Structure and electronic properties of the quasi-one-dimensional Ba₂Co₁₋ₓZnₓS₃ series

This work focuses on the structure and physical properties of the solid solution Ba₂Co₁₋ₓZnₓS₃ (0 ≤ x ≤ 1), a family of quasi-one-dimensional sulfides with end members Ba₂CoS₃ and Ba₂ZnS₃. The structure of selected compounds with increasing Zn²⁺ content has been analysed using, neutron diffraction, TEM and EXAFS and the physical properties via magnetic susceptibility and resistivity measurements. The progressive substitution of the non-magnetic Zn²⁺ cation for Co²⁺ rapidly destroys the antiferromagnetic transition present at 46 K in the quasi one-dimensional Ba₂CoS₃, leading to paramagnetic behaviour down to the lowest investigated temperature (5K) for compounds with x > 0.25. For compounds with x ≥ 0.4, a pure CW regime is recovered around 300 K, yielding effective moments consistent with the g factor of the tetrahedrally coordinated Co²⁺ previously determined for Ba₂CoS₃. The Zn²⁺/Co²⁺ substitution also removes the metallic-like behaviour of Ba₂CoS₃ causing an increase in the value of the resistivity with all the Ba₂Co₁₋ₓZnₓS₃ compounds showing semiconducting behaviour. The negative magnetoresistance of Ba₂CoS₃ is improved by the Zn²⁺/Co²⁺ substitution, with values of – 6% for Ba₂Co₀.₇₅Zn₀.₂₅S₃, – 9% for Ba₂Co₀.₅Zn₀.₅S₃ and – 8% for Ba₂Co₀.₂₅Zn₀.₇₅S₃. However, there does not seem to be a correlation between the values of the resistivity and the magnetoresistance and the content of Zn²⁺, leading to the hypothesis that transport properties may be linked more closely to extrinsic properties

A synchrotron study of Ba5Ta2Cl2O9

The structure of pentabarium ditantalum dichloride nonaoxide, Ba5Ta2Cl2O9, is isotypic with Ba5Ru1.6W0.4Cl2O9 and with one polymorph of Ba5Ru2Cl2O9. It is related to the perovskite structure and shows a ten-layer stacking of BaO3 and BaCl blocks along the c axis. The Ta cations occupy octahedral interstices, forming Ta2O9 dimers of distorted face-shared TaO6 octahedra. Except for one O atom, all atoms are situated on special positions: Ba1 (Wyckoff position (6) over bar m2), Ba2 and Ba3 (3m.), Ta (3m.), Cl (3m.) and O1 (mm2)

Direct amine-functionalisation of γ-Fe2O3nanoparticles

A novel and simple preparation of amine-modified γ-Fe2O3 nanoparticles is described. The presence of amine groups on the surface, instead of hydroxyl groups, will allow conjugation of biologically active molecules to the iron oxide nanoparticles without the need for a size increasing silica shell. Furthermore, the outer amine-layer increases the temperature of the γ-Fe2O3 to α-Fe2O3 structural transition in a similar way to previously reported cationic substitutions. This may suggest the formation of an oxide–nitride outer layer. Re-dispersion of the amine-modified γ-Fe2O3 nanoparticles led to the preparation of stable ferrofluids

Synthesis and antibacterial effects of cobalt–cellulose magnetic nanocomposites

© The Royal Society of Chemistry. Green synthesis is employed to prepare cobalt/cellulose nanocomposites with cubic (α-cobalt) cobalt as a main component with antibacterial and magnetic properties. An in situ reduction of aqueous solutions of cobalt ions on a model cellulose substrate surface using hydrogen gas affords spherical, cellulose-stabilised cobalt nanoclusters with magnetic properties and an average diameter of 7 nm that are distributed evenly over the surface of the cellulose fibres. These cobalt/cellulose nanocomposites exhibit good antibacterial action against opportunistic pathogens both Gram-positive (S. aureus) and Gram-negative (E. coli, A. baumannii and P. aeruginosa), with zones of inhibition up to 15 mm, thereby encouraging the deployment of these advanced materials for the treatment of wastewater or within medical dressings. This method of preparation is compared with the analogous in situ reduction of cobalt ions on a cellulose surface using sodium borohydride as reducing agent

The preparation of magnetic iron oxide nanoparticles in microreactors

The preparation of magnetic iron oxide nanoparticles within microreactors is reported. The proportion of γ-Fe2O3 and Fe 3O4 in the sample was determined, an important parameter for reproducibility in applications. © 2013 Akadémiai Kiadó

Doping of inorganic materials in microreactors – preparation of Zn doped Fe₃O₄ nanoparticles

Microreactor systems are now used more and more for the continuous production of metal nanoparticles and metal oxide nanoparticles owing to the controllability of the particle size, an important property in many applications. Here, for the first time, we used microreactors to prepare metal oxide nanoparticles with controlled and varying metal stoichiometry. We prepared and characterised Zn-substituted Fe₃O₄ nanoparticles with linear increase of Zn content (ZnxFe₃−xO₄ with 0 ≤ x ≤ 0.48), which causes linear increases in properties such as the saturation magnetization, relative to pure Fe₃O₄. The methodology is simple and low cost and has great potential to be adapted to the targeted doping of a vast array of other inorganic materials, allowing greater control on the chemical stoichiometry for nanoparticles prepared in microreactors

Stabilization of Pd3−xIn1+x polymorphs with Pd-like crystal structure and their superior performance as catalysts for semi-hydrogenation of alkynes

Selective hydrogenation (semi-hydrogenation) reactions of alkynes rely on Pd-based catalysts to provide the correct pathway to favour formation of double bonds and avoid full hydrogenation to single bonds. Here, we present the preparation and characterisation of "Pd3In"/TiO2 nanocatalysts, which show improved activity and selectivity compared to pure Pd catalysts, towards the liquid phase semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE), a fundamental step in the preparation of pharmaceuticals, and other industrially produced substances, as well as a model reaction for the semi-hydrogenation of alkynes. For both the supported and unsupported "Pd3In" alloys (later redefined as Pd3-xIn1+x), we stabilised two new cubic polymorphs with a Pd-like structure, instead of the tetragonal structure as reported so far in the literature. The stabilisation of these new polymorphs was made possible by using a solution-based synthesis and, thanks to the use of different solvents, the reaction was 2 carried out at different temperatures and the Pd/In ratio could be tuned. The same synthetic approach was adapted to prepare two "Pd3In"/TiO2 catalysts by adding the TiO2 support to the reaction mixture, in a practical one-step, one-pot reaction. HREM and X-Ray maps show that the cubic crystal structure of "Pd3In" is maintained when prepared in the presence of the support, however, the support seems to influence the Pd/In ratio

Bi2WO6/C-dots/TiO2: A novel z-scheme photocatalyst for the degradation of fluoroquinolone levofloxacin from aqueous medium

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. Photocatalytic materials and semiconductors of appropriate structural and morphological architectures as well as energy band gaps are materials needed for mitigating current environmental problems, as these materials have the ability to exploit the full spectrum of solar light in several applications. Thus, constructing a Z-scheme heterojunction is an ideal approach to overcoming the limitations of a single component or traditional heterogeneous catalysts for the competent removal of organic chemicals present in wastewater, to mention just one of the areas of application. A Z-scheme catalyst possesses many attributes, including enhanced light-harvesting capacity, strong redox ability and different oxidation and reduction positions. In the present work, a novel ternary Z-scheme photocatalyst, i.e., Bi2WO6/C-dots/TiO2, has been prepared by a facile chemical wet technique. The prepared solar light-driven Z-scheme composite was characterized by many analytical and spectroscopic practices, including powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), N2 adsorption–desorption isotherm, Fourier-transform infrared spectroscopy (FT-IR), photoluminescence (PL) and UV-vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity of the Bi2WO6/C-dots/TiO2 composite was evaluated by studying the degradation of fluoroquinolone drug, levofloxacin under solar light irradiation. Almost complete (99%) decomposition of the levofloxacin drug was observed in 90 min of sunlight irradiation. The effect of catalyst loading, initial substrate concentration and pH of the reaction was also optimized. The photocatalytic activity of the prepared catalyst was also compared with that of bare Bi2WO6, TiO2 and TiO2/C-dots under optimized conditions. Scavenger radical trap studies and terephthalic acid (TPA) fluorescence technique were done to understand the role of the photo-induced active radical ions that witnessed the decomposition of levofloxacin. Based on these studies, the plausible degradation trail of levofloxacin was proposed and was further supported by LC-MS analysis

Pd₃Sn nanoparticles on TiO₂ and ZnO supports as catalysts for semi-hydrogenation : synthesis and catalytic performance

The two catalysts Pd₃Sn/TiO₂and Pd3Sn/ZnO were prepared via a one-pot procedure based on the “polyol method” with the addition of a capping agent (polyvinylpyrrolidone) to control the particle size distribution. The same procedure was used to prepare Pd/TiO2 and Pd/ZnO for comparison. All four catalysts showed high activity and selectivity for the selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) in the liquid phase under identical conditions. However, Pd₃Sn/TiO₂and Pd₃Sn/ZnO show selectivities to alkene significantly higher than that of the Pd catalysts. Specifically, the selectivity increases from 96.4% to 97.4% on TiO₂support, and 96.2% to 97.6% on ZnO support, at 90% conversion. Transition electron microscopy shows nanoparticles evenly dispersed on the support, with mean particle sizes as low as 4.1 (±0.8) nm when Sn is incorporated into the catalyst. Unsupported Pd3Sn was prepared using the same method and characterised by powder X-Ray diffraction followed by the Rietveld refinement. Pd3Sn was found to be single-phase and isostructural to Pd metal with a face centred cubic unit cell

Effect of inorganic ions on pyrite catalyzed Fenton reaction

© 2018, Avestia Publishing. Industrial wastewaters contain not only organic pollutants but also considerable amounts of inorganic ions that may affect the efficiency of wastewater remediation processes. Thus, it is important to study the influence of such ions in the respective chemical reactions. Here we performed Fenton reactions for the decolourization of Rhodamine B dye using the naturally occurring mineral pyrite (FeS2) as heterogeneous catalyst in presence of different inorganic ions that are typically present in wastewater. Additionally, the effect of milling time of the pyrite powder on the performance of the heterogeneous Fenton reaction has also been investigated