Showing papers by "Vadim G. Kessler published in 2013"

Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide

Abstract: Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8·4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions.

Facile non-hydrolytic synthesis of highly water dispersible, surfactant free nanoparticles of synthetic MFe2O4 (M–Mn2+, Fe2+, Co2+, Ni2+) ferrite spinel by a modified Bradley reaction

Abstract: A series of the highly crystalline MFe2O4 ferrite spinel nanoparticles were synthesized via a modified Bradley reaction using microwave stimulation. Particle size was estimated using theoretical calculations from the X-ray data (Scherrer and Rietveld methods) as well as by direct experimental techniques such as TEM, DLS and NTA. The calculated average grain size for dry powders is in the range 10 to 23 nm. Hydrodynamic size was measured using DLS on non-modified, surfactant free particles of the whole MFe2O4 series. Raman spectra used for additional verification of the structure features of the produced spinel phases showed strong asymmetric behavior of the A1g mode, which was deconvoluted revealing additional components. Among all the products the lowest site inversion was found for the manganese ferrite (MnFe2O4). The oxidation of Fe3O4 leading to the formation of the Fe2O3 hematite phase induced by laser irradiation was observed. Magnetic characterization of the MFe2O4 family was carried out, showing that superparamagnetic blocking temperatures and calculated anisotropy constants K are in good agreement with the data for similar fine-particle systems.

Urease adsorption and activity on magnetite nanoparticles functionalized with monofunctional and bifunctional surface layers

Abstract: The surface of magnetite nanoparticles was coated with functional polysiloxane layers using reaction of hydrolytic copolycondensation of tetraethoxysilane and 3-aminopropyltriethoxysilane (or N-[3-trimethoxysilylpropyl]ethylendiamine), and also that of tetraethoxysilane, 3-aminopropyltriethoxysilane and methyltriethoxysilane (or n-propyltriethoxysilane). It was shown that these functionalized magnetically controllable particles (about 60–150 nm in size as aggregates), as opposed to magnetite, adsorb urease well from aqueous solutions (up to 1 g/g), and that the level of residual activity of adsorbed layers is up to 84 % in the case of a bifunctional sample. It was established that the activity of immobilized urease is normally gradually reduced during storage of the samples, but in the case of ethylenediamine functional group is not decreased for 45 days. The synthesized samples are promising for use as magnetically directed biocatalysts.

Mesoporous Anatase TiO2 Nanorods as Thermally Robust Anode Materials for Li-Ion Batteries: Detailed Insight into the Formation Mechanism

Abstract: Uniformly mesoporous and thermally robust anatase nanorods were produced with quantitative yield by a simple and efficient one-step approach. The mechanism of this process was revealed by insertion of Eu(3+) cations from the reaction medium as luminescent probes. The obtained structure displays an unusually high porosity, an active surface area of about 300 m(2) g(-1) and a specific capacity of 167 mA h g(-1) at a C/3 rate, making it attractive as an anode electrode for Li-ion batteries. An additional attractive feature is its remarkable thermal stability; heating to 400 °C results in a decrease in the active surface area to a still relatively high value of 110 m(2) g(-1) with conservation of open mesoporosity. Thermal treatment at 800 °C or higher, however, causes transformation into a non-porous rutile monolith, as commonly observed with nanoscale titania.

Aqueous route to TiO2-based nanomaterials using pH-neutral carboxylate precursors

Abstract: The review presents the industrial and laboratory synthesis, molecular structure and reactivity of titanium(IV) carboxylate complexes stable in aqueous medium. A special accent is made on the solution ligand-transfer equilibria that are able to provide uniform TiO2 nanoparticles under rather mild conditions starting from these easily commercially available species. Application of titanium oxide nanostructures derived from solution-generated titania nanoparticles is described in detail.

One-pot synthesis of mesoporous SBA-15 containing protonated 3-aminopropyl groups

Abstract: A new technique of synthesis of mesoporous silica with protonated amino groups avoiding microwave treatment of mesophase was developed using a template method. The block-copolymer P123 was used as a template and sodium meta-silicate with 3-aminopropyltriethoxysilane as precursors. After the removal of template from mesophase with boiling ethanol, the obtained sample displayed highly ordered hexagonal structure with attractive textural parameters: SBET = 460 m2 g−1, Vtotal = 0.79 cm3g−1 and d = 7.1 nm. FTIR and 13C CP/MAS NMR spectroscopy revealed the presence of alkyl ammonium groups (0.7 mmol g−1) that were able to attach anions of molybdophosphoric acid to the surface of the synthesized mesoporous material. The resulting anion-ion exchange phase can find applications in many areas (adsorption, catalysis, etc.).

Sol–gel synthesis, characterization and catalytic activity of γ-alumina with bimodal mesopore distribution

Abstract: In this study, boehmite sols were used for preparation of mesoporous γ-alumina with bimodal mesopore distribution. Superfine nanospheres of poly(methyl methacrylate) (PMMA) prepared by water based emulsion polymerization method were used as a template. Nitrogen sorption revealed that aluminas prepared using this approach demonstrated bimodal mesopore size distribution with maxima at 3.8 and 25.7 nm, respectively. Catalytic tests showed that bimodal mesopore distribution within γ-Al2O3 prepared with PMMA nanospheres as a template provides improved catalytic activity in the methanol dehydration reaction.

Alkoxides and Alkoxosynthesis

Abstract: This chapter summarizes modern approaches in the synthesis of metal alkoxides, provides an overview of their physical and chemical properties, with a special focus on molecular structure and reactivity, and gives a brief but up-to-date presentation of the reaction mechanisms in the synthesis of inorganic materials from metal alkoxides as precursors (alkoxosynthesis). A critical overview of molecular precursor approaches exploiting homo- and heteroleptic alkoxide complexes is provided, explaining the role of heteroligands in nucleation and subsequent growth of the resulting nanostructured materials. This chapter also provides a brief summary of other principal applications of metal alkoxides, such as homogeneous catalysts and molecular magnets, with a special focus on the synthesis and structure of these functional molecules.