Exceptional activity of gallium(III) chloride and chlorogallate(III) ionic liquids for Baeyer–Villiger oxidation

Baeyer–Villiger oxidation of cyclic ketones, using H2O2 as the oxidising agent, was systematically studied using a range of metal chlorides in different solvents, and in neat chlorogallate(III) ionic liquids. The extremely high activity of GaCl3 in promoting oxidation with H2O2, irrespective of solvent, was reported for the first time. The activity of all other metal chlorides was strongly solvent-dependent. In particular, AlCl3 was very active in a protic solvent (ethanol), and tin chlorides, SnCl4 and SnCl2, were active in aprotic solvents (toluene and dioxane). In order to eliminate the need for volatile organic solvent, a Lewis acidic chlorogallate(III) ionic liquid was used in the place of GaCl3, which afforded typically 89–94% yields of lactones in 1–120 min, at ambient conditions. Raman and 71Ga NMR spectroscopic studies suggest that the active species, in both GaCl3 and chlorogallate(III) ionic liquid systems, are chlorohydroxygallate(III) anions, [GaCl3OH]−, which are the products of partial hydrolysis of GaCl3 and chlorogallate(III) anions; therefore, the presence of water is crucial.

The effect of ionic Co presence on the structural, optical and photocatalytic properties of modified cobalt–titanate nanotubes

With the aim of producing materials with enhanced optical and photocatalytic properties, titanate nanotubes (TNTs) modified by cobalt doping (Co-TNT) and by Na+ -> Co ion-exchange (TNT/Co) were successfully prepared by a hydrothermal method. The influence of the doping level and of the cobalt position in the TNT crystalline structure was studied. Although no perceptible influence of the cobalt ion position on the morphology of the prepared titanate nanotubes was observed, the optical behaviour of the cobalt modified samples is clearly dependent on the cobalt ions either substituting the Ti4+ ions in the TiO6 octahedra building blocks of the TNT structure (doped samples) or replacing the Na+ ions between the TiO6 interlayers (ion-exchange samples). The catalytic ability of these materials on pollutant photodegradation was investigated. First, the evaluation of hydroxyl radical formation using the terephthalic acid as a probe was performed. Afterwards, phenol, naphthol yellow S and brilliant green were used as model pollutants. Anticipating real world situations, photocatalytic experiments were performed using solutions combining these pollutants. The results show that the Co modified TNT materials (Co-TNT and TNT/Co) are good catalysts, the photocatalytic performance being dependent on the Co/Ti ratio and on the structural metal location. The Co(1%)-TNT doped sample was the best photocatalyst for all the degradation processes studied.

Toxic metal recovery from spent hydroprocessing catalyst

Spent hydroprocessing catalysts (HPCs) are solid wastes generated in refinery industries and typically contain various hazardous metals, such as Co, Ni, and Mo. These wastes cannot be discharged into the environment due to strict regulations and require proper treatment to remove the hazardous substances. Various options have been proposed and developed for spent catalysts treatment; however, hydrometallurgical processes are considered efficient, cost-effective and environmentally-friendly methods of metal extraction, and have been widely employed for different metal uptake from aqueous leachates of secondary materials. Although there are a large number of studies on hazardous metal extraction from aqueous solutions of various spent catalysts, little information is available on Co, Ni, and Mo removal from spent NiMo hydroprocessing catalysts. In the current study, a solvent extraction process was applied to the spent HPC to specifically remove Co, Ni, and Mo. The spent HPC is dissolved in an acid solution and then the metals are extracted using three different extractants, two of which were aminebased and one which was a quaternary ammonium salt. The main aim of this study was to develop a hydrometallurgical method to remove, and ultimately be able to recover, Co, Ni, and Mo from the spent HPCs produced at the petrochemical plant in Come By Chance, Newfoundland and Labrador. The specific objectives of the study were: (1) characterization of the spent catalyst and the acidic leachate, (2) identifying the most efficient leaching agent to dissolve the metals from the spent catalyst; (3) development of a solvent extraction procedure using the amine-based extractants Alamine308, Alamine336 and the quaternary ammonium salt, Aliquat336 in toluene to remove Co, Ni, and Mo from the spent catalyst; (4) selection of the best reagent for Co, Ni, and Mo extraction based on the required contact time, required extractant concentration, as well as organic:aqueous ratio; and (5) evaluation of the extraction conditions and optimization of the metal extraction process using the Design Expert® software. For the present study, a Central Composite Design (CCD) method was applied as the main method to design the experiments, evaluate the effect of each parameter, provide a statistical model, and optimize the extraction process. Three parameters were considered as the most significant factors affecting the process efficiency: (i) extractant concentration, (ii) the organic:aqueous ratio, and (iii) contact time. Metal extraction efficiencies were calculated based on ICP analysis of the pre- and post–leachates, and the process optimization was conducted with the aid of the Design Expert® software. The obtained results showed that Alamine308 can be considered to be the most effective and suitable extractant for spent HPC examined in the study. Alamine308 is capable of removing all three metals to the maximum amounts. Aliquat336 was found to be not as effective, especially for Ni extraction; however, it is able to separate all of these metals within the first 10 min, unlike Alamine336, which required more than 35 min to do so. Based on the results of this study, a cost-effective and environmentally-friendly solventextraction process was achieved to remove Co, Ni, and Mo from the spent HPCs in a short amount of time and with the low extractant concentration required. This method can be tested and implemented for other hazardous metals from other secondary materials as well. Further investigation may be required; however, the results of this study can be a guide for future research on similar metal extraction processes.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Fabrication and optimizing of metal nano silicate as toxic metal absorbent from sea water

Pure Water, is a crucial demand of creature life. Following industrial development, extra amount of toxic metals such as chromium enters the environmental cycle through the sewage, which is considered as a serious threat for organisms. One of the modern methods of filtration and removal of contaminants in water, is applying Nano-technology. According to specific property of silicate materials, in this article we try to survey increased power in composites and various absorption in several morphologies and also synthesis of Nano-metal silicates with different morphologies as absorbent of metal toxic ions. At first, we synthesize nano zink silicate with three morphologies considering context and the purpose of this survey. 1) Nano synthesis of zink silicate hollow cavity by hydrothermal method in mixed solvent system of ethanol/glycol polyethylene. 2) Zink nano wires silicate in a water-based system by controlling the amount of sodium silicate. 3) Synthesis of nano zink silicate membrane. After synthesizing, we measured the cadmium ion absorbance by synthesized nano zink silicates. Controlling PH, is the applied absorption method. Next step, we synthesized nano zink-magnesium silicate composite in two various morphologies of nanowires and membrane by different precent of zink and magnesium, in order to optimize synthesized nano metal silicate. We used zink nitrate and magnesium nitrate and also measured cadmium absorption by synthesized nano metal silicates in the same way of PH control absorption. In the 3rd step, in order to determine the impact of the type of metal in nano metal silicate, we synthesized nano magnesium silicate and compared its absorption with nano zink silicate. Furthermore, we calculated the optimal concentration in one of synthesizes. Optimal concentration is the process which has the maximum absorption. While applying two methods of absorption in the test, finally we compared the effect of absorption method on the absorption level. Below you find further steps of synthesis: 1) Using IR, RAMAN, XRD spectroscopy to check the accuracy of synthesis. 2) Checking the dispersion of nano particles in ethanol solution by light microscope. 3) Measuring and observing particles with scanning electron microscope (SEM). 4) Using atomic absorption device for measuring the cadmium concentration in water-based solutions. The nano metal silicates were synthesized successfully. All of synthesized nano absorbents have the cadmium ion absorbency. The cadmium absorption via nano absorbents depend on various factors such as kind of metal in nano silicate and percent of metal in nano metal silicate composite. Meanwhile the absorption and PH control of medium containing the absorbent and solution would affect the cadmium absorption.

Characterization of Post-Consumer PET after Removal of the Original Surface: Influence of Raw Material

Post-consumer cooking oil and soft drink PET bottles (PEToil and PETsoft drink) were ground and washed only with water (conventional washing). The polymer was then chemically washed (10min in an aqueous solution of sodium hydroxide 5mol center dot L-1 at 90 degrees C) and rinsed. The materials before and after chemical washing were characterized by intrinsic viscosity, differential scanning calorimetry, thermogravimetry, elemental analysis, scanning electron microscopy with X-ray spectrum microanalysis, and gas chromatography coupled to mass spectrometry. The results indicated that conventionally washed PEToil is the material that most differs among the four tested ones, and that the other three are more similar to each other and to what is expected for pure PET. For example, the composition of PEToil washed only in water contained 30 volatile organic compounds, 5 nonvolatile compounds, and 7 metals, while PETsoft drink washed conventionally and chemically contained 5 volatile organic compounds and no metal or nonvolatile organic compounds.

Appraisal of open software for finite element simulation of 2D metal sheet laser cut.

FEA simulation of thermal metal cutting is central to interactive design and manufacturing. It is therefore relevant to assess the applicability of FEA open software to simulate 2D heat transfer in metal sheet laser cuts. Application of open source code (e.g. FreeFem++, FEniCS, MOOSE) makes possible additional scenarios (e.g. parallel, CUDA, etc.), with lower costs. However, a precise assessment is required on the scenarios in which open software can be a sound alternative to a commercial one. This article contributes in this regard, by presenting a comparison of the aforementioned freeware FEM software for the simulation of heat transfer in thin (i.e. 2D) sheets, subject to a gliding laser point source. We use the commercial ABAQUS software as the reference to compare such open software. A convective linear thin sheet heat transfer model, with and without material removal is used. This article does not intend a full design of computer experiments. Our partial assessment shows that the thin sheet approximation turns to be adequate in terms of the relative error for linear alumina sheets. Under mesh resolutions better than 10e−5 m , the open and reference software temperature differ in at most 1 % of the temperature prediction. Ongoing work includes adaptive re-meshing, nonlinearities, sheet stress analysis and Mach (also called ‘relativistic’) effects.

Self-expanding metal stents in postoperative esophageal leaks

Background: Postoperative esophageal leaks have a high morbidity and mortality. Self-expanding metal stents (SEMS) have been used as an alternative to re-operation. Aim: Evaluating predictors of success of SEMS in postoperative esophageal leaks. Methods: Retrospective study of patients with postoperative esophageal leaks referred for SEMS placement in a reference center during a period of 3 years. Technical success was defined as closure of the leak in barium swallow at 15 days. Clinical success was considered as endoscopic and/or radiographic confirmation of closure after stent removal. Results: Thirteen patients placed SEMS. Median follow-up was 58 days. Leaks had a median size of 20 mm. Time between surgery and SEMS placement was 20 days. One patient died 2 days after SEMS placement and one had worsening of the fistula after SEMS expansion. Time till stent migration was 9 days. Technical success was achieved in 9 of 11 patients, with clinical success without recurrence in 5 patients. All leaks with less than 20 mm were solved endoscopically. Technical and clinical success was higher when time between surgery and SEMS placement was lower, even though without statistical significance (respectively, p = 0.228 and 0.374). In the 8 patients who died during follow-up, median survival was 59 days. Conclusions: Technical success of SEMS was higher than 80%; however, due to high morbidity and mortality, only 45% of patients had their stent removed. Lower time from diagnosis to SEMS placement and leak size less than 20 mm may be associated with better results.

Determination of the Side-Reaction Coefficient of Desferrioxamine B in Trace-Metal-Free Seawater

Partial funding for open access provided by the UMD Libraries' Open Access Publishing Fund.

Biosorción en tanque agitado de Cd(+2) y Pb(+2) con cáscara de cacao

En la búsqueda de tecnologías más limpias para el tratamiento de efluentes que contienen metales pesados se ha dirigido la atención hacia la biosorción. Este estudio permitió abordar el proceso de biosorción de 〖Cd〗^(+2)y 〖Pb〗^(+2) en efluentes mineros a través de la cáscara de cacao. Se determinó las características físico-químicas del biosorbente y el resultado obtenido fue: la cáscara de cacao tiene una superficie neutra, compuesta principalmente por grupos ésteres alifáticos; además se estudió los factores que afectan este proceso como son: pH, tamaño de partícula, tiempo de contacto, Temperatura, y la concentración inicial del metal. El pH óptimo para la biosorción de plomo es entre 4 y 5 y para el cadmio fue entre 5 y 6; con respecto al tiempo de contacto necesario para eliminar la mayor cantidad de iones metálicos fue de 10 minutos, siendo el resultado obtenido en la remoción tanto de cadmio como de plomo de 86,92% y 96,74% respectivamente. Se observó que la temperatura no afecta significativamente el proceso de biosorción como el pH y se determinó como óptima 25℃ ; también se analizó que la cáscara de cacao tiene mayor afinidad por el cadmio por tener un radio iónico más pequeño que el plomo permitiéndole alcanzar poros reducidos; además al aumentar la concentración, la eliminación de cadmio disminuyó y para el plomo aumentó pero no de forma significativa. Los datos experimentales de la biosorción de plomo y cadmio en cáscara de cacao, reproducen favorablemente el modelo cinético Pseudo Segundo Orden, con coeficientes de correlación (R^2) para 〖Pb〗^(+2) de 0,999 y 〖Cd〗^(+2) de 1. Finalmente en el estudio de equilibrio el modelo de Langmuir describe el proceso de adsorción para 〖Cd〗^(+2) y el modelo de Fleundlich se ajustó mejor a los datos experimentales para 〖Pb〗^(+2).

Physico-chemical characterization of metal-doped bone chars and their adsorption behavior for water defluoridation

New bone chars for fluoride adsorption from drinking water have been synthetized via metallic doping using aluminum and iron salts. A detailed statistical analysis of the metal doping process using the signal-to-noise ratios from Taguchi's experimental designs and its impact on the fluoride adsorption properties of modified bone chars have been performed. The best conditions, including the proper metallic salt, for metal doping were identified to improve the fluoride uptakes of modified bone chars. Results showed that the fluoride adsorption properties of bone chars can be enhanced up to 600% using aluminum sulfate for the surface modification. This aluminum-based adsorbent showed an adsorption capacity of 31 mg/g, which outperformed the fluoride uptakes reported for several adsorbents. Surface interactions involved in the defluoridation process were established using FTIR, DRX and XPS analysis. Defluoridation using the metal-doped bone chars occurred via an ion exchange process between fluoride ions and the hydroxyl groups on the adsorbent surface, whereas the Al(OH)xFy, FexFy, and CaF2 interactions could play also an important role in the removal process. These metal-doped adsorbents anticipate a promising behavior in water treatment, especially in developing countries where the efficiency – cost tradeoff is crucial for implementing new defluoridation technologies.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.