Insight into the structure-property relationship of UO2_{2} nanoparticles

Highly crystalline UO$_{2}$ nanoparticles (NPs) with sizes of 2–3 nm were produced by fast chemical deposition of uranium(IV) under reducing conditions at pH 8–11. The particles were then characterized by microscopy and spectroscopy techniques including high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), high-energy resolution fluorescence detection (HERFD) X-ray absorption spectroscopy at the U M$_{4}$ edge and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U L$_{3}$ edge. The results of this investigation show that despite U(IV) being the dominant oxidation state of the freshly prepared UO$_{2}$ NPs, they oxidize to U$_{4}$O$_{9}$ with time and under the X-ray beam, indicating the high reactivity of U(IV) under these conditions. Moreover, it was found that the oxidation process of NPs is accompanied by their growth in size to 6 nm. We highlight here the major differences and similarities of the UO$_{2}$ NP properties to PuO$_{2}$, ThO$_{2}$ and CeO$_{2}$ NPs

Use of Reduced Graphene Oxide to Modify Melamine and Polyurethane for the Removal of Organic and Oil Wastes

Methods for obtaining efficient sorption materials based on highly porous melamine and polyurethane matrices modified with reduced graphene oxide were developed. These materials are promising for solving environmental problems such as water pollution with organic products by sorption treatment. Reduced graphene oxides (rGOs) were synthesized from graphene oxide suspensions using potassium hydroxide, ascorbic acid or hydrazine hydrate. Composites with obtained rGO and melamine and polyurethane foam were produced for further characterization. The composites demonstrate high sorption of organic pollutants (oil, diesel fuel and gasoline) and low sorption of water. The composites were comprehensively analyzed by physicochemical techniques (SEM, XPS, Raman spectroscopy, UV–Vis) to elucidate the mechanism of sorption

Use of Reduced Graphene Oxide to Modify Melamine and Polyurethane for the Removal of Organic and Oil Wastes

Methods for obtaining efficient sorption materials based on highly porous melamine and polyurethane matrices modified with reduced graphene oxide were developed. These materials are promising for solving environmental problems such as water pollution with organic products by sorption treatment. Reduced graphene oxides (rGOs) were synthesized from graphene oxide suspensions using potassium hydroxide, ascorbic acid or hydrazine hydrate. Composites with obtained rGO and melamine and polyurethane foam were produced for further characterization. The composites demonstrate high sorption of organic pollutants (oil, diesel fuel and gasoline) and low sorption of water. The composites were comprehensively analyzed by physicochemical techniques (SEM, XPS, Raman spectroscopy, UV–Vis) to elucidate the mechanism of sorption

Sorption of Eu (III) onto Nano-Sized H-Titanates of Different Structures

Hydrogen titanates (H-titanates) of different nanostructures (nanotubes, nanowires, nanosheets) have been synthesized by hydrothermal methods. The europium (III) sorption from aqueous solutions onto nano-sized H-titanates was studied as a function of contact time, pH values, and initial Eu (III) concentration in batch experiments. Reversibility of adsorption of europium has been investigated as well. Nano-sized H-titanates can be used for tri-valent f-elements removal in polluted water treatment due to fast and efficient sorption of Eu (III)

Super-oxidized “activated graphene” as 3D analogue of defect graphene oxide : oxidation degree vs U(VI) sorption

Porous carbons are not favorable for sorption of heavy metals and radionuclides due to absence of suitable binding sites. In this study we explored the limits for surface oxidation of “activated graphene” (AG), porous carbon material with the specific surface area of ∼2700 m2/g produced by activation of reduced graphene oxide (GO). Set of “Super-Oxidized Activated Graphene” (SOAG) materials with high abundance of carboxylic groups on the surface were produced using “soft” oxidation. High degree of oxidation comparable to standard GO (C/O=2.3) was achieved while keeping 3D porous structure with specific surface area of ∼700–800 m2/. The decrease in surface area is related to the oxidation-driven collapse of mesopores while micropores showed higher stability. The increase in the oxidation degree of SOAG is found to result in progressively higher sorption of U(VI), mostly related to the increase in abundance of carboxylic groups. The SOAG demonstrated extraordinarily high sorption of U(VI) with the maximal capacity up to 5400 μmol/g, that is 8.4 – fold increase compared to non-oxidized precursor AG, ∼50 –fold increase compared to standard graphene oxide and twice higher than extremely defect-rich graphene oxide. The trends revealed here show a way to further increase sorption if similar oxidation degree is achieved with smaller sacrifice of surface area

The Application of HEXS and HERFD XANES for Accurate Structural Characterisation of Actinide Nanomaterials: The Case of ThO 2

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To form or not to form : PuO2 nanoparticles at acidic pH

The aim of this study is to synthesize PuO2 nanoparticles (NPs) at low pH values and characterize the materials using laboratory and synchrotron-based methods. Properties of the PuO2 NPs formed under acidic conditions (pH 1-4) are explored here at the atomic scale. High-resolution transmission electron microscopy (HRTEM) is applied to characterize the crystallinity, morphology and size of the particles. It is found that 2 nm crystalline NPs are formed with a PuO2 crystal structure. High energy resolution fluorescence detected (HERFD) X-ray absorption spectroscopy at the Pu M-4 edge has been used to identify the Pu oxidation states and recorded data are analysed using the theory based on the Anderson impurity model (AIM). The experimental data obtained on NPs show that the Pu(iv) oxidation state dominates in all NPs formed at pH 1-4. However, the suspension at pH 1 demonstrates the presence of Pu(iii) and Pu(vi) in addition to the Pu(iv), which is associated with redox dissolution of PuO2 NPs under acidic conditions. We discuss in detail the mechanism that affects the PuO2 NPs synthesis under acidic conditions and compare it with one in neutral and alkaline conditions. Hence, the results shown here, together with the first Pu M-4 HERFD data on PuF3 and PuF4 compounds, are significant for the colloid facilitated transport governing the migration of plutonium in a subsurface environment

Oxidation and Nanoparticle Formation during Ce(III) Sorption onto Minerals

The sorption of Ce(III) on three abundant environmental minerals (goethite, anatase, and birnessite) was investigated. Batch sorption experiments using a radioactive 139Ce tracer were performed to investigate the key features of the sorption process. Differences in sorption kinetics and changes in oxidation states were found in the case of the sorption of Ce(III) on birnessite compared to that on other minerals. Speciation of cerium onto all of the studied minerals was investigated using spectral and microscopic methods: high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and X-ray absorption spectroscopy (XAS) in conjunction with theoretical calculations. It was found that during the sorption process onto birnessite, Ce(III) was oxidized to Ce(IV), while the Ce(III) on goethite and anatase surfaces remained unchanged. Oxidation of Ce(III) by sorption on birnessite was also accompanied by the formation of CeO2 nanoparticles on the mineral surface, which depended on the initial cerium concentration and pH value

Insight into the structure-property relationship of UO2 nanoparticles

Highly crystalline UO2 nanoparticles (NPs) with sizes of 2–3 nm were produced by fast chemical deposition of uranium(IV) under reducing conditions at pH 8–11. The particles were then characterized by microscopy and spectroscopy techniques including high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), high-energy resolution fluorescence detection (HERFD) X-ray absorption spectroscopy at the U M4 edge and extended X-ray absorption fine structure (EXAFS) spectroscopy at the U L3 edge. The results of this investigation show that despite U(IV) being the dominant oxidation state of the freshly prepared UO2 NPs, they oxidize to U4O9 with time and under the X-ray beam, indicating the high reactivity of U(IV) under these conditions. Moreover, it was found that the oxidation process of NPs is accompanied by their growth in size to 6 nm. We highlight here the major differences and similarities of the UO2 NP properties to PuO2, ThO2 and CeO2 NPs