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基于壳聚糖聚合物基质和4-氨基-N'-羟基-1,2,5-恶二唑-3-甲脒衍生物的复合吸附剂用于从液态矿化介质中去除铀

Composite Sorbents Based on Chitosan Polymer Matrix and Derivatives of 4-Amino-N'-hydroxy-1,2,5-oxadiazole-3-carboximidamide for Uranium Removal from Liquid Mineralized Media.

作者信息

Matskevich Anna I, Maslov Konstantin V, Prokudina Veronika A, Churakova Daria D, Slabko Oleg Yu, Patrushev Dmitry K, Markin Nikita S, Tokar' Eduard A

机构信息

Institute of Natural Sciences and Technosphere Safety, Sakhalin State University, Sakhalin Region, 693000 Yuzhno-Sakhalinsk, Sakhalin Oblast, Russia.

Institute of High Technologies and Advanced Materials, Far Eastern Federal University, 690922 Vladivostok, Primorsky Krai, Russia.

出版信息

Gels. 2025 Jan 1;11(1):24. doi: 10.3390/gels11010024.

Abstract

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. 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.

摘要

合成了基于壳聚糖天然生物聚合物基质的复合吸附剂,其中连接了4-氨基-N'-羟基-1,2,5-恶二唑-3-甲脒及其硒衍生物。多种物理化学分析方法表明,将具有高离子渗透性的基质直接引入反应混合物中有助于形成具有发达表面形态的复合均匀颗粒,这提高了液体介质中铀吸附的动力学和电容参数。已经确定,将具有高离子渗透性的基质直接引入反应混合物中有助于形成具有发达表面形态的均匀颗粒,这提高了液体介质中铀吸附的动力学和电容参数。在静态吸附条件下,合成材料在pH值为4至9的范围内对铀具有更高的吸附选择性。与4-氨基-N'-羟基-1,2,5-恶二唑-3-甲脒与壳聚糖直接结合(43AF-chit)相比,偕胺肟在附着于聚合物基质(Se-chit)过程中形成硒衍生物有助于创建一种化学稳定性更高且高效的吸附剂。确定了材料合成的最佳参数。结果表明,偕胺肟与壳聚糖的比例应在2:1至1:2的范围内。随着壳聚糖质量含量的增加,材料逐渐溶解并转变为凝胶,导致形成化学成分复杂的液体放射性废物。发现复合材料的动力学吸附参数比非复合材料提高了2至10倍。在pH值为6和pH值为8的溶液中,铀的吸附容量可达到约400 - 450 mg/g。在动态吸附条件下,从非复合吸附剂转变为复合吸附剂时,有效过滤循环值(铀滑入滤液前≥50%)显著提高:pH值为6时从50增加到800床体积,pH值为8时从2700增加到4000床体积。这些结果表明,合成的吸附剂是从液体介质中去除铀的有前景的材料,适用于净化和回收作为有价值原材料的放射性核素。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61e1/11765316/9dcae0767fd5/gels-11-00024-g001.jpg

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