Photocatalytic properties of Cu-containing ZnO nanoparticles and their antifungal activity against agriculture-pathogenic fungus.

In this work, nanoparticles (NPs) of ZnO, ZnO with Cu incorporated at 2 and 30 wt%, and CuO were prepared by the hydrothermal method. X-ray diffraction pattern (DRX) analysis showed that ZnO with high Cu incorporation (30 wt%) generates the formation of a composite oxide (ZnO/CuO), while X-ray photoelectron spectroscopy (XPS) of the Cu (2 wt%) sample indicated that Cu is incorporated as a dopant (ZnO/Cu2%). The samples with Cu incorporated had enhanced visible light absorption. Methyl orange (MO) dye was used to perform photocatalytic tests under UV radiation. The antifungal activity of the NPs was tested against four agricultural phytopathogenic fungi: Neofusicoccum arbuti, Alternaria alternata, Fusarium solani, and Colletotrichum gloeosporioides. The ZnO/Cu2% nanoparticles showed adequate photocatalytic and high antifungal activity in comparison to pure oxides and the composite sample.

Complex dielectric function and opto-electronic characterization using VEELS for the lead-free BCZT electro-ceramic perovskite.

The current work presents the complex dielectric function and the opto-electronic properties of lead-free Ba0.8Ca0.2Ti0.9Zr0.1O3 (BCZT) electro-ceramic, derived from valence electron energy loss spectroscopy, in transmission electron microscopy (VEELS-TEM). A single tetragonal perovskite phase, with P4mm space group, was determined by Rietveld refinement of the x-ray diffraction pattern. The VEELS-TEM experiment scanned the energy interval from 0-50 eV. The spectroscopic analysis started with the chemical identification of the atoms that conforms the BCZT solid-solution. Bulk and surface plasmons were located at 27.2 eV and 12.9 eV, respectively in the energy loss function. Complex dielectric function was obtained using Kramers-Kronig analysis from the Gatan Microscopy Suite software. Dielectric constant was calculated from the real part of the complex dielectric function, while the inter-band transitions were identified in the joint density of states function. The refraction index n and the extinction coefficient k, as a function of energy, were obtained from the complex dielectric function. The bandgap energy was determined using a polynomial fit in the optical absorption coefficient plot with an Eg = 3.2 eV.

Aqueous-phase synthesis of nanoparticles of copper/copper oxides and their antifungal effect against Fusarium oxysporum.

Different copper based-materials have been used for controlling some fungal and bacterial pathogens. However, the antifungal activity of the copper-based materials depends on different parameters, such as the crystal phase, synthesis route, and size of the particles. Herein a facile route synthesis method of Cu/CuxO-NPs was achieved through the aqueous phase. The influence of NaBH4 concentration on the phase composition was studied. The synthesized Cu/CuxO-NPs were characterized by X-Ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and dynamic light scattering. Five Cu/CuxO-NPs with different phase composition and nanoparticle size were obtained. The antifungal activity of the synthesized Cu/CuxO-NPs was studied in vitro against Fusarium oxysporum. The results indicate that a high percent of inhibition of radial growth (IGR) was obtained with NPs, which have a higher proportion of Cu2O phase and relatively smaller size particles. Furthermore, hypha morphology, membrane damage and production of reactive oxygen species (ROS) was evaluated with SEM and confocal microscopy.

Green-synthesized copper nanoparticles as a potential antifungal against plant pathogens.

The fabrication of fungicides in cost-effective and eco-friendly ways is particularly important for agriculture. Plant pathogenic fungi produce many economic and ecological problems worldwide, which must be controlled with potent fungicides. Here we propose the green synthesis of fungicides, which consist of copper nanoparticles (Cu-NPs) prepared in aqueous media. Through in vitro experiments, the antifungal efficacy against Fusarium solani, Neofusicoccum sp., and Fusarium oxysporum was investigated. Although the antifungal activity differs for each fungal species, it was found that the Cu-NPs induce strong morphological changes in the mycelium. Additionally, the damage of the cell membranes of the pathogens was revealed by microscopic observations. For the three evaluated fungi, fluorescence microscopy demonstrated the intracellular generation of reactive oxygen species in the mycelium. This work proves that the green-synthesized Cu-NPs are potential fungicides against F. solani, Neofusicoccum sp., and F. oxysporum.

Synthesis and structural characterization of Mo-Ni-W oxide nanostructures.

In this work, we report the synthesis and characterization of Mo-Ni-W oxides. The precursor was prepared from an aqueous solution of ammonium heptamolibdate, ammonium metatungstate, and nickel nitrate with an atomic ratio of 1:1:1 (Mo:W:Ni). The solution was then transferred to a Teflon-lined stainless steel autoclave and heated to 200 degrees C and left at this temperature for 48 h. The resulting material was then washed and dried. The morphology and elemental composition were studied by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. The porosity was studied by the Brunauer, Emmett, and Teller method. The materials synthesized at 200 degrees C remained amorphous and had a specific surface area of 114 m2/g with pore size of 34 A. The average length was 1 microm and the average diameter was 60 nm. The crystalline phase of synthesized material corresponded to W0.4Mo0.6O3 and WO3. After annealing at 550 degrees C for two hours, the material was polycrystalline with a segregated structure of MoO3, WO3; NiMoO4 was observed. The sublimation of the molybdenum oxide was evident when annealed at 900 degrees C for two hours and finally two crystalline phases of material remained; roundish WO3 and elongated particles of NiWO4.

Synthesis of Ni-Mo-W sulfide nanorods as catalyst for hydrodesulfurization of dibenzothiophene.

Two trimetallic sulfurs, MoWNiS and MoWSNi, were synthesized to be used as a catalyst in hydrodesulfurization reactions. The mixed oxide mesoporous nanostructured MoO3 -WO3 with an Mo:W atomic ratio of 1:1 was used as the precursor. The first catalyst was prepared by impregnating nickel in the oxide precursor and then subsequent sulfiding with an H2S/H2 mix at 400 degrees C for 2 hours. The second catalyst was prepared by sulfiding the precursor and then impregnating the nickel, and finally reducing the material with a H2/N2 at 350 degrees C. In both catalysts the Mo:W:Ni atomic ratio was maintained at 1:1:0.5. The materials obtained were characterized by physical adsorption of nitrogen, X-ray diffraction, scanning electron microscopy, transmission electron microscopy. Furthermore, the materials obtained were evaluated by a dibenzothiophene hydrodesulfuration reaction. The diffraction patterns show that both materials are polycrystalline and mainly of MoS2 and WS2 phases.

Synthesis and characterization of porous Mo-W oxide nanostructures.

The present study reports the synthesis method, microstructure characterization, and thermal stability of nanostructured porous mixed oxide (MoO3-WO3) at 550 and 900 degrees C of annealing. The material was synthesized using a hydrothermal method. The precursor was prepared by aqueous solution using ammonium heptamolibdate and ammonium metatungstate, with an atomic ratio of Mo/W = 1. The pH was adjusted to 5, and then the solution was transferred to a teflon-lined stainless steel autoclave and heated at 200 degrees C for 48 h. The resultant material was washed using deionized water. The specific surface area, morphology, composition, and microstructure before and after annealing were studied by N2 physisorption, scanning electron microscopy (SEM), analytical transmission electron microscopy (TEM), and X-Ray diffraction (XRD). The initial synthesized materials showed low crystallinity and high specific surface area around (141 m2/g). After thermal annealing the material showed higher crystallinity and diminished its specific surface area drastically.

Co(Ni)/MoS2 nanostructured catalysts for the hydrodesulphurization of dibenzothiophene.

In this study Co(Ni)/MoS2 unsupported nanocatalysts (nanorods and nanoribbons) were synthesized with Co(Ni)/(Co(Ni) + Mo) = 0.3, 0.5 molar ratios for Co and Ni respectively. First the alpha-MoO3 nanostructures were impregnated with an aqueous solution of Co(Ni)Cl2 x 6H2O or Co(Ni)(NO3)2 x 6H2O, then were treated for 2 h at 473 K, and finally the precursors were activated under a H2S/H2 mixture (15% v/v H2S) by ramping the temperature from room temperature to 773 K and keeping it at that value for 2 h. The resulting materials were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, specific surface area and X-ray photoelectron spectroscopy, and tested as catalysts for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). It was found that these materials presented specific surface areas below 25 m2/g. The catalytic test showed that only when Co is added a promoter effect is observed compared with MoS2 unpromoted catalysts. Among the materials prepared, the Co/MoS2 catalyst made from cobalt chloride presented the highest catalytic activity (6.95 mol s(-1) g(-1)catalyst) for the HDS of DBT. The selectivity for the latter indicated a clear preference for the direct desulphurization over the hydrogenating pathway.

Optimization of the synthesis of alpha-MoO3 nanoribbons and hydrodesulfurization (HDS) catalyst test.

An optimized process for synthesis of alpha-MoO3 nanoribbons characterized by uniform morphology and composition was carried out. The optimized process turned out to be the aging of a precursor of an aqueous solution of ammonium heptamolybdate for a week under constant stirring at 333 K; followed by hydrothermal treatment for 36 h up to 48 h at 473 K. The dimensions of the nanoribbons were between 5 and 10 microm in length and a width between 100 and 600 nm. The thickness was between 60 and 200 nm. This material was tested for hydrodesulfurization (HDS) of dibenzothiophene (DBT) by in situ activation and showed its catalytic activities to be similar to those of unsupported MoS2 catalysts. The structure and morphology of these materials was characterized by analytical transmission electron microscopy, scanning electron microscopy, and X-ray diffraction using the Rietveld method to determine the quantitative crystallographic phases. A chemical semiquantitative analysis was carried out by energy dispersive spectroscopy and a qualitative analysis was carried out by electron energy loss spectroscopy.

Synthesis of MoS(2) nanorods and their catalytic test in the HDS of dibenzothiophene.

Partially sulfided nanostructures were synthesized by direct sulfurization of alpha-MoO(3) nanorods using a mixture of H(2)S/H(2), 15 vol%, at several temperatures (400, 500, 600, 700, and 800 degrees C). These materials were tested as catalysts in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and characterized by specific surface areas using the expression developed by Brunauer, Emmett, and Teller (BET equation), x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The TEM images show a gradual evolution from a smooth surface to a rough material, presenting some type of holes all over the particles, but keeping their rod-like structure throughout sulfidation. The results of evaluating the catalysts in the HDS of DBT showed that the best temperature for sulfidation is 500 degrees C. In all samples, a higher selectivity for hydrogenation over sulfur removal was observed.