Conventional electrolytic methods for separating chemically similar lanthanides(Ln)and actinides(An)are limited by thermodynamics and slow reaction kinetics,restricting their efficiency in rare-earth refining and nucl...Conventional electrolytic methods for separating chemically similar lanthanides(Ln)and actinides(An)are limited by thermodynamics and slow reaction kinetics,restricting their efficiency in rare-earth refining and nuclear fuel recycling.Herein,we report an electroextraction and oxidative back-extraction(EOB)strategy utilizing a LiCl-KCl-KAlCl_(4) molten salt that overcomes these limitations by leveraging divergent interfacial reactivity.The EOB process achieves an exceptional separation factor for Ln/An(>1000),while simultaneously increasing the separation rate by at least one order of magnitude.Through in-situ synchrotron radiation X-ray micro-computed tomography(SR-μCT)and X-ray diffraction(SR-XRD),we capture selective oxidation-induced destabilization of Ln-Al alloys while actinides retain phase stability-directly visualizing the electrochemical alloy transition mechanism.This research redefines the separation of f-block elements in molten salt systems and introduces a multimodal approach to investigating transient interfacial phenomena that are usually inaccessible to conventional metallurgical diagnostics under extreme conditions.展开更多
Natural zircon was used as precursor material to produce a zircon waste form bearing 20wt% simulated actinides (Nd2O3 and UO2) through a solid state reaction by a typical synroc fabrication process. The fabricated zir...Natural zircon was used as precursor material to produce a zircon waste form bearing 20wt% simulated actinides (Nd2O3 and UO2) through a solid state reaction by a typical synroc fabrication process. The fabricated zir- con waste form has relatively good physical properties (density 5.09g/cm3, open porosity 4.0%, Vickers hardness 715kg/mm2). The XRD, SEM/EDS and TEM/EDS analyses indicate that there are zircon phases containing waste elements formed through the reaction. The chemical durability and radiation stability are determined by the MCC-1 method and heavy ion irradiation; the results show that the zircon waste form is highly leach resistance and relatively stable under irradiation (amorphous dose 0.7dpa). From this study, the method of using a natural mineral to solidify radioactive waste has proven to be feasible.展开更多
One of the urgent tasks of the uranium industry in Kazakhstan is the extraction of radionuclide residues from spent uranium wells.We proposed to extract the remains of radionuclides from the drilled wells and to impro...One of the urgent tasks of the uranium industry in Kazakhstan is the extraction of radionuclide residues from spent uranium wells.We proposed to extract the remains of radionuclides from the drilled wells and to improve the radiation safety of the contaminated area.We conducted a chemical analysis of the content of radionuclides in the ore material.The radionuclides U,Th,Pa,Ra,Ac,Rn were extracted,which can be used in industry and medicine in Kazakhstan.展开更多
Individual monitoring of workers exposed to the risk of intake of actinides requires suitable methods for measuring low level of excreted activity. The current protocols used for actinides analysis in bioassay are usu...Individual monitoring of workers exposed to the risk of intake of actinides requires suitable methods for measuring low level of excreted activity. The current protocols used for actinides analysis in bioassay are usually complicated and highly time consuming. In this work, a protocol based on the microwave digestion of urines followed by the separation of actinides using calix[6]arene-based chromatography columns and their measurement by a quadrupole ICP-MS is developed and validated, for the first time, on urine samples containing the three actinides, U, Pu and Am. With this protocol, the total analysis time is about 2 days, including the mineralization of urine and the chromatographic separation of actinides. Detection limits of actinides in urine are determined and compared to those obtained after “dilute and shoot” ICP-MS analysis or after alpha spectrometry measurement.展开更多
Basic properties of a silica-based octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) extraction resin (CMPO/SiO2-P) was investigated.Adsorption behavior for some rare earth elements (RE) which are con...Basic properties of a silica-based octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) extraction resin (CMPO/SiO2-P) was investigated.Adsorption behavior for some rare earth elements (RE) which are constituents of high level liquid waste (HLLW) and the long-term stability of the extraction resin in nitric acid solution were examined.The CMPO extraction resin was significantly stable in 3 mol·L?1 HNO3 solution at 50oC.Furthermore,the RE(III) were efficiently separated from non-adsorptive fission product (FP) elements such as Sr(II) in a column experiment using a highly nitric acid solution.The separation behaviors of the elements are considered to result from the difference in their adsorption and elution selectivity based on the complex formation with CMPO.There was no strong dependency of RE(III) separation efficiency on feed solution flow rate.Only from the perspectives of the acid-resistant behavior of CMPO extraction resin and the elution kinetics for the metal ions with the extraction resin,the CMPO extraction resin can be used in the modified MAREC process for HLLW partitioning.展开更多
Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development,yet it remains a formidable challenge due to the intricate chemical behaviors of t...Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development,yet it remains a formidable challenge due to the intricate chemical behaviors of these f-block elements.In this study,we introduce 3,6-di-2-pyridyl-1,2,4,5-tetrazine(L1),whose hydrolysis product of pyridine-2-carbox-aldehyde(pyridine-2-carbonyl)-hydrazone(L2)can fractionally crystallize U(Ⅵ)ions over Ln(Ⅲ)cations with high selectivity and efficiency.Through hydrolysis-induced C–N bond cleavage,L2 acts as a tetradentate ligand,coordinating with two UO_(2)^(2+) ions in a planar arrangement to form a zerodimensional cluster,[(UO_(2))2(μ_(3)-O)(L2)(CH_(3)COO)]·DMF(U-L2),while lanthanide ions(Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Yb,and Lu)remain in solution due to their inability to achieve similar coordination.This selective crystallization strategy yields exceptional separation factors(SFs)between U(Ⅵ)and Ln(Ⅲ),with a value of 756276 between U(Ⅵ)and Sm(Ⅲ),the highest reported to date.Furthermore,this fractional crystallization separation process can be achieved under mild ambient conditions with high SFs,enabling the development of a rapid,safe and energy-efficient strategy for once-through separation of high oxidation state actinides from lanthanides.展开更多
本刊已加入《中国期刊全文数据库》(中国知网)、《中文科技期刊数据库》(维普网)、《中国核心期刊(遴选)数据库》(万方网)、《超星期刊数据库》(超星移动“域出版”平台)、钛学术智慧平台、中邮阅读网、博看网、美国化学文摘(CAS)、EBSC...本刊已加入《中国期刊全文数据库》(中国知网)、《中文科技期刊数据库》(维普网)、《中国核心期刊(遴选)数据库》(万方网)、《超星期刊数据库》(超星移动“域出版”平台)、钛学术智慧平台、中邮阅读网、博看网、美国化学文摘(CAS)、EBSCO数据库(EBSCO Information Services),许可在其网站及其系列数据库产品中以数字化方式复制、发行、信息网络传播本刊全文。展开更多
基金supported by the National Science Fund for Distinguished Young Scholars(21925603)the National Natural Science Foundation of China(22306185)the China Postdoctoral Science Foundation(2023M732032)。
文摘Conventional electrolytic methods for separating chemically similar lanthanides(Ln)and actinides(An)are limited by thermodynamics and slow reaction kinetics,restricting their efficiency in rare-earth refining and nuclear fuel recycling.Herein,we report an electroextraction and oxidative back-extraction(EOB)strategy utilizing a LiCl-KCl-KAlCl_(4) molten salt that overcomes these limitations by leveraging divergent interfacial reactivity.The EOB process achieves an exceptional separation factor for Ln/An(>1000),while simultaneously increasing the separation rate by at least one order of magnitude.Through in-situ synchrotron radiation X-ray micro-computed tomography(SR-μCT)and X-ray diffraction(SR-XRD),we capture selective oxidation-induced destabilization of Ln-Al alloys while actinides retain phase stability-directly visualizing the electrochemical alloy transition mechanism.This research redefines the separation of f-block elements in molten salt systems and introduces a multimodal approach to investigating transient interfacial phenomena that are usually inaccessible to conventional metallurgical diagnostics under extreme conditions.
基金Partly supported by the International Atomic Energy Agency as part of the Coordinated Research Programme (Contract No.10637).
文摘Natural zircon was used as precursor material to produce a zircon waste form bearing 20wt% simulated actinides (Nd2O3 and UO2) through a solid state reaction by a typical synroc fabrication process. The fabricated zir- con waste form has relatively good physical properties (density 5.09g/cm3, open porosity 4.0%, Vickers hardness 715kg/mm2). The XRD, SEM/EDS and TEM/EDS analyses indicate that there are zircon phases containing waste elements formed through the reaction. The chemical durability and radiation stability are determined by the MCC-1 method and heavy ion irradiation; the results show that the zircon waste form is highly leach resistance and relatively stable under irradiation (amorphous dose 0.7dpa). From this study, the method of using a natural mineral to solidify radioactive waste has proven to be feasible.
文摘One of the urgent tasks of the uranium industry in Kazakhstan is the extraction of radionuclide residues from spent uranium wells.We proposed to extract the remains of radionuclides from the drilled wells and to improve the radiation safety of the contaminated area.We conducted a chemical analysis of the content of radionuclides in the ore material.The radionuclides U,Th,Pa,Ra,Ac,Rn were extracted,which can be used in industry and medicine in Kazakhstan.
文摘Individual monitoring of workers exposed to the risk of intake of actinides requires suitable methods for measuring low level of excreted activity. The current protocols used for actinides analysis in bioassay are usually complicated and highly time consuming. In this work, a protocol based on the microwave digestion of urines followed by the separation of actinides using calix[6]arene-based chromatography columns and their measurement by a quadrupole ICP-MS is developed and validated, for the first time, on urine samples containing the three actinides, U, Pu and Am. With this protocol, the total analysis time is about 2 days, including the mineralization of urine and the chromatographic separation of actinides. Detection limits of actinides in urine are determined and compared to those obtained after “dilute and shoot” ICP-MS analysis or after alpha spectrometry measurement.
文摘Basic properties of a silica-based octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) extraction resin (CMPO/SiO2-P) was investigated.Adsorption behavior for some rare earth elements (RE) which are constituents of high level liquid waste (HLLW) and the long-term stability of the extraction resin in nitric acid solution were examined.The CMPO extraction resin was significantly stable in 3 mol·L?1 HNO3 solution at 50oC.Furthermore,the RE(III) were efficiently separated from non-adsorptive fission product (FP) elements such as Sr(II) in a column experiment using a highly nitric acid solution.The separation behaviors of the elements are considered to result from the difference in their adsorption and elution selectivity based on the complex formation with CMPO.There was no strong dependency of RE(III) separation efficiency on feed solution flow rate.Only from the perspectives of the acid-resistant behavior of CMPO extraction resin and the elution kinetics for the metal ions with the extraction resin,the CMPO extraction resin can be used in the modified MAREC process for HLLW partitioning.
基金supported by the National Natural Science Foundation of China(U22B20139,22322609,22076152,and 22476158).
文摘Partitioning of actinides from lanthanides is pivotal for advancing nuclear waste management and sustaining nuclear energy development,yet it remains a formidable challenge due to the intricate chemical behaviors of these f-block elements.In this study,we introduce 3,6-di-2-pyridyl-1,2,4,5-tetrazine(L1),whose hydrolysis product of pyridine-2-carbox-aldehyde(pyridine-2-carbonyl)-hydrazone(L2)can fractionally crystallize U(Ⅵ)ions over Ln(Ⅲ)cations with high selectivity and efficiency.Through hydrolysis-induced C–N bond cleavage,L2 acts as a tetradentate ligand,coordinating with two UO_(2)^(2+) ions in a planar arrangement to form a zerodimensional cluster,[(UO_(2))2(μ_(3)-O)(L2)(CH_(3)COO)]·DMF(U-L2),while lanthanide ions(Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Yb,and Lu)remain in solution due to their inability to achieve similar coordination.This selective crystallization strategy yields exceptional separation factors(SFs)between U(Ⅵ)and Ln(Ⅲ),with a value of 756276 between U(Ⅵ)and Sm(Ⅲ),the highest reported to date.Furthermore,this fractional crystallization separation process can be achieved under mild ambient conditions with high SFs,enabling the development of a rapid,safe and energy-efficient strategy for once-through separation of high oxidation state actinides from lanthanides.
文摘本刊已加入《中国期刊全文数据库》(中国知网)、《中文科技期刊数据库》(维普网)、《中国核心期刊(遴选)数据库》(万方网)、《超星期刊数据库》(超星移动“域出版”平台)、钛学术智慧平台、中邮阅读网、博看网、美国化学文摘(CAS)、EBSCO数据库(EBSCO Information Services),许可在其网站及其系列数据库产品中以数字化方式复制、发行、信息网络传播本刊全文。
