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Weiqun Shi - One of the best experts on this subject based on the ideXlab platform.
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paving the way for the synthesis of a series of divalent Actinide complexes a theoretical perspective
Dalton Transactions, 2016Co-Authors: Jian Hui Lan, Zhifang Chai, Chao Wang, Zhongping Cheng, John K Gibson, Weiqun ShiAbstract:Recently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La–Nd, Sm–Lu) and Actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent Actinide complexes, a series of divalent Actinide species, [AnCp′3]− (AnTh–Am, Cp′ = [η5-C5H4(SiMe3)]−) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the +2 Actinide ions and Cp′ ligands. The ground state electron configurations for the [AnCp′3]− species are [ThCp′3]− 6d2, [PaCp′3]− 5f26d1, [UCp′3]− 5f36d1, [NpCp′3]− 5f5, [PuCp′3]− 5f6, and [AmCp′3]− 5f7, respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the Actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp′3 → [AnCp′3]− should become increasingly facile across the Actinide series from Th to Am, in accord with the known An(III/II) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of Actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.
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exploring Actinide materials through synchrotron radiation techniques
Advanced Materials, 2014Co-Authors: Weiqun Shi, Liyong Yuan, Chengliang Xiao, Zhifang Chai, Congzhi Wang, Yuliang Zhao, Lin Wang, Lei Mei, Li ZhangAbstract:Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of Actinide-based materials. This trend is partially driven by the basic needs for multi-scale Actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on Actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize Actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with Actinides are illustrated as well.
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excellent selectivity for Actinides with a tetradentate 2 9 diamide 1 10 phenanthroline ligand in highly acidic solution a hard soft donor combined strategy
Inorganic Chemistry, 2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 219-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.
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Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard–soft donors combined in the same molecule, N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV–vis spectrometry. Density functional theory (DFT) calculations reveal that the An–N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu–N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning
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recent advances in computational modeling and simulations on the an iii ln iii separation process
Coordination Chemistry Reviews, 2012Co-Authors: Jian Hui Lan, Liyong Yuan, Weiqun Shi, Yuliang Zhao, Zhifang ChaiAbstract:The selective extraction of minor Actinides(III) from the lanthanides(III) is a key step for spent fuel reprocessing. Theoretical calculations of geometries, electronic structures, coordination complexion, and thermodynamic properties of the Actinides are essential for understanding the separation mechanisms and relevant reactions. This article presents a critical review of theoretical studies on Actinide systems involved in the An(III)/Ln(III) separation process. We summarize various theoretical methods for electronic and molecular scale modeling and simulations of Actinide coordination systems. The complexing mechanisms between metal cations and organic ligands and the strategies for the design of novel ligands for separation are discussed as well. (C) 2012 Elsevier B.V. All rights reserved.
Zhifang Chai - One of the best experts on this subject based on the ideXlab platform.
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paving the way for the synthesis of a series of divalent Actinide complexes a theoretical perspective
Dalton Transactions, 2016Co-Authors: Jian Hui Lan, Zhifang Chai, Chao Wang, Zhongping Cheng, John K Gibson, Weiqun ShiAbstract:Recently, the +2 formal oxidation state in soluble molecular complexes for lanthanides (La–Nd, Sm–Lu) and Actinides (Th and U) has been discovered [W. J. Evans, et al., J. Am. Chem. Soc., 2011, 133, 15914; J. Am. Chem. Soc., 2012, 134, 8420; J. Am. Chem. Soc., 2013, 135, 13310; Chem. Sci., 2015, 6, 517]. To explore the nature of the bonding and stabilities of the low-valent Actinide complexes, a series of divalent Actinide species, [AnCp′3]− (AnTh–Am, Cp′ = [η5-C5H4(SiMe3)]−) have been investigated in THF solution using scalar relativistic density functional theory. The electronic structures and electron affinity properties were systematically studied to identify the interactions between the +2 Actinide ions and Cp′ ligands. The ground state electron configurations for the [AnCp′3]− species are [ThCp′3]− 6d2, [PaCp′3]− 5f26d1, [UCp′3]− 5f36d1, [NpCp′3]− 5f5, [PuCp′3]− 5f6, and [AmCp′3]− 5f7, respectively, according to the MO analysis. The total bonding energy decreases from the Th- to the Am-complex and the electrostatic interactions mainly dominate the bonding between the Actinide atom and ligands. The electron affinity analysis suggests that the reduction reaction of AnCp′3 → [AnCp′3]− should become increasingly facile across the Actinide series from Th to Am, in accord with the known An(III/II) reduction potentials. This work expands the knowledge on the low oxidation state chemistry of Actinides, and further motivates and guides the synthesis of related low oxidation state compounds of 5f elements.
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advances in computational Actinide chemistry in china
ChemInform, 2015Co-Authors: Dongqi Wang, Zhifang ChaiAbstract:The advances in computational Actinide chemistry made in China are reviewed. Several areas relevant to chemistry of Actinides in gas, liquid, and solid phases have been explored. However, we limit the scope to selected contributions in the chemistry of molecular Actinide systems in gas and liquid phases. These studies may be classified into two categories: treatment of relativistic effects, which cover the development of two- and four-component Hamiltonians and the optimization of relativistic pseudopotentials, and the applications of theoretical methods in Actinide chemistry. The applications include (1) the electronic structures of actinocene, noble gas complexes, An-C multiple bonding compounds, uranyl and its isoelectronic species, fluorides and oxides, molecular systems withmetal-metal bonding in their isolated forms (U-2, Pu-2) and in fullerene (U-2@C-60), and the excited states of Actinide complexes; (2) chemical reactions, including oxidation, hydrolysis of UF6, ligand exchange, reactivities of thorium oxo and sulfido metallocenes, CO2/CS2 functionalization promoted by trivalent uranium complex; and (3) migration of Actinides in the environment. A future outlook is discussed.
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exploring Actinide materials through synchrotron radiation techniques
Advanced Materials, 2014Co-Authors: Weiqun Shi, Liyong Yuan, Chengliang Xiao, Zhifang Chai, Congzhi Wang, Yuliang Zhao, Lin Wang, Lei Mei, Li ZhangAbstract:Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of Actinide-based materials. This trend is partially driven by the basic needs for multi-scale Actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on Actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize Actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with Actinides are illustrated as well.
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excellent selectivity for Actinides with a tetradentate 2 9 diamide 1 10 phenanthroline ligand in highly acidic solution a hard soft donor combined strategy
Inorganic Chemistry, 2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 219-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.
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Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard–soft donors combined in the same molecule, N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV–vis spectrometry. Density functional theory (DFT) calculations reveal that the An–N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu–N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning
Liyong Yuan - One of the best experts on this subject based on the ideXlab platform.
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exploring Actinide materials through synchrotron radiation techniques
Advanced Materials, 2014Co-Authors: Weiqun Shi, Liyong Yuan, Chengliang Xiao, Zhifang Chai, Congzhi Wang, Yuliang Zhao, Lin Wang, Lei Mei, Li ZhangAbstract:Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of Actinide-based materials. This trend is partially driven by the basic needs for multi-scale Actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on Actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize Actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with Actinides are illustrated as well.
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excellent selectivity for Actinides with a tetradentate 2 9 diamide 1 10 phenanthroline ligand in highly acidic solution a hard soft donor combined strategy
Inorganic Chemistry, 2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 219-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.
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Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard–soft donors combined in the same molecule, N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV–vis spectrometry. Density functional theory (DFT) calculations reveal that the An–N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu–N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning
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recent advances in computational modeling and simulations on the an iii ln iii separation process
Coordination Chemistry Reviews, 2012Co-Authors: Jian Hui Lan, Liyong Yuan, Weiqun Shi, Yuliang Zhao, Zhifang ChaiAbstract:The selective extraction of minor Actinides(III) from the lanthanides(III) is a key step for spent fuel reprocessing. Theoretical calculations of geometries, electronic structures, coordination complexion, and thermodynamic properties of the Actinides are essential for understanding the separation mechanisms and relevant reactions. This article presents a critical review of theoretical studies on Actinide systems involved in the An(III)/Ln(III) separation process. We summarize various theoretical methods for electronic and molecular scale modeling and simulations of Actinide coordination systems. The complexing mechanisms between metal cations and organic ligands and the strategies for the design of novel ligands for separation are discussed as well. (C) 2012 Elsevier B.V. All rights reserved.
Yuliang Zhao - One of the best experts on this subject based on the ideXlab platform.
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exploring Actinide materials through synchrotron radiation techniques
Advanced Materials, 2014Co-Authors: Weiqun Shi, Liyong Yuan, Chengliang Xiao, Zhifang Chai, Congzhi Wang, Yuliang Zhao, Lin Wang, Lei Mei, Li ZhangAbstract:Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of Actinide-based materials. This trend is partially driven by the basic needs for multi-scale Actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on Actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize Actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with Actinides are illustrated as well.
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excellent selectivity for Actinides with a tetradentate 2 9 diamide 1 10 phenanthroline ligand in highly acidic solution a hard soft donor combined strategy
Inorganic Chemistry, 2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 219-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.
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Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard–soft donors combined in the same molecule, N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV–vis spectrometry. Density functional theory (DFT) calculations reveal that the An–N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu–N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning
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recent advances in computational modeling and simulations on the an iii ln iii separation process
Coordination Chemistry Reviews, 2012Co-Authors: Jian Hui Lan, Liyong Yuan, Weiqun Shi, Yuliang Zhao, Zhifang ChaiAbstract:The selective extraction of minor Actinides(III) from the lanthanides(III) is a key step for spent fuel reprocessing. Theoretical calculations of geometries, electronic structures, coordination complexion, and thermodynamic properties of the Actinides are essential for understanding the separation mechanisms and relevant reactions. This article presents a critical review of theoretical studies on Actinide systems involved in the An(III)/Ln(III) separation process. We summarize various theoretical methods for electronic and molecular scale modeling and simulations of Actinide coordination systems. The complexing mechanisms between metal cations and organic ligands and the strategies for the design of novel ligands for separation are discussed as well. (C) 2012 Elsevier B.V. All rights reserved.
Chengliang Xiao - One of the best experts on this subject based on the ideXlab platform.
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exploring Actinide materials through synchrotron radiation techniques
Advanced Materials, 2014Co-Authors: Weiqun Shi, Liyong Yuan, Chengliang Xiao, Zhifang Chai, Congzhi Wang, Yuliang Zhao, Lin Wang, Lei Mei, Li ZhangAbstract:Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of Actinide-based materials. This trend is partially driven by the basic needs for multi-scale Actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on Actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize Actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with Actinides are illustrated as well.
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excellent selectivity for Actinides with a tetradentate 2 9 diamide 1 10 phenanthroline ligand in highly acidic solution a hard soft donor combined strategy
Inorganic Chemistry, 2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard-soft donors combined in the same molecule, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV-vis spectrometry. Density functional theory (DFT) calculations reveal that the An-N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu-N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 219-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning.
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Excellent Selectivity for Actinides with a Tetradentate 2,9-Diamide-1,10-Phenanthroline Ligand in Highly Acidic Solution: A Hard–Soft Donor Combined Strategy
2014Co-Authors: Chengliang Xiao, Liyong Yuan, Zhifang Chai, Congzhi Wang, Shuao Wang, Yuliang Zhao, Weiqun ShiAbstract:In this work, we reported a phenanthroline-based tetradentate ligand with hard–soft donors combined in the same molecule, N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), for the group separation of Actinides over lanthanides. The synthesis and solvent extraction as well as complexation behaviors of the ligand with Actinides and lanthanides are studied experimentally and theoretically. The ligand exhibits excellent extraction ability and high selectivity toward hexavalent, tetravalent, and trivalent Actinides over lanthanides in highly acidic solution. The chemical stoichiometry of Th(IV) and U(VI) complexes with Et-Tol-DAPhen is determined to be 1:1 using X-ray crystallography. The stability constants of some typical Actinide and lanthanide complexes of Et-Tol-DAPhen are also determined in methanol by UV–vis spectrometry. Density functional theory (DFT) calculations reveal that the An–N bonds of the Et-Tol-DAPhen complexes have more covalent characters than the corresponding Eu–N bonds, which may in turn lead to the selectivity of Et-Tol-DAPhen toward Actinides. This ligand possesses merits of both alkylamide and 2,9-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (R-BTPhen) extractants for efficient Actinide extraction and the selectivity toward minor Actinides over lanthanides and hence renders huge potential opportunities in high-level liquid waste (HLLW) partitioning
