Technetium-99 (99Tc) is a challenging radionuclide from presents many problems related to safe disposal. The measurement of 99Tc is of particular interest due to its high mobility, and the fact that it is a beta-emitter with a long half-life (t1/2=2.13×105 years) with long-term radiological effects[1]. As an isotopes of 99Tc, 99mTc has been widely applied for medical diagnosis and medical research. It is reported that the 99mTc has been used in 80% of diagnostic nuclear medicine procedures and almost 30 million examinations are conducted worldwide using this isotope. Because 99mTc has a short half-life of 6 h and decays to 99Tc, monitoring and safe disposal of 99Tc from human urine is very important, and concern is increasing every day as global use of 99mTc has increased by more than 4.5×1014 Bq per week and is increasing continuously[2]. However, the current methods for the detection of this radionuclide in such mdium are time consuming and can not satisfy for the low level urine sample analysis. In this work, a method for rapid determination of 99Tc in urine samples was developed. The sample was firstly pre-treated with K2S2O8 to decompose the organic matters combined with 99Tc in 0.5 mol·L−1 HNO3 medium at 100°C. Then the sample solution was loaded to a TEVA column (2 mL) for 99Tc separation and purification. The target element was finally measured by high resolution inductively coupled plasma mass spectrometry (HR-ICPMS). The developed analytical method was proved to be reliable and can be used to rapid determine low-level 99Tc in urine samples.
The effect of hydrogen peroxide on the electrochemical behavior of iron was investigated in perchlorate solutions. Iron showed four distinct behaviors in the perchlorate solutions of pH 3.0. First, the active dissolution regions of Fe with two current waves were observed in the potential range of −0.7 to 0 V (vs. SCE). Second, the stable passivation was found in the potential range between 0 and 0.3 V (vs. SCE). Third, unstable passivation region was observed in the potential range of 0.3 to 1.2 V (vs. SCE). Finally, pitting corrosion was observed at a potential above 1.2 V (vs. SCE). The pH increase stabilized the passivation process of iron, whereas the increase in temperature had a negative influence by enhancing the passivation and pitting behaviors of iron. The presence of hydrogen peroxide at the concentrations below 1.45 mM had an adverse effect on the formation of the passive layer. However, at concentrations above 1.45 mM, hydrogen peroxide affected a beneficial influence on the formation of stable iron oxide layer in the active dissolution region. In addition, regardless of the hydrogen peroxide concentration, the presence of hydrogen peroxide mitigated the pitting corrosion of iron.
Density of chloride molten salts is an essential physical property in the reactor core design and thermal-hydraulic design simulation, especially in molten salt reactor (MSR) design currently under development in Korea. NaCl-MgCl2-UCl3 pseudo-ternary system is one of the various candidate chloride-based salt mixtures because it has relatively-low melting point, very low vapor pressure, high thermal conductivity, etc. However, to the best of our knowledge, the density data of NaCl-MgCl2- UCl3 have not yet been measured or published worldwide, and therefore the ballpark figures of the density should be given for the preliminary reactor design. In our present study, the density estimation of NaCl-MgCl2-UCl3 based on the pseudo-binary data, i.e., NaCl-MgCl2, MgCl2-UCl3, and NaCl- UCl3, reported in the literature previously were performed using the Redlich-Kister model. Binary interaction parameter for MgCl2-UCl3 was higher than that for NaCl-MgCl2 and lower than that for NaCl-UCl3. As an example, calculated density of 0.62 NaCl: 0.18 MgCl2: 0.20 UCl3 at 873 K was 2.578 g·cm−3. In our further study, the methodology using Redlich-Kister model will be applied to more complex multicomponent systems and to other physical properties such as viscosity, thermal conductivity, surface tension, etc.
The sorption behavior of Se(IV) on montmorillonite clay, a promising buffer and backfill material, was investigated in the presence of aquatic fulvic acid. Selenium-79 is one of the major radioactive nuclides which are long-lived and highly mobile in subsurface environments. Moreover, it is highly toxic even in small amounts, so the selenium quantity in soil and groundwater should be assessed. Although natural organic matters such as humic and fulvic acids are present in the environment, the influence of natural organic matters on Se(IV) migration has not yet been extensively studied. The batch sorption experiments were performed under oxic conditions. Suwannee River III standard aquatic fulvic acid (International Humic Substances Society) was used to build an organicrich environment. The N2 – BET surface area of the montmorillonite (Clay Minerals Society) was 97 ± 5 m2·g−1. The montmorillonite suspensions with/without fulvic acid were equilibrated with air before adding Na2SeO3. The solid-to-liquid ratio was 5 g·L−1, the ionic medium was 0.1 M NaCl, fulvic acid concentration was 50 mg·L−1, and the final pH was 3. The horizontal vial roller was used to prevent the clay from sinking. After 7 days of sorption at room temperature, the suspensions were centrifuged at 10,600 g for 15 min and filtered through 0.2 μm PTFE filters. The colloidal fulvic selenide and free Se(IV) concentrations were entirely measured by inductively coupled plasma–mass spectrometry (ICP-MS). The sorption results were fitted with Langmuir and Freundlich models. At concentrations lower than 20 μM, the distribution coefficients (Kd) were 50 ± 9 L·kg−1 without fulvic acid, and 36 ± 5 L·kg−1 with 50 mg·L−1 fulvic acid. For the concentrations between 20 and 100 μM, the Kd values without and with fulvic acid were 16 ± 7 L·kg−1 and 10 ± 1 L·kg−1, respectively. As a result, it turned out that fulvic acid interferes with the sorption of Se(IV) on montmorillonite in competition with the selenite anion. This indicates that such organic matter may facilitate the migration of selenium in deep geological groundwaters.
According to the article 18 of NSSC notice “Regulations on the delivery of low-and intermediatelevel radioactive wastes”, the consignor shall establish and implement the quality assurance program about waste management to ensure conformity with the criteria set forth in the regulations and detailed criteria proposed by the disposal facility operator, including matters related to characterization of the waste concerned. To meet the above requirement, commercially available laboratory information management system, STARLIMS from Abbott Informatics was introduced in the late of 2019 and was customized to our standardized test method in 2020. In that time, Electronic Lab Notebook (ELN), which is an electronic system to create, store, retrieve, and share fully electronic records, was tailored to replace paper lab notebook. Scientific Data Management System (SDMS), which is computer system used to capture, centrally store, catalog, and manage data, was installed. Due to the parsing ability of SDMS, human error like mistake while data entry was reduced by extracting data from measurement sheet and exporting measurement data to designated area of ELN and this feature made work efficiency improved. Afterward, validation of STARLIMS was conducted following the procedure of user acceptance testing including Operational Qualification and Performance Qualification. As a result of these activities, STARLIMS has been officially operated and applied to means to manage test results since 2021. In 2021, for user-friendly environment, updating STARLIMS was also conducted by applying SDMS to import data from other radiometric measurements including gas proportional counter (GPC), liquid scintillation counter (LSC), and low-energy Ge detector (LEGe) besides HPGe detector for gamma measurement. From implementation to operation, it is confirmed that STARLIMS has been providing reliable and stable platforms to manage laboratory information regarding measurement records and playing a significant role in tool to meet the quality assurance required.
Complexation of actinides and lanthanides with carboxylic organic ligands is known to facilitate migration of radionuclides from deep geological disposal systems of spent nuclear fuel. In order to examine the ligand-dependent structures of trivalent actinides and lanthanides, a series of Eu(III)-aliphatic dicarboxylate compounds, Eu2(oxalate)3(H2O)6, Eu2(malonate)3(H2O)6, and Eu2(succinate)3(H2O)2, were synthesized and characterized by using X-ray crystallography and time-resolved laser fluorescence spectroscopy. Powder X-ray diffraction results captured the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence of these solid compounds, especially on the hypersensitive peak, indicates a low site symmetry of these solid compounds. Luminescence lifetimes of the compounds were measured to be increased, which is ascribed to the displacement of water molecules in the innersphere of Eu center upon bindings of the organic ligands. The numbers of remaining bound water molecules estimated from the increased luminescence lifetimes were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that oxalate ligands promote the sensitized luminescence of Eu(III), especially in the UV region. In the case of malonate and succinate ligands, charge transfer occurs in the opposite direction from Eu(III) to the ligands under UV excitation, resulting in weaker luminescence.
Appropriateness of the minimum detectable activity in the analysis of gamma radionuclides is very important. This is reason determine the time factor among the conditions of the analysis when it is rationally determined has the advantage that radioactivity analysis can be performed accurately and quickly. In this study, 100 mL of an unknown sample was diluted in Marinelli Beaker 1L to obtain, review data on gamma radiation analysis results and minimum detectable activity for each measurement time. The measurement was used High Purity Germanium detector, target nuclides are Co-57, Co-58, Y-88 and Cs-137. Since the radioactivity analysis sample will be expected to be the waste subject to selfdisposal or less during the radioactive waste classification, the minimum detectable activity standard was set based on the detection of less than the permissible activity for self-disposal for each nuclide. The measurement methods were measured by classifying it into seven categories: 1000 seconds, 3600 seconds, 10000 seconds, 30000 seconds, 80000 seconds, 100000 seconds, and 150000 seconds. The radioactivity from this measurement are Co-57 2.89 Bq·g−1, Co-58 0.19 Bq·g−1, Y-88 0.20 Bq·g−1, Cs-137 0.15 Bq·g−1, the measurement results under all conditions were similar. On the other hand, the minimum detectable activity showed values above the allowable activity for self-disposal in not but Co-58 at 1000 and 3600 seconds. Only after taking the measurement time of 10000 seconds, the result was derived Co-57 0.0095 Bq·g−1, Co-58 0.0068 Bq·g−1, Y-88 0.0052 Bq·g−1, Cs-137 0.0062 Bq·g−1, which was confirmed to less than the allowable activity for self-disposal by nuclide. Reasonably determining the measurement time in gamma radionuclide analysis is a very important issue in terms of economy of time and accuracy of measurement. Although this study cannot be said to be able to determine a reasonable measurement time for all gamma radionuclide analysis, it is hoped that research on various samples will be made to contribute to the efficient measurement of gamma radioactivity.
To predict the long-term behaviors of actinides in aqueous environments, complexation behaviors of actinides should be understood. Various organic ligands of chelating aromatic structure appearing in humic substances are known to form stable aqueous complexes. In this study, a benzene diol (or catechol) derivative, i.e., 4-nitrocatechol (nCA) is selected and its chemical equilibria including acid dissociation and complexation with U(VI) ion were examined using spectroscopic methods. In addition, the effect of ionic strength (Is) on those equilibria was evaluated by adjusting the level of NaClO4 in aqueous solutions. First, the experiments to determine the acid dissociation constant (pKa) of nCA were carried out in aqueous solutions with different ionic strengths from 0.01–2.0 M. The acid dissociation constants of nCA (pKa1) were measured to 6.73 ± 0.07, 6.69 ± 0.03, 6.38 ± 0.03, 6.09 ± 0.12, and 6.04 ± 0.07 at Is = 0.01, 0.1, 0.5, 1.0, and 2.0, respectively. These results were confirmed through the UV-Vis absorption spectral data analysis using the HypSpec program. As the pKa1 decreases as the ionic strength increases, except for Is = 2.0, these data were further analyzed with SIT (Specific ion Interaction Theory). Typically, as the solution becomes basic, a red shift is shown in the absorption spectrum. This effect can be understood from the intramolecular charge transfer (ICT) occurring in the deprotonated structures of nCA. At higher pH similar trends were also observed for measurement of pKa2. However, the determination of pKa2 is found not to be straightforward since a dimer formation equilibrium of nCA was observed as the ionic strength increased. This phenomenon will be discussed in detail with other supporting experimental results. Second of all, the complexation between the U(VI) and nCA in aqueous solutions was also examined. It was shown that nCA can easily form complexes with U(VI) ions at a wide range of pH via the deprotonation of their hydroxyl groups. U(VI)-nCA complexation will be further characterized by UV-Vis spectroscopy, IR and NMR by varying the solution ionic strength. The metal-ligand binding stoichiometry will be confirmed, for example, through the Job’s method. Finally, the acid dissociations constant and stability constants that were determined in this study will be used to provide species diagrams of aqueous U(VI)-nCA systems at a wide range of pH considering the effect of solution ionic strengths.
This study presents a rapid and quantitative sequential separation method for H-3 and C-14 isotopes with distillation apparatus in environmental samples released from nuclear facilities. After adding 200 mg of granulated potassium permanganate and 500 mg of sodium hydroxide in 100 mL of sample solution, the sample solution was heated until approximately 10 mL of distillate, and the distillate fraction was removed. The sample solution was heated again until a minimum 10 mL of additional distillate was collected. 10 mL of distillate was transferred to the LSC vail and the measurement sample for H-3 was made by adding 10 mL of Ultima Gold LLT to the LSC vial. After adding 2.5 g of potassium persulfate, 2 mL of 1M silver nitrate and 15 mL of concentrated nitric acid to the remained sample solution, the sample solution was heated for 90 minutes and C-14 isotopes were adsorbed into 10 mL of Carbo-Sorb solution in glass vial. The measurement sample for C-14 was made by adding 10 mL of Permafluor to the C-14 fraction in glass vial. The purified H-3 and C-14 samples were measured by the liquid scintillation counter after quenching correction. The average recoveries of H-3 and C-14 with CRM were measured to be 96% and 85%, respectively. The sequential separation method for H-3 and C-14 investigated in this study was applied to activated charcoal filter produced from nuclear power plants after validating the reliability by result of proficiency test (KOLAS-KRISS, PT-2021-51).
Graphite is widely used as a reflector or moderator in nuclear reactors, and since it is exposed to high flux neutron irradiation, long-lived radioactive isotopes such as C-14 are formed. Therefore, quantitatively prediction of production amount is a very essential task for reliable radioactive waste management. In this study, considering nuclear reactions such as (, ) reaction by thermal neutrons and elastic scattering, various characteristics such as the rate of formation of C-14 and energy distribution of thermal neutrons according to the penetration depth from the graphite surface were numerically analyzed. The evaluation was carried out in consideration of the average energy of neutrons and reaction/collision cross-sectional area at given energy, and a comparative study was also performed when the thermal neutrons were in thermal equilibrium and when they were not. The numerically evaluated results were compared qualitatively with the experimental study, and methods to further increase the accuracy were also discussed.
An elevated temperature is expected at the deep geological repository (DGR) due to the decay heat from spent nuclear fuel and the positive geothermal gradient. The resulting elevated temperature would change the aqueous speciation and surface complexation of uranium, which is the major component in spent nuclear fuel. Since sorption reactions of uranium species on natural minerals determine the extent of uranium retardation, in this work the temperature-dependent adsorption of hexavalent uranium, U(VI), was studied by choosing alumina as the basic component mineral for complex aluminosilicates. Time-resolved laser fluorescence spectroscopy (TRLFS) was used to assess the dissolved and adsorbed U(VI) species on γ-Alumina in the pH range of 6.5–9.0 at temperatures of 25 to 70°C. Initial concentrations of U(VI), carbonate and calcium were 89 μM, 25 mM, and 3.0 mM, respectively. The parallel factor analysis (PARAFAC) was used for chemical speciation by spectrum deconvolution. In addition, a separate solution system with higher U(VI) concentrations (0.1 mM, 1.0 mM) and carbonate concentration of 25 mM was studied with attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy for adsorbed species at 25°C. The electrophoretic mobility measurements were also conducted at 25°C to assess the coordination mechanism of adsorbed species at 25°C. The uranyl hydrolysis species and uranyl tricarbonato species coexist in solution at 25°C. At the same temperature, both species were found to be adsorbed. ATR-FTIR could confirm the adsorption of uranyl tricarbonato species at 25°C, and the electrophoretic mobility measurements suggested that the reaction mechanism is an inner-sphere coordination. However, in comparison with aqueous speciation at 25°C, at elevated temperatures the available pH range of uranyl tricarbonato species was narrow and that for uranyl hydrolysis species was wider. It was evident that two hydrolysis species are adsorbed at elevated temperatures, but no tricarbonato species. The enhanced U(VI) adsorption was observed with temperatures. This could result from the transition of dominance from the concurrent adsorption of uranyl hydrolysis species and uranyl tricarbonato species to two hydrolysis species. It was seen that the trend of enthalpy of adsorption was endothermic. Combining the present results with temperature-dependent adsorption studies on silica and aluminosilicates, a reliable SCM for the subsurface system can be proposed to explain U(VI) migration.
Molten salt reactors and pyroprocessing are widely considered for various nuclear applications. The main challenges for monitoring these systems are high temperature and strong radiation. Two harsh environments make the monitoring system needs to measure nuclides at a long distance with sufficient resolution for discriminating many different elements simultaneously. Among available methodologies, laser-induced breakdown spectroscopy (LIBS) has been the most studied. The LIBS method can provide the required stand-off and desired multi-elemental measurable ability. However, the change of the level for molten salts induces uncertainty in measuring the concentration of the nuclides for LIBS analysis. The spectra could change by focusing points due to the different laser fluence and plasma shape. In this study, to prepare for such uncertainties, we evaluated a LIBS monitoring system with machine learning technology. While the machine learning technology cannot use academic knowledge of the atomic spectrum, this technique finds the new variable as a vector from any data including the noise, target spectrum, standard deviation, etc. Herein, the partial least squares (PLS) and artificial neural network (ANN) were studied because these methods represent linear and nonlinear machine learning methods respectively. The Sr (580–7200 ppm) and Mo (480–4700 ppm) as fission products were investigated for constructing the prediction model. For acquiring the data, the experiments were conducted at 550°C in LiCl-KCl using a glassy carbon crucible. The LIBS technique was used for accumulating spectra data. In these works, we successfully obtained a reasonable prediction model and compared each other. The high linearities of the prediction model were recorded. The R2 values are over 0.98. In addition, the root means square of the calibration and cross-validation were used for evaluating the prediction model quantitatively.
To evaluate the chemical properties of the epsilon particle present as a precipitate in the high-level radioactive waste, we performed the experiments for the samples fabricated by CeO2 containing 1, 3, and 5wt%Mo, where CeO2 is used as the simulated high-level radioactive waste to replace the real one, using X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEMEDS). Moreover, to evaluate the chemical behavior of Mo epsilon particle in CeO2 at high temperature, the manufactured CeO2-1wt%Mo, CeO2-3wt%Mo, and CeO2-5wt%Mo samples were heated at 100, 300, 500, 700 and 900ºC for 7 h in a tube furnace under Ar atmosphere. In this study, the results of comprehensive analysis including the crystal structure, chemical state, and elemental distribution will be presented to verify the chemical properties for CeO2 samples containing Mo epsilon particle, depending on the Mo content and heating temperature.
According to Article 4 and 5 of the Nuclear Safety and Security Commission (NSSC) Notice No. 2020-6, radioactive waste packages should be classified by radioactive levels, and finally permanently shipped to underground or surface disposal facilities. The level of the radioactive waste package is determined based on the concentrations of the radionuclides suggested in Article 8 of NSSC Notice No. 2021-26. Since most of the radionuclides in radioactive wastes are beta nuclides, chemical separation and quantification of the target nuclides are essential. Conventional methods to classify chemically non-volatile radionuclides such as Tc-99, Sr-90, Nb- 94, Fe-55 take a lot of time (about 5 days) and have low efficiency. An automated non-volatile nuclide analysis system based on the continuous chemical separation method of radionuclides has been developed to compensate for this disadvantages of the conventional method in this study. The features of the automated non-volatile nuclide separation system are as follows. First, the amount of secondary waste generated during the chemical separation process is very small. That is, by adopting an open-bed resin column method instead of a closed-bed resin column method, additional fittings and connector are unnecessary during the chemical separation. In addition, because the peristaltic pump is supplied for the sample and solution respectively, it is great effective to prevent cross-contamination between radioactive samples and the acid stock solution for analysis. Second, the factors that may affect results, such as solution amount, operating time and flow rate, are almost constant. By mechanically controlling the flow rate precisely, the operating time and additional factors required during the separation process can be adjusted and predicted in advance, and the uncertainty of the chemical separation process can be significantly reduced. Finally, it is highly usable not only in the continuous separation process but also in the individual separation process. It can be applied to the individual separation process because the user can set the individual sequence using the program. As a result of the performance evaluation of the automation system, recovery rates of about 80–90% and reproducibility within 5% were secured for all of the radionuclides. Furthermore, it was confirmed that the actual work time was reduced by more than 50% compared to the previous manual method. (It was confirmed that the operation time required during the separation process was reduced from 6 days to 3 days.) Based on these results, the automation system is expected to improve the safety of workers in radiation exposure, reduce human error, and improve data reliability.
The lattice thermal expansion of zirconium-based samples containing tin, niobium, and iron elements at a temperature range of 30–870°C with intervals of 40°C was studied by in situ hightemperature X-ray diffraction (HT-XRD). The a- and c-axes lattice constants of the hexagonal Zr crystal structure for the zirconium-based samples were calculated by Pawley refinement using the in situ HT-XRD spectra. The a-axis lattice parameters for the zirconium-based samples with tin element overall decreased, whereas those for the samples containing niobium or iron elements are not declined, as compared to those for a pure zirconium sample. It suggests that the lattice thermal expansion along the a-axis direction of the hexagonal Zr crystal structure for zirconium-based samples was suppressed by the tin element. This effect is the greatest when the content of tin element added in zirconiumbased sample is 3wt%. On the other hand, the c-axis lattice parameters for all the zirconium-based samples overall increase as compared to the pure zirconium, indicating no suppression effect by tin, niobium, and iron elements, in contrast to the a-axis lattice constants.
Elucidating the redox behavior of actinide elements in aqueous solution is important for the safety assessments of nuclear waste disposal. Despite ongoing endeavors for decades, some points of uranium and plutonium redox mechanism are ambiguous and unclear. In this study, the electrochemical redox behaviors of U(VI) and Pu(III and VI) ions in perchloric acid media were investigated by using a gold (Au) working electrode via cyclic voltammetry (CV) and cyclic square wave voltammetry (CSWV) with the temperature control (10–55°C). The cyclic voltammograms of U(V/VI), Pu(III/IV) and Pu(V/VI) redox couple were transformed to semi-integral form to calculate the diffusion coefficient and formal potential in the electrochemical quasi-reversibility prevailed system. The CSWV was additionally used for a more precise interpretation of the redox mechanism. From the investigation of the redox chemistry of U(VI) ions, a clear U(V/VI) redox peak and one unidentified oxidation peak appear around pH 2. With the temperature control and CSWV, the relevance of the oxidation peak and U(IV) was confirmed. In the case of voltammetry of Pu(VI) solution, Pu(V/VI) redox peak and an additional reduction peak appear. The redox behavior resposible for this additional reduction peak are also examined. The cyclic voltammograms of Pu(III) solution show a clear reversible redox reaction of Pu(III/IV) couple. With the temperature control, using the change of formal potential at ionic strength 1 M (ClO4 −), thermodynamic parameters of conditional molar enthalpy and entropy change were evaluated in this system.
A molten salt reactor (MSR) has considerably attracted attention due to its several advantages for the safety and efficiency over the light water reactors. Because the structural material in MSR is contacted with high-temperature liquid fuel during long-term, the excellent material for corrosion resistance is required to be applied in MSR. In this study, we evaluated the corrosion resistance for alloy 600 and 617, which are the nickel-based materials, in KCl molten salt at 800ºC for 100 h under Ar atmosphere containing less than 1 ppm of moisture and oxygen. After the corrosion experiments of alloy 600 and 617, the amount of the weight loss for them caused by the KCl molten salt were determined. In addition, the variation in the crystal structure, surface morphology, and elemental distribution was examined using X-ray diffraction and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy.
Efficient capture and storage of radioactive iodine (consisting of two isotopes: 129I and 131I), produced or released from nuclear activities, are of paramount importance for sustainable development of nuclear energy due to their volatility and long half-life. Therefore, it is very important to develop new adsorbents for efficient utilization of radioactive iodine from nuclear waste. Various methods and materials are used for I2 capturing and removing, including MOFs due to their high porosity and fast adsorption kinetics, which are rightfully considered effective sorbents for removing I2. Metal–organic frameworks (MOFs) are porous crystalline materials which have diverse pore geometry and unique physicochemical properties, have attracted enormous attention for use in gas storage, separation and catalysis. The ability of MOFs to adsorb volatile products at room temperature can significantly improve the cost-effectiveness of the utilization process. This work describes the synthesis and characterization of three new metal-organic frameworks based on pyrazine (pyz), 44’bipyridine (bpy), 1,2 -bis(4 - pyridyl) – ethane (bpe) and copper (II) hexafluorozironate, as potential adsorbents for I2 capture. All of these three MOFs exhibit a two - dimensional (2D) crystal structure consisting from infinity non-crossing linear chains. The crystal structure of [Cu(pyz)2(ZrF6)2(H2O)2], [Cu(bpy)4(H2O)2ZrF6] and [Cu(bpe)4(H2O)2ZrF6] were characterized using powder X-ray diffraction (PXRD), single crystal X-ray diffraction (SC-XRD). Comparative characteristics of synthesized MOFs, including Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) were also performed. The I2 sorption experiments were examined by UV-vis spectroscopy.
Polyoxometalates (POMs) are nanoclusters composed of transition metals with high oxidation states. Owing to their redox properties and structural diversity, POMs have been applied to broad fields, such as catalysis, materials, and medicine. Among various fields of application, POMs play an important role in radiochemistry. POMs can form complexes with tri- and tetravalent lanthanides and actinides (radioactive elements), which may be good sequestrators or agents for separating nuclear wastes. Among the most prominent POM structures, Anderson-type POMs with a general formula of [Hy(XO6)M6O18]n− (y=0–6, n=2–8, M=addenda atom, X=heteroatom) represent one of the basic topological structures of the POM family. An important feature of Anderson type POMs is incorporating a large number of various heteroatoms with different size and oxidation states, which can lead to tune chemical properties. Interestingly, no example of Anderson type POMs with early transition metal ions in the heteroatom site has been reported to date. Herein, we discovered that the Anderson POM Na2K6Ti0.92W6.08O24·12H2O, which consists of pure inorganic framework built from a central Ti core supported by six WO6 inorganic scaffold, and the crystal structure was confirmed and refined using single-crystal X-ray diffraction (SC-XRD). In addition, structural characterizations, including, Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and Inductively coupled plasma-optical emission spectroscopy (ICP-OES) were performed.
Spent nuclear fuel is a very complex material because various elements such as fission products, transuranium elements and activation products are produced from initial fresh UO2 fuel after irradiation. These elements exist in UO2 with various forms and can change the structure and of physicochemical properties of UO2. These changes could provide the surface activation site that could enhance chemical reactions and corrosion processes, and would significantly affect the storage environment for long-term disposal of spent nuclear fuel. Therefore, it can be important to understand the characteristics of spent nuclear fuel to design reliable and safe geological repositories. However, it is too hard to study the characteristics of spent nuclear fuel, because it is a very complex material by itself and not easy to handle due to its radioactivity, and it is also difficult to independently understand the effects of each element. Therefore, a simulated spent nuclear fuel containing an element that forms a solid solution and epsilon particle was manufactured to understand the change in characteristics of each element. Most of the elements that form solid solutions are lanthanides or actinides and can change the structure of the UO2 lattice itself. The epsilon particles exist as metals at the grain boundaries of UO2. In this study, structural changes were measured using XRD, SEM, and Raman spectroscopy, and physical and chemical properties were also identified by measuring electrical conductivity and electrochemical properties. The results were summarized, and the effects of solid solution elements and epsilon particles on the structure and properties of UO2 matrix were compared and discussed.