Synthesis and characterization of cobalt nanoparticles for application in the removal of textile dye.

In this work, magnetic cobalt nanoparticles (CoNPs) were synthesized and applied to the removal of Remazol golden yellow RNL (RGY) from aqueous solutions and textile wastewater. The CoNPs were characterized and the Co content found in the CoNPs was 60.38% (m/m). The analysis of X-ray Diffraction (XRD) and Raman Spectroscopy indicated the presence of Co0 and CoO in the composition of the material, as confirmed by Thermogravimetric Analysis coupled to Mass Spectrometry (TG-MS). Images obtained by the Transmission Electron Microscope (TEM) showed that the CoNPs have sizes smaller than 10 nm, sphere morphology and high agglomeration capacity. The results obtained by nitrogen adsorption-desorption suggested that the nanomaterial presented a mesoporous characteristic, low specific surface area (15.70 m2 g-1) and a pore volume and pore diameter of 0.072 cm3 g-1 and 3.64 nm, respectively. CoNPs removed the RGY with high efficiency, reaching almost 100% removal in 30 min. The kinetic results showed that the reaction followed pseudo-second-order kinetics. Additionally, the removal process can be altered depending on the experimental condition. For instance, under acidic conditions, the reductive degradation prevailed, while in neutral or basic conditions, two simultaneous processes occur: reductive degradation and adsorption. Finally, CoNPs were applied to textile wastewater. The results showed high discoloration, reaching almost 88%. However, there was only a 32% decrease in chemical oxygen demand, showing that CoNPs are efficient at removing organic dyes from aqueous solutions.

Comparative study of the direct black removal by Fe, Cu, and Fe/Cu nanoparticles.

In this study, direct black dye removal was investigated using iron nanoparticles (Fe NPs), copper (Cu NPs), and Fe/Cu (Fe/Cu NPs). NPs were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Using a dose of 0.25 g L-1 of Fe, Cu, and Fe/Cu NPs, a degradation efficiency of 13, 26, and 43% respectively was obtained. For the 1.00 g L-1 dose, the efficiency increased to 100, 43, and 100%, respectively. Studies in anoxic and oxic conditions presented degradation rates, respectively, of 100 and 30% for Fe NPs, 90 and 50% for Fe/Cu NPs, and 40% in both reactions for Cu NPs, indicating that the mechanism of dye degradation by NPs is predominantly reducing under the conditions studied. The addition of EDTA decreased the dye removal rate for Fe, Cu, and Fe/Cu NPs at 27, 10, and 35%, respectively. In addition to the degradation, the adsorption phenomena of the by-products formed during the reaction were confirmed by the Fourier transform infrared (FTIR) analysis and verified by the desorption tests. Fe and Fe/Cu NPs showed the highest efficiency in direct black dye reductive degradation and adsorption of by-products, removing 100% of the dye at a dose of 1 g L-1 within 10 min of reaction. Graphical abstracts ᅟ.

Sulfentrazone dechlorination by iron-nickel bimetallic nanoparticles.

The sulfentrazone dechlorination using bimetallic nanoparticles of Fe/Ni was studied. Different variables that could influence the sulfentrazone conversion were investigated, such as nitrogen atmosphere, pH and dosage of the nanoparticles and initial concentration of sulfentrazone. The best results were obtained using controlled pH (pH 4.0) and 1.0 g L(-1) of nanomaterials, resulting in 100 % conversion in only 30 min. Kinetic studies were also conducted, evaluating the influence of different nanoparticle dosages (1.0 to 4.0 g L(-1)), system temperatures (20 to 35 °C) and nickel levels in the composition of the nanomaterials (0.025 to 0.10 gNi/gFe). The mechanism of sulfentrazone conversion has changed due a direct reduction on the catalytic activity sites and indirect reduction by atomic hydrogen. Both mechanisms have followed pseudo-first order models. The conversion rate improved when the dosage of the nanomaterials, system temperature and nickel content in the composition of the nanocomposites were increased. Finally, the conversion products were elucidated by mass spectrometry and toxicity assays were performed using Daphnia Similis. The results showed that the dechlorination product is less toxic than sulfentrazone.

Degradation of the insecticides thiamethoxam and imidacloprid by zero-valent metals exposed to ultrasonic irradiation in water medium: electrospray ionization mass spectrometry monitoring.

The degradation of thiamethoxam (1) and imidacloprid (2), prototype neonicotinoid insecticides bearing a characteristic N-NO2 moiety in their structures, promoted by a number of zero-valent metals (Fe, Sn, Zn) upon ultrasonic irradiation in acidic aqueous solution (pH 2) was investigated. It was verified that thiamethoxam (1) and imidacloprid (2) are quickly and almost completely consumed under these experimental conditions (degradation >90% after a reaction time of 30 min) and that ultrasonic irradiation strongly enhances the degradation rate for both insecticides, especially when zinc and tin are employed. Based on the results from electrospray ionization mass (and tandem mass) spectrometry in the positive ion mode, degradation routes for both insecticides, comprising an initial NO2 --> NH2 reduction, were proposed. In addition, products from the dehydrochlorination of imidacloprid were also found to be formed under these conditions.

Advanced oxidation of caffeine in water: on-line and real-time monitoring by electrospray ionization mass spectrometry.

High performance liquid chromatography (HPLC), ultraviolet spectroscopy (UV), and total organic carbon (TOC) analyses show that caffeine is quickly and completely degraded underthe oxidative conditions of the UV/H2O2,TiO2/ UV, and Fenton systems but that the organic carbon content of the solution decreases much more slowly. Continuous on-line and real-time monitoring by electrospray ionization mass (ESI-MS) and tandem mass spectrometric experiments (ESI-MS/MS) as well as high accuracy MS measurements and gas chromatography-mass spectrometry analysis show that caffeine is first oxidized to N-dimethylparabanic acid likely via initial OH insertion to the C4=C8 caffeine double bond. A second degradation intermediate, di(N-hidroxymethyl)parabanic acid, has been identified by ESI-MS and characterized by ESI-MS/MS and high accuracy mass measurements. This polar and likely relatively unstable compound, which is not detected by off-line GC-MS analysis, is likely formed via further oxidation of N-dimethylparabanic acid at both of its N-methyl groups and constitutes an unprecedented intermediate in the degradation of caffeine.