Binary metal oxides for composite ultrafiltration membranes

A new ultrafiltration membrane was developed by the incorporation of binary metal oxides inside polyethersulfone. Physico-chemical characterization of the binary metal oxides demonstrated that the presence of Ti in the TiO2?ZrO2 system results in an increase of the size of the oxides, and also their dispersity. The crystalline phases of the synthesized binary metal oxides were identified as srilankite and zirconium titanium oxide. The effect of the addition of ZrO2 can be expressed in terms of the inhibition of crystal growth of anocrystalline TiO2 during the synthesis process. For photocatalytic applications the band gap of the synthesized semiconductors was determined, confirming a gradual increase (blue shift) in the band gap as the amount of Zr loading increases. Distinct distributions of binary metal oxides were found along the permeation axis for the synthesized membranes. Particles with Ti are more uniformly dispersed throughout the membrane cross-section. The physico-chemical characterization of membranes showed a strong correlation between some key membrane properties and the spatial particle distribution in the membrane structure. The proximity of metal oxide fillers to the membrane surface determines the hydrophilicity and porosity of modified membranes. Membranes incorporating binary metal oxides were found to be promising candidates for wastewater treatment by ultrafiltration, considering the observed improvement influx and anti-fouling properties of doped membranes. Multi-run fouling tests of doped membranes confirmed the stability of permeation through membranes embedded with binary TiO2?ZrO2 particles.

meso-Porphyrinylphosphine Oxides: Mono- and Bidentate Ligands for Supramolecular Chemistry and the Crystal Structures of Monomeric [10,20-Diphenylporphyrinatonickel(II)-5,15-diyl]-bis-[P(O)Ph2] and Polymeric Self-Coordinated ([10,20-Diphenylporphyrinatozinc(II)-5,15-diyl]-bis-[P(O)Ph2])

A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Nanowires of metal oxides for gas sensing applications

Nanowires of different metal oxides (SnO2, ZnO) have been grown by evaporation-condensation process. Their chemical composition has been investigated by using XPS. The standard XPS quantification through main photoelectron peaks, modified Auger parameter and valence band spectra were examined for the accurate determination of oxidation state of metals in the nanowires. Morphological investigation has been conducted by acquiring and analyzing the SEM images. For the simulation of working conditions of sensor, the samples were annealed in ultra high vacuum (UHV) up to 500°C and XPS analysis repeated after this treatment. Finally, the nanowires of SnO 2 have were used to produce a novel gas sensor based on Pt/oxide/SiC structure and operating as Schottky diode. Copyright © 2008 John Wiley & Sons, Ltd.

Reduction of functionalized graphite oxides by trioctylphosphine in non-polar organic solvents

Graphene, functionalized with oleylamine (OA) and soluble in non-polar organic solvents, was produced on a large scale with a high yield by combining the Hummers process for graphite oxidation, an amine-coupling process to make OA-functionalized graphite oxide (OA-GO), and a novel reduction process using trioctylphosphine (TOP). TOP acts as both a reducing agent and an aggregation-prevention surfactant in the reduction of OA-GO in 1,2-dichlorobenzene (DCB). The reduction of OA-GO is confirmed by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and Raman spectroscopy. The exfoliation of GO, OA GO, and OA-functionalized graphene (OA-G) is verified by atomic force microscopy. The conductivity of TOP-reduced OA G, which is deduced from the current–voltage characteristics of a vacuum-filtered thin film, shows that the reduction of functionalized GO by TOP is as effective as the reduction of GO by hydrazine.

Interstellar titanium-oxides in interplanetary dust

Interstellar gas abundances (Clayton et al., 1986) suggest that titanium may be bound up in dust and indeed, excess titanium in carbonaceous chondrites is attributed to mixing of interstellar and Solar System materials (Morton, 1974). Fine-grained chondritic interplanetary dust particles (lOPs) of cometary origin are relatively pristine early Solar System materials (Mackinnon and Rietmeijer, 1987; Rietmeijer, 1987) and show chemical and mineralogical signatures related to a pre-solar or nebular origin. For example, large OtH ratios suggest a presolar or interstellar dust component in some chondritic lOPs(Mackinnon and Rietmeijer, 1987). Ti/Si ratios (normalized to bulk CI) in lOPs and carbonaceous chondrite matrices exceed solar abundances but are similar to dust from comet Halley (Jessberger et al., 1987). The Ti-distribution in chondritic lOPs shows major, small-scale « 0.1 urn) variations (Flynn et al., 1978) consistent with heterogeneously distributed Ti-bearingphases. Analytical electron microscope (AEM) studies, in fact, have identified platey grains of Ti-metal, Ti407 and Ti s09 in two different lOPs (Mackinnon and Rietmeijer, 1987). The occurrence of Ti407 was related in situ low-temperature aqueous alteration and therefore implied the presence of BaTi03 (Rietmeijer and Mackinnon, 1984). Yet, the presence ofTis09 in an lOp which shows no evidence of aqueous alteration (Rietmeijer.and McKay, 1986) requires a different interpretation. The distribution of Ti-oxides in chondritic lOPs were investigated with ultra-microtomed thin sections of fluffy chondri tic lOP U2011*B (lSC allocation U2011C2) using a lEOL 2000FX AEM operating at an accelerating voltage of 200kV and with an attached Tracor Northern TN5500 energy dispersive spectrometer.

Final-state effects in neutron Compton scattering measurements on zirconium deuteride and beryllium

We report inelastic neutron scattering measurements of the neutron Compton profile, J(y), for Be and for D in polycrystalline ZrD2 over a range of momentum transfers, q between 27 and 178 °A−1. The measurements were performed using the inverse geometry spectrometer eVS which is situated at the UK pulsed spallation neutron source ISIS. We have investigated deviations from impulse approximation (IA) scattering which are generically referred to as final state effects (FSEs) using a method described by Sears. This method allows both the magnitude and the q dependence of the FSE to be studied. Analysis of the measured data was compared with analysis of numerical simulations based on the harmonic approximation and good agreement was found for both ZrD2 and Be. Finally we have shown how (∇2V), where V is the interatomic potential, can be extracted from the antisymmetric component of J(y).

Process and catalysts for the methanation of oxides of carbon

The present invention is directed to catalysts for the conversion of oxides of carbon to methane and/or other hydrocarbons and to precursors of such catalysts. The catalyst precursors include one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth contg. perovskites, the precursor including nickel or nickel cations sufficient for a catalyst obtainable by reducing the precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product. Processes for the prepn. of such catalysts and catalyst precursors are also disclosed, as are processes for the conversion of oxides of carbon to methane and/or other hydrocarbons. [on SciFinder(R)]

Method of making metal oxides

A method for producing particles having at least regions of at least one metal oxide having nano-sized grains comprises providing particles of material having an initial, non-equiaxed particle shape, making a mixture of the particles of material and one or more precursors of the metal oxide, and treating the mixture such that the one or more precursors of the metal oxide react with the particles of material to thereby form at least regions of metal oxide on or within the particles, wherein atoms from the particles of material form part of a matrix of the at least one metal oxide and the at least one metal oxide has nano-sized grains and wherein at least some of the regions of metal oxide on or within the particles have a non-equiaxed grain shape.

Method for the production of porous complex metal oxides using a porogen

A method of producing porous complex oxides includes the steps of providing a mixt. of (a) precursor elements suitable to produce the complex oxide, or (b) one or more precursor elements suitable to produce particles of the complex oxide and one or more metal oxide particles; and (c) a particulate carbon-contg. pore-forming material selected to provide pore sizes in the range of 7-250 nm, and treating the mixt. to (i) form the porous complex oxide in which two or more of the precursor elements from (a) above or one or more of the precursor elements and one or more of the metals in the metal oxide particles from (b) above are incorporated into a phase of the complex metal oxide and the complex metal oxide has grain sizes in the range of 1-150 nm, and (ii) removing the pore-forming material under conditions such that the porous structure and compn. of the complex oxide is substantially preserved. The method may be used to produce nonrefractory metal oxides as well. The mixt. further includes a surfactant, or a polymer. [on SciFinder(R)]