作者： Fang Wang;Zhuo Chen;Yue Wu;Yating Peng;Tingting Li;...

期刊： Applied Surface Science,2025年680:161491 ISSN：0169-4332

通讯作者： Fang Wang<&wdkj&>Tingting Li<&wdkj&>Liangshu Xia

作者机构： [Fang Wang; Zhuo Chen; Yue Wu; Yating Peng] School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan 421001, China;[Tingting Li; Liangshu Xia] School of Nuclear Science and Technology, University of South China, Hengyang, Hunan 421001, China

通讯机构： [Fang Wang; Tingting Li; Liangshu Xia] S;School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan 421001, China<&wdkj&>School of Nuclear Science and Technology, University of South China, Hengyang, Hunan 421001, China

语种： 英文

作者： 黄文珑;谭盛恒;李春光;于明玥;夏良树

期刊： 化学工程,2024年52(03):6-12 ISSN：1005-9954

作者机构： 南华大学核科学技术学院,湖南衡阳 421001;[李春光] 中国原子能科学研究院放射化学研究所,北京 102413;[李春光] 南华大学放射性废物处理处置与数学模型研发中心,湖南衡阳 421001;[夏良树; 黄文珑; 于明玥] 南华大学;[谭盛恒] 中国原子能科学研究院

关键词： 玻璃固化;高放废物;铀;热学性能

摘要： 玻璃固化技术是目前国内外HLW(高放废液)固化处理最主要的手段.高放废液中含有镧和铀,但镧、铀对固化工艺的影响鲜有报道.为对比镧、铀对玻璃固化体熔制工艺和产品性能的影响,分析不同镧铀比例下的各方面差异,以模拟高放废液的硼硅酸盐玻璃固化体作为实验材料,采用XRD(X射线衍射)、SEM(扫描电子显微镜)等表征方法研究玻璃固化体在不同热处理温度下的析晶行为和热稳定性.结果表明:在800、900、1 000℃下,不同镧/铀配比的样品外观差别不大,热处理实验证实固化体样品在800-900℃热处理温度内有晶体析出,其中800℃热处理温度析晶最为严重.

语种： 中文

作者： 卢金成;张晓腾;刘郢;纪雷鸣;夏良树

期刊： 核科学与工程,2024年44(1):201-205 ISSN：0258-0918

作者机构： 中国核电工程有限公司北京核化工研究设计院,北京 100840;南华大学核科学技术学院,湖南衡阳 421001;[纪雷鸣; 卢金成; 张晓腾; 刘郢] 中国核电工程有限公司;[夏良树] 南华大学

关键词： 三氧化铀;溶解;后处理工艺;工艺条件

摘要： 三氧化铀是乏燃料后处理厂的一种产品,可用于制备工厂开车、铀尾端调试、制备四价铀等工艺环节所需的硝酸铀酰溶液。为明确三氧化铀粉末溶解制备硝酸铀酰溶液的最优工艺条件,有针对性地提高三氧化铀溶解工艺水平,探索其溶解特性,有必要...展开更多 三氧化铀是乏燃料后处理厂的一种产品,可用于制备工厂开车、铀尾端调试、制备四价铀等工艺环节所需的硝酸铀酰溶液。为明确三氧化铀粉末溶解制备硝酸铀酰溶液的最优工艺条件,有针对性地提高三氧化铀溶解工艺水平,探索其溶解特性,有必要研究三氧化铀溶解过程中工艺条件对溶解过程的影响。本文研究了不同搅拌速度、温度、初始酸度条件下,硝酸溶解三氧化铀粉末的过程,分析了反应条件对溶解过程的影响方式,并得到了最优工艺条件。结果表明:提高反应温度、初始酸度均有利于三氧化铀的溶解,随着搅拌速度的提高溶解时间呈现先减小后增大的趋势。收起

语种： 中文

作者： 李斌;郝帅;张秋月;夏良树;何辉

期刊： 核化学与放射化学,2024年46(01):54-59 ISSN：0253-9950

作者机构： 中国原子能科学研究院放射化学研究所,北京 102413;南华大学核科学技术学院,湖南衡阳 421001;[李斌; 张秋月; 何辉] 中国原子能科学研究院;[夏良树; 郝帅] 南华大学

关键词： 肼;催化;自由基

摘要： 采用电子自旋共振（electron spin resonance spectroscopy, ESR）法，探讨高氯酸体系和氢氧化钠体系中H+浓度与OH-浓度对催化剂催化肼断键及断键产生的自由基的状态及行为的影响，明确了酸碱体系下Pt/SiO2催化肼分解产生自由基的差异。结果表明：碱性体系中，随着OH-浓度升高，N-H断键速率显著升高，肼分解以氢解反应为主；酸性体系中，在pH=6.9到pH=1.1范围内，随着H+浓度升高，N-N断键速率急速升高并远大于N-H断键速率，在pH＜1.1范围内，随着H+浓度升高，N-H断键速率和N-N断键速率均快速下降。在酸碱变化过程中，N-H断键起着主导作用，决定了肼分解速率，随着酸度升高，N-H断键速率下降，肼分解速率下降。

语种： 中文

作者： Li, Tingting;Wang, Fang;Xia, Liangshu

期刊： RADIOCHIMICA ACTA,2024年112(5):301-313 ISSN：0033-8230

通讯作者： Wang, F;Xia, LS

作者机构： [Li, Tingting; Xia, Liangshu] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.;[Wang, F; Wang, Fang] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.

通讯机构： [Xia, LS ; Wang, F ] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.

关键词： uranium;adsorption;ferrocyanide;kinetics;isotherm

摘要： <jats:title>Abstract</jats:title> <jats:p>With the rapid development of the atomic energy industry, the demand for nuclear fuel has risen, while the limited resources of uranium mines make it difficult to meet the needs of the future development of nuclear energy. Expanding sources of uranium acquisition is necessary, and the enrichment and recovery of precious uranium from uranium-containing wastewater is invaluable. By synthesizing alginate supported potassium manganese ferrocyanide nanocomposites with magnetic response (KMnFC/MA/Fe<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub>), the high efficiency adsorption and separation of uranium in acidic uranium-containing wastewater can be realized conveniently and quickly. The magnetic composite was characterized by a variety of technical means, and the adsorption behavior of the magnetic material on uranium was studied by static adsorption experiments under different environmental conditions. The adsorption kinetics and isotherm of uranium by KMnFC/MA/Fe<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub> were studied by using some common linear adsorption models. The results show that the adsorption rate of KMnFC/MA/Fe<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub> on uranium is fast, and the adsorption equilibrium can be reached within 90 min. The adsorption process conforms to a pseudo-secondary kinetic model and is dominated by chemisorption. The adsorption of uranium by KMnFC/MA/Fe<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub> magnetic material is single molecular layer adsorption, and the maximum adsorption capacity is 425.5 mg g<jats:sup>−1</jats:sup> at 35 °C. KMnFC/MA/Fe<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub> is a promising adsorbent in the field of acidic low-concentration uranium wastewater treatment because of its good effect on the treatment of low concentration uranium wastewater, the concentration of uranium in the wastewater reaches the emission standard after treatment and it is easy to be separated magnetically after adsorption.</jats:p>

语种： 英文

作者： Zhou, Yiru;Yang, Yihan;Li, Guanghui;Zhang, Chuanfei;Xu, Ying;...

期刊： Journal of Radioanalytical and Nuclear Chemistry,2024年:1-13 ISSN：0236-5731

通讯作者： Xia, LS

作者机构： [Xia, Liangshu; Zhou, Yiru] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.;[Zhou, Yiru; Li, Guanghui; Ren, Baoan; Yang, Yihan; Zhang, Chuanfei] CNNC Inner Mongolia Mining Co Ltd, Hohhot 010020, Inner Mongolia, Peoples R China.;[Xu, Ying] Beijing Inst Chem Engn & Met, Nucl Ind, Beijing 101149, Peoples R China.

通讯机构： [Xia, LS ] U;Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.

关键词： Contaminated resin;Ultrasound;(HCl+H2O2) regeneration;Intensive regeneration;Industrial application;Working exchange capacity

摘要： Ion exchange resins used in uranium mines for neutral in-situ leaching mining often experience a reduction in their working exchange capacity owing to contamination. Three regeneration techniques-ultrasonic regeneration, (HCl+H2O2) regeneration, and (HCl+H2O2) treatment-ultrasonication regeneration methods-were employed to treat the resin, and the efficiencies of the methods were compared. The results indicated that the combination of (1 mol HCl+0.5% H2O2) treatment with 10 min ultrasonication exhibited the highest regeneration effectiveness. The industrial applicability verification test showed that the combined method improved the working performanceof the resin from 62.50 to 80.88% after regeneration. Regenerating the contaminated resin in the leachate treatment plant can enhance the efficiency operation of the leachate treatment process.

语种： 英文

作者： Wang, Fang;Li, Tingting;Liao, Yun;Xia, Liangshu

期刊： Applied Surface Science,2023年638:157969 ISSN：0169-4332

通讯作者： Xia, LS

作者机构： [Wang, Fang; Liao, Yun] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Hunan, Peoples R China.;[Li, Tingting; Xia, Liangshu] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.

通讯机构： [Xia, LS ] U;Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.

关键词： Core-shell Fe3O4 Silica Amino U(VI)

摘要： With the rapid development of nuclear industry, a large amount of U(VI)-containing wastewater is inevitably generated and poses a serious threat to the environment. Hence, it is of great significance to remove U(VI) from aqueous solution. Herein, a novel magnetic absorbent (Fe3O4@DFNS-NH2) with core–shell and fibrous structure for U(VI) capture was fabricated. The magnetic core can make the adsorbent separated conveniently from solution and the functional porous shell facilitates the fast capture of U(VI). Batch experiments were carried out to investigate the performance of the magnetic absorbent. The U(VI) adsorption onto Fe3O4@DFNS-NH2 reached equilibrium within 60 min at pH 6 and the adsorption capacity reached 255.2 mg g−1. The adsorption followed the pseudo-second order model and Langmuir isotherm model, indicating the nature of monolayer chemisorption. In addition, Fe3O4@DFNS-NH2 exhibited good selectivity toward U(VI) in the presence of metal ions (K+, Cs+, Ca2+, Mg2+, Sr2+and Eu3+). FT-IR and XPS analysis demonstrated that U(VI) was anchored onto Fe3O4@DFNS-NH2 through the surface complexation with amino groups. These findings manifest that Fe3O4@DFNS-NH2 shows great potential to remove U(VI) from nuclear wastewater. © 2023 Elsevier B.V.

语种： 英文

作者： 郝帅;李斌;李先俊;刘占元;刘敏;...

期刊： 原子能科学技术,2023年57(3):469-477 ISSN：1000-6931

通讯作者： Xia, Liangshu

作者机构： [郝帅; 刘敏; 夏良树] School of Nuclear Science and Technology, University of South China, Hengyang;421001, China;[李斌; 刘占元] Department of Radiochemistry, China Institute of Atomic Energy, Beijing;102413, China;[李先俊] China Nuclear Power Technology Research Institute Co., Ltd., Shenzhen

关键词： 亚硝酸;催化氧化;自由基

摘要： 为明确硝酸溶液中以Mn2+作催化剂时,亚硝酸氧化破坏H2C2O4的具体化学行为和反应机理,本文考察了在硝酸和硫酸体系中以Mn展开更多 为明确硝酸溶液中以Mn2+作催化剂时,亚硝酸氧化破坏H2C2O4的具体化学行为和反应机理,本文考察了在硝酸和硫酸体系中以Mn2+作催化剂时亚硝酸氧化H2C2O4的差异、Mn2+与草酸络合对亚硝酸氧化Mn(Ⅱ)到Mn(Ⅲ)的作用以及Mn(Ⅲ)破坏H2C2O4过程中产生的自由基,获得了具体的催化反应历程,推测了反应机理。结果表明,亚硝酸在催化反应过程中起主导作用,加入亚硝酸可有效消除反应初期存在的诱导期;反应过程中,溶液中游离的Mn2+与H2C2O4络合生成了MnC2O4,而作为配体的草酸降低了Mn(Ⅱ)被氧化到Mn(Ⅲ)的反应活化能,使得亚硝酸能氧化MnC2O4并生成[Mn(C2O4)3]3-,Mn(Ⅲ)会将所络合的草酸氧化生成·OOC—COOH并被还原成Mn(Ⅱ),·OOC—COOH在酸性溶液中稳定性差,会迅速分解并释放出还原性物质,最终实现了H2C2O4的氧化分解。

语种： 中文

作者： Hao, Shuai;Li, Bin;Liu, Zhanyuan;Huang, Wenlong;Jiang, Dongmei;...

期刊： RSC Advances,2023年13(33):22758-22768 ISSN：2046-2069

通讯作者： Xia, LS;Li, B

作者机构： [Xia, Liangshu; Hao, Shuai; Huang, Wenlong] Univ South China, Sch Nucl Sci & Technol, Hengyang, Peoples R China.;[Li, B; Li, Bin; Liu, Zhanyuan] China Inst Atom Energy, POB 275-88, Fangshan, Peoples R China.;[Jiang, Dongmei] Univ South China, Inst Innovat & Entrepreneurship, Hengyang, Peoples R China.

通讯机构： [Xia, LS ] U;[Li, B ] C;Univ South China, Sch Nucl Sci & Technol, Hengyang, Peoples R China.;China Inst Atom Energy, POB 275-88, Fangshan, Peoples R China.

摘要： Large quantities of solutions containing oxalic acid and nitric acid are produced from nuclear fuel reprocessing, but oxalic acid must be removed before nitric acid and plutonium ions can be recovered in these solutions. The degradation of oxalic acid with Pt/SiO(2) as a catalyst in nitric acid solutions has the characteristics of a fast and stable reaction, recyclable catalyst, and no introduction of impurity ions into the system. This method is one of the preferred alternatives to the currently used reaction of KMnO(4) with oxalic acid but lacks theoretical support. Therefore, this study attempts to clarify the reaction mechanism of the method. First, there was no induction period for this catalytic reaction, and no evidence was found that the nitrous acid produced in the solution could have an effect on oxalic acid degradation. Furthermore, oxidation intermediates (structures of Pt-O) were formed through this reaction between NO(3)(-) adsorbed on the active sites and Pt on the catalyst surface, but H(+) greatly promoted the reaction. Additionally, oxalic acid degradation through the oxidative dehydrogenation reaction occurred between oxalic acid molecules (HOOC-COOH) and Pt-O, with ·OOC-COOH, which is easily self-decomposable especially in acidic solution, generated simultaneously, and finally CO(2) was produced.

语种： 英文

作者： Li, Tingting;Xu, Yihong;Wang, Fang;Xia, Liangshu

期刊： JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING,2023年11(5):111133 ISSN：2213-2929

通讯作者： Xia, LS

作者机构： [Li, Tingting; Xia, Liangshu; Xu, Yihong] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.;[Wang, Fang] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.

通讯机构： [Xia, LS ] U;Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.

关键词： Adsorption;Calcium;Carbon nanotubes;Cyanides;Desorption;Ion exchange;Potassium;Reusability;Sodium;Sodium alginate;Adsorption capacities;Adsorption mechanism;Alginate beads;Calcium alginate;Ferrocyanide;Low-costs;Preparation process;Simple++;Uranium adsorption;Uranium removals;Metal ions

摘要： The separation and enrichment of uranium from uranium containing wastewater is important for the sustainable development of nuclear energy. Therefore, there is an urgent need to develop a low-cost, readily available, simple preparation process and environmentally friendly adsorbent. In this study, potassium manganese ferrocyanide and carbon nanotube encapsulated calcium alginate beads (KMnFC/CNT@SA) for uranium adsorption was prepared by a simple method using the inexpensive natural polymer material sodium alginate and the ion exchange material potassium manganese ferricyanide as well as carbon nanotubes capable of enhancing the spatial structure. Static adsorption experiments show that the adsorption capacity of KMnFC/CNT@SA for uranium is significantly affected by pH, contact time, U(VI) concentration and temperature, but is not affected by sodium ion concentration in solution. Furthermore, desorption and cycling tests demonstrate that KMnFC/CNT@SA has good reusability, with the adsorption capacity remaining above 89.83% of the maximum adsorption capacity after 10 adsorption-desorption cycles. It is worth noting that KMnFC/CNT@SA can adsorb uranium well under acidic conditions, and is easy to solid-liquid separation and recovery. This work provides an effective strategy for the development of high-quality, inexpensive, practical and durable adsorbents for uranium extraction from acidic uranium-containing wastewater. © 2023 Elsevier Ltd

语种： 英文

作者： 栾雪菲;王聪芝;夏良树;石伟群

期刊： 中国化学,2022年80(6):708-713 ISSN：1001-604X

通讯作者： Shi, W.;Xia, L.

作者机构： [栾雪菲] 南华大学核科学技术学院 衡阳421001;[栾雪菲] 中国科学院高能物理研究所 北京100049;[夏良树] 南华大学;[石伟群; 王聪芝] 中国科学院高能物理研究所

通讯机构： [Xia, L.] S;[Shi, W.] I;Institute of High Energy Physics, China;School of Nuclear Science and Technology, China

关键词： 铀酰配合物;碳酸铀酰;密度泛函理论;吡啶二羧酸;戊二酰偕亚胺二肟

摘要： 深入了解各种功能基团与铀酰离子的络合行为有助于设计和开发高效海水提铀吸附剂.本工作通过密度泛函理论(DFT)方法系统地研究了两种典型铀酰络合配体吡啶-2,6-二羧酸(H_2DPA)和戊二酰偕亚胺二肟(H_2A)与铀酰离子及碳酸根离子形成的配合物的结构、成键性质以及热力学稳定性.研究结果表明,所有配合物中,配体与铀酰离子之间具有不同强度的共价相互作用.由于H_2A配位时发生了质子重排,而且配体的解离能较高,使其更难与[UO_2(CO_3)_3]~(4-)发生取代反应,因此H_2DPA配体是海水提铀中一种潜在的有效配体.本工作的相关研究结果为海水提铀中高效吸附基团的设计和开发提供了理论线索.

语种： 中文

作者： Wang, Fang;Liao, Yun;Li, Tingting;Xia, Liangshu

期刊： Separation and Purification Technology,2022年299:121707 ISSN：1383-5866

通讯作者： Xia, Liangshu(2000000476@usc.edu.cn)

作者机构： [Li, Tingting; Wang, Fang; Xia, Liangshu] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.;[Wang, Fang; Liao, Yun] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Hunan, Peoples R China.;[Liao, Yun] Univ South China, Hunan Key Lab Design & Applicat Actinide Complexe, Hengyang 421001, Hunan, Peoples R China.

通讯机构： [Liangshu Xia] S;School of Nuclear Science and Technology, University of South China, Hengyang, Hunan 421001, China

关键词： Nano-silica;g-C3N4;Photocatalysis;Uranium;Reduction

摘要： Uranium (VI) removal and recovery from wastewater is crucial for sustainable development of nuclear energy and environmental remediation. Among various techniques, the photocatalytic reducing uranium (VI) to immobile uranium (IV) has been regarded as one of the most effective strategies. As a result, the design and fabrication of photocatalysts have attracted extensive attention. In this study, g-C3N4 decorated dendritic fibrous nano-silica was fabricated first and then coupled with CdS. The fibrous photocatalyst showed high surface area and extended visible light absorption. More importantly, it exhibited a satisfying performance for the photocatalytic reduction of uranium (VI) under air atmosphere with solar irradiation. The SEM images and XPS spectrum confirmed that uranium (VI) was indeed photo-reduced to uranium (IV). Meanwhile, quenching experiments showed that [rad]O2− played a key role in uranium (VI) reduction. © 2022 Elsevier B.V.

语种： 英文

作者： Li, Tingting;Xia, Liangshu;Wang, Fang

期刊： JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING,2022年10(6):108884 ISSN：2213-2929

通讯作者： Liangshu Xia

作者机构： [Li, Tingting; Wang, Fang; Xia, Liangshu] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.

通讯机构： [Liangshu Xia] S;School of Nuclear Science and Technology, University of South China, Hengyang 421001, China

关键词： Cyanides;Liquid films;Manganese;Potassium compounds;Acidic solutions;Adsorption amounts;Adsorption mechanism;Ecological protection;Potassium manganese ferrocyanide;Prussian blue;Sustainable economic development;Synthesised;Uranium enrichment;Uranium removals;Adsorption

摘要： Rapid and effective uranium removal and enrichment from water is necessary for sustainable economic development and ecological protection. In this paper, an efficient adsorbent Prussian blue compound, potassium manganese ferrocyanide (KMnFC), was synthesized and characterized for the separation of uranium. Its effectiveness in U(VI) removal and adsorption amount were evaluated using batch static adsorption experiments. The adsorption effect of the compound on U(VI) in aqueous solution was investigated, and the maximum adsorption capacity of the compound was 469.48 mg g-1. The adsorption-diffusion kinetic study showed that liquid film diffusion was the main rate control step. The adsorption process of uranium (VI) on KMnFC is a heat absorption reaction and chemisorption of uranium ions in exchange with potassium ions occurs. Most importantly, the compound is uranium selective, and its uranium removal ability is relatively effective even under high acidity circumstances. © 2022 Elsevier Ltd.

语种： 英文

作者： Xue-Fei Luan;Cong-Zhi Wang*;Qun-Yan Wu;Jian-Hui Lan;Zhi-Fang Chai;...

期刊： JOURNAL OF PHYSICAL CHEMISTRY A,2022年126(3):406-415 ISSN：1089-5639

通讯作者： Cong-Zhi Wang;Shi, WQ

作者机构： [Xue-Fei Luan; Jian-Hui Lan; Cong-Zhi Wang; Wang, CZ; Zhi-Fang Chai; Wei-Qun Shi; Shi, WQ; Qun-Yan Wu] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Xue-Fei Luan; Liang-Shu Xia] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.;[Zhi-Fang Chai] Chinese Acad Sci, Engn Lab Adv Energy Mat, Ningbo Inst Mat Technol & Engn, Ningbo 315201, Peoples R China.

通讯机构： [Wang, CZ; Shi, WQ ] C;Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.

关键词： Binding energy;Complexation;Extraction;Hydrogen bonds;Ions;Quantum chemistry;Seawater;Thermoanalysis;Thermodynamic properties;Uranium dioxide;Amidoxime;Functionalized;In-depth understanding;Methoxy;Quantum chemistry calculations;Uranium extraction;Uranium resources;Uranyl complexes;Uranyl ions;Vanadium ions;Ligands

摘要： Extraction of uranium from seawater is one of the important ways to solve the shortage of terrestrial uranium resources. Thereinto, the competition between uranyl and vanadium cations is a significant challenge in the commonly used amidoxime-based adsorbents for extracting uranium from seawater. An in-depth understanding of the extraction behaviors of modified amidoxime groups with uranyl and vanadium ions is one of the effective means to design and develop efficient adsorbents for selective uranium sequestration. In this work, we have designed and systematically investigated the alkyl and amino functionalized amidoxime, (Z)-2-amino-N′-hydroxy-N,N-dimethylbenzimidamide (L1), and its phenyl and methoxy derivatives ((Z)-3-amino-N′-hydroxy-N,N-dimethyl-2-naphthimidamide (L2) and (Z)-2-amino-N′-hydroxy-4-methoxy-N,N-dimethylbenzimidamide (L3)) by quantum chemistry calculations. In the uranyl complexes, the amidoxime groups prefer to act as η2-coordinated ligands as the amidoximes increase, and there exist substantial hydrogen bond interactions, which are different from the vanadium complexes. Various bonding analyses show that the L1 ligand possesses a stronger binding affinity to UO22+, and the −C6H5 and −CH3O substituent groups seem to have no effect on the improvement of extraction ability. Thermodynamic analysis confirms that the L1 ligand has a stronger extraction capability to uranyl ion compared to L2 and L3. According to the calculations of the vanadium (V) (VO2+ and VO3+) complexes with the L1 ligand, L1 is more likely to react with [H2VO4]− and [HVO4]2– to form VO2+ complexes. Expectantly, thermodynamic analysis displays a higher extraction capacity for uranyl ions than vanadium ions. Therefore, these alkyl and amino functionalized amidoxime ligands demonstrate high selectivity for uranyl over vanadium ions, which is mainly due to the coordination mode changes of these ligands toward vanadium in conjunction with the considerable hydrogen bonds in the uranyl complexes. These results are expected to afford useful clues for the design of efficient adsorbents for uranium extraction from seawater. © 2022 American Chemical Society

语种： 英文

作者： Luan, Xue-Fei;Wang, Cong-Zhi;Wu, Qun-Yan;Lan, Jian-Hui;Chai, Zhi-Fang;...

期刊： DALTON TRANSACTIONS,2022年51(30):11381-11389 ISSN：1477-9226

通讯作者： Wang, Cong-Zhi(wangcongzhi@ihep.ac.cn);Xia, Liang-Shu(xls1966@hotmail.com);Shi, Wei-Qun(shiwq@ihep.ac.cn)

作者机构： [Wu, Qun-Yan; Chai, Zhi-Fang; Luan, Xue-Fei; Wang, Cong-Zhi; Lan, Jian-Hui; Shi, Wei-Qun] Chinese Acad Sci, Inst High Energy Phys, Lab Nucl Energy Chem, Beijing 100049, Peoples R China.;[Xia, Liang-Shu; Luan, Xue-Fei] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Hunan, Peoples R China.

通讯机构： [Cong-Zhi Wang; Wei-Qun Shi] L;[Liang-Shu Xia] S;Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China<&wdkj&>School of Nuclear Science and Technology, University of South China, Hengyang 421001, Hunan Province, China

摘要： The competition of uranium and vanadium ions is a major challenge in extracting uranium from seawater. In-depth exploration of the complexation of uranium and vanadium ions with promising ligands is essential to design highly efficient ligands for selective recovery of uranium. In this work, we systematically explored the uranyl and vanadium extraction complexes with three tetradentate N,O-mixed donor analogues including the rigid backbone ligands 1,10-phenanthroline-2,9-dicarboxylic acid (PDA, L1) and 5H-cyclopenta[2,1-b:3,4-b′]dipyridine-2,8-dicarboxylate acid (L3), as well as the flexible ligand [2,2′-bipyridine]-6,6′-dicarboxylate acid (L2) using density functional theory (DFT). These ligands coordinate to the uranyl cation in a tetradentate fashion, while L1 and L3 act as tridentate ligands toward VO2+ due to the smaller ionic radius of VO2+ and larger cleft sizes of L1 and L3. Bonding analyses show that the metal-ligand bonding orbitals of the uranyl complexes [UO2L(CO3)]2−, [UO2L(OH)]−, and [UO2L(H2O)] mainly arise from the interactions of the U 5f, 6d orbitals and N, O 2p orbitals. Because of the rigid structure and more suitable chelate ring size, the L1 ligand possesses a stronger complexing ability for uranyl ions than other ligands, while the L3 ligand has weaker binding affinity than L1 and L2. All these ligands prefer to coordinate with the uranyl cation rather than vanadium ion, indicating the selectivity of these ligands to [UO2(CO3)3]4− over H2VO4− and HVO42− in seawater. This is mainly attributed to the metal ion size-based selectivity and structural preorganization of the ligands. These results demonstrate that the backbone of these ligands affect their extraction behaviors. It is expected that this work might prove useful in designing efficient ligands for uranium extraction from seawater. © 2022 The Royal Society of Chemistry.

语种： 英文

作者： 郝帅;李先俊;蒋冬梅;夏良树

期刊： 核科学与工程,2022年42(3):670-676 ISSN：0258-0918

作者机构： [郝帅; 李先俊; 夏良树] 南华大学核科学技术学院;[蒋冬梅] 南华大学创新创业学院

关键词： 草酸;吸光度;分光光度法

摘要： 乏燃料后处理中，草酸常作为沉淀剂实现锕系元素与其他元素的分离，在处理过程中需要控制溶液中的草酸浓度，因此需要测定草酸浓度。Mn（Ⅲ）可以迅速氧化草酸而转化为稳定的 Mn（Ⅱ），利用 Mn（Ⅲ）在波长 485 nm 附近有强吸收峰而 Mn（Ⅱ）没有吸收峰的特性，建立了一种分光光度法快速、简便、准确测定 Mn（Ⅲ）氧化草酸溶液中草酸浓度的方法，并考察了硫酸和硝酸浓度对 Mn（Ⅲ）氧化草酸反应的影响。结果表明：保存 Mn（Ⅲ）并测定草酸的最适硫酸浓度为 2.625 mol/L，检测波长为 485 nm，检测前等待反应时间为 60 s。待测样品中 0.057 5 mol/L≥c（H2C2O4）≥10-3 mol/L 时，硫酸浓度约为 2.625 mol/L 的 Mn（Ⅲ）溶液与样品溶液体积比为 50:1时，吸光度 A 与草酸浓度间的回归方程为 c（H2C2O4） = （0.677 1 - A）/4.327 7 相关系数 R2 = 0.999 9，使用该体积比应用于实际样品测定时，平均回收率为 100.009%,c（H2C2O4） = 10-3 mol/L 测定结果的相对标准偏差为 0.637 8%（n = 10），当样品中 c（H2C2O4）≥0.057 5 mol/L 稀释一定倍数再进行即可测量。样品中 10-3 mol/L≥c（H2C2O4）≥10-4 mol/L 时，硫酸浓度为 2.625 mol/L 的 Mn（Ⅲ）溶液与样品溶液体积比为 4:1 时，吸光度 A 与草酸浓度间的回归方程为 c（H2C2O4） = （0.539 0 - A）/41.145 相关系数 R2 = 0.999 9，使用该体积比应用于实际样品测定时，平均回收率为 100.281%,c（H2C2O4） = 10-4 mol/L 测定结果的相对标准偏差为 1.706 1%（n = 10）。待测液中含有大量硝酸时并不影响此方法的检测准确度。Mn（Ⅲ）与草酸反应迅速，以 Mn（Ⅲ）溶液作为检测剂，利用分光光度法可快速测定待测样品中草酸浓度，可满足检测常量草酸的需求。

语种： 中文

作者： 李先俊;郝帅;张晓腾;蒋冬梅;夏良树

期刊： 核科学与工程,2022年42(3):677-683 ISSN：0258-0918

作者机构： [郝帅; 张晓腾; 李先俊; 夏良树] 南华大学核科学技术学院;[蒋冬梅] 南华大学创新创业学院

关键词： 草酸;ESR法;动力学;机理

摘要： 为明确Mn(Ⅲ)氧化破坏草酸的反应机理和反应历程,优化该反应的工艺条件,开展了动力学过程及机理研究。通过考察草酸浓度、Mn(Ⅲ)浓度和酸度等反应条件对反应历程的影响,确定了该反应的初始动力学速率方程为: -dc(Mn(Ⅲ))/dt = kc~(0.885 5)(H_2C_2O_4)c~( 0.727 4)(Mn(Ⅲ)),在温度为298.15 K时,速率常数k = 2.0 × 10~2(mol/L)~(-0.612 9)/min。研究了甲醇体系下Mn(Ⅲ)与草酸反应过程中产生的自由基,由此推测了Mn(Ⅲ)氧化破坏草酸过程的反应机理:Mn(Ⅲ)氧化破坏草酸的过程为单电子氧化过程,反应速度极快,能够迅速使草酸分解。

语种： 中文

作者： Zhang, Xiao-teng;Hao, Shuai;Tang, Fei-fei;Li, Bin;Zhou, Xian-ming;...

期刊： 化学物理学报(英文版),2022年35(5):813-822 ISSN：1674-0068

通讯作者： Xia, Liang-Shu(2000000476@usc.edu.cn)

作者机构： [Hao, Shuai; Zhang, Xiao-teng; Xia, Liang-shu; Tang, Fei-fei] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.;[Li, Bin; Zhou, Xian-ming; Liu, Li-sheng] China Inst Atom Energy, Inst Radiat Chem, Beijing 102413, Peoples R China.

通讯机构： [Liang-shu Xia] S;School of Nuclear Science and Technology, University of South China , Hengyang 421001, China

关键词： Uranium;Reaction kinetics;Electron spin resonance;Hydrazine;Density functional theory

摘要： The kinetics of U(IV) produced by hydrazine reduction of U(VI) with platinum as a catalyst in nitric acid media was studied to reveal the reaction mechanism and optimize the reaction process. Electron spin resonance (ESR) was used to determine the influence of nitric acid oxidation. The effects of nitric acid, hydrazine, U(VI) concentration, catalyst dosage and temperature on the reaction rate were also studied. In addition, the simulation of the reaction process was performed using density functional theory. The results show that the influence of oxidation on the main reaction is limited when the concentration of nitric acid is below 0.5 mol/L. The reaction kinetics equation below the concentration of 0.5 mol/L is found as: -dc(UO22+)/dt=kc0.5323(UO22+)c0.2074(N2H5+)c-0.2009(H+). When the temperature is 50 °C, and the solid/liquid ratio r is 0.0667 g/mL, the reaction kinetics constant is k=0.00199 (mol/L)0.4712/min. Between 20 °C and 80 °C, the reaction rate gradually increases with the increase of temperature, and changes from chemically controlled to diffusion-controlled. The simulations of density functional theory give further insight into the influence of various factors on the reaction process, with which the reaction mechanisms are determined according to the reaction kinetics and the simulation results. © 2022 Chinese Physical Society.

语种： 英文

作者： Li, Tingting;Wang, Fang;Xia, Liangshu

期刊： Journal of Radioanalytical and Nuclear Chemistry,2022年331(6):2655-2665 ISSN：0236-5731

通讯作者： Xia, LS

作者机构： [Li, Tingting; Xia, Liangshu; Wang, Fang] Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.

通讯机构： [Xia, LS ] U;Univ South China, Sch Nucl Sci & Technol, Hengyang 421001, Peoples R China.

关键词： ferrocyanide;potassium derivative;potassium titanium ferrocyanide;titanium derivative;unclassified drug;uranium;adsorption kinetics;aqueous solution;Article;chemisorption;controlled study;energy dispersive X ray spectroscopy;Fourier transform infrared spectroscopy;inductively coupled plasma optical emission spectrometer;ion exchange;Langmuir isotherm model;mathematical model;pH;radioactive waste;thermodynamics;waste component removal;waste water management;water pollution;water temperature;X ray photoemission spectroscopy

摘要： Uranium, as a highly toxic radioactive contaminant existing in mine wastewater and contaminated groundwater, has sparked widespread alarm in recent years. This work demonstrates the technological possibility of recovering uranium from aqueous solutions using potassium titanium ferrocyanide (KTiFC). The adsorption behavior, kinetics, isotherms, and thermodynamic investigations were systematically examined. The maximum capacities were achieved at pH3.8, and KTiFC was proven to be stable across a wide pH range. The adsorption process was best represented by a pseudo-second order rate equation and the Langmuir isotherm model, with 90% of the uranium eliminated in 60min. The adsorption process was endothermic and spontaneous, adsorption efficiency of uranium is highly related to water temperature. The integrated analysis of EDS, ICP-OES, FTIR and XPS suggested that chemisorption combined with ion exchange between K and U can describe the adsorption mechanism of uranium sorption on KTiFC. This study points the way toward developing effective and low-cost materials with practical functionality for uranium extraction from polluted water. © 2022, Akadémiai Kiadó, Budapest, Hungary.

语种： 英文

作者： 田文江;梅雷;孔祥鹤;耿峻山;梁媛媛;...

期刊： 核化学与放射化学,2022年44(2):127-140 ISSN：0253-9950

作者机构： [田文江] 南华大学 核科学技术学院,湖南 衡阳 421001;[柴之芳; 田文江] 中国科学院 高能物理研究所 核能放射化学实验室,北京 100049;[柴之芳] 中国科学院 宁波工业技术研究所 先进能源材料工程实验室,浙江 宁波 315201;[耿峻山; 胡孔球; 梅雷; 孔祥鹤; 石伟群; 梁媛媛; 曾立雯] 中国科学院高能物理研究所;[夏良树] 南华大学

关键词： 铀酰配合物;氯代异烟酸;混合配体;异质金属;竞争配位

摘要： 本工作从基于2,6-二氯异烟酸(H-2,6-dcpca)和2,2′-联吡啶(2,2′-bpy)混合配体的卤代异烟酸铀酰配合物((UO2)(2,6-dcpca)2 (2,2′-bpy))出发,通过进一步引入第二金属中心(Ag~+、Zn~(2+)和Cu~(2+))进行竞争配位,实现了对这一混合配体型氯代异烟酸铀酰配合物的结构调控,并成功合成了六种新型混合配体型异质金属铀酰配合物。单晶结构分析表明,这些异质金属节点具有不同的配位行为,可以参与2,2′-bpy和[2,6-dcpca]-配体的竞争配位并改变铀酰中心的配位环境,导致最终形成的水热产物具有不同铀酰配位模式和化学结构。同时,由于晶体结构的不同,这些化合物在超分子晶格中的弱相互作用和晶格堆积方式也表现出较大变化。通过第二金属中心的竞争配位策略,实现了混合配体型铀酰配合物中铀酰配位模式的调控及多种异质金属铀酰化合物的制备,证明了基于多重竞争配位的合成调控策略的可行性,并有望在未来用于更多的功能性锕系-有机杂化材料的合成。

语种： 中文