An Se-derivative of amidoxime was synthesized for the first time as a result of the reaction of oxidative polycondensation of N’-hydroxy-1,2,5-oxadiazole-3-carboximidamide with SeO2: its elementary units are linked to each other due to the formation of strong diselenide bridges. The element composition of the material was established, and the structure of the elementary unit was suggested. The sorption-selective properties were evaluated, and it was found that the adsorbent can be used for the selective recovery of U (VI) from liquid media with a pH of 6–9. The effect of some anions and cations on the efficiency of recovery of U (VI) was estimated. Composite materials were fabricated, in which silica gel with a content of 35, 50, and 65 wt.% was used as a matrix to be applied in sorption columns. The maximum values of adsorption of U (VI) calculated using the Langmuir equation were 620–760 mg g−1 and 370 mg g−1 for the composite and non-composite adsorbents, respectively. The increase in the kinetic parameters of adsorption in comparison with those of the non-porous material was revealed, along with the increase in the specific surface area of the composite adsorbents. In particular, the maximum sorption capacity and the rate of absorption of uranium from the solution increased two-fold.
A new composite material with enhanced sorption-selective properties for uranium recovery from liquid media has been obtained. Sorbents were synthesized through a polycondensation reaction of a mixture of 4-amino-N’-hydroxy-1,2,5-oxadiazole-3-carboximidamide (hereinafter referred to as amidoxime) and SiO2 in an environment of organic solvents (acetic acid, dioxane) and highly porous SiO2. To establish optimal conditions for forming the polymer sorption-active part and the synthesis as a whole, a series of composite adsorbents were synthesized with varying amidoxime/matrix ratios (35/65, 50/50, 65/35). The samples were characterized with FT-IR, XRD, SEM, EDX, XRFES spectroscopy and TGA. Under static conditions of uranium sorption, the dependence of the efficiency of radionuclide recovery from mineralized solutions of various acidities on the ratio of the initial components was established. In the pH range from 4 to 8 (inclusive), the uranium removal efficiency exceeds 95%, while the values of the distribution coefficients (Kd) exceed 104 cm3g−1. It was demonstrated that an increase in the surface development of the sorbents enhances such kinetic parameters of uranium sorption as diffusion rate by 10–20 times compared to non-porous materials. The values of the maximum static capacity exceed 700 mg g−1. The enhanced availability of adsorption centers, achieved through the use of a porous SiO2 matrix, significantly improves the kinetic parameters of the adsorbents. A composite with optimal physicochemical and sorption properties (amidoxime/matrix ratio of 50/50) was examined under dynamic conditions of uranium sorption. It was found that the maximum dynamic sorption capacity of porous materials is four times greater compared to that of a non-porous adsorbent Se-init. The effective filter cycle exceeds 3200 column volumes—twice that of an adsorbent with a monolithic surface. These results indicate the promising potential of the developed materials for uranium sorption from liquid mineralized media under dynamic conditions across a wide pH range.
Composite adsorbents based on a natural biopolymer matrix of chitosan, to which 4-amino-N′-hydroxy-1,2,5-oxadiazole-3-carboximidamide and its Se derivative were attached, were synthesized. A complex of physicochemical analysis methods indicates that the direct introduction of a matrix with high ionic permeability into the reaction mixture contributes to the formation of homogeneous particles of composite with developed surface morphology, which enhances the kinetic and capacitive parameters of uranium sorption in liquid media. It has been established that the direct introduction of a matrix with high ionic permeability into the reaction mixture contributes to the formation of homogeneous particles with a developed surface morphology, which enhances the kinetic and capacitive parameters of uranium sorption in liquid media. The synthesized materials had increased sorption-selective properties towards uranium in the pH range from 4 to 9 under static sorption conditions. The formation of the Se derivative of amidoxime during its attachment to the polymer matrix (Se-chit) contributes to the creation of a more chemically stable and highly effective adsorbent, compared to the direct binding of 4-amino-N′-hydroxy-1,2,5-oxadiazole-3-carboximidamide with chitosan (43AF-chit). The optimal parameters for the synthesis of materials were established. It was demonstrated that the ratio of amidoxime to chitosan should be within the range of 2:1 to 1:2. As the mass content of chitosan increases, the material gradually dissolves and transforms into a gel, resulting in the formation of liquid radioactive waste with a complex chemical composition. It was found that the kinetic sorption parameters of composite materials increase 2–10 times compared to those of non-composite materials. The sorption capacity of uranium in solutions with pH 6 and pH 8 can reach approximately 400–450 mg g−1. Under dynamic sorption conditions, the effective filtration cycle values (before uranium slips into the filtrate ≥ 50%) improve significantly when transitioning from a non-composite adsorbent to a composite one: increasing from 50 to 800 b.v. for pH 6 and from 2700 to 4000 b.v. for pH 8. These results indicate that the synthesized sorbents are promising materials for uranium removal from liquid media, suitable for both purification and the recovery of radionuclides as valuable raw materials.
1 November 2016 in Russian Journal of Organic Chemistry
Isatin and its 5-bromo derivative react with о-phenylenediamine and acetone in formic acid; products of this three-component condensation were isolated as perchlorates, from which for the first time bases were obtained, derivatives of 3-[(2,3-dihydro-1Н-1,5-benzodiazepin-4-yl)methylidene]indolin-2-one. The reduction of these derivatives with sodium cyanoborohydride is followed by intramolecular cyclization affording a bridged 2,3,4,5-tetrahydro-1,4-methano-1Н-1,5-benzodiazepine system.
The article presents a comprehensive comparative performance evaluation and validation of composite adsorbents based on the Se-derivative of 4-amino-N′-hydroxy-1,2,5-oxadiazole-3-carboximidamide for U (VI) recovery from complex multicomponent aqueous media. Our results indicate the composite materials to be comparable to, and in some cases to surpass, existing adsorbents in recovery efficiency. Under static sorption conditions for trace U (VI) from real multicomponent solutions (tap, river, and sea water), the sorption efficiency reached 80–98%, while the distribution coefficients ranged from 104 to 106 cm3 g−1. The sorption-selectivity properties of the materials were evaluated in the presence of competing ions (EDTA and oxalate ions), which possess a high chelating capacity and a strong tendency to form complexes with uranium. The dependence of sorption efficiency on the concentration of these ions and the solution pH was investigated. The possibility of reusing the materials over multiple sorption-desorption cycles was assessed. An optimal regenerating eluent agent was identified (NaHCO3/NH4NO3), providing a desorption efficiency of >95% without degrading the material’s sorption properties over repeated cycles. Using a combination of physicochemical methods, including sorption techniques, the mechanism of uranium sorption and its dependence on the material structure were determined. The efficiency of uranium recovery from multicomponent natural waters was also investigated under dynamic conditions over repeated sorption-desorption cycles. The results demonstrate through comparative analysis that the developed composites exhibit a high sorption capacity and possess a high practical potential for the concentration and recovery of uranium from high-salinity solutions with complex composition.
В данной работе исследуется возможность оптимизации синтеза N-замещенных 5-(4,5,6,7-тетрагидро-1H-индол-2-ил)пентановых кислот из 2,2'-метиленбисциклогексанона через его бисульфитный аддукт, увеличения выходов этих гетероциклических кислот, с перспективой разработки нового универсального синтетического метода получения подобных соединений. Показано, что использование метабисульфита натрия увеличивает скорость реакции и степень конверсии дикетона в бисульфитный аддукт. Достигнуто увеличение выхода продукта реакции при оптимизации его выделения из реакционной смеси. Предложен новый возможный механизм реакции бисульфитного аддукта дикетона с первичными аминами.