Recovery of Cerium Dioxide from Spent Glass-Polishing Slurry and Its Utilization as a Reactive Sorbent for Fast Degradation of Toxic Organophosphates

The recovery of cerium (and possibly other rare earth elements) from the spent glass-polishing slurries is rather difficult because of a high resistance of polishing-grade cerium oxide toward common digestion agents. It was shown that cerium may be extracted from the spent polishing slurries by leaching with strong mineral acids in the presence of reducing agents; the solution may be used directly for the preparation of a ceria-based reactive sorbent. A mixture of concentrated nitric acid and hydrogen peroxide was effective in the digestion of partially dewatered glass-polishing slurry. After the removal of undissolved particles, cerous carbonate was precipitated by gaseous NH3 and CO2. Cerium oxide was prepared by a thermal decomposition of the carbonate precursor in an open crucible and tested as reactive sorbent for the degradation of highly toxic organophosphate compounds. The samples annealed at the optimal temperature of approximately 400°C exhibited a good degradation efficiency toward the organophosphate pesticide fenchlorphos and the nerve agents soman and VX. The extraction/precipitation procedure recovers approximately 70% of cerium oxide from the spent polishing slurry. The presence of minor amounts of lanthanum does not disturb the degradation efficiency

Possibilities of Electrochemical Analysis Using a System of Electrodes With Non-Specific Response

The master thesis present the possibilities of processing of electrochemical data from a group of four electrodes with non-selective response (simple sensor array) for electrochemical analysis with potential application of the results achieved in the construction of the sensor field type "electronic tongue". This simple system was applied to the sample simulating the food product. Electrochemical data were processed through mathematical operations such as Gaussian approximation, deconvolution or using basic mathematical operations

Electrochemical determination of carboxylic acids in wine

Katedra analytické chemieDepartment of Analytical ChemistryPřírodovědecká fakultaFaculty of Scienc

Some Environmentally Relevant Reactions of Cerium Oxide

Reactive forms of cerium oxide were prepared by a thermal decomposition of various precursors, namely carbonates, oxalates and citrates, commercially available nanocrystalline cerium oxide (nanoceria) was involved in the study for comparison. Scanning electron microscopy (SEM) and x-ray diffraction analysis (XRD) were used to examine the morphology and crystallinity of the samples, respectively, whereas the Brunauer-Emmett-Teller (BET) method of nitrogen adsorption was used to determine surface areas. Interactions of cerium oxide with some phosphorus-containing compounds were investigated. Some of the examined samples, especially those prepared by annealing from carbonate precursors, exhibited an outstanding ability to destroy highly toxic organophosphates, such as pesticides (parathion methyl), or nerve agents (soman, VX). There were identified some relations between the degradation efficiency of cerium oxides and their crystallinity. It was also shown that cerium oxide is able to destroy one of widely used flame retardants - triphenyl phosphate. A phosphatase-mimetic activity of various cerium oxides was examined with the aid of a standardized phosphatase test

Influence of annealing temperature on degradation efficiency and iron oxide transformations in CeO2/Fe-oxide sorbents

The microstructural and physical properties of magnetically separable CeO2 (5 wt.%)/Fe-oxide sorbents, applicable for the decomposition of organophosphorus pesticides, are analyzed in dependence on calcination temperature. The sorbents are prepared using a two-step procedure: (1) synthesis of magnetite core from cheap and commercially available raw materials; and (2) the formation of cerium (III) carbonate by precipitation with the ammonium hydrogen carbonate, containing re-dispersed magnetite. The cerous carbonate/magnetite precursor is annealed in a muffle furnace at temperatures ranging from 473 to 1073 K for 2 h to obtain the CeO2/Fe-oxide reactive sorbents. Structural characterization of the samples is performed using X-ray diffraction, scanning electron microscopy, Raman and Fourier transform infrared spectroscopy. Magnetic properties are obtained from hysteresis loops, field-cooled and zero-field-cooled curves, first-order reversal curve (FORC) diagrams, and Henkel plots. Sorbents exhibit an increase in coercivity from 0.2 kA/m to about 20 kA/m and a decrease in saturation magnetization from roughly 50 Am-2/kg to 1 Am-2/kg after annealing at 973 K. This deterioration of magnetic properties is caused by the transformation of magnetite and maghemite into weakly ferromagnetic hematite, with a typical peak in FORC diagram and a Morin transition at about 200 K. The degradation efficiency towards parathion and paraoxon methyl is about 30% for samples annealed from 473 K to 773 K.Web of Science111art. no. 01530

Effect of magnetite transformations on degradation efficiency of cerium dioxide-magnetite composite

Present investigations are focused on synthesis of magnetite/cerium dioxide reactive sorbents in various weight ratios of components and their characterization of chemical and magnetic properties. The morphology and changes in magnetic transformations in dependence on composition are followed by electron microscopy, X-ray diffraction, Mossbauer spectroscopy and magnetic measurements at room and low temperatures. Degradation efficiency is evaluated from a decomposition of the organophosphorus pesticide parathion methyl using prepared reactive sorbents. The experimental results reveal that the degradation efficiency, expressed by rate constant (mol/h) in dependence on amount of cerium dioxide content (vol.%), is independent on kind of iron oxide but increases with cerium dioxide content. On the contrary, saturation and remanent magnetizations are highly sensitive to relative ratio of iron oxides; magnetite, maghemite and hematite, originating from the initial magnetite transformations in dependence on sample composition.Web of Science934439443

Nanostructured magnetite-ceria-based composite: Synthesis, calcination, properties, and applications

Magnetite and magnetite/ceria composites prepared by chemical procedures in various mutual ratios were exposed to calcination treatment in a temperature interval between 473 K and 1073 K. A combination of several experimental methods has provided detailed structural, phase, and magnetic properties utilisable for selection of optimal compositions and calcination conditions from the viewpoint of degradation ability tested using parathion methyl and paraoxon. It was shown that the ceria content, selected between 5 wt% and 50 wt%, influences magnetic properties. Its optimal amount was determined to be above 20 wt% and the calcination temperature of 773 K when the highest rate constant, slightly above 0.06 min-1, was obtained for parathion methyl in acetonitrile using a degradation test.Web of Science916art. no. 16548

Ceria-Catalyzed Hydrolytic Cleavage of Sulfonamides

Nanoceria is a promising nanomaterial for the catalytic hydrolysis of a wide variety of substances. In this study, it was experimentally demonstrated for the first time that CeO2 nanostructures show extraordinary reactivity toward sulfonamide drugs (sulfadimethoxine, sulfamerazine, and sulfapyridine) in aqueous solution without any illumination, activation, or pH adjustment. Hydrolytic cleavage of various bonds, including S–N, C–N, and C–S, was proposed as the main reaction mechanism and was indicated by the formation of various reaction products, namely, sulfanilic acid, sulfanilamide, and aniline, which were identified by HPLC-DAD, LC-MS/MS, and NMR spectroscopy. The kinetics and efficiency of the ceria-catalyzed hydrolytic cleavage were dependent on the structure of the sulfonamide molecule and physicochemical properties of Nanoceria prepared by three different precipitation methods. However, in general, all three ceria samples were able to cleave SA drugs tested, proving the robust and unique surface reactivity toward these compounds inherent to cerium dioxide. The demonstrated reactivity of CeO2 to molecules containing sulfonamide or even sulfonyl (and similar) functional groups may be significant for both heterogeneous catalysis and environmentally important degradation reactions

Cerium–Bismuth Oxides/Oxynitrates with Low Toxicity for the Removal and Degradation of Organophosphates and Bisphenols

Nanoscale cerium–bismuth oxides/oxynitrates were prepared by a scalable low-temperature method at ambient pressure using water as the sole solvent. Solid solutions were formed up to a 1:1 Ce/Bi molar ratio, while at higher doping levels, bismuth oxynitrate photocatalysts with a pronounced layered structure were formed. Bismuth caused significant changes in the structure and surface properties of nanoceria, such as the formation of defects, oxygen-containing surface groups, and Lewis and Brønsted acid sites. The prepared bifunctional adsorbents/photocatalysts were efficient in the removal of toxic organophosphate (methyl paraoxon) from water by reactive adsorption followed by photocatalytic decomposition of the parent compound and its degradation product (p-nitrophenol). Bi-doped ceria also effectively adsorbed and photodegraded the endocrine disruptors bisphenols A and S and outperformed pure ceria and the P25 photocatalyst in terms of efficiency, durability, and long-term stability. The very low toxicity of Bi-nanoceria to mammalian cells, aquatic organisms, and bacteria has been demonstrated by comprehensive in vivo/in vitro testing, which, in addition to its simple “green” synthesis, high activity, and durability, makes Bi-doped ceria promising for safe use in abatement of toxic chemicals