-state 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. The size effect caused by confinement of electrons’ movement and the defect centres caused by unpaired electrons on oxygen vacancies or ionized impurity heteroatoms in the crystal lattices are monitored by UV-visible spectroscopy, electron paramagnetic resonance (EPR) and photoluminescent (PL) spectroscopy, respectively. Based on the types of defects determined by EPR signals and correspondingly defect-induced probably appeared PL peak position compared to actual obtained PL spectra, we find that it is difficult to establish a direct relationship between defect types and PL peak position, revealing the complication of the formation of defect types and photoluminescence properties. PMID:29300343

Continuous Catalytic Production of Methyl Acrylates from Unsaturated Alcohols by Gold: The Strong Effect of C=C Unsaturation on Reaction Selectivity

DOE PAGES

Zugic, Branko; Karakalos, Stavros; Stowers, Kara J.; ...

2016-02-02

We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achievemore » comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work then provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.« less

Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Treadwell, LaRico J.; Boyle, Timothy J.; Phelan, W. Adam

2017-02-22

We synthesized a series of nickel(II) aryloxide ([Ni(OAr) 2(py) x]) precursors from an amide-alcohol exchange using [Ni(NR 2) 2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). Furthermore, the crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr) 2(py) x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excitedmore » states (singlet or triplet) and various geometries of 1–6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μ B consistent with a Ni 2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Finally, the materials isolated from 1 and 6 were found by TEM to form irregular shape nanomaterials (8–15 nm), which by PXRD were found to be Ni 0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.« less

A new route for the synthesis of titanium silicalite-1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasile, Aurelia, E-mail: aurelia_vasile@yahoo.com; Busuioc-Tomoiaga, Alina Maria; Catalysis Research Department, ChemPerformance SRL, Iasi 700337

2012-01-15

Graphical abstract: Well-prepared TS-1 was synthesized by an innovative procedure using inexpensive reagents such as fumed silica and TPABr as structure-directing agent. This is the first time when highly crystalline TS-1 is obtained in basic medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source has been prevented by titanium complexation with acetylacetone before structuring gel. Highlights: Black-Right-Pointing-Pointer TS-1 was obtained using cheap reagents as fumed silica and tetrapropylammonium bromide. Black-Right-Pointing-Pointer First time NaOH was used as source of OH{sup -} ions required for crystallization process. Black-Right-Pointing-Pointer The hydrolysis Ti alkoxides wasmore » controlled by Ti complexation with 2,4-pentanedione. -- Abstract: A new and efficient route using inexpensive reagents such as fumed silica and tetrapropylammonium bromide is proposed for the synthesis of titanium silicalite-1. High crystalline titanium silicalite-1 was obtained in alkaline medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source with formation of insoluble oxide species was prevented by titanium complexation with before structuring gel. The final solids were fully characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance, Raman and atomic absorption spectroscopies, as well as nitrogen sorption analysis. It was found that a molar ratio Ti:Si of about 0.04 in the initial reaction mixture is the upper limit to which well formed titanium silicalite-1 with channels free of crystalline or amorphous material can be obtained. Above this value, solids with MFI type structure containing both Ti isomorphously substituted in the network and extralattice anatase nanoparticles inside of channels is formed.« less

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

DOE PAGES

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

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 (AYO 2) nanomaterials. The reaction of yttrium amide ([Y(NR 2) 3] where R=Si(CH 3) 3) with four equivalents of H-ONep followed by addition of [A(NR 2)] (A=Li, Na, K) or A o (A o=Rb, Cs) led to the formation of a complex series of A nY(ONep) 3+n species, crystallographically identified as [Y 2Li 3(μ 3-ONep)(μ 3-HONep)(μ-ONep) 5(ONep) 3(HONep) 2] (1), [YNa 2(μ 3-ONep) 4(ONep)] 2 (2), {[Y 2K 3(μ 3-ONep) 3(μ-ONep) 4(ONep) 2(ηξ-tol) 2][Y 4K 2(μ 4-O)(μ 3-ONep) 8(ONep)more » 4]•η x-tol]} (3), [Y 4K 2(μ 4-O)(μ 3-ONep) 8(ONep) 4] (3a), [Y 2Rb 3(μ 4-ONep) 3(μ-ONep) 6] (4), and [Y 2Cs 4(μ 6-O)(μ 3-ONep) 6(μ 3-HONep) 2(ONep) 2(η x-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 were found by powder X-ray diffraction experiments to be Y 2O 3 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

Nano-casted Metal Oxide Aerogels as Dual Purpose Structural Components for Space Exploration

NASA Technical Reports Server (NTRS)

Vassilaras, Plousia E.

2004-01-01

NASA missions and space exploration rely on strong, ultra lightweight materials. Such materials are needed for building up past and present space vehicles such as the Sojourner Rover (1997) or the two MERs (2003), but also for a number of components and/or systems including thermal insulators, Solar Sails, Rigid Aeroshells, and Ballutes. The purpose of my internship here at Glenn Research Center is to make dual purpose materials; materials that in addition to being lightweight have electronic, photophysical and magnetic properties and, therefore, act as electronic components and sensors as well as structural components. One type of ultra lightweight material of great interest is aerogels, which have densities ranging from 0.003 g/cc to 0.8 g/cc . However, aerogels are extremely fragile and, as a result, have limited practical applications. Recently, Glenn Research Center has developed a process of nano-casting polymers onto the inorganic network of silica-based aerogels increasing the strength 300 fold while only increasing the density 3 fold. By combining the process of nano-casting polymers with inorganic oxide networks other than silica, we are actively pursuing lightweight dual purpose materials. To date, thirty different inorganic oxide aerogels have been prepared using either standard sol-gel chemistry or a non-alkoxide method involving metal chloride precursors and an epoxide; epichlorohydrin, propylene oxide or trimethylene oxide, as proton scavengers. More importantly, preliminary investigations show that the residual surface hydroxyl groups on each of these inorganic oxide aerogels can be successfully crosslinked with urethane. In addition to characterizing physical and mechanical properties such as density, strength and flexibility, each of these metal oxide aerogels are being characterized for thermal and electronic conductivity and magnetic and optical properties.

Characteristics and properties of nano-LiCoO2 synthesized by pre-organized single source precursors: Li-ion diffusivity, electrochemistry and biological assessment.

PubMed

Brog, Jean-Pierre; Crochet, Aurélien; Seydoux, Joël; Clift, Martin J D; Baichette, Benoît; Maharajan, Sivarajakumar; Barosova, Hana; Brodard, Pierre; Spodaryk, Mariana; Züttel, Andreas; Rothen-Rutishauser, Barbara; Kwon, Nam Hee; Fromm, Katharina M

2017-08-22

LiCoO 2 is one of the most used cathode materials in Li-ion batteries. Its conventional synthesis requires high temperature (>800 °C) and long heating time (>24 h) to obtain the micronscale rhombohedral layered high-temperature phase of LiCoO 2 (HT-LCO). Nanoscale HT-LCO is of interest to improve the battery performance as the lithium (Li + ) ion pathway is expected to be shorter in nanoparticles as compared to micron sized ones. Since batteries typically get recycled, the exposure to nanoparticles during this process needs to be evaluated. Several new single source precursors containing lithium (Li + ) and cobalt (Co 2+ ) ions, based on alkoxides and aryloxides have been structurally characterized and were thermally transformed into nanoscale HT-LCO at 450 °C within few hours. The size of the nanoparticles depends on the precursor, determining the electrochemical performance. The Li-ion diffusion coefficients of our LiCoO 2 nanoparticles improved at least by a factor of 10 compared to commercial one, while showing good reversibility upon charging and discharging. The hazard of occupational exposure to nanoparticles during battery recycling was investigated with an in vitro multicellular lung model. Our heterobimetallic single source precursors allow to dramatically reduce the production temperature and time for HT-LCO. The obtained nanoparticles of LiCoO 2 have faster kinetics for Li + insertion/extraction compared to microparticles. Overall, nano-sized LiCoO 2 particles indicate a lower cytotoxic and (pro-)inflammogenic potential in vitro compared to their micron-sized counterparts. However, nanoparticles aggregate in air and behave partially like microparticles.

Simultaneous determination of suspended particulate trace metals (Co, Ni, Cu, Zn, Cd and Pb) in seawater with small volume filtration assisted by microwave digestion and flow injection inductively coupled plasma mass spectrometer.

PubMed

Nakatsuka, Seiji; Okamura, Kei; Norisuye, Kazuhiro; Sohrin, Yoshiki

2007-06-26

A new technique for the determination of suspended particulate trace metals (P-metals >0.2 microm), such as Co, Ni, Cu, Zn, Cd and Pb, in open ocean seawater has been developed by using microwave digestion coupled with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS). Suspended particulate matter (SPM) was collected from 500 mL of seawater on a Nuclepore filter (0.2 microm) using a closed filtration system. Both the SPM and filter were completely dissolved by microwave digestion. Reagents for the digestion were evaporated using a clean evaporation system, and the metals were redissolved in 0.8 M HNO3. The solution was diluted with buffer solution to give pH 5.0 and the metals were determined by FI-ICP-MS using a chelating adsorbent of 8-hydroxyquinoline immobilized on fluorinated metal alkoxide glass (MAF-8HQ). The procedure blanks with a filter were found to be 0.048+/-0.008, 10.3+/-0.3, 0.27+/-0.05, 3.3+/-1.8, 0.02+/-0.03 and 0.85+/-0.09 ng L(-1) for Co, Ni, Cu, Zn, Cd and Pb, respectively (n=14). Detection limits defined as 3 times the standard deviation of the blanks were 0.023, 0.90, 0.14, 5.3, 0.078 and 0.28 ng L(-1) for Co, Ni, Cu, Zn, Cd and Pb, respectively. Accuracy was evaluated using certified reference materials of chlorella (NES CRM No. 3) and marine sediment (HISS-1). The method was applied to the determination of vertical distributions for P-Co, Ni, Cu, Zn, Cd and Pb in the Western North Pacific.

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

DOE PAGES

Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh; ...

2015-11-04

The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe 2) 4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe 2) n@MSN. Exhaustive characterization of Zr(NMe 2) n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe 2) 3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe 2) n@MSN material reacts with pinacolborane (HBpin) to provide Me 2NBpin and the material ZrH/Bpin@MSN thatmore » is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/ 2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D 2. The zirconium hydride material or the zirconium amide precursor Zr(NMe 2) n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eedugurala, Naresh; Wang, Zhuoran; Chaudhary, Umesh

The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe 2) 4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe 2) n@MSN. Exhaustive characterization of Zr(NMe 2) n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe 2) 3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe 2) n@MSN material reacts with pinacolborane (HBpin) to provide Me 2NBpin and the material ZrH/Bpin@MSN thatmore » is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/ 2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D 2. The zirconium hydride material or the zirconium amide precursor Zr(NMe 2) n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.« less

Carbonate formation within a nickel dimer: synthesis of a coordinatively unsaturated bis(mu-hydroxo) dinickel complex and its reactivity toward carbon dioxide.

PubMed

Wikstrom, Jeffrey P; Filatov, Alexander S; Mikhalyova, Elena A; Shatruk, Michael; Foxman, Bruce M; Rybak-Akimova, Elena V

2010-03-14

The tridentate aminopyridine ligand bearing a bulky tert-butyl substituent at the amine nitrogen, tert-butyl-dipicolylamine (tBuDPA), occupies three coordination sites in six-coordinate complexes of nickel(ii), leaving the remaining three sites available for additional ligand binding and activation. New crystallographically characterized complexes include two mononuclear species with 1:1 metal:ligand complexation: a trihydrate solvate (1.3H(2)O) and a monohydrate biacetonitrile solvate (1.H(2)O.2CH(3)CN). Complexation in the presence of sodium hydroxide results in a bis(mu-hydroxo) complex (2), the bridging hydroxide anions of which are labile and become displaced by methoxide anions in methanol solvent, affording bis-methoxo-bridged (4). Nickel(II) centers in 2 are five-coordinate and antiferromagnetically coupled (with J = -31.4(5) cm(-1), H = -2JS(1)S(2), in agreement with Ni-O-Ni angle of 103.7 degrees). Bridging hydroxide or alkoxide anions in coordinatively unsaturated dinuclear nickel(II) complexes with tBuDPA react as active nucleophiles. 2 readily performs carbon dioxide fixation, resulting in the formation of a bis(mu-carbonato) tetrameric complex (3), which features a novel binding geometry in the form of an inverted butterfly-type nickel-carbonate core. Temperature-dependent magnetic measurements of tetranuclear carbonato-bridged revealed relatively weak antiferromagnetic coupling (J(1) = -3.1(2) cm(-1)) between the two nickel centers in the core of the cluster, as well as weak antiferromagnetic pairwise interactions (J(2) = J(3) = -4.54(5) cm(-1)) between central and terminal nickel ions.

Fabrication of ceramic layer-by-layer infrared wavelength photonic band gap crystals

NASA Astrophysics Data System (ADS)

Kang, Henry Hao-Chuan

Photonic band gap (PBG) crystals, also known as photonic crystals, are periodic dielectric structures which form a photonic band gap that prohibit the propagation of electromagnetic (EM) waves of certain frequencies at any incident angles. Photonic crystals have several potential applications including zero-threshold semiconductor lasers, the inhibiting spontaneous emission, dielectric mirrors, and wavelength filters. If defect states are introduced in the crystals, light can be guided from one location to another or even a sharp bending of light in submicron scale can be achieved. This generates the potential for optical waveguide and optical circuits, which will contribute to the improvement in the fiber-optic communications and the development of high-speed computers. The goal of this dissertation research is to explore techniques for fabricating 3D ceramic layer-by-layer (LBL) photonic crystals operating in the infrared frequency range, and to characterize the infilling materials properties that affect the fabrication process as well as the structural and optical properties of the crystals. While various approaches have been reported in literature for the fabrication of LBL structure, the uniqueness of this work ties with its cost-efficiency and relatively short process span. Besides, very few works have been reported on fabricating ceramic LBL crystals at mid-IR frequency range so far. The fabrication techniques reported here are mainly based on the concepts of microtransfer molding with the use of polydimethyl siloxane (PDMS) as molds/stamps. The infilling materials studied include titanium alkoxide precursors and aqueous suspensions of nanosize titania particles (slurries). Various infilling materials were synthesized to determine viscosities, effects on drying and firing shrinkages, effects on film surface roughness, and their moldability. Crystallization and phase transformation of the materials were also monitored using DTA, TGA and XRD. Mutilayer crystal structures of 2.5 and 1.0 mum periodicity have been successfully built. The structures of the fabricated crystals are inspected with scanning electron microscopy (SEM) and the optical characteristics are examined with optical microscopy and FtIR spectroscopy.

Evidence for proton tunneling and a transient covalent flavin-substrate adduct in choline oxidase S101A.

PubMed

Uluisik, Rizvan; Romero, Elvira; Gadda, Giovanni

2017-11-01

The effect of temperature on the reaction of alcohol oxidation catalyzed by choline oxidase was investigated with the S101A variant of choline oxidase. Anaerobic enzyme reduction in a stopped-flow spectrophotometer was biphasic using either choline or 1,2-[ 2 H 4 ]-choline as a substrate. The limiting rate constants k lim1 and k lim2 at saturating substrate were well separated (k lim1 /k lim2 >9), and were >15-fold slower than for wild-type choline oxidase. Solvent deuterium kinetic isotope effects (KIEs) ~4 established that k lim1 probes the proton transfer from the substrate hydroxyl to a catalytic base. Primary substrate deuterium KIEs ≥7 demonstrated that k lim2 reports on hydride transfer from the choline alkoxide to the flavin. Between 15°C and 39°C the k lim1 and k lim2 values increased with increasing temperature, allowing for the analyses of H + and H - transfers using Eyring and Arrhenius formalisms. Temperature-independent KIE on the k lim1 value ( H2O k lim1 / D2O k lim1 ) suggests that proton transfer occurs within a highly reorganized tunneling-ready-state with a narrow distribution of donor-acceptor distances. Eyring analysis of the k lim2 value gave lines with the slope (choline) >slope (D-choline) , suggesting kinetic complexity. Spectral evidence for the transient occurrence of a covalent flavin-substrate adduct during the first phase of the anaerobic reaction of S101A CHO with choline is presented, supporting the notion that an important role of amino acid residues in the active site of flavin-dependent enzymes is to eliminate alternative reactions of the versatile enzyme-bound flavin for the reaction that needs to be catalyzed. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, characterization and single crystal structures of chiral Schiff base and its tetranuclear palladium complex with Pdsbnd Osbnd Pd bridging and Pdsbnd Pd bonds

NASA Astrophysics Data System (ADS)

Rajegowda, H. R.; Kumar, P. Raghavendra; Hosamani, Amar; Butcher, R. J.; Naveen, S.; Lokanath, N. K.

2018-03-01

A new chiral Schiff base ligand 2-{N-[(2S)-(1-hydroxy-3-phenylpropan-2-yl]ethanimidoyl} phenol ((S)sbnd H2L) was obtained by acid catalyzed condensation of (2S)-(-)-2-amino-3-phenyl-1-propanol with 2‧-hydroxyacetophenone. The palladium complex was prepared by treating a solution of (S)sbnd H2L in acetone with a solution of Na2PdCl4 in water in 1:1 M ratio. The new ligand and its complex were characterized by FT-IR, 1H, 13C{1H} NMR spectroscopy, polarimetry and elemental analysis and their molecular structures were determined by single crystal X-ray diffraction. Both the compounds crystallizes in monoclinic system in the space group P21. There exists an intra [Osbnd H ⋯N (1.62(5) Å)] and intermolecular [Osbnd H ⋯O (1.53(5) Å) and Csbnd H ⋯O (2.59 Å)] hydrogen bonding and secondary interactions in the crystal of (S)sbnd H2L. The structure of the palladium complex was found very interesting wherein the ligand coordinated to metal center as tridentate dianionic (O-, N, O-) fashion, (S)-L, resulting in a tetranuclear palladium cluster, [Pd4((S)-L)4]. In these supramolecular structures phenolate oxygen coordinated to Pd(II) ion as Pdsbnd O terminal bonds [1.934(12) - 1.977(11) Å] and the alkoxide oxygen coordinated as Pdsbnd Osbnd Pd bridging bonds [1.993(11) - 2.012(12) Å]. The Pdsbnd N bond lengths found were in the range of 1.949(13) to 1.919(12) Å. There exists two asymmetric tetranuclear complex molecules in its crystal lattice. There exists very strong metal-metal bond interaction, Pd(2)sbnd Pd(3) [3.0410(18) Å] and Pd(6)sbnd Pd(7) [3.0517(19) Å] respectively in the two asymmetric units.

Using the water signal to detect invisible exchanging protons in the catalytic triad of a serine protease

PubMed Central

Lauzon, Carolyn B.; van Zijl, Peter; Stivers, James T.

2011-01-01

Chemical Exchange Saturation Transfer (CEST) is an MRI approach that can indirectly detect exchange broadened protons that are invisible in traditional NMR spectra. We modified the CEST pulse sequence for use on high-resolution spectrometers and developed a quantitative approach for measuring exchange rates based upon CEST spectra. This new methodology was applied to the rapidly exchanging Hδ1 and Hε2 protons of His57 in the catalytic triad of bovine chymotrypsinogen-A (bCT-A). CEST enabled observation of Hε2 at neutral pH values, and also allowed measurement of solvent exchange rates for His57-Hδ1 and His57-Hε2 across a wide pH range (3–10). Hδ1 exchange was only dependent upon the charge state of the His57 (kex,Im+ = 470 s−1, kex,Im = 50 s−1), while Hε2 exchange was found to be catalyzed by hydroxide ion and phosphate base (kOH− = 1.7 × 1010 M−1s−1, kHPO42−=1.7×106M−1s−1), reflecting its greater exposure to solute catalysts. Concomitant with the disappearance of the Hε2 signal as the pH was increased above its pKa, was the appearance of a novel signal (δ = 12 ppm), which we assigned to Hγ of the nearby Ser195 nucleophile, that is hydrogen bonded to Nε2 of neutral His57. The chemical shift of Hγ is about 7 ppm downfield from a typical hydroxyl proton, suggesting a highly polarized O-Hγ bond. The significant alkoxide character of Oγ indicates that Ser195 is preactivated for nucleophilic attack before substrate binding. CEST should be generally useful for mechanistic investigations of many enzymes with labile protons involved in active site chemistry. PMID:21809183

Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

PubMed

Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

2017-12-06

Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 < MoF 3 < MoF 6 before sharply decreasing for MoF 9 , with a similar effect for the supported systems (MoF 0 ≈ MoF 9 < MoF 6 < MoF 3 ). This is consistent with the different kinetic behavior (zeroth order in alkyne for MoF 9 derivatives instead of first order for the others) and the isolation of stable metallacyclobutadiene intermediates of MoF 9 for both molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

Preparation and characterization of bio-diesels from various bio-oils.

PubMed

Lang, X; Dalai, A K; Bakhshi, N N; Reaney, M J; Hertz, P B

2001-10-01

Methyl, ethyl, 2-propyl and butyl esters were prepared from canola and linseed oils through transesterification using KOH and/ or sodium alkoxides as catalysts. In addition, methyl and ethyl esters were prepared from rapeseed and sunflower oils using the same catalysts. Chemical composition of the esters was determined by HPLC for the class of lipids and by GC for fatty acid compositions. The bio-diesel esters were characterized for their physical and fuel properties including density, viscosity, iodine value, acid value, cloud point, pure point, gross heat of combustion and volatility. Methyl and ethyl esters prepared from a particular vegetable oil had similar viscosities, cloud points and pour points, whereas methyl, ethyl, 2-propyl and butyl esters derived from a particular vegetable oil had similar gross heating values. However, their densities, which were 2 7% higher than those of diesel fuels, statistically decreased in the order of methyl approximately 2-propyl > ethyl > butyl esters. Butyl esters showed reduced cloud points (-6 degrees C to -10 degrees C) and pour points (-13 degrees C to -16 degrees C) similar to those of summer diesel fuel having cloud and pour points of -8 degrees C and -15 degrees C, respectively. The viscosities of bio-diesels (3.3-7.6 x 10(-4) Pa s at 40 degrees C) were much less than those of pure oils (22.4-45.1 x 10(-4) Pa s at 40 degrees C) and were twice those of summer and winter diesel fuels (3.50 and 1.72 x 10(-4) Pa s at 40 degrees C), and their gross heat contents of approximately 40 MJ/kg were 11% less than those of diesel fuels (approximately 45 MJ/kg). For different esters from the same vegetable oil, methyl esters were the most volatile, and the volatility decreased as the alkyl group grew bulkier. However, the bio-diesels were considerably less volatile than the conventional diesel fuels.

Sol-gel approach to in situ creation of high pH-resistant surface-bonded organic-inorganic hybrid zirconia coating for capillary microextraction (in-tube SPME).

PubMed

Alhooshani, Khalid; Kim, Tae-Young; Kabir, Abuzar; Malik, Abdul

2005-01-07

A novel zirconia-based hybrid organic-inorganic sol-gel coating was developed for capillary microextraction (CME) (in-tube SPME). High degree of chemical inertness inherent in zirconia makes it very difficult to covalently bind a suitable organic ligand to its surface. In the present work, this problem was addressed from a sol-gel chemistry point of view. Principles of sol-gel chemistry were employed to chemically bind a hydroxy-terminated silicone polymer (polydimethyldiphenylsiloxane, PDMDPS) to a sol-gel zirconia network in the course of its evolution from a highly reactive alkoxide precursor undergoing controlled hydrolytic polycondensation reactions. A fused silica capillary was filled with a properly designed sol solution to allow for the sol-gel reactions to take place within the capillary for a predetermined period of time (typically 15-30 min). In the course of this process, a layer of the evolving hybrid organic-inorganic sol-gel polymer got chemically anchored to the silanol groups on the capillary inner walls via condensation reaction. At the end of this in-capillary residence time, the unbonded part of the sol solution was expelled from the capillary under helium pressure, leaving behind a chemically bonded sol-gel zirconia-PDMDPS coating on the inner walls. Polycyclic aromatic hydrocarbons, ketones, and aldehydes were efficiently extracted and preconcentrated from dilute aqueous samples using sol-gel zirconia-PDMDPS coated capillaries followed by thermal desorption and GC analysis of the extracted solutes. The newly developed sol-gel hybrid zirconia coatings demonstrated excellent pH stability, and retained the extraction characteristics intact even after continuous rinsing with a 0.1 M NaOH solution for 24 h. To our knowledge, this is the first report on the use of a sol-gel zirconia-based hybrid organic-inorganic coating as an extraction medium in solid phase microextraction (SPME).

Atomic-Resolution Structures of Horse Liver Alcohol Dehydrogenase with NAD[superscript +] and Fluoroalcohols Define Strained Michaelis Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plapp, Bryce V.; Ramaswamy, S.; Iowa)

2013-01-16

Structures of horse liver alcohol dehydrogenase complexed with NAD{sup +} and unreactive substrate analogues, 2,2,2-trifluoroethanol or 2,3,4,5,6-pentafluorobenzyl alcohol, were determined at 100 K at 1.12 or 1.14 {angstrom} resolution, providing estimates of atomic positions with overall errors of 0.02 {angstrom}, the geometry of ligand binding, descriptions of alternative conformations of amino acid residues and waters, and evidence of a strained nicotinamide ring. The four independent subunits from the two homodimeric structures differ only slightly in the peptide backbone conformation. Alternative conformations for amino acid side chains were identified for 50 of the 748 residues in each complex, and Leu-57 andmore » Leu-116 adopt different conformations to accommodate the different alcohols at the active site. Each fluoroalcohol occupies one position, and the fluorines of the alcohols are well-resolved. These structures closely resemble the expected Michaelis complexes with the pro-R hydrogens of the methylene carbons of the alcohols directed toward the re face of C4N of the nicotinamide rings with a C-C distance of 3.40 {angstrom}. The oxygens of the alcohols are ligated to the catalytic zinc at a distance expected for a zinc alkoxide (1.96 {angstrom}) and participate in a low-barrier hydrogen bond (2.52 {angstrom}) with the hydroxyl group of Ser-48 in a proton relay system. As determined by X-ray refinement with no restraints on bond distances and planarity, the nicotinamide rings in the two complexes are slightly puckered (quasi-boat conformation, with torsion angles of 5.9{sup o} for C4N and 4.8{sup o} for N1N relative to the plane of the other atoms) and have bond distances that are somewhat different compared to those found for NAD(P){sup +}. It appears that the nicotinamide ring is strained toward the transition state on the path to alcohol oxidation.« less

Heterodinuclear titanium/zinc catalysis: synthesis, characterization and activity for CO2/epoxide copolymerization and cyclic ester polymerization.

PubMed

Garden, Jennifer A; White, Andrew J P; Williams, Charlotte K

2017-02-21

The preparation of heterodinuclear complexes, especially those comprising early-late transition metals coordinated by a simple or symmetrical ancillary ligand, represents a fundamental challenge and an opportunity to prepare catalysts benefitting from synergic properties. Here, two new mixed titanium(iv)-zinc(ii) complexes, [LTi(O i Pr) 2 ZnEt] and [LTi(O i Pr) 2 ZnPh], both coordinated by a diphenolate tetra(amine) macrocyclic ligand (L), are prepared. The synthesis benefits from the discovery that reaction of the ligand with a single equivalent of titanium tetrakis(iso-propoxide) allows the efficient formation of a mono-Ti(iv) complex, [LTi(O i Pr) 2 ]. All new complexes are characterized by a combination of single crystal X-ray diffraction, multinuclear NMR spectroscopy and mass spectrometry techniques. The two heterobimetallic complexes, [LTi(O i Pr) 2 ZnEt] and [LTi(O i Pr) 2 ZnPh], feature trianionic coordination by the macrocyclic ligand and bridging alkoxide groups coordinate to both the different metal centres. The heterodinuclear catalysts are compared to the mono-titanium analogue, [LTi(O i Pr) 2 ], in various polymerization reactions. In the alternating copolymerizations of carbon dioxide and cyclohexene oxide, the mono-titanium complex is totally inactive whilst the heterodinuclear complexes show moderate activity (TOF = 3 h -1 ); it should be noted the activity is measured using just 1 bar pressure of carbon dioxide. In the ring opening polymerization of lactide and ε-caprolactone, the mono-Ti(iv) complex is totally inactive whilst the heterodinuclear complexes show moderate-high activities, qualified by comparison to other known titanium polymerization catalysts (l-lactide, k obs = 11 × 10 -4 s -1 at 70 °C, 1 M in [lactide]) and ε-caprolactone (k obs = 5 × 10 -4 s -1 at 70 °C, 0.9 M in [ε-caprolactone]).

In situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion as potential electrode materials for energy applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mombrú, Dominique; Romero, Mariano, E-mail: mromero@fq.edu.uy; Faccio, Ricardo, E-mail: rfaccio@fq.edu.uy

In situ preparation of polyaniline-ceramic nanocomposites has recently demonstrated that the electrical properties are highly improved with respect to the typical ex situ preparations. In this report, we present for the first time, to the best of our knowledge, the in situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion as an easily adaptable route to prepare other ceramic-polymer nanocomposites. The main relevance of this method is the possibility to prepare ceramic quantum dots from alkoxide precursors using water vapor flow into any hydrophobic polymer host and to achieve good homogeneity and size-control. Inmore » addition, we perform full characterization by means of high-resolution transmission electron microscopy, X-ray powder diffraction, small angle X-ray scattering, thermogravimetric and calorimetric analyses, confocal Raman microscopy and impedance spectroscopy analyses. The presence of the polymer host and interparticle Coulomb repulsive interactions was evaluated as an influence for the formation of ~3–8 nm equally-sized quantum dots independently of the concentration. The polyaniline polaron population showed an increase for the quantum dots diluted regime and the suppression at the concentrated regime, ascribed to the formation of chemical bonds at the interface, which was confirmed by theoretical simulations. In agreement with the previous observation, the in situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion could be very useful as a novel approach to prepare electrode materials for energy conversion and storage applications. - Highlights: • In situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion. • Polyaniline charge carriers at the interface and charge interactions between quantum dots. • Easy extrapolation to sol-gel derived quantum dots into polymer host as potential electrode materials.« less

Sol-Gel Precursors for Ceramics from Minerals Simulating Soils from the Moon and Mars

NASA Technical Reports Server (NTRS)

Sibille, Laurent; Gavira-Gallardo, Jose-Antonio; Hourlier-Bahloul, Djamila

2003-01-01

Recent NASA mission plans for the human exploration of our Solar System has set new priorities for research and development of technologies necessary to enable a long-term human presence on the Moon and Mars. The recovery and processing of metals and oxides from mineral sources on other planets is under study to enable use of ceramics, glasses and metals by explorer outposts. We report some preliminary results on the production of sol-gel precursors for ceramic products using mineral resources available in Martian or Lunar soil. The presence of SiO2, TiO2, and A12O3 in both Martian (44 wt.% SiO2, 1 wt.% TiO2, 7 wt.% Al2O3) and Lunar (48 wt.% SiO2, 1.5 wt.% TiO2, 16 wt.% Al2O3) soils and the recent developments in chemical processes to solubilize silicates using organic reagents and relatively little energy indicate that such an endeavor is possible. In order to eliminate the risks involved in the use of hydrofluoric acid to dissolve silicates, two distinct chemical routes are investigated to obtain soluble silicon oxide precursors from Lunar and Martian simulant soils. Clear sol-gel precursors have been obtained by dissolution of silica from Lunar simulant soil in basic ethylene glycol (C2H4(OH)2) solutions to form silicon glycolates. Thermogravimetric Analysis and X-ray Photoelectron Spectroscopy were used to characterize the elemental composition and structure of the precursor molecules. Further concentration and hydrolysis of the products was performed to obtain gel materials for evaluation as ceramic precursors. In the second set of experiments, we used the same starting materials to synthesize silicate esters in acidified alcohol mixtures. Preliminary results indicate the presence of silicon alkoxides in the product of distillation.

A two-metal ion mechanism operates in the hammerhead ribozyme-mediated cleavage of an RNA substrate

PubMed Central

Lott, William B.; Pontius, Brian W.; von Hippel, Peter H.

1998-01-01

Evidence for a two-metal ion mechanism for cleavage of the HH16 hammerhead ribozyme is provided by monitoring the rate of cleavage of the RNA substrate as a function of La3+ concentration in the presence of a constant concentration of Mg2+. We show that a bell-shaped curve of cleavage activation is obtained as La3+ is added in micromolar concentrations in the presence of 8 mM Mg2+, with a maximal rate of cleavage being attained in the presence of 3 μM La3+. These results show that two-metal ion binding sites on the ribozyme regulate the rate of the cleavage reaction and, on the basis of earlier estimates of the Kd values for Mg2+ of 3.5 mM and >50 mM, that these sites bind La3+ with estimated Kd values of 0.9 and >37.5 μM, respectively. Furthermore, given the very different effects of these metal ions at the two binding sites, with displacement of Mg2+ by La3+ at the stronger (relative to Mg2+) binding site activating catalysis and displacement of Mg2+ by La3+ at the weaker (relative to Mg2+) (relative to Mg2+) binding site inhibiting catalysis, we show that the metal ions at these two sites play very different roles. We argue that the metal ion at binding site 1 coordinates the attacking 2′-oxygen species in the reaction and lowers the pKa of the attached proton, thereby increasing the concentration of the attacking alkoxide nucleophile in an equilibrium process. In contrast, the role of the metal ion at binding site 2 is to catalyze the reaction by absorbing the negative charge that accumulates at the leaving 5′-oxygen in the transition state. We suggest structural reasons why the Mg2+–La3+ ion combination is particularly suited to demonstrating these different roles of the two-metal ions in the ribozyme cleavage reaction. PMID:9435228

Layered Lepidocrocite Type Structure Isolated by Revisiting the Sol–Gel Chemistry of Anatase TiO 2 : A New Anode Material for Batteries

DOE PAGES

Ma, Jiwei; Reeves, Kyle G.; Porras Gutierrez, Ana-Gabriela; ...

2017-09-19

Searches for new electrode materials for batteries must comply on financial and environmental costs to be useful in practical devices. The sol-gel chemistry has been widely used to design and implemented new concepts for the emergence of advanced materials such as hydride organic-inorganic composites. Here, we show that the simple reaction system including titanium alkoxide and water can be used to stabilize a new class of electrode materials. By investigating the crystallization path of anatase TiO2, an X-ray amorphous intermediate phase has been identified whose local structure probed by the pair distribution function, 1H solid-state NMR and DFT calculations, consistsmore » of a layered-type structure as found in the lepido-crocite. This phase presents the following general formula Ti 2-x⟂ xO 4-4x(OH) 4x.nH 2O (x ~ 0.5) where the substitution of oxide by hydroxide anions leads to the formation of titanium vacancies (•) and H 2O molecules are located in interlayers. Solid-state 1H NMR has enabled to characterize three main hydroxide environments that are Ti⟂-OH, Ti 2⟂ 2-OH and Ti3⟂-OH and layered H 2O molecules. The electrochemical properties of this phase were further investigated versus lithium and is shown to be very promising with reversible capacities of around 200 mAh.g -1 and an operating voltage of 1.55 V. We further showed that the lithium intercalation proceeds via a solid-solution mechanism. 7Li solid-state NMR and DFT calculations allowed to identify lithium host sites that are located at the titanium vacancies and interlayer space with lithium being solvated by structural water molecules. The easy fabrication, the absence of lithium and easier recycling and the encouraging properties makes this class of materials very attractive for competitive electrodes for batteries. We thus demonstrate that the revisit of an “old” chemistry with advanced characterization tools allows discovering new materials of technological relevance.« less

Thin sol-gel-derived silica coatings on dental pure titanium casting.

PubMed

Yoshida, K; Kamada, K; Sato, K; Hatada, R; Baba, K; Atsuta, M

1999-01-01

The sol-gel dipping process, in which liquid silicon alkoxide is transformed into a solid silicon-oxygen network, can produce a thin film coating of silica (SiO(2)). The features of this method are high homogeneity and purity of the thin SiO(2) film and a low sinter temperature, which are important in the preparation of coating films that can protect metallic ion release from the metal substrate and prevent attachment of dental plaque. We evaluated the surface properties of dental pure titanium casting coated with a thin SiO(2) or SiO(2)/F-hybrid film by the sol-gel dipping process. The metal specimens were pretreated by dipping in isopropylalcohol solution containing 10 wt% 3-aminopropyl trimethoxysilane and treated by dipping in the silica precursor solution for 5 min, withdrawal at a speed of 2 mm/min, air-drying for 20 min at room temperature, heating at 120 degrees C for 20 min, and then storing at room temperature. Both SiO(2) and SiO(2)/F films bonded strongly (above 55 MPa) to pure titanium substrate by a tensile test. SiO(2(-)) and SiO(2)/F-coated specimens immersed in 1 wt% of lactic acid solution for two weeks showed significantly less release of titanium ions (30. 5 ppb/cm(2) and 9.5 ppb/cm(2), respectively) from the substrate than noncoated specimens (235.2 ppb/cm(2)). Hydrophobilization of SiO(2(-)) and SiO(2)/F-coated surfaces resulted in significant increases of contact angle of water (81.6 degrees and 105.7 degrees, respectively) compared with noncoated metal specimens (62.1 degrees ). The formation of both thin SiO(2) and SiO(2)/F-hybrid films by the sol-gel dipping process on the surface of dental pure titanium casting may be useful clinically in enhancing the bond strength of dental resin cements to titanium, preventing titanium ions release from the substrate, and reducing the accumulation of dental plaque attaching to intraoral dental restorations. Copyright 1999 John Wiley & Sons, Inc.

Protective performances of two anti-graffiti treatments towards sulfite and sulfate formation in SO 2 polluted model environment

NASA Astrophysics Data System (ADS)

Carmona-Quiroga, Paula María; Panas, Itai; Svensson, Jan-Erik; Johansson, Lars-Gunnar; Blanco-Varela, María Teresa; Martínez-Ramírez, Sagrario

2010-11-01

Specific strategies for protection are being developed to counter both the staining and corrosive effects of polluted air in cities, as well as to allow for efficient removal of unwanted graffiti paintings. These protection strategies employ molecules with tailored functionalities, e.g. being hydrophobic, while maintaining porosity for molecular water vapour permeation. The present study employs SO 2 and water to probe the behaviors of two anti-graffiti treatments, a water-base fluoroalkylsiloxane ("Protectosil Antigraffiti" marketed by Degussa) and an organically modified silicate (Ormosil) synthesized from a polymer chain (polydimethyl siloxane, PDMS) and two network forming alkoxides (Zr propoxide and methyl triethoxy silane, MTES) dissolved in n-propanol, on five building materials, comprising limestone, aged lime mortar, hydrated cement mortar, granite, and brick material. The materials were exposed to a synthetic atmosphere for 20 h in a climate chamber, 0.78 ± 0.03 ppm of SO 2 and 95% RH. Diffuse reflectance Fourier transform infrared (DR-FTIR) spectra were registered before and after exposure in the climate chamber in the cases of both treated and untreated samples. DR-FTIR, scanning electron microscope (SEM) images and energy dispersive X-ray (EDX) analyses, suggest the anti-graffiti Ormosil to suppress formation of calcium sulfite hemihydrate (the primary initial product of the reaction of calcium compounds with SO 2 and water) on carbonate materials (limestone and lime mortar). In case of the granite, brick and cement mortar, Ormosil has a negligible influence on the SO 2 capture. While no sulfite formation was detected by DR-FTIR, gypsum is inferred to form due to metal oxides and minority compounds catalysed oxidation of sulfite to sulfate. In case of brick, this understanding finds support from SEM images as well as EDX. A priori presence of gypsum in hydrated cement mortars prevents positive identification by SEM. However, support for sulfur accumulation in hydrated cement mortar is provided by means of EDX. In case of a second anti-graffiti considered, Protectosil, no influence of the anti-graffiti treatment on the SO 2 uptake of any of the building materials was observed.

Layered Lepidocrocite Type Structure Isolated by Revisiting the Sol–Gel Chemistry of Anatase TiO 2 : A New Anode Material for Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Jiwei; Reeves, Kyle G.; Porras Gutierrez, Ana-Gabriela

Searches for new electrode materials for batteries must comply on financial and environmental costs to be useful in practical devices. The sol-gel chemistry has been widely used to design and implemented new concepts for the emergence of advanced materials such as hydride organic-inorganic composites. Here, we show that the simple reaction system including titanium alkoxide and water can be used to stabilize a new class of electrode materials. By investigating the crystallization path of anatase TiO2, an X-ray amorphous intermediate phase has been identified whose local structure probed by the pair distribution function, 1H solid-state NMR and DFT calculations, consistsmore » of a layered-type structure as found in the lepido-crocite. This phase presents the following general formula Ti 2-x⟂ xO 4-4x(OH) 4x.nH 2O (x ~ 0.5) where the substitution of oxide by hydroxide anions leads to the formation of titanium vacancies (•) and H 2O molecules are located in interlayers. Solid-state 1H NMR has enabled to characterize three main hydroxide environments that are Ti⟂-OH, Ti 2⟂ 2-OH and Ti3⟂-OH and layered H 2O molecules. The electrochemical properties of this phase were further investigated versus lithium and is shown to be very promising with reversible capacities of around 200 mAh.g -1 and an operating voltage of 1.55 V. We further showed that the lithium intercalation proceeds via a solid-solution mechanism. 7Li solid-state NMR and DFT calculations allowed to identify lithium host sites that are located at the titanium vacancies and interlayer space with lithium being solvated by structural water molecules. The easy fabrication, the absence of lithium and easier recycling and the encouraging properties makes this class of materials very attractive for competitive electrodes for batteries. We thus demonstrate that the revisit of an “old” chemistry with advanced characterization tools allows discovering new materials of technological relevance.« less

Analytical chemistry at the interface between materials science and biology

NASA Astrophysics Data System (ADS)

O'Brien, Janese Christine

This work describes several research efforts that lie at the new interfaces between analytical chemistry and other disciplines, namely materials science and biology. In the materials science realm, the search for new materials that may have useful or unique chromatographic properties motivated the synthesis and characterization of electrically conductive sol-gels. In the biology realm, the search for new surface fabrication schemes that would permit or even improve the detection of specific biological reactions motivated the design of miniaturized biological arrays. Collectively, this work represents some of analytical chemistry's newest forays into these disciplines. This dissertation is divided into six chapters. Chapter 1 is an introductory chapter that provides background information pertinent to several key aspects of the work contained in this dissertation. Chapter 2 describes the synthesis and characterization of electrically conductive sol-gels derived from the acid-catalyzed hydrolysis of a vanadium alkoxide. Specifically, this chapter describes our attempts to increase the conductivity of vanadium sol-gels by optimizing the acidic and drying conditions used during synthesis. Chapter 3 reports the construction of novel antigenic immunosensing platforms of increased epitope density using Fab'-SH antibody fragments on gold. Here, X-ray photoelectron spectroscopy (XPS), thin-layer cell (TLC) and confocal fluorescence spectroscopies, and scanning force microscopy (SFM) are employed to characterize the fragment-substrate interaction, to quantify epitope density, and to demonstrate fragment viability and specificity. Chapter 4 presents a novel method for creating and interrogating double-stranded DNA (dsDNA) microarrays suitable for screening protein:dsDNA interactions. Using the restriction enzyme ECoR1, we demonstrate the ability of the atomic force microscope (AFM) to detect changes in topography that result from the enzymatic cleavage of dsDNA microarrays containing the correct recognition sequence. Chapter 5 explores more fully the microarray fabrication process described in Chapter 4. Specifically, experiments characterizing the effect of deposition conditions on oligonucleotide topography and as well as those that describe array density optimization are presented. Chapter 6 presents general conclusions from the work recorded in this dissertation and speculates on its extension.

The Domestication of ortho-Quinone Methides

PubMed Central

2015-01-01

Conspectus An ortho-quinone methide (o-QM) is a highly reactive chemical motif harnessed by nature for a variety of purposes. Given its extraordinary reactivity and biological importance, it is surprising how few applications within organic synthesis exist. We speculate that their widespread use has been slowed by the complications that surround the preparation of their precursors, the harsh generation methods, and the omission of this stratagem from computer databases due to its ephemeral nature. About a decade ago, we discovered a mild anionic triggering procedure to generate transitory o-QMs at low temperature from readily available salicylaldehydes, particularly OBoc derivatives. This novel reaction cascade included both the o-QM formation and the subsequent consumption reaction. The overall transformation was initiated by the addition of the organometallic reagent, usually a Grignard reagent, which resulted in the formation of a benzyloxy alkoxide. Boc migration from the neighboring phenol produced a magnesium phenoxide that we supposed underwent β-elimination of the transferred Boc residue to form an o-QM for immediate further reactions. Moreover, the cascade proved controllable through careful manipulation of metallic and temperature levers so that it could be paused, stopped, or restarted at various intermediates and stages. This new level of domestication enabled us to deploy o-QMs for the first time in a range of applications including diastereocontrolled reactions. This sequence ultimately could be performed in either multipot or single pot processes. The subsequent reaction of the fleeting o-QM intermediates included the 1,4-conjugate additions that led to unbranched or branched ortho-alkyl substituted phenols and Diels–Alder reactions that provided 4-unsubstituted or 4-substituted benzopyrans and chroman ketals. The latter cycloadducts were obtained for the first time with outstanding diastereocontrol. In addition, the steric effects of the newly created stereocenters in subsequent reactions of chroman ketals and acetals were studied and proved predictable. Through the use of a chiral auxiliary, Diels–Alder products were deployed in numerous enantioselective reactions including several complex natural products syntheses. In this Account, we summarize our efforts, which we hope have contributed to the synthetic renaissance for this venerable species. PMID:25469551

Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions.

PubMed

Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Zhiping; Nichol, Gary; Huang, Rong-Bin; Zheng, Lan-Sun

2008-04-07

Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.

Optical properties of Na2O-TiO2-SiO2 glass films prepared by the sol-gel method

NASA Astrophysics Data System (ADS)

Barton, Ivo; Matejec, Vlastimil; Mrazek, Jan; Predoana, Luminita; Zaharescu, Maria

2017-12-01

Layers based on TiO2-SiO2 systems fabricated by sol-gel method have been investigated for the preparation of planar waveguides, antireflective coatings, Bragg mirrors, etc. However, at high titania contents such materials exhibit high viscosities and tendency to phase separation. In this paper we present optical properties of films containing TiO2 which are prepared via a novel approach sol-gel on the basis of ternary Na2O-TiO2-SiO2 glasses and which can exhibit lower viscosities. Films of Na2O-TiO2-SiO2 systems were prepared from input sols mixed of silica, titania and sodium oxide sols. The silica sol was prepared from tetraethyl orthosilicate (TEOS), ethanol, hydrochloric acid and water, with a TEOS c= 2 mol/l and water/alkoxide ratio 1.75. The titania sol was mixed from titanium tetraisopropoxide (TiPr), propan-2-ol, nitric acid and water, c= 0.5 mol/l, RW= 0.42. The sodium oxide sols with c= 0.474 mol/l were prepared from sodium ethoxide and ethanol. Input sols were prepared by mixing the silica and titania sols first and then the sodium sol was added. The input sols were aged for one hour. Stable input sols were obtained. The input sols were deposited on glass and silica slides by dip-coating technique at a withdrawing speeds of 200 mm/min. Applied gel layers were thermally treated at temperatures of 450 and 900°C. Layers containing sodium oxide and titania in concentration ranges of 0-20 mol.% and 0-30 mol.% respectively have been fabricated. Optical properties of layers were determined by UV-VIS-NIR transmission and reflection spectrophotometry. Refractive indices of layers were determined by spectral ellipsometry and from transmission spectra. Optical properties were correlated with results of XRD spectroscopy, optical microscopy, and atomic force microscopy. Transparent homogenous films with a maximum refractive index of 1.61 at a wavelength of 600 nm have been obtained.

Probing the mer- to fac-isomerization of tris-cyclometallated homo- and heteroleptic (C,N)3 iridium(III) complexes.

PubMed

McDonald, Aidan R; Lutz, Martin; von Chrzanowski, Lars S; van Klink, Gerard P M; Spek, Anthony L; van Koten, Gerard

2008-08-04

We have developed techniques which allow for covalent tethering, via a "hetero" cyclometallating ligand, of heteroleptic tris-cyclometallated iridium(III) complexes to polymeric supports (for application in light-emitting diode technologies). This involved the selective synthesis and thorough characterization of heteroleptic [Ir(C,N) 2(C',N')] tris-cyclometallated iridium(III) complexes. Furthermore, the synthesis and characterization of heteroleptic [Ir(C,N) 2OR] complexes is presented. Under standard thermal conditions for the synthesis of the facial ( fac) isomer of tris-cyclometallated complexes, it was not possible to synthesize pure heteroleptic complexes of the form [Ir(C,N) 2(C',N')]. Instead, a mixture of homo- and heteroleptic complexes was acquired. It was found that a stepwise procedure involving the synthesis of a pure meridonial ( mer) isomer followed by photochemical isomerization of this mer to the fac isomer was necessary to synthesize pure fac-[Ir(C,N) 2(C',N')] complexes. Under thermal isomerization conditions, the conversion of mer-[Ir(C,N) 2(C',N')] to fac-[Ir(C,N) 2(C',N')] was also not a clean reaction, with again a mixture of homo- and heteroleptic complexes acquired. An investigation into the thermal mer to fac isomerization of both homo- and heteroleptic tris-cyclometallated complexes is presented. It was found that the process is an alcohol-catalyzed reaction with the formation of an iridium alkoxide [Ir(C,N) 2OR] intermediate in the isomerization process. This catalyzed reaction can be carried out between 50 and 100 degrees C, the first such example of low-temperature mer-fac thermal isomerization. We have synthesized analogous complexes and have shown that they do indeed react so as to give fac-tris-cyclometallated products. A detailed explanation of the intermediates (and all of their stereoisomers, in particular when systems of the generic formula [M(a,b) 2(a',b')] are synthesized) formed in the mer to fac isomerization process is presented, including how the formed intermediates react further, and the stereoisomeric products they yield.

Atomic and Molecular Layer Deposition for Enhanced Lithium Ion Battery Electrodes and Development of Conductive Metal Oxide/Carbon Composites

NASA Astrophysics Data System (ADS)

Travis, Jonathan

The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films is presented as a method for enabling non-conductive, but possibly electrochemically active materials, to be used for electrochemical applications.

Formation mechanism and characteristics of lanthanum-doped BaTiO{sub 3} powders and ceramics prepared by the sol–gel process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ianculescu, Adelina Carmen; Vasilescu, Catalina Andreea, E-mail: katyvasilescu85@yahoo.com; National Institute for Lasers, Plasma and Radiation Physics, P.O. Box MG54, 077125 Magurele

2015-08-15

Pure and lanthanum-doped barium titanate nanopowders described by two different formulae, as Ba{sub 1−x}La{sub x}TiO{sub 3}, for lower La concentrations (0 ≤ x ≤ 0.005) and Ba{sub 1−x}La{sub x}Ti{sub 1−x/4}O{sub 3} for higher La concentration (x = 0.025) were prepared by an alkoxide sol–gel method. Single phase compositions were obtained after annealing at 900 °C for 2 h, in air. The increase of the lanthanum content causes structural and morphological changes in the oxide powders, including the evolution of the unit cell from tetragonal toward a cubic symmetry, the particle size decrease and a higher aggregation tendency. SEM investigations ofmore » the ceramics sintered at 1300 °C for 4 h indicate significant changes of the microstructural features (strong decrease of the average grain size and increase of the intergranular porosity) with the raise of La amount. Lanthanum addition to barium titanate prepared by sol–gel induces a more significant shift of the Curie temperature toward lower values, than that one reported in literature for ceramics of similar compositions, but processed by the conventional solid state method. The compositions with smaller La amount (x ≤ 0.005) show semiconducting properties at room temperature and high relative dielectric permittivity values, while the undoped ceramics and those doped with higher La content (x = 0.025) are good dielectrics. The ceramic with x = 0.025 exhibits acceptable low losses, a very diffuse ferroelectric–paraelectric transition and Curie temperature closed to the room temperature, being thus susceptible for high tunability applications. - Highlights: • Ba{sub 1−x}La{sub x}TiO{sub 3} (x ≤ 0.005) and Ba{sub 1−x}La{sub x}Ti{sub 1−x/4}O{sub 3} (x = 0.025) were prepared by sol–gel. • Ceramics with x < 0.5 exhibit semiconductor and high dielectric properties. • Ceramic with x = 0.025 exhibits acceptable low losses and diffuse phase transition.« less

Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-opening polymerization of ℇ-caprolactone with initiators of different natures.

PubMed

Minyaev, Mikhail E; Nifant'ev, Ilya E; Shlyakhtin, Andrey V; Ivchenko, Pavel V; Lyssenko, Konstantin A

2018-05-01

A new packing polymorph of bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(tetrahydrofuran-κO)magnesium, [Mg(C 15 H 23 O) 2 (C 4 H 8 O) 2 ] or Mg(BHT) 2 (THF) 2 , (BHT is the 2,6-di-tert-butyl-4-methylphenoxide anion and THF is tetrahydrofuran), (1), has the same space group (P2 1 ) as the previously reported modification [Nifant'ev et al. (2017d). Dalton Trans. 46, 12132-12146], but contains three crystallographically independent molecules instead of one. The structure of (1) exhibits rotational disorder of the tert-butyl groups and positional disorder of a THF ligand. The complex of bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(μ 2 -ethyl glycolato-κ 2 O,O':κO)dimethyldialuminium, [Al 2 (CH 3 ) 2 (C 4 H 7 O 3 ) 2 (C 15 H 23 O) 2 ] or [(BHT)AlMe(OCH 2 COOEt)] 2 , (2), is a dimer located on an inversion centre and has an Al 2 O 2 rhomboid core. The 2-ethoxy-2-oxoethanolate ligand (OCH 2 COOEt) displays a μ 2 -κ 2 O,O':κO semi-bridging coordination mode, forming a five-membered heteronuclear Al-O-C-C-O ring. The same ligand exhibits positional disorder of the terminal methyl group. The redetermined structure of the heptanuclear complex octakis(μ 3 -benzyloxo-κO:κO:κO)hexaethylheptazinc, [Zn 7 (C 2 H 5 ) 6 (C 7 H 7 O) 8 ] or [Zn 7 (OCH 2 Ph) 8 Et 6 ], (3), possesses a bicubic Zn 7 O 8 core located at an inversion centre and demonstrates positional disorder of one crystallographically independent phenyl group. Cambridge Structural Database surveys are given for complexes structurally analogous to (2) and (3). Complexes (2) and (3), as well as derivatives of (1), are of interest as catalysts for the ring-opening polymerization of ℇ-caprolactone, and polymerization results are reported.

Choosing the best molecular precursor to prepare Li4Ti5O12 by the sol-gel method using (1)H NMR: evidence of [Ti3(OEt)13](-) in solution.

PubMed

García-Herbosa, Gabriel; Aparicio, Mario; Mosa, Jadra; Cuevas, José V; Torroba, Tomás

2016-09-21

(1)H NMR spectroscopy at 400 MHz in toluene-d8 of evaporated mixtures of lithium ethoxide and titanium(iv) isopropoxide in ethanol, used to prepare the spinel Li4Ti5O12 by the sol-gel method, may help clarify why the atomic ratio 5Li : 5Ti and not 4Li : 5Ti is the right choice to obtain the pure phase when performing hydrolysis at room temperature. The mixtures xLiOEt/yTi(OPr(i))4 in ethanol undergo alcohol exchange at room temperature, and the evaporated residues contain double lithium-titanium ethoxide [LiTi3(OEt)13] rather than simple mixtures of single metal alkoxides; this is of great relevance to truly understanding the chemistry and structural changes in the sol-gel process. Detailed inspection of the (1)H and (13)C VT NMR spectra of mixtures with different Li/Ti atomic ratios unequivocally shows the formation of [LiTi3(OEt)13] in a solution at low temperature. The methylene signals of free lithium ethoxide and Li[Ti3(OEt)13] coalesce at 20 °C when the atomic ratio is 5 : 5; however, the same coalescence is only observed above 60 °C when the atomic ratio is 4 : 5. We suggest that the highest chemical equivalence observed by (1)H NMR spectroscopy achieved through chemical exchange of ethoxide groups involves the highest microscopic structural homogeneity of the sol precursor and will lead to the best gel after hydrolysis. Variable temperature (1)H NMR spectra at 400 MHz of variable molar ratios of LiOEt/Ti(OPr(i))4 are discussed to understand the structural features of the sol precursor. While the precursor with the atomic ratio 5Li : 5Ti shows no signal of free LiOEt at 20 °C, both 4Li : 5Ti and 7Li : 5Ti show free LiOEt at 20 °C in their (1)H NMR spectra, indicating that the molar ratio 5Li : 5Ti gives the maximum rate of chemical exchange. DFT calculations have been performed to support the structure of the anion [Ti3(OEt)13](-) at room temperature.

Waterless TiO{sub 2} atomic layer deposition using titanium tetrachloride and titanium tetraisopropoxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Virginia R.; Cavanagh, Andrew S.; Abdulagatov, Aziz I.

2014-01-15

The surface chemistry for TiO{sub 2} atomic layer deposition (ALD) typically utilizes water or other oxidants that can oxidize underlying substrates such as magnetic disks or semiconductors. To avoid this oxidation, waterless or oxidant-free surface chemistry can be used that involves titanium halides and titanium alkoxides. In this study, waterless TiO{sub 2} ALD was accomplished using titanium tetrachloride (TiCl{sub 4}) and titanium tetraisopropoxide (TTIP). In situ transmission Fourier transform infrared (FTIR) studies were employed to study the surface species and the reactions during waterless TiO{sub 2} ALD. At low temperatures between 125 and 225  °C, the FTIR absorbance spectra revealed thatmore » the isopropoxide species remained on the surface after TTIP exposures. The TiCl{sub 4} exposures then removed the isopropoxide species and deposited additional titanium species. At high temperatures between 250 and 300  °C, the isopropoxide species were converted to hydroxyl species by β-hydride elimination. The observation of propene gaseous reaction product by quadrupole mass spectrometry (QMS) confirmed the β-hydride elimination reaction pathway. The TiCl{sub 4} exposures then easily reacted with the hydroxyl species. QMS studies also observed the 2-chloropropane and HCl gaseous reaction products and monitored the self-limiting nature of the TTIP reaction. Additional studies examined the waterless TiO{sub 2} ALD growth at low and high temperature. Quartz crystal microbalance measurements observed growth rates of ∼3 ng/cm{sup 2} at a low temperature of 150  °C. Much higher growth rates of ∼15 ng/cm{sup 2} were measured at a higher temperature of 250  °C under similar reaction conditions. X-ray reflectivity analysis measured a growth rate of 0.55 ± 0.05 Å/cycle at 250  °C. X-ray photoelectron depth-profile studies showed that the TiO{sub 2} films contained low Cl concentrations <1 at. %. This waterless TiO{sub 2} ALD process using TiCl{sub 4} and TTIP should be valuable to prevent substrate oxidation during TiO{sub 2} ALD on oxygen-sensitive substrates.« less

In Situ Infrared Spectroscopic Studies of Molecular Layer Deposition and Atomic Layer Etching Processes

NASA Astrophysics Data System (ADS)

DuMont, Jaime Willadean

In this thesis, in situ Fourier transform infrared (FTIR) spectroscopy was used to study: i) the growth and pyrolysis of molecular layer deposition (MLD) films. ii) the surface chemistry of atomic layer etching (ALE) processes. Atomic layer processes such as molecular layer deposition (MLD) and atomic layer etching (ALE) are techniques that can add or remove material with atomic level precision using sequential, self-limiting surface reactions. Deposition and removal processes at the atomic scale are powerful tools for many industrial and research applications such as energy storage and semiconductor nanofabrication. The first section of this thesis describes the chemistry of reactions leading to the MLD of aluminum and tin alkoxide polymer films known as "alucone" and "tincone", respectively. The subsequent pyrolysis of these films to produce metal oxide/carbon composites was also investigated. In situ FTIR spectroscopy was conducted to monitor surface species during MLD film growth and to monitor the films background infrared absorbance versus pyrolysis temperature. Ex situ techniques such as transmission electron microscopy (TEM), four-point probe and X-ray diffraction (XRD) were utilized to study the properties of the films post-pyrolysis. TEM confirmed that the pyrolyzed films maintained conformality during post-processing. Four-point probe monitored film resistivity versus pyrolysis temperature and XRD determined the film crystallinity. The second section of this thesis focuses on the surface chemistry of Al2O3 and SiO2 ALE processes, respectively. Thermal ALE processes have been recently developed which utilize sequential fluorination and ligand exchange reactions. An intimate knowledge of the surface chemistry is important in understanding the ALE process. In this section, the competition between the Al2O3 etching and AlF 3 growth that occur during sequential HF (fluorinating agent) and TMA (ligand exchange) exposures is investigated using in situ FTIR spectroscopy. Also included in this section is the first demonstration of thermal ALE for SiO2. In situ FTIR spectroscopy was conducted to monitor the loss of bulk Si-O vibrational modes corresponding to the removal of SiO2. FTIR was also used to monitor surface species during each ALE half cycle and to verify self-limiting behavior. X-ray reflectivity experiments were conducted to establish etch rates on thermal oxide silicon wafers.

Development of highly porous crystalline titania photocatalysts

NASA Astrophysics Data System (ADS)

Marszewski, Michal

The objectives of this dissertation are the design, synthesis, and characterization of titania materials with surface area, porosity, crystallinity and doping tailored toward photocatalytic applications. Ultimately, the research should result in a strategy allowing the synthesis of titania with all these important features. The synthetic methods investigated in this research will include: i) soft-templating, ii) hard-templating, and iii) modified precursor strategy. Soft-templating strategy uses organic templates--either block copolymers or surfactants--that under specific conditions assemble into micelles, and later, these micelles are used to template the desired material around them. The resulting organic-inorganic composite is then calcined in air to remove the organic template and recover the final material with high surface area and large pore volume. This work explores 1) synthesis of titania materials in the presence of polymer templates, and the effects of different synthetic conditions on the structure of the resulting materials. Hard-templating, in contrast to soft-templating, uses inorganic templates. The hard template is introduced during the synthesis to cast its shape onto the fabricated material and removed afterwards, when the material has formed. The final material is an inverse replica of the hard template used, typically with a well-developed mesostructure. This work explores 1) hard templating synthesis of titania materials using silica and alumina, and 2) the effects of the template amount and type. The modified precursor strategy is a novel synthetic method, developed in this research, and designed specifically to achieve titania material with high surface area, large pore volume, high crystallinity, and possibly doping. The modified precursors are prepared by reacting generic titania precursors, such as titanium isopropoxide (TIPO), with organic acids, which results in substitution of some or all alkoxide groups in TIPO structure. The goal is to introduce new, easily carbonizable groups in TIPO structure so that the modified precursor can serve as titania and carbon precursor simultaneously. Subsequently, during carbonization in inert atmosphere, a carbon framework is formed that works as a scaffold, protecting titania during its crystallization. Afterwards, the carbon scaffold is removed by calcination in air. This work explores the modified precursor strategy by 1) preparing titania materials from TIPO modified with different carboxylic acids and 2) investigating the effect of the modifying acid on the properties of the carbon-titania composites and the final titania materials.

Novel processing to produce polymer/ceramic nanocomposites by atomic layer deposition

NASA Astrophysics Data System (ADS)

Liang, Xinhua

Polymeric materials can be greatly influenced by nanoscale inclusions of inorganic materials. The main goal of this thesis is to fabricate novel polymer/ceramic composite materials for two different applications using atomic layer deposition (ALD) or molecular layer deposition (MLD) methods. One is to produce well-dispersed polymer/ceramic nanocomposites with improved barrier properties for packaging applications. The other is to produce porous polymer/ceramic composites with improved bioactivity for tissue engineering applications. ALD has been successfully utilized for the conformal and uniform deposition of ultra-thin alumina and titania films on primary micron-sized polymer particles. The mechanism to initiate alumina and titania ALD on polymer particles without chemical functional groups was confirmed. A nucleation period was needed for both alumina and titania ALD on high density polyethylene (HDPE) particles and no nucleation period was needed for alumina ALD on polymethyl methacrylate particles. Titania ALD films deposited at low temperatures had an amorphous structure and showed much weaker photoactivity than common pigment-grade anatase TiO2 particles. Highly uniform and conformal ultra-thin aluminum alkoxide (alucone) polymer films were deposited on primary silica and titania nanoparticles using MLD in a fluidized bed reactor. The deposition chemistry and properties of alucone MLD films were investigated. The photoactivity of pigment-grade TiO2 particles was quenched after 20 cycles of an alucone MLD film, but the films shrank and decomposed in the presence of water, which decreased the passivation effect of the photoactivity of TiO2 particles. Well-dispersed polymer/ceramic nanocomposites were obtained by extruding alumina ALD coated HDPE particles. The diffusion coefficient of the fabricated nanocomposite membranes can be reduced by half with the inclusion of 7.3 vol.% alumina flakes. However, a corresponding increase in permeability was also observed due to the voids formed at or near the interface of the polymer and alumina flakes during the extrusion process. Efforts to improve the barrier properties of the membranes included 3-aminopropyltriethoxysilane treatment and coating alucone MLD films on alumina coated particles prior to extrusion. The porous polymer/ceramic particles were synthesized by depositing ultra-thin alumina or titania films on highly porous poly(styrene-divinylbenzene) particles using a low-temperature ALD process. Analytical characterization revealed that conformal alumina and titania films were grown on internal and external polymer particle surfaces, and the pore filling mechanism was a uniform coating of the pore walls. The ALD layers can improve the bioactivity and protein adsorption of the polymer substrates.

A computational study of the CO dissociation in cyclopentadienyl ruthenium complexes relevant to the racemization of alcohols.

PubMed

Stewart, Beverly; Nyhlen, Jonas; Martín-Matute, Belén; Bäckvall, Jan-E; Privalov, Timofei

2013-01-28

The formation of an active 16-electron ruthenium sec-alkoxide complex via loss of the CO ligand is an important step in the mechanism of the racemization of sec-alcohols by (η(5)-Ph(5)C(5))Ru(CO)(2)X ruthenium complexes with X = Cl and O(t)Bu. Here we show with accurate DFT calculations the potential energy profile of the CO dissociation pathway for a series of relevant (η(5)-Ph(5)C(5))Ru(CO)(2)X complexes, where X = Cl, O(t)Bu, H and COO(t)Bu. We have found that the CO dissociation energy increases in the following order: O(t)Bu (lowest), Cl, COO(t)Bu and H (highest). Using the distance between ruthenium and C(CO), r = Ru-C(CO), as a constraint, and by optimizing all other degrees of freedom for a range of Ru-CO distances, we obtained relative energies, ΔE(r) and geometries of a sufficient number of transient structures with the elongated Ru-CO bond up to r = 3.4 Å. Our calculations provide a quantitative understanding of the CO ligand dissociation in (η(5)-Ph(5)C(5))Ru(CO)(2)Cl and (η(5)-Ph(5)C(5))Ru(CO)(2)(O(t)Bu) complexes, which is relevant to the mechanism of their catalytic activity in the racemization of alcohols. We recently reported that exchange of the CO ligand by isotopically labeled (13)CO in the Ru-O(t)Bu complex occurs twenty times faster than that in the Ru-Cl complex. This corresponds to a difference of 1.8 kcal mol(-1) in the CO dissociation energy (at room temperature). This is in very good agreement with the calculated difference between the two potential energy curves for Ru-O(t)Bu and Ru-Cl complexes, which is about 1.8-2 kcal mol(-1) around the corresponding transition states of the CO dissociation. The calculated difference in the total energy for CO dissociation in (η(5)-Ph(5)C(5))Ru(CO)(2)X complexes is related to the stabilization provided by the X group in the final 16-electron complexes, which are formed via product-like transition states. In addition to the calculated transition states of CO dissociation in Ru-O(t)Bu and Ru-Cl complexes, the calculated transient structures with the elongated Ru-CO bond provide insight into how the geometry of the ruthenium complex with a potent heteroatom donor group (X) gradually changes when one of the COs is dissociating.

Highly active, low-valence molybdenum- and tungsten-amide catalysts for bifunctional imine-hydrogenation reactions.

PubMed

Chakraborty, Subrata; Blacque, Olivier; Fox, Thomas; Berke, Heinz

2014-01-01

The reactions of [M(NO)(CO)4(ClAlCl3)] (M=Mo, W) with (iPr2PCH2CH2)2NH, (PN(H)P) at 90 °C afforded [M(NO)(CO)(PN(H)P)Cl] complexes (M=Mo, 1a; W, 1b). The treatment of compound 1a with KOtBu as a base at room temperature yielded the alkoxide complex [Mo(NO)(CO)(PN(H)P)(OtBu)] (2a). In contrast, with the amide base Na[N(SiMe3 )2 ], the PN(H) P ligand moieties in compounds 1a and 1b could be deprotonated at room temperature, thereby inducing dehydrochlorination into amido complexes [M(NO)(CO)(PNP)] (M=Mo, 3a; W, 3b; PNP=(iPr2PCH2CH2)2N)). Compounds 3a and 3b have pseudo-trigonal-bipyramidal geometries, in which the amido nitrogen atom is in the equatorial plane. At room temperature, compounds 3a and 3b were capable of adding dihydrogen, with heterolytic splitting, thereby forming pairs of isomeric amine-hydride complexes [Mo(NO)(CO)H(PN(H)P)] (4a(cis) and 4a(trans)) and [W(NO)(CO)H(PN(H)P)] (4b(cis) and 4b(trans); cis and trans correspond to the position of the H and NO groups). H2 approaches the Mo/W=N bond in compounds 3a,b from either the CO-ligand side or from the NO-ligand side. Compounds 4a(cis) and 4a(trans) were only found to be stable under a H2 atmosphere and could not be isolated. At 140 °C and 60 bar H2 , compounds 3a and 3b catalyzed the hydrogenation of imines, thereby showing maximum turnover frequencies (TOFs) of 2912 and 1120 h(-1), respectively, for the hydrogenation of N-(4-methoxybenzylidene)aniline. A Hammett plot for various para-substituted imines revealed linear correlations with a negative slope of -3.69 for para substitution on the benzylidene side and a positive slope of 0.68 for para substitution on the aniline side. Kinetics analysis revealed the initial rate of the hydrogenation reactions to be first order in c(cat.) and zeroth order in c(imine). Deuterium kinetic isotope effect (DKIE) experiments furnished a low kH /kD value (1.28), which supported a Noyori-type metal-ligand bifunctional mechanism with H2 addition as the rate-limiting step. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isomorphic introduction of d(0) transition metals to mesoporous silica

NASA Astrophysics Data System (ADS)

Morey, Mark Sanson

1998-12-01

Early transition metals (Ti, V, Zr, Mo, W) have been incorporated in the mesoporous silicate system by hydrothermal and post-synthesis treatments. The materials were studied by diffraction, adsorption and spectroscopic techniques and were found to have catalytic, halogenation activity toward organic substrates at neutral pH. Intense interest has been shown in the new class of silica-based, mesoporous materials due to their high potential for catalytic applications. Their synthesis occurs via a cooperative self-assembly of surfactant/silicate pairs to form numerous, extended network structures upon silicate condensation based on liquid crystal phases of surfactant/water systems. Surfactant micelle removal by calcination generates a well defined pore system with a narrow pore size distribution. Of these phases, the cubic MCM-48 form possesses a high surface area (1200-1500msp2/g), a 3-D array of pores, and a large pore diameter (20-100A) so that selectivity for large (>10A kinetic diameter) molecules is possible. For this work, the MCM-48 phase was chosen since its branched, bi-continuous pore array would be less likely to clog during use than a one dimensional array. Two techniques for transition metal incorporation are compared consisting of hydrothermal and post-synthesis treatment. A brief description of an attempt to synthesize mesoporous molybdena will be included. The first approach consists of combining various metal and Si precursors in the starting gel, while exploring a broad region of the multi-component phase diagram. The second pathway involves grafting metal species on a pure silica, MCM-48 support by anchoring them to surface silanols using reactive metal alkoxides. Bulk structural characterization by X-ray powder diffraction and nitrogen adsorption shows that the pore structure is maintained after incorporation of metal species by both methods. Spectroscopic methods (FTIR/RAMAN and UV/VIS) are used to gain insight into the local metal/silica environments. The post-synthesis and grafted materials have been shown to exhibit activity in the bromination of large, organic molecules such as phenol red at neutral pH and is a first for a non-biological system. In nature, vanadium bromoperoxidase accomplishes this task, effectively producing brominated, marine natural products with interesting pharmacological properties. The five metals were meticulously chosen based on their well known oxidative properties and ease of incorporation into the silica matrix. A discussion of the relative rates of halogenation will be based on the metal's ability to coordinate and activate peroxide ligands.

Structural and optical characterizations of Ca2Al2SiO7:Ce3+, Mn2+ nanoparticles produced via a hybrid route

NASA Astrophysics Data System (ADS)

Teixeira, V. C.; Montes, P. J. R.; Valerio, M. E. G.

2014-07-01

Pure, Ce3+ doped and Ce3+ and Mn2+ co-doped Ca2Al2SiO7 ceramic powders were prepared by two different methodologies which are the proteic sol-gel process and a new hybrid route combining the proteic sol-gel with solid state reaction processes. The second one is an eco-friendly method because it uses natural raw materials in replacement of the metal alkoxides used in the traditional sol-gel routes. X-ray diffraction showed that Ca2Al2SiO7 crystalline phase was obtained for both preparations. Differential thermal analysis indicated that the exothermic event around 850 °C, for sample produced by proteic sol-gel method, and around 927 °C, for ceramics prepared by hybrid synthesis, can be associated to crystallization of Ca2Al2SiO7. Transmission electron microscope indicates that regular and spherical nanoparticles were obtained with average sizes of about 12 nm. The Scherrer's method was used to determine the average crystallite sizes and it was shown that nanometric crystallites were obtained of about 74 nm for samples produced via hybrid route. For all the single phase samples, the crystallite sizes are about the same and that agrees with TEM results. Diffuse optical reflectance measurements were used to estimate the Ca2Al2SiO7 optical band gap and the obtained value is about 6 eV, photoluminescence (PL) spectra presented typical emissions of Ce3+ and Mn2+ ions. Upon excitation at 352 nm the emission spectra showed a broad band centered at 415 nm due to the Ce3+ 4f1 → 5d1 typical transition. This emission is resonant with Mn2+ excitation and it transfers energy to Mn ions generating a second broad emission band centered at 620 nm due to the Mn2+. The PL results were used to obtain, as a fist approach, the Ce3+ energy levels diagram and, using the Tanabe-Sugano diagrams, the transitions due to the Mn2+ were calculated. X-ray excited optical luminescence measurements showed the same emission spectra as the PL emission spectra. Luminescence lifetime decay constants were measured for Ce and Mn co-doped and for Ce doped samples and the results indicate Ca2Al2SiO7:Ce3+, Mn2+ showed quite fast responses with main time constants below 30 ns.

Mesostructured Hydrophobic-Oleophobic Silica Films for Sustained Functionality in Tribological Environments

NASA Astrophysics Data System (ADS)

Kessman, Aaron J.

The primary goal of this research was to synthesize water- and oil-repellent coatings that offer sustained functionality and durability. Engineered low surface energy materials generally suffer from a lack of mechanical robustness, which makes them susceptible to damage by abrasive wear. Fluorinated silanes are often combined with alkoxide precursors via sol-gel co-condensation to create coatings with high hardness and good substrate adhesion. However, a common problem with these materials is that the organic moieties that provide low surface energy also become surface segregated and highly concentrated at the solid-air interface. With such a structure, mechanical removal of the top surface by abrasion, for example, reveals subsurface areas that are then much less concentrated in terms of functional chemistry. The material developed in this study was designed to overcome this problem by means of a tailored and templated mesostructure that effectively encapsulated the low surface energy functional moieties, and thus achieves sustained functionality during abrasive wear. This material, applied as a thin coating to a variety of substrates, has the potential to reduce waste and pollution and the environmental degradation of materials and structures. Improving the performance of such materials can benefit a wide variety of applications. These include optoelectronic devices including photovoltaic panels; automobile and aircraft; architectural structures; the chemical, food, and medical industries for hygienic and anti-fouling requirements; textiles; and household applications. This approach has further implications in areas such as boundary lubrication and drug delivery systems. Hydrophobic-oleophobic mesoporous fluorinated silica films were synthesized via sol-gel co-condensation and coated on glass substrates. Fluorosilane and surfactant template concentrations were varied to elucidate the effect of organic functionality and porosity on performance. Structural, chemical, mechanical, surface, and tribological properties were investigated to examine the performance of functionalized mesostructured thin films in abrasive environments. Analytical techniques included XPS depth profiling, porosimetry, AFM and friction force microscopy, nanoindentation, contact angle goniometry, and stylus profilometry. Controlled abrasion was conducted using a lab-built instrument. Hydrophobic and oleophobic properties were monitored ex-situ during abrasion to observe and quantify changes in functionality as the material is worn. Experimental results show that surfactant templating aids in generating an internal mesostructure that facilitates encapsulation of functional moieties. This encapsulation allows exposed surfaces to be sacrificially worn away while maintaining much of the original functionality. The results of tribological measurements, as observed through abrasive wear testing, friction force mapping, and wear rate calculations, suggest that the low-friction surface generate by fluorosilane moieties grafted to internal pore surfaces mitigates to some extent the detrimental effect of film porosity on hardness and wear resistance.

Nanoconfinement Effects in Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kung, Harold H.

In this investigation, the unique properties that stem from the constrained environment and enforced proximity of functional groups at the active site were demonstrated for a number of systems. The first system is a nanocage structure with silicon-based, atom-thick shells and molecular-size cavities. The shell imparts the expected size exclusion for access to the interior cavity, and the confined space together with the hydrophobic shell strongly influences the stability of charged groups. One consequence is that the interior amine groups in a siloxane nanocage exhibit a shift in their protonation ability that is equivalent to about 4 pH units. Inmore » another nanocage structure designed to possess a core-shell structure in which the core periphery is decorated with carboxylic acid groups and the shell interior is populated with silanol groups, the restricted motion of the core results in limiting the stoichiometry of reaction between carboxylic acid and a Co 2CO 8 complex, which leads to formation and stabilization of Co(I) ions in the nanocage. The second designed catalytic structure is a supported, isolated, Lewis acid Sn-oxide unit derived from a (POSS)-Sn-(POSS) molecular complex (POSS = incompletely condensed silsesquioxane). The Sn center in the (POSS)-Sn-(POSS) complex is present in a tetrahedral coordination, as confirmed by single crystal x-ray crystallography and Sn NMR, and its Lewis acid character is demonstrated with its binding to amines. The retention of the tetrahedral coordination of Sn after heterogenization and mild oxidative treatment is confirmed by characterization using EXAFS, NMR, UV-vis, and DRIFT, and its Lewis acid character is confirmed by stoichiometric binding with pyridine. This Sn-catalyst is active in hydride transfer reactions as a typical solid Lewis acid. In addition, the Sn centers can also create Brønsted acidity with alcohol by binding the alcohol strongly as alkoxide and transferring the hydroxyl H to the neighboring Sn-O-Si bond. The resulting acidic silanol is active in epoxide ring opening and acetalization reactions. The open structure of the Sn center makes it accessible to larger molecules, including cellobiose which can be converted to 5-(hydroxymethyl)-furfural. The third structure is a support planted with functional group pairing of a known separation distance. Using a precursor molecule that contains a hydrolysable silyl ester bond, and making use of known chemistry to convert silanol groups into amino/pyridyl and phosphinyl groups, silica surfaces with carboxylic acid/silanol, carboxylic acid/amine, carboxylic acid/pyridine, and carboxylic acid/phosphine pairs can be constructed. The amino groups paired with carboxylic acid on such a surface is more active in the Henry reaction of 4-nitobenzaldehyde with nitromethane.« less

Development of Aerogel Molds for Metal Casting Using Lunar and Martian Regolith

NASA Technical Reports Server (NTRS)

2003-01-01

In the last few years NASA has set new priorities for research and development of technologies necessary to enable long-term presence on the Moon and Mars. Among these key technologies is what is known as in situ resource utilization, which defines all conceivable usage of mineral, liquid, gaseous, or biological resources on a visited planet. In response to this challenge, we have been focusing on developing and demonstrating the manufacturing of a specific product using Lunar and Martian soil simulants (i.e., a mold for the casting of metal and alloy parts) which will be an indispensable tool for the survival of outposts on the Moon and Mars. In addition, our purpose is to demonstrate the feasibility of using mesoporous materials such as aerogels to serve as efficient casting molds for high quality components in propulsion and other aerospace applications. The first part of the project consists of producing aerogels from the in situ resources available in Martian and Lunar soil. The approach we are investigating is to use chemical processes to solubilize silicates using organic reagents at low temperatures and then use these as precursors in the formation of aerogels for the fabrication of metal casting molds. One set of experiments consists of dissolving silica sources in basic ethylene glycol solution to form silicon glycolates. When ground silica aerogel was used as source material, a clear solution of silicon glycolate was obtained and reacted to form a gel thus proving the feasibility of this approach. The application of this process to Lunar and Martian simulants did not result in the formation of a gel; further study is in progress. In the second method acidified alcohol is reacted with the simulants to form silicate esters. Preliminary results indicate the presence of silicon alkoxide in the product distillation. However, no gel has been obtained so further characterization is ongoing. In the second part of the project, the focus has been on developing a series of aerogel plates suitable for thin plate metal casting and ingot metal castings. The influence of aerogels on thin wall metal castings was studied by placing aerogel plates into the cavities of thin sections of resin bonded sand molds. An 1 based commercial alloy ( 356) containing 7 percent Si was poured into these molds. Post-solidification studies provide evidence that aerogel inserts significantly reduce the cooling rate during solidification. The advantage of a lower rate using aerogel inserts was reflected in the reduction of casting defects such as shrinkage porosity. Quantitative results support the hypothesis that using aerogels as a mold material can offer definite advantages when used as casting thin sections. As a separate effort, silica aerogel with cylindrical cavities have been prepared and will be evaluated for casting commercial alloys.

Synthesis, integration, and characterization of metal oxide films as alternative gate dielectric materials

NASA Astrophysics Data System (ADS)

Lin, You-Sheng

ZrO2 and HfO2 were investigated in this study to replace SiO2 as the potential gate dielectric materials in metal-oxide-semiconductor field effect transistors. ZrO2 and HfO2 films were deposited on p-type Si (100) wafers by an atomic layer chemical vapor deposition (ALCVD) process using zirconium (IV) t-butoxide and hafnium (IV) t-butoxide as the metal precursors, respectively. Oxygen was used alternatively with these metal alkoxide precursors into the reactor with purging and evacuation in between. The as-deposited ZrO2 and HfO2 films were stoichiometric and uniform based on X-ray photoemission spectroscopy and ellipsometry measurements. X-ray diffraction analysis indicated that the deposited films were amorphous, however, the high-resolution transmission electron microscopy showed an interfacial layer formation on the silicon substrate. Time-of-flight secondary ion mass spectrometry and medium energy ion scattering analysis showed significant intermixing between metal oxides and Si, indicating the formation of metal silicates, which were confirmed by their chemical etching resistance in HF solutions. The thermal stability of ZrO2 and HfO2 thin films on silicon was examined by monitoring their decomposition temperatures in ultra-high vacuum, using in-situ synchrotron radiation ultra-violet photoemission spectroscopy. The as-deposited ZrO2 and HfO2 thin films were thermally stable up to 880°C and 950°C in vacuum, respectively. The highest achieveable dielectric constants of as-deposited ZrO 2 and HfO2 were 21 and 24, respectively, which were slightly lower than the reported dielectric constants of bulk ZrO2 and HfO 2. These slight reductions in dielectric constants were attributed to the formation of the interfacial metal silicate layers. Very small hysteresis and interface state density were observed for both metal oxide films. Their leakage currents were a few orders of magnitude lower than that of SiO 2 at the same equivalent oxide thickness. NMOSFETs were also fabricated with the as-deposited metal oxide films, and reasonable ID-V D and IG-VG results were obtained. The electron mobilities were high from devices built using a plasma etching process to pattern the metal oxide films. However, they can be degraded if an HF wet etching process was used due to the large contact resistences. Upon oxygen annealing, the formation of SiOx at the interface improved the thermal stability of the as-deposited metal oxide films, however, lower overall dielectric constant and higher leakage current were observed. Upon ammonia annealing, the formation of SiOxNy improved not only the thermal stability but also reduced the leakage current. However, the overall dielectric constant of the film was still reduced due to the formation of the additional interfacial layer.

Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution

PubMed Central

Hartwig, John F.; Stanley, Levi M.

2010-01-01

Conspectus Enantioselective allylic substitution reactions comprise some of the most versatile methods for preparing enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon–nitrogen, carbon–oxygen, carbon–carbon, and carbon–sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals have revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsymmetrical allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, we describe an iridium precursor and a phosphoramidite ligand that catalyze reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or separately in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prepare intermediates containing allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from our laboratory on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields, with high branched-to-linear ratios and high enantioselectivities. Parallel mechanistic studies had revealed the metallacyclic structure of the active catalyst, and subsequent experiments with the purposefully formed metallacycle increased the reaction scope dramatically. Aromatic amines, azoles, ammonia, and amides and carbamates as ammonia equivalents all reacted with high selectivities and yields. Moreover, weakly basic enolates (such as silyl enol ethers) and enolate equivalents (such as enamines) also reacted, and other research groups have used this catalyst to conduct reactions of stabilized carbon nucleophiles in the absence of additional base. One hallmark of the reactions catalyzed by this iridium system is the invariably high enantioselectivity, which reflects a high stereoselectivity for formation of the allyl intermediate. Enantioselectivity typically exceeds 95%, regioselectivity for formation of branched over linear products is usually near 20:1, and yields generally exceed 75% and are often greater than 90%. Thus, the development of iridium catalysts for enantioselective allylic substitution shows how studies of reaction mechanism can lead to a particularly active and a remarkably general system for an enantioselective process. In this case, a readily accessible catalyst effects allylic substitution, with high enantioselectivity and regioselectivity complementary to that of the venerable palladium systems. PMID:20873839

Synthesis of Inorganic-Organic Hybrid Materials Designed for Radiation Detection, Luminescence, and Gas Storage

NASA Astrophysics Data System (ADS)

Vaughn, Shae Anne

Materials discovery is the driving force behind the research presented herein. Basic research has been conducted in order to obtain a better understanding of coordination chemistry and structural outcomes, particularly within the area of trivalent lanthanides. Discovering new materials is one route to further advancement of technology; another one is the focus on incremental changes to already existing materials. Often the building blocks of a compound are chosen in an effort to synthesize a material that makes use of the properties of each individual component and may result in a better, more robust, applicable material. The combination of organic and inorganic components for the synthesis of novel materials with potential applications such as scintillation photoluminescence, catalysis, and gas storage are the focus of the research presented herein. The first part focuses on lanthanide organic hybrid materials, where the synthesis of a new family of potential scintillating materials was undertaken and yielded improved understanding of the control that can be achieved over the topological structure of these materials by controlling the coordinating crystallization solvents. This research has led to the synthesis of an array of unique motifs, ranging from dimeric complexes, tetrameric complexes, to 1-D chains, and most intriguing of all, catenated tetradecanuclear rings. These rings represent the largest lanthanide rings synthesized to date, the next largest multinuclear rings, until now, were dodecanuclear complexes of alkoxides. From a basic research standpoint this is an exciting new development in lanthanide coordination chemistry and illustrates the importance of steric effects upon a system. These complexes are potential scintillators, supported by their luminescence and measurements of similar compounds that demonstrate surprising scintillation efficiencies. In the second part, other hybrid materials that have also been prepared are discussed, including the synthesis of a polyoxometallate compound (POM) containing a typical Keggin ion, which is charge-balanced via protonated organic ligands. POMs are one of the most studied inorganic clusters owing to their potential catalytic capabilities. A third part concerns a pseudo hybrid material consisting of boron, a metalloid, and a polymeric network, which includes a site of contortion, provided by the incorporation of a disulfide linkage and polymerized through boronate ester linkages. Tuning of this disulfide-linked polymer of intrinsic microporosity has the potential to lead to a dynamic material that may have gas sorption properties. The fourth part describes research in which the goal was to synthesize novel metal organic frameworks (MOFs) for solid state lighting applications via the synthesis of long, rigid, highly conjugated ligands. The successful synthesis of these ligands and optimization of the reaction conditions through the use of cyano derivatives as intermediates was discovered. Subsequent incorporation into coordination polymers with the transition elements was unsuccessful. This is believed to be the case due to the rigidity of the ligands and their inability to be flexible enough to successfully coordinate to a metal cation in a crystalline form.

Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV) alkoxide pincer complex.

PubMed

Pedziwiatr, Jakub; Ghiviriga, Ion; Abboud, Khalil A; Veige, Adam S

2017-02-01

This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H 3 [NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-di-methylpropanimido-yl)- N -[2-(2,2-di-methyl-propanimido-yl)-4-methyl-phen-yl]-4-methylaniline}-bis-[(diethyl ether)lithium], [Li 2 Br 2 (C 24 H 33 N 3 )(C 4 H 10 O) 2 ] ( 1 ) and a dinuclear metal complex, namely di-μ-bromido-2:3κ 4 Br : Br -bis-{2-(2,2-di-methylpropanimido-yl)- N -[2-(2,2-di-methyl-propanimido-yl)-4-methyl-phen-yl]-4-methylaniline}-1κ 3 N , N ', N '';4κ 3 N , N ', N ''-tetra-μ-iso-propano-lato-1:2κ 4 O : O ;3:4κ 4 O : O -diiso-propano-lato-1κ O ,4κ O -2,3-dilithium-1,4-dititanium, [Li 2 Ti 2 Br 2 (C 24 H 32 N 3 ) 2 (C 3 H 7 O) 6 ] or {[NHNNH]Ti(O i Pr) 3 (LiBr) 2 } 2 ( 2 ). Complex 1 , which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et 2 O) fragment bonded to them, with the Li atom adopting a distorted tetra-hedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a Ti IV metal atom in an octa-hedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12)/0.372 (12)], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetra-hedral coordination as in 1 ). The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert -butyl groups (occupation factors fixed at 0.6/0.4). The novel [NNN]H 3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N-H groups, no hydrogen bonding is found in either one, perhaps due to the bulky groups around them. One of the ethyl groups of the ether ligand of 1 is disordered and refined in two parts with site-occupation factors of 0.812 (8) and 0.188 (8). One and a half toluene solvent mol-ecules are also present in the asymmetric unit of 2 . The toluene mol-ecules were significantly disordered and could not be modeled properly, thus SQUEEZE [Spek (2015 ▸). Acta Cryst. C 71 , 9-18] was used to remove their contributions to the overall intensity data.

Design and synthesis of single-source molecular precursors to homogeneous multi-component oxide materials

NASA Astrophysics Data System (ADS)

Fujdala, Kyle Lee

This dissertation describes the syntheses of single-source molecular precursors to multi-component oxide materials. These molecules possess a core metal or element with various combinations of -OSi(O tBu)3, -O2P(OtBu) 2, and -OB[OSi(OtBu)3] 2 ligands. Such molecules decompose under mild thermolytic conditions (<200°C) to provide homogeneous carbon-free materials via the elimination of isobutylene and water. A gel is formed when thermolyses are performed in non-polar solvents, and subsequent drying of the gel in a conventional manner yields high surface area xerogels. This thermolytic molecular precursor (TMP) approach has been utilized to provide a variety of oxide materials with tailored properties. In addition, the oxygen rich environment of the molecular precursors coupled with the presence of M-O-E heterolinkages permits use of them as models for oxide-supported metal species and multi-component oxides. Significantly, the first complexes to contain three or more heteroelements suitable for use in the TMP method have been synthesized. Compounds for use as single-source molecular precursors have been synthesized containing Al, B, Cr, Hf, Mo, V, W, and Zr, and their thermal transformations have been examined. Heterogeneous catalytic reactions have been examined for selected materials. Also, cothermolyses of molecular precursors and additional molecules (i.e., metal alkoxides) have been utilized to provide materials with several components for potential use as catalysts or catalyst supports. Reactions of one and two equivs of HOSi(OtBu) 3 with Cr(OtBu)4 afforded the first Cr(IV) alkoxysiloxy complexes (tBuO) 3CrOSi(OtBu)3 and ( tBuO)2Cr[OSi(OtBu) 3]2, respectively. The high-yielding, convenient synthesis of (tBuO)3CrOSi(O tBu)3 make this complex a useful single-source molecular precursor, via the TMP method, to Cr/Si/O materials. The thermal transformations of (tBuO)3CrOSi(O tBu)3 and (tBuO) 2Cr[OSi(OtBu)3]2 to chromia-silica materials occurr at low temperatures (≤180°C), to give isobutene as the major carbon-containing product. The material generated from the solid-state conversion of (tBuO) 3CrOSi(OtBu)3 (CrOS ss) has an unexpectedly high surface area of 315 m2 g-1 that is slightly reduced to 275 m2 g-1 after calcination at 500°C in O2. The xerogel obtained by the thermolysis of an n-octane solution of (tBuO)3CrOSi(O tBu)3 (CrOSixg) has a surface area of 315 m2 g-1 that is reduced to 205 m2 g-1 upon calcination at 500°C. Powder X-ray diffraction (PXRD) analysis revealed that Cr2O 3 is the only crystalline species present in CrOSiss and CrOSixg after calcination at temperatures up to 1200°C in O2. (Abstract shortened by UMI.)

Synthesis and characterizations of novel polymer electrolytes

NASA Astrophysics Data System (ADS)

Chanthad, Chalathorn

Polymer electrolytes are an important component of many electrochemical devices. The ability to control the structures, properties, and functions of polymer electrolytes remains a key subject for the development of next generation functional polymers. Taking advantage of synthetic strategies is a promising approach to achieve the desired chemical structures, morphologies, thermal, mechanical, and electrochemical properties. Therefore, the major goal of this thesis is to develop synthetic methods for of novel proton exchange membranes and ion conductive membranes. In Chapter 2, new classes of fluorinated polymer- polysilsesquioxane nanocomposites have been designed and synthesized. The synthetic method employed includes radical polymerization using the functional benzoyl peroxide initiator for the telechelic fluorinated polymers with perfluorosulfonic acids in the side chains and a subsequent in-situ sol-gel condensation of the prepared triethoxylsilane-terminated fluorinated polymers with alkoxide precursors. The properties of the composite membranes have been studied as a function of the content and structure of the fillers. The proton conductivity of the prepared membranes increases steadily with the addition of small amounts of the polysilsesquioxane fillers. In particular, the sulfopropylated polysilsesquioxane based nanocomposites display proton conductivities greater than Nafion. This is attributed to the presence of pendant sulfonic acids in the fillers, which increases ion-exchange capacity and offers continuous proton transport channels between the fillers and the polymer matrix. The methanol permeability of the prepared membranes has also been examined. Lower methanol permeability and higher electrochemical selectivity than those of Nafion have been demonstrated in the polysilsesquioxane based nanocomposites. In Chapter 3, the synthesis of a new class of ionic liquid-containing triblock copolymers with fluoropolymer mid-block and imidazolium methacrylate end-blocks is described for the first time. The synthetic strategy involves the preparation of the telechelic fluoropolymers using a functional benzoyl peroxide initiator as the macro-chain transfer agent for subsequent RAFT polymerization of the imidazolium methacrylate monomer. As revealed in DSC, SAXS and dielectric relaxation spectroscopy (DRS) measurements, there was no microphase separation in the triblock copolymers, likely due to solubility of ionic liquid moieties in the fluoropolymer matrix. The anionic counterion has direct impact on the thermal properties, ionic conductivity and segmental dynamics of the polymers. The temperature dependence of the ionic conductivity is well described by the Vogel-Tamman-Fulcher model, suggesting that ion motion is closely coupled to segmental motion. In Chapter 4 and 5, new solid electrolytes for lithium cations have been synthesized by catalyzed hydrosilylation reaction involving hydrogen atoms of polysiloxane and polyhedral oligomeric silsesquioxane (POSS) and double bonds of vinyl tris17-bromo-3,6,9,12,15- pentaoxaheptadecan-1-ol silane. The obtained structures are based on branched or dendritic with ionic liquid-ethylene oxide oligomer. High room temperature ionic conductivities have been obtained in the range of 10-4-10-5 can be regarded as solid electrolytes. This is attributed to the high concentration of ions from ionic liquid moieties in the tripodand molecule, high segmental mobility, and high ion dissociation from ethylene oxide spacers. The influence of anion structures and lithium salts and concentration has been investigated.

Low Temperature Regolith Bricks for In-Situ Structural Material

NASA Technical Reports Server (NTRS)

Grossman, Kevin; Sakthivel, Tamil S.; Mantovani, James; Seal, Sudipta

2016-01-01

Current technology for producing in-situ structural materials on future missions to Mars or the moon relies heavily on energy-intensive sintering processes to produce solid bricks from regolith. This process requires heating the material up to temperatures in excess of 1000 C and results in solid regolith pieces with compressive strengths in the range of 14000 to 28000 psi, but are heavily dependent on the porosity of the final material and are brittle. This method is currently preferred over a low temperature cementation process to prevent consumption of precious water and other non-renewable materials. A high strength structural material with low energy requirements is still needed for future colonization of other planets. To fulfill these requirements, a nano-functionalization process has been developed to produce structural bricks from regolith simulant and shows promising mechanical strength results. Functionalization of granular silicate particles into alkoxides using a simple low temperature chemical process produces a high surface area zeolite particles that are held together via inter-particle oxygen bonding. Addition of water in the resulting zeolite particles produces a sol-gel reaction called "inorganic polymerization" which gives a strong solid material after a curing process at 60 C. The aqueous solution by-product of the reaction is currently being investigated for its reusability; an essential component of any ISRU technology. For this study, two batches of regolith bricks are synthesized from JSC-1A; the first batch from fresh solvents and chemicals, the second batch made from the water solution by-product of the first batch. This is done to determine the feasibility of recycling necessary components of the synthesis process, mainly water. Characterization including BET surface area, SEM, and EDS has been done on the regolith bricks as well as the constituent particles,. The specific surface area of 17.53 sq m/g (average) of the granular regolith material was obtained from nitrogen adsorption isotherm measurement. The size, shape and textures of regolith from SEM shows that the particles are 25-50 micrometers in size and mostly irregular in shape (Figure 1a). The elemental composition of regolith was identified from EDS analysis showed the presence of Si, Al, Fe, Na, Mg, Ca, Ti, O and C (see figure 1b). Each set of cylindrical brick samples were prepared by low energy process, and cured for 21 and 28 days, respectively to compare their compressive strength. Figure 1c, and d shows the JSC-1A brick and the compressive strength measurements. The results from the 21 day cured bricks (2 bricks) have been done and yielded an aver-age strength of 3050 psi, considerably higher than Portland cement mortars (Type IV and V). This promising technology provides the benefits of construction material similar to concrete, with a low complexity, low energy synthesis process and the likelihood of complete reusability of precious resources. Compressive strength using this method can be improved by increasing the surface area of the particles, using bi-modal particle size distribution, and adding certain additives to increase inter-particle forces.

The synthesis and application of fine particles for coatings and composites

NASA Astrophysics Data System (ADS)

Stephenson, Richard Charles

A variety of coating methods are presented for producing titanium and zirconium oxide coatings on spherical alpha-alumina substrates. Some methods did not completely coat the alumina substrate leaving surface areas exposed. Techniques such as surface modifications with PDVB and 4-VP did produce coatings of metal oxides of very high quality. The best metal oxide coatings are produced from pre-treatment of the alumina microspheres followed by the acid catalyzed hydrolysis of the metal tetra-alkoxides. Methods to investigate converting titanium oxide and zirconium oxide coated alumina microspheres to the corresponding metal carbide coated alumina microspheres have been done. The methods involving direct reduction of the metal oxides by methane and methane-hydrogen gas proved inefficient in producing high quality metal carbide coatings. It is evident higher processing temperatures are required to achieve good metal carbide yield by these methods. Metal oxide coated products carbided by ART (Buffalo, NY) proved the carbiding can be accomplished at higher temperatures and with a different carburizing gas. In addition to the ART carbiding method, the magnesium thermite reaction is a promising method in converting metal oxides to metal carbides at much lower temperatures and shorter processing times. The electrophoretic deposition of Bi2Sr2CaCu 2O8 powder was in ethanol. Of critical consequence were the design of the cathode geometry and the arrangement of the electrodes so that all faces and edges of the silver anode were coated simultaneously. This was achieved by shaping the platinum cathode into a configuration that allowed the silver tape to be completely surrounded by the platinum. The electrophoretic cell was set up to keep the electrodes stationary thereby maintaining a constant distance from the cathode and anode (3 mm). The relationship between deposition time and coating thickness was determined for various powder loadings for a given electric field strength (62 V). For low powder loadings (10 and 20 g/L), the thickness of the coating increases with increasing deposition time (6, 12, and 24 hours). At a powder loading of 30 g/L, the thickness of the BSCCO layer decreases from a deposition time of 6 to 12 hours. At 24 hours, the layer thickness increases. Very high powder loadings (40 g/L) showed a linear decrease in the BSCCO layer thickness with increasing deposition time. Analysis by XRD showed the EPD superconductor exhibited preferential orientation on the silver tape. The degree of orientation was related to the layer thickness and hence the deposition times. Thermal treatment at 800°C in 90% Ar-10% O2 improved the orientation effects. A marked improvement in the surface texture was also observed by SEM. Carbon nanotubes were synthesized via Fe catalysis in an aerosol column in the presence of Ar, CO, and H2 gas. Fe particles were generated by the thermal decarbonylation of Fe(CO)5. Multiwalled and single-walled carbon nanotubes were grown from the decomposition of CO gas on the forming Fe particles. Optimal conditions were determined for producing high yields of single-walled nanotubes. A growth theory is proposed based on the results. (Abstract shortened by UMI.)

Catalytic Stereoselective Installation of Boron Via C-C Bond Formation and Stereoselective Synthesis of N-Heterocyclic Scaffolds Via Main Group Lewis Acid Catalysis

NASA Astrophysics Data System (ADS)

Moyer, Brandon S.

CATALYTIC STEREOSELECTIVE INSTALLATION OF BORON VIA C-C BOND FORMATION. Enantiomerically pure chiral boron-containing molecules provide enabling platforms for chemical synthesis in that they are configurationally stable, they function as useful synthons for various functional groups, and their transformations into those diverse functionalities are stereospecific. With consensus that chiral alkyl sp3 C-B bond-containing compounds are desirable building blocks, and given that most enantioselective preparations to date focus on installing a stereodefined C-B bond, our group sought to develop catalytic methods to generate and use chiral alpha-boron-containing nucleophiles that would enable the direct formation of a new C-C bond. To this extent, we exploited the utility of alkyl 1,1-diboron reagents, which have been shown to readily undergo facile activation and transmetalation in the presence of alkoxide bases to form chiral alpha-boryl nucleophiles. The result of these investigations was the development of the first catalytic enantio- and diastereoselective synthesis of syn-1,2-hydroxyboronates via addition to aldehydes (Ch. 1). The reactions are promoted by a readily available chiral monodentate phosphoramidite-Cu(I) complex in the presence of an alkyl 1,1-diboron reagent. The products contain two contiguous stereogenic centers and are obtained in up to 91% yield, >98:2 d.r., and 98:2 e.r. The reaction is tolerant of aryl and vinyl aldehydes, and the 1,2-hydroxyboronate products can be transformed into versatile derivatives. Mechanistic experiments indicate that control of absolute stereochemistry resides at the alpha-boryl component. Further investigations resulted in the development of a substantially more reactive Ag(I) catalytic protocol for the diastereoselective synthesis of complementary anti-1,2-hydroxyboronates with up to 99:1 d.r. (Ch. 2). We found that the increased reactivity of Ag(I), in conjunction with stoichiometric KOtBu, allowed for a substantial broadening of substituted 1,1-diboronates that participate in the reaction. In addition, alkyl aldehydes were found to be suitable electrophiles with n-BuLi as an activator. STEREOSELECTIVE SYNTHESIS OF N-HETEROCYCLIC SCAFFOLDS VIA MAIN GROUP LEWIS ACID CATALYSIS. Silylium ions (formally [R 3Si]+) have long been the subject of investigations and significant debate in both theoretical and experimental chemistry, but few catalytic, synthetic applications have been reported due to the exceptionally high reactivity and Lewis acidity of these elusive species. Chapter 3 discusses the application of easily accessible silylium ion catalysts to the stereoselective synthesis of various N-heterocyclic pyrrolidine and piperidine scaffolds. The tested substrates are derived from the chiral pool and can be obtained in three high-yielding steps from amino alcohols; subsequent stereoselective silylium ion-catalyzed Prins-cyclization and trapping with R3Si-Nu nucleophiles (e.g. Nu = H, allyl, azide, and enol ethers) results in novel nitrogen-containing polycyclic scaffolds with potential medicinal chemistry applications. An appendix to this chapter (A) discusses the substrate scope of the unpublished discovery that the Lewis acid B(C6F5)3 catalyzes a stereospecific Prins cyclization followed by an elimination (formally a carbonyl-ene reaction) to form trans-tetrahydropyridine products in exceptionally high yield and diastereoselectivity.

The protein and peptide mediated syntheses of non-biologically-produced oxide materials

NASA Astrophysics Data System (ADS)

Dickerson, Matthew B.

Numerous examples exist in nature of organisms which have evolved the ability to produce sophisticated structures composed of inorganic minerals. Studies of such biomineralizing organisms have suggested that specialized biomolecules are, in part, responsible for the controlled formation of these structures. The research detailed in this dissertation is focused on the use of biomolecules (i.e., peptides and proteins) to form non-biologically produced materials under mild reaction conditions (i.e., neutral pH, aqueous solutions, and room temperature). The peptides utilized in the studies detailed in this dissertation were identified through the screening of single crystal rutile TiO2 substrates or Ge powder with a phagedisplayed peptide library. Twenty-one peptides were identified which possessed an affinity for Ge. Three of these twenty one peptides were tested for germania precipitation activity. Those peptides possessing a basic isoelectric point as well as hydroxyl- and imidazole-containing amino acid residues were found to be the most effective in precipitating amorphous germania from an alkoxide precursor. The phage-displayed peptide library screening of TiO2 substrates yielded twenty peptides. Four of these peptides, which were heavily enriched in histidine and/or basic amino acid residues, were found to possess signficant titania precipitation activity. The activity of these peptides was found to correlate with the number of positive charges they carried. The sequence of the most active of the library-identified peptides was modified to yield two additional peptides. The titania precipitation activity of these designed peptides was higher than the parent peptide, with reduced pH dependence. The titania materials generated by the library-identified and designed peptides were found to be composed of amorphous titania as well as <10 nm anatase and/or monoclinic TiO2 crystallites. The production of titania and zirconia resulting from the interaction of the cationic enzyme, hen egg white lysozyme, with Ti- or Zr-lactate precursors is also presented in this dissertation. Lysozyme was found to entrap itself in an active form within the nanoparticles of amorphous titania or zirconia precipitated by this protein under ambient conditions. The lysozyme synthesized titania was observed to be superior to the lysozyme-zirconia materials in preserving the activity of the enzyme under denaturing conditions. Four recombinant proteins, derived from the amino acid sequences of proteins (silaffins) associated with biosilicification in diatoms, were also investigated for titania precipitation activity. The two most basic of these recombinant silaffins, rSil1L and rSilC, were able to induce the formation of titania. The titania precipitates generated by rSil1L were found to be similar to those produced by the phage-displayed library identified peptides. The second recombinant silaffin, rSilC, was found to produce hollow spheres of titania, which, following dehydration, were observed to transform into larger, solid spheres composed of radially aligned columns of rutile TiO2. The highly repetitive nature of the rSilC's amino acid sequence is believed to be responsible for the differences in TiO2 polymorph generated by the different recombinant silaffins and peptides. This dissertation also details research conducted on the formation of titania utilizing rSilC conjugated to synthetic and biogenic silica surfaces. These silica surfaces were functionalized with a newly developed drendritic growth technique. The dendritic functional-group amplification process was demonstrated to increase the loading of hexahisitidine tagged proteins on silica surfaces by more than 40%, as compared to traditional immobilization procedures. The higher loadings of rSilC provided by this dendritic growth method were observed to have a positive impact on the extent of surface mineralization. The titania formed by immobilized rSilC was observed to be composed of amorphous and crystalline TiO2.

Molecular-level Design of Heterogeneous Chiral Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilfred T. Tysoe

2007-04-25

It has been shown previously that the adsorption of a chiral 2-butanol template on Pd(111) leads to enantioselective adsorption of chiral propylene oxide probe molecules. Enantioselectivity is expressed over a narrow coverage range where the maximum value of enantioselectivity ratio (ER defined as Θ(R-propylene oxide)/Θ(S-propylene oxide), where Θ is the coverage) reaches ~2. Probe coverages in this case were measured using either reflection-absorption infrared spectroscopy (RAIRS) or temperature-programmed desorption (TPD) [1,2]. The enantioselectivity disappears when the 2-butanol-covered surface was heated to ~200 K since the adsorbed butoxy species decomposes by a β-hydride elimination reaction to yield a non-chiral ketone. Montemore » Carlo calculations of the effect of chiral modifiers have yielded results that are consistent with these experimental observations [3,4]. Similar experiments using 2-methyl butanoic acid as a template, where the chiral center is identical to that in 2-butanol but is now anchored by a carboxylate group rather than by an alkoxide, shows no enantioselectivity. In this case, propylene oxide coverages were measured using the King and Wells method. RAIRS experiments and density functional calculations suggest that the 2-butyl group of the 2-butoxy species is oriented parallel to the surface. A possible origin for the lack of enantioselectivity of a 2-methyl butanoic acid-covered surface may be that the 2-butyl group is farther from the surface, allowing it to rotate more freely, averaging out any asymmetry, resulting in a loss of chirality. In order to test this idea, the alkyl group on the carboxylic acid was functionalized with an amine to anchor the chiral center to the surface. Using the amino-acids alanine and 2-amino butanoic acid as templates restored the enantioselectivity and yielded ER values of 2.0 ± 0.2 and 1.75 ± 0.15 respectively. These results suggest that a two-point attachment of the chiral template is required, one for surface adsorption and the other to allow the enantioselectivity to be expressed. Low-energy electron diffraction (LEED) intensity versus energy (I/E) measurements are used to measure the structure of templates and probes on the Pd(111) surface, where these results will be compared with calculations carried out by the Sholl group. Since the aminoacids are relatively large, initial experiments were carried out to determine the structure of carboxylates on the surface to determine the carboxylate group anchoring site. Since carboxylates do not form ordered structures on Pd(111), we have exploited a method recently developed in collaboration with Professor Saldin to measure structures of disordered overlayers [5]. Results show that the formate OCO plane is oriented perpendicular to the surface with the oxygen atoms located across a short bridge on the (111) surface. The effect of the size of the functional group on the amino acid template (RCH(NH2)COOH) was also investigated where the maximum ER values obtained using propylene oxide were 2.0 ± 0.2 (R=CH3), 1.75 ± 0.15 (R=C2H5), 1.65 ± 0.15 (R=C3H6) and 1.30 ± 0.15 (R=CH2CH(CH3)2) thus showing a decreasing trend with increasing size of the side chain. The enantioselectivity of S-(1-naphthyl) ethylamine-covered surfaces have been explored using propylene oxide as a probe, but these systems showed no enantioselectivity. However, using 2-butanol as a probe lead to enantioselective chemisorption implying that one-to-one modification requires a direct hydrogen-bonding interaction between the probe and modifier. 1. Enantioselective Chemisorption on a Chirally Patterned Surface in Ultrahigh Vacuum: Adsorption of Propylene Oxide on 2-butoxy-Covered Pd(111), D. Stacchiola, L. Burkholder and W.T. Tysoe, J. Am. Chem. Soc., 124, 8984 (2002) 2. Enantioselective Chemisorption on a Chirally Modified Surface in Ultrahigh Vacuum: Adsorption of Propylene Oxide on 2-butoxide-Covered Pd(111), Darío Stacchiola, Luke Burkholder and Wilfred T. Tysoe, J. Mol. Catal A: Chemical, 216, 215 (2004) 3. Theoretical Analysis of the Coverage Dependence of Enantioselective Chemisorption on a Chirally Patterned Surface, F. Roma, D. Stacchiola, G. Zgrablich and W. T. Tysoe, Journal of Chemical Physics, 118, 6030 (2003) 4. Lattice-gas Modeling of Enantioselective Adsorption by Template Chiral Substrates, F. Romá, D. Stacchiola, W.T. Tysoe and G. Zgrablich, Physica A., 338, 493 (2004) 5. Structure Determination of Disordered Organic Molecules on Surfaces from the Bragg Spots of Low Energy Electron Diffraction and Total Energy Calculations, H. C. Poon, M. Weinert, D. K. Saldin, D. Stacchiola, T. Zheng and W. T. Tysoe, Phys. Rev. B., 69, 35401 (2004)« less

Microstructure and Mechanics of Superconductor Epitaxy via the Chemical Solution Deposition Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frederick F. Lange

2006-11-30

Executive Summary: Initially the funds were sufficient funds were awarded to support one graduate student and one post-doc. Lange, though other funds, also supported a graduate intern from ETH Zurich, Switzerland for a period of 6 months. The initial direction was to study the chemical solution deposition method to understand the microstructural and mechanical phenomena that currently limit the production of thick film, reliable superconductor wires. The study was focused on producing thicker buffer layer(s) on Ni-alloy substrates produced by the RABiTS method. It focused on the development of the microstructure during epitaxy, and the mechanical phenomena that produce cracksmore » during dip-coating, pyrolysis (decomposition of precursors during heating), crystallization and epitaxy. The initial direction of producing thicker layers of a know buffer layer material was redirected by co-workers at ORNL, in an attempt to epitaxially synthesize a potential buffer layer material, LaMnO3, via the solution route. After a more than a period of 6 months that showed that the LaMnO3 reacted with the Ni-W substrate at temperatures that could produce epitaxy, reviewers at the annual program review strongly recommended that the research was not yielding positive results. The only positive result presented at the meeting was that much thicker films could be produce by incorporating a polymer into the precursor that appeared to increase the precursor’s resistance to crack growth. Thus, to continue the program, the objectives were changed to find compositions with the perovskite structure that would be a) chemically compatible with either the Ni-W RABiTS or the MgO IBAD Ni-alloy substrates, and produce a better lattice parameter fit between either of the two substrates. At the start of the second year, the funding was reduced to 2/3’s of the first year level, which required the termination of the post-doc after approximately 5 months into the second year. From then on, further funding was intermittent to say the least, and funding to support the student and the research expenses has to be supplemented by Lange’s gift funds. During the first part of the second year, strontium zirconate was identified as an alternative to lanthanum manganite as a buffer layer for use on the IBAD MgO superconducting wire. A lattice parameter of 4.101 Angstroms offers a reduced lattice mismatch between the MgO and SrZrO3. Studies were focused on investigating hybrid precursor routes, combining Sr acetate with a number of different Zr alkoxides. Initial results from heat treating precursors to form powders are positive with the formation of orthorhombic SrZrO3 at temperatures between 800°C and 1100°C under a reducing atmosphere of Ar – 5% H2. Buffer layer research on RABiTS substrates were centered on GdAlO3 (3.71 Å) and YAlO3 (3.68 Å) buffer layer materials. Powder experiments in YAlO3 have shown the perovskite phase to be metastable at processing temperatures below 1500 °C. Experiments involving spin coating of YAlO3 precursors have found significant problems involved with wettability of the YAlO3 precursor (Yttrium acetate, Aluminum tri-sec butoxide, DI water and Formic Acid) on RABiTS substrates; this, and the demise of the funds precluded further research using YAlO3. The diminished funds for the second year, and the small, tricked funds during the third year lead to a redirection of the student to another research area., and a stop to any experimental achievements that were much too ambition relative to the available funds. The only positive results obtained during this latter period was the understanding why two dissimilar structures could result in an epitaxial relation. It was shown that two rules of crystal chemistry, cation/anion coordination and charge balance, could be applied to understand the epitaxy of SrTiO3 on Ni c(2 X 2)S, TiO2 (anatase) on LaAlO3, TiO2 (rutile) on r-plane Al2O3, and Zr1-x(Yx)O2 on (0001) Al2O3. This new understanding of the interface between two dissimilar structures has important implications that include the buffer layers used for the superconductor program, namely, the epitaxy of perovskites such as the epitaxy of SrTiO3 on the Ni c(2 X 2)S wire. This discovery is the major part of the finial report that follows.« less

Synthesis, Characterization, and Catalytic Applications of Transition Metal Oxide/Carbonate Nanomaterials

NASA Astrophysics Data System (ADS)

Jin, Lei

2011-12-01

This thesis contains two parts: 1) Studies of novel synthesis methods and characterization of advanced functional manganese oxide octahedral molecular sieves (OMS) and their applications in Li/Air batteries, solvent free toluene oxidations, and ethane oxydehydrogenation (ODH) in the presence of CO2, recycling the green house gas. 2) Development of unique Ln2O2CO3 (Ln = rare earth) layered materials and ZnO/La2O2CO3 composites as clean energy biofuel catalysts. These parts are separated into five different focused topics included in this thesis. The first topic presents studies of catalytic activities of a single step synthesized gamma-MnO2 octahedral molecular sieve nano fiber in solvent free atmospheric oxidation of toluene with molecular oxygen. Solvent free atmospheric oxidation of toluene is a notoriously difficult liquid phase oxidation process due to the challenge of oxidizing sp³ hybridized carbon in inactive hydrocarbons. The synthesized gamma-MnO2 showed excellent catalytic activity and good selectivity under the mild atmospheric reflux system. Under optimized conditions, a 47.8% conversion of toluene, along with 57% selectivity of benzoic acid and 15% of benzaldehyde were obtained. The effects of reaction time, amount of catalyst and initiator, and the reusability of the catalyst were investigated. The second topic involves developing titanium containing gamma-MnO 2 (TM) hollow spheres as electrocatalysts in Li/Air Batteries. Li/air batteries have recently attracted interest because they have the largest theoretical specific energy (11,972 Wh.kg-1) among all practical electrochemical couples. In this study, unique hollow aspheric materials were prepared for the first time using a one-step synthesis method and fully characterized by various techniques. These prepared materials were found to have excellent electrocatalytic activation as cathode materials in lithium-air batteries with a very high specific capacity (up to 2.3 A.h/g of carbon). The third topic in this thesis presents studies of ethane oxydehydrogenation (ODH) in the presence of CO2 over the octahedral molecular sieve (OMS-2) catalyst. Conversion of CO2 into organic compounds has been studied intensively. Ethane catalytic oxydehydrogenation in the presence of CO2 offers an attractive route for converting CO2. In this study, using OMS-2 as the catalyst in C2H6 dehydrogenation in the presence of CO2 is an example where extreme conditions are used to drive high conversions of ethane (> 70%) and CO2 (up to 56%) with high selectivity towards ethylene (87%) with a short contact time (0.6 s). This inexpensive material also showed high stability during the process, and the presence of CO2 removed coke depositions throughout the catalyst. The results obtained from this study open up new possibilities for olefin dehydrogenations in the presence of CO2, a perfect feedstock for any process involving ethylene carbonylation with the recycling of the greenhouse gas. The fourth part of this thesis presents a ZnO/La2O2CO 3 composite prepared by a new and easy method and discusses the use of these materials as heterogeneous catalysts for ultra-fast microwave biodiesel production at low temperatures. The search for solid state materials with high catalytic activities is one of the key steps toward reducing the cost of producing biodiesel. We present a high biodiesel yield (> 95%) in less than 5 minutes under mild reaction conditions (< 100°C) on a ZnO/La 2O2CO3 heterogeneous catalyst, showing no Zn and La leaching into the reaction medium. The catalyst has a higher reaction rate than the homogeneous KOH catalyst with the assistance of microwave irradiation. All of these results promote the industrial application of the synthesized ZnO/La2O2CO3 as a potential heterogeneous catalyst for fast biodiesel production, avoiding many of the issues found in both commercial and independently published catalysts. Following the fourth part of this thesis, the fifth part presents the synthesis and characterization of a series of rare earth Ln2O 2CO3 (Ln = La, Eu, Nd, and Sm) layered materials as novel basic materials for the biodiesel production. Reports on rare earth oxycarbonate Ln2O2CO3 (Ln = rare earths) layered materials as heterogeneous basic catalysts having novel low temperature catalytic activities are rare. In this thesis I successfully synthesized active rare earth (Ln = La, Nd, Eu, and Sm) metal oxycarbonate based layered materials to catalyze the transesterification process under mild conditions (< 85°C), obtaining a high fatty acid methyl ester (FAME) yield (> 95%) in a short reaction time (< 20 minutes). The results of low temperature activities and short reaction times with minimum energy consumption show them to have solid potential as alkali metal hydroxide/alkoxide alternatives for industrial applications.