Carbon dots decorated magnetite nanocomposite obtained using yerba mate useful for remediation of textile wastewater through a photo-Fenton treatment: Ilex paraguariensis as a platform of environmental interest-part 2.

Two carbon dots (CD) with diameters of 4.9 ± 1.5 and 4.1 ± 1.2 nm were successfully synthesized through an acid ablation route with HNO3 or H2SO4, respectively, using Ilex paraguariensis as raw material. The CD were used to produce magnetite-containing nanocomposites through two different routes: hydrothermal and in situ. A thorough characterization of the particles by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), dynamic light scattering (DLS), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) indicates that all nanomaterials have spherical-like morphology with a core-shell structure. The composition of this structure depends on the route used: with the hydrothermal route, the shell is composed of the CD, but with the in situ process, the CD act as nucleation centers, and so the iron oxide domains are in the shell. Regarding the photocatalytic mechanism for the degradation of methyl orange, the interaction between the CD and the magnetite plays an important role in the photo-Fenton reaction at pH 6.2, in which ligand-to-metal charge transfer processes (LTMCT) allow Fe2+ regeneration. All materials (100 ppm) showed catalytic activity in the elimination of methyl orange (8.5 ppm), achieving discoloration of up to 98% under visible irradiation over 400 nm in 7 h. This opens very interesting possibilities for the use of agro-industrial residues for sustainable synthesis of catalytic nanomaterials, and the role of the interaction of iron-based catalysts with organic matter in heterogeneous Fenton-based processes.

Iron oxide nanoparticles embedded in organic microparticles from Yerba Mate useful for remediation of textile wastewater through a photo-Fenton treatment: Ilex paraguariensis as a platform of environmental interest - Part 1.

Seven composites of iron oxide nanoparticles embedded in organic microparticles mediated by Cu(II) were synthesized using yerba mate (Ilex paraguariensis) dry leaf extract as precipitant, capping agent, and dispersant medium, using different Cu/Fe molar ratios. A thorough characterization of the particles by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis-mass spectrometry (TGA-MS), Fourier transform infrared spectrometer (FTIR), and atomic absorption-spectrometry (AA) indicates that all materials have spheric-like morphology with nanoparticles composed by metal oxide phases embedded into organic microparticles. Interestingly, this organic matter is proposed to play an important role in the solids' photocatalytic activity in a photo-Fenton reaction, in which iron photo-leaching was elucidated, and a mechanism through ligand-to-metal charge transfer processes was proposed. All materials showed catalytic activity in the methyl orange elimination, achieving discolorations up to 96% in 2 h under UV irradiation at 375 nm. An experimental correlation between all samples' UV/Vis spectra and their performances for methyl orange discoloration was observed. This process opens a landscape very interesting for the use of agroindustrial residues for green synthesis of metal oxide nanomaterials and their use and understanding of organo-metallic systems participation in Fenton-based processes.

Reaction kinetics and mechanisms of organosilicon fungicide flusilazole with sulfate and hydroxyl radicals.

Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 × 109 s-1M-1 for the reaction of the fungicide with HO and 4.6 × 108 s-1 M-1 for the same reaction with SO4- radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S2O82- with flusilazole, were identified as α-aminoalkyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively.

Paramagnetic iron-doped hydroxyapatite nanoparticles with improved metal sorption properties. A bioorganic substrates-mediated synthesis.

This paper describes the synthesis of paramegnetic iron-containing hydroxyapatite nanoparticles and their increased Cu(2+) sorbent capacity when using Ca(2+) complexes of soluble bioorganic substrates from urban wastes as synthesis precursors. A thorough characterization of the particles by TEM, XRD, FTIR spectroscopy, specific surface area, TGA, XPS, and DLS indicates that loss of crystallinity, a higher specific area, an increased surface oxygen content, and formation of surface iron phases strongly enhance Cu(2+) adsorption capacity of hydroxyapatite-based materials. However, the major effect of the surface and morphologycal modifications is the size diminution of the aggregates formed in aqueous solutions leading to an increased effective surface available for Cu(2+) adsorption. Maximum sorption values of 550-850 mg Cu(2+) per gram of particles suspended in an aqueous solution at pH 7 were determined, almost 10 times the maximum values observed for hydroxyapatite nanoparticles suspensions under the same conditions.