Th6-Based Multicomponent Heterometallic Metal-Organic Frameworks Featuring 6,12-Connected Topology for Iodine Adsorption.

Its high coordination number and tendency to cluster make Th4+ suitable for constructing metal-organic frameworks (MOFs) with novel topologies. In this work, two novel thorium-based heterometallic MOF isomers (IHEP-17 and IHEP-18) were assembled from a Th6 cluster, a multifunctional organic ligand [4-(1H-pyrazol-4-yl)benzoic acid (HPyba)], and Cu2+/Ni2+ cations via the one-pot solvothermal synthesis strategy. The framework features a 6,12-connected new topology net and contains two kinds of supramolecular cage structures, Th36M4 and Th24M2, suitable for guest exchange. Both MOF materials can efficiently adsorb I2. X-ray photoelectron spectroscopy, Raman spectroscopy, and single-crystal X-ray diffraction indicate that the adsorbed iodine is uniformly distributed within the Th36M4 cage but not the Th24M2 cage in the form of I3-.

The effect of air on oxidation decomposition of uranium-containing cationic exchange resins in Li2CO3-Na2CO3-K2CO3 molten-salt system.

With the development of nuclear energy, spent cationic exchange resins after purification of radioactive wastewater must be treated. Molten-salt oxidation (MSO) can minimize the disposal content of resins and capture SO2. In this work, the decomposition of uranium-containing resins in carbonate molten salt in N2 and air atmospheres was investigated. Compared to N2 atmosphere, the content of SO2 released from the decomposition of resins was relatively low at 386-454 °C in an air atmosphere. The SEM morphology indicated that the presence of air facilitated the decomposition of the resin cross-linked structure. The decomposition efficiency of resins in an air atmosphere was 82.6% at 800 °C. The XRD analysis revealed that uranium compounds had the reaction paths of UO3 → UO2.92 → U3O8 and UO3 → K2U2O7 → K2UO4 in the carbonate melt, and sulfur elements in resins were fixed in the form of K3Na(SO4)2. The XPS result illustrated that peroxide and superoxide ions accelerated the conversion of sulfone sulfur to thiophene sulfur and further oxidized to CO2 and SO2. Besides, the ion bond formed by uranyl ions on the sulfonic acid group was decomposed at high temperature. Finally, the decomposition of uranium-containing resins in the carbonate melt in an air atmosphere was explained. This study provided more theoretical guidance and technical support for the industrial treatment of uranium-containing resins.

Effect of copper ions on transformation of organic sulfur in cationic exchange resins in Li2CO3-Na2CO3-K2CO3 molten-salt system.

Cationic exchange resins (CERs) were applied for purification and clarifying process of radioactive wastewater in nuclear industry, which was a kind of sulfur-containing organic material. Molten-salt oxidation (MSO) method can be applied for the treatment of spent CERs and the absorption of acid gas (such as SO2). The experiments about the molten salt destruction of the original resin and Cu ions doped resin were conducted. The transformation of organic sulfur in Cu ions doped resin was investigated. Compared with the original resin, the content of tail gas (such as CH4, C2H4, H2S and SO2) released from the decomposition of Cu ions doped resin was relatively high at 323-657 °C. Sulfur elements in the form of sulfates and copper sulfides were fixed in spent salt through XRD analysis. The XPS result revealed that the portion of functional sulfonic acid groups (-SO3H) in Cu ions doped resin was converted into sulfonyl bridges (-SO2-) at 325 °C. With the enhancement of temperature, sulfonyl bridges (-SO2-) were further decomposed to sulfoxides sulfur (-SO-) and organic sulfide sulfur. The destruction of thiophenic sulfur to H2S and CH4 was prompted by copper ions in copper sulfide. Sulfoxide were oxidized to the sulfone sulfur in molten salt. Sulfones sulfur consumed by reduction of Cu ions at 720 °C was more than it produced by oxidation of sulfoxide through XPS analysis, and the relative proportion of sulfone sulfur was 16.51%.

Effects of oxygen content on gaseous and solid products during molten salt oxidation of cation exchange resins.

Molten salt oxidation (MSO) is an advanced method for waste resins treatment; nevertheless, the research about gas product variations of resins under different stoichiometric air feed coefficient (α) is rare. The optimal working condition of hazardous waste disposal is obtained through thermodynamic equilibrium calculation, and the method to improve the treatment efficiency is found to guide the optimization of the actual experiment. In this paper, Fact Sage was used to calculate the oxidation products of cation exchange resins (CERs) at different temperatures and α, focusing on the similarities and differences through the contents of CO, CH4, CO2, and SO2 during the oxidation of CERs, the MSO of CERs, and the theoretical calculation. The results indicated that the gas products of the calculation and reality of the oxidation process of CERs are quite different, while the CO contents of CERs during MSO are close to the calculated values. The main reason for this consequence is that in the oxidation process of CERs, the S in the sulfonic acid group will form thermally stable C-S with the styrene-divinylbenzene skeleton. Moreover, the introduction of carbonate can promote the destruction of C-S and absorb SO2 as sulfate, weakening the influence of C-S on the oxidation products of CERs. The gas chromatograph results indicated that the SO2 content is reduced from 0.66% in the process of CERs oxidation to 0.28% in MSO of CERs. When 1.25 times stoichiometric air feed coefficient is fed, the sulfate content in the carbonate is the highest at 900 °C, which is 23.4%.

Catalytic effect of cesium on the oxidation behavior of cation exchange resins in Li2CO3-Na2CO3-K2CO3 melt.

After the treatment of liquid radioactive waste, there is a certain amount of Cs in the waste resin, and these Cs-doped resins are prone to volatilize during the thermal treatment process and cause radionuclide leakage. The molten salt oxidation (MSO) can effectively prevent the volatilization of toxic metal, especially the volatilization of Cs. Under nitrogen and air conditions, it is found that the oxidation behavior between Cs-doped and clean cation exchange resins (CERs) is quite different. In the presence of oxygen and molten carbonate salt, Cs2CO3 is generated by the destruction of functional groups in Cs-doped CERs. The Cs2CO3 in Na2CO3-K2CO3-Li2CO3 reacts with oxygen to form Li2O2, which reduces the content of S in residue from 26.33 to 13.38% in air conditions at 400 °C and promotes the generation of sulfate in the molten carbonate salt. The elements Cs and S in the Cs doped CERs spontaneously form thermally stable Cs2SO4 in the molten carbonate salt.