Article
Chemistry, Multidisciplinary
Florian Glasneck, Quirina Roode-Gutzmer, Thorsten Stumpf, Berthold Kersting
Summary: A new series of lanthanide and uranyl complexes with a tetra-substituted bifunctional calixarene ligand H2L were synthesized and characterized. The results showed that the ligand has higher affinity for uranyl cation compared to lanthanide ions, and demonstrated good selectivity and extraction efficiency in solvent extraction process.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Engineering, Chemical
Long Li, Xiaoyang Hu, Zhuang Wang, Qiao Yu, Fengfeng Li, Fangxiang Luo, Qingjiang Pan, Songdong Ding
Summary: This study investigates the influence of ligand structure on the extraction of Am3+ over Eu3+ in the efficient separation of trivalent actinides over lanthanides. Among the three ligands tested, N,N-diethyl-N',N',N'',N''-tetraoctylnitrilotriacetamide shows the highest extraction ability for Am3+. The study reveals that unsymmetrical NTAamides have higher extraction efficiency to Am3+ and relatively lower selectivity for Am3+ over Eu3+ than the symmetrical NTAamide due to steric hindrance.
SEPARATION AND PURIFICATION TECHNOLOGY
(2024)
Article
Biochemistry & Molecular Biology
Ming-Ming Li, Xiao-Juan Liu, Qi Yang, Yue-Kun Liu, Jiang Nie, Shu-Ming Yang, Ya-Ya Yang, Fu-Yan Lou, Song-Tao Xiao, Ying-Gen Ouyang, Guo-An Ye
Summary: This study compared the solvent extraction, complexing ability, and basicity of tetradentate N-donor 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline (CyMe4-BT-Phen) and its derivatives. It was found that 5-nitryl-CyMe4-BTPhen has a lower distribution ratio for Eu(lll) compared to CyMe4-BTPhen. The study also analyzed the effect of substituents on the affinity to lanthanides using UV/vis and fluorescence spectroscopic titration, and determined the basicity of different ligands through NMR in CD3OD with DClO4.
Article
Engineering, Chemical
Jinglu Han, Guolong Wu, Yanling Li, Songsong Li, Wuping Liao
Summary: In order to overcome the drawbacks of the commonly used naphthenic acid (NA) system for yttrium (Y) separation, a novel extractant, 2-(bis((2-ethylhexyl)oxy)phosphoryl)-2-hydroxy-acetic acid (HPOAc, HL), was designed and synthesized by combining the functional groups of commercial organophosphorus extractants, carboxylic acids, and alcohol phase modifiers. HPOAc showed higher extraction ability for REEs(III) and better performance in the separation of Ln(III) and Y(III) compared to NA and CA-12. A cascade extraction process using HPOAc as the extractant was developed, achieving a Y product with a purity of 99.31 wt% through 20 stages of extraction and 4 stages of scrubbing.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Engineering, Chemical
Vera V. Belova, Yulia V. Tsareva, Yulia A. Zakhodyaeva, Vladimir K. Ivanov, Andrey A. Voshkin
Summary: A new extraction system containing a mixture of Cyanex 272 and caprylic acid was proposed for the extraction and separation of lanthanides(III) with high level of extraction ability and capacity. It was shown that the composition of the synergistic mixture of Cyanex 272-caprylic acid established demonstrates highly efficient separation of rare-earth metal ions, especially for La(III). The efficiency of lanthanum(III) extraction was affected by the pH changes in the aqueous phase.
Article
Engineering, Chemical
Jessica A. Jackson, Vanessa Linero, Nathan P. Bessen, Kenneth L. Nash, Jenifer C. Shafer
Summary: This study explores a new approach using kinetic control in metal ion extraction systems, showing that the rate constant of lanthanide-DOTA complexes increases with the lanthanide series, exhibiting non-monotonic behavior in terbium and thulium. Results suggest that separations between metals are more effective in the early phase of contact, diminishing over longer contact times. The use of slowly complexing ligands like DOTA may be suitable for kinetically based systems, providing a new design basis for f-element separations.
SEPARATION AND PURIFICATION TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Ziye Dong, Joseph A. Mattocks, Gauthier J. -P. Deblonde, Dehong Hu, Yongqin Jiao, Joseph A. Cotruvo, Dan M. Park
Summary: The study demonstrates a biobased, all-aqueous rare earth element extraction and separation approach using lanmodulin protein, which shows high efficiency in REE purification and separation under flow-through conditions. The immobilized lanmodulin maintains excellent REE selectivity and stability, allowing high-purity separation from complex aqueous feedstock solutions.
ACS CENTRAL SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Ye Yuan, Yajie Yang, Katie R. Meihaus, Shenli Zhang, Xin Ge, Wei Zhang, Roland Faller, Jeffrey R. R. Long, Guangshan Zhu
Summary: The use of coordination complexes within covalent organic frameworks can enhance their structures and properties. In this study, a series of crystalline covalent organic frameworks with tunable scandium incorporation were prepared by combining organic ligands and scandium coordination complexes. These frameworks showed high selectivity for Sc3+ ions over common impurity ions.
Article
Engineering, Environmental
Lanlan He, Xueyu Wang, Qiuju Li, Xiao Xiao, Fengfeng Li, Fangxiang Luo, Qingjiang Pan, Songdong Ding
Summary: Two novel water-soluble aromatic bisdiglycolamides (BisDGAs) were synthesized and used as masking agents for the selective extraction and separation of Am3+ over Eu3+. The masking effects of SO3-TEX(m)-BisDGA and SO3-TEX(p)-BisDGA were significantly better than that of TEE-BisDGA. The masking selectivity for Eu3+ over Am3+ followed the order of SO3-TEX(m)-BisDGA > SO3-TEX(p)-BisDGA > TEE-BisDGA.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2023)
Article
Chemistry, Inorganic & Nuclear
Tyler L. King, Orhi Esarte Palomero, Dawson A. Grimes, Sean T. Goralski, Richard A. Jones, Emily L. Que
Summary: This study investigates the extraction of metal ions using a fluorinated acetylacetonate pro-ligand into a perfluorocarbon phase, with a focus on characterizing the speciation of the extracted metal complexes. The findings suggest that the formation of coordinatively saturated mononuclear metal complexes in the fluorous phase is crucial for retaining the extracted species, and synergistic extraction plays an important role for metal ions that do not form these types of metal complexes with acetylacetonate ligands alone.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Debasish Das, Meenakshi Joshi, S. Kannan, Mukesh Kumar, Tapan K. Ghanty, A. S. Pente, Arijit Sengupta, C. P. Kaushik
Summary: This study investigated the coordination chemistry of three ligands with uranyl nitrate and lanthanide nitrates, characterized by various analytical techniques. The behavior and stability of the ligands in metal ion extraction were explored through theoretical calculations and solvent extraction studies. Results showed different bonding modes and extraction preferences for uranium and europium ions, along with the radiation and chemical stability of the ligands.
Article
Chemistry, Inorganic & Nuclear
Logan J. Augustine, Joseph M. Kasper, Tori Z. Forbes, Sara E. Mason, Enrique R. Batista, Ping Yang
Summary: Neptunium is the major minor actinide in spent nuclear fuel, and its difficult separation is due to its redox chemistry. Understanding Np oxidation state and ligand interactions is crucial for developing new reprocessing techniques. Ligands with carboxylate or pyridine functional groups are preferred in emerging technologies. DFT calculations are used to study neptunyl cation interactions with carboxylate and polypyridine ligands and investigate the effects of different electron-withdrawing and electron-donating R groups on geometric properties and bonding in Np ligand design principles.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xiaofan Yang, Lei Xu, Anyun Zhang, Chengliang Xiao
Summary: The separation of actinides from lanthanides is a crucial step in the spent nuclear fuel reprocessing. Organophosphorus extractants, such as tributyl phosphate (TBP) and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), have been widely used due to their strong extraction ability and low cost. This article discusses the application scope, extraction mechanism, structure-function relationships, and newly developed organophosphorus extractants for the separation of actinides over lanthanides. The important role of these extractants and their potential applications in future advanced nuclear fuel cycle are also emphasized.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Multidisciplinary Sciences
Zhipeng Wang, Liqin Huang, Xue Dong, Tong Wu, Qi Qing, Jing Chen, Yuexiang Lu, Chao Xu
Summary: An efficient separation strategy based on ion sieving in graphene oxide membrane is reported for the separation of actinides from lanthanides. This work realizes the group separation of actinides from lanthanides under highly acidic conditions by a simple ion sieving strategy and highlights the great potential of utilizing graphene oxide membrane for nuclear waste treatment.
NATURE COMMUNICATIONS
(2023)
Article
Metallurgy & Metallurgical Engineering
V. V. Belova, M. M. Petyaeva, J. Tsareva, A. E. Kostanyan
Summary: This study explores the use of multicomponent biphasic solvent systems in liquid-liquid chromatography for extracting lanthanides in hydrometallurgy. It was found that the addition of sodium acetate or mixtures can enhance the extraction efficiency, and effective separation methods were observed in the experiments.
Review
Chemistry, Applied
Lisette R. Warren, Zixuan Wang, Colin R. Pulham, Carole A. Morrison
Summary: This article introduces the main concepts and terminologies in the combustion chemistry of double-base propellants and evaluates four theories to account for the ballistic modifier effect. It also reviews current trends in ballistic modifier research and notes the emerging potential of oxide nanoparticles and Cu/Bi encapsulated in carbon nanotubes as lead-free additives.
PROPELLANTS EXPLOSIVES PYROTECHNICS
(2021)
Article
Chemistry, Inorganic & Nuclear
Anand J. Gaston, Zoe Greindl, Carole A. Morrison, Jennifer A. Garden
Summary: This study describes four heterobimetallic (salen)Al catalysts and demonstrates that cooperative Al/Mg and Al/Zn combinations can significantly enhance catalyst activity, compared to mono-Al analogues. In contrast, Al/Li and Al/Ca combinations were found to inhibit the polymerization rate. Kinetic and computational studies suggest that chloride bridging in close intermetallic proximity enhances initiation and increases available monomer coordination sites in Al/Mg and Al/Zn complexes. Additionally, ab initio molecular dynamics calculations were utilized to investigate catalyst flexibility and reveal that ligand strain and molecular rigidity can enhance the performance of heterometallic catalysts.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Adam A. L. Michalchuk, Jack Hemingway, Carole A. Morrison
Summary: The development of new energetic materials comes with significant hazards, prompting interest in their computational design. This study introduces a fully ab initio model based on phonon up-pumping, successfully ranking the relative impact sensitivity of a series of organic EMs. The methodology relies solely on crystallographic unit cell and Brillouin zone center vibrational frequencies, making it a potentially integral tool for large-scale screening of potential EMs.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Andrew Carrick, Euan D. Doidge, Alexander Bouch, Gary S. Nichol, Jane Patrick, Emma R. Schofield, Carole A. Morrison, Jason B. Love
Summary: The study successfully extracted over 85% of rhodium from hydrochloric acid by utilizing the synergistic combination of a primary amine and a primary amide. This work highlights the need for ligands targeting specific metal complexes in the aqueous phase and provides an efficient synergistic solution for the solvent extraction of rhodium.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Liam J. Donnelly, Teresa Faber, Carole A. Morrison, Gary S. Nichol, Stephen P. Thomas, Jason B. Love
Summary: Transition metal complexes with metal-boron bonds, particularly iridium polyboryl and polyhydrido-boryl complexes, are important catalysts for C-H borylation reactions. In this study, polyhydride boryl phosphine rhenium complexes were shown to be capable of catalyzing the C-H borylation of heteroaromatic substrates. The boryl complex derived from the rhenium complex acted as a catalyst for various heteroarenes, exhibiting similar reactivity to iridium analogues.
Article
Chemistry, Multidisciplinary
Imogen L. Christopher, Adam A. L. Michalchuk, Colin R. Pulham, Carole A. Morrison
Summary: This study critically evaluated the ability of PM7 to calculate gas-phase and solid-state heats of formation, and assessed the routes to obtain solid-state heats of formation for a variety of compounds. The use of local vibrational mode analysis allowed for rapid identification of the weakest chemical bond in CHNO-containing molecules, potentially rationalizing decomposition pathways effectively. Both metrics serve as important tools in rationalizing the design of new energetic materials through computational screening processes.
FRONTIERS IN CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Luke M. M. Kinsman, Bryne T. Ngwenya, Carole A. Morrison, Jason B. Love
Summary: This study demonstrates a simple tertiary diamide precipitation method for selectively precipitating gold from aqueous solutions, showing potential applications in metal separation and recycling industries.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fiona M. MacIver-Jones, Polly Sutcliffe, Margaret C. Graham, Carole A. Morrison, Caroline A. Kirk
Summary: The study successfully determined the hydrogen positions within metatorbernite using neutron powder diffraction and AIRSS, finding two groups of water molecules within the structure critical for stability. The agreement between neutron powder diffraction data and the computational simulations suggests a promising approach for studying other uranium materials where hydrogen bonding plays a key role in phase stability.
Article
Metallurgy & Metallurgical Engineering
Mudila Dhanunjaya Rao, Kamalesh K. Singh, Carole A. Morrison, Jason B. Love
Summary: In this study, the selective recovery of nickel from a leach solution of delaminated metal clads from obsolete mobile phone PCBs has been investigated using the industrial reagent ACORGA M5640. The most suitable conditions for nickel extraction and stripping have been explored, and quantitative extraction of nickel can be achieved under certain conditions. Additionally, the separation of other trace elements has also been studied to ensure a sustainable metal recovery process.
Article
Chemistry, Multidisciplinary
Abhijit Nag, Carole A. Morrison, Jason B. Love
Summary: A new approach using mixtures of triphenylphosphine dichloride or oxalyl chloride and hydrogen peroxide in organic solvents was developed for the rapid dissolution of elemental noble metals (NMs). Almost complete dissolution of gold, palladium, and copper was observed within minutes at room temperature. This method has potential applications in the hydrometallurgical leaching and purification of NMs from ores, spent catalysts, and electronic and nano-wastes.
Article
Multidisciplinary Sciences
Joseph G. O'Connell-Danes, Bryne T. Ngwenya, Carole A. Morrison, Jason B. Love
Summary: Researchers report the selective precipitation of light rare-earth elements as supramolecular capsules from acidic, industrially relevant, mixed-metal solutions. This self-assembly approach, which exploits size and shape complementarity, has the potential to integrate into conventional processes.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Imogen L. Christopher, Colin R. Pulham, Adam A. L. Michalchuk, Carole A. Morrison
Summary: Impact-sensitivity predictions based on the vibrational up-pumping model reveal a strong dependence on polymorphs for RDX. One high-pressure form formed during shock-wave experiments is notably more susceptible to mechanical initiation. The variations in impact sensitivity can be attributed to vibrational mode hardening and differences in the molecular conformation of RDX in different polymorphs.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Lisette R. Warren, Aaron Rowell, Patrick Mcmaster, Colin R. Pulham, Carole A. Morrison
Summary: This study presents a computational investigation of the role of lead and copper-based ballistic modifiers in the combustion of double-base propellants. The results show that lead oxide clusters can be easily broken down by carbon, forming a graphitic matrix with exposed Pb sites that can bind small molecule Lewis bases formed during the combustion flame, enhancing the fuel burn rate. In contrast, carbon binding to copper oxide retains cluster integrity but has negligible interaction with the Lewis bases. The calculations support a general model explaining the super-, plateau-, and mesa-rate burning effects of the ballistic modifiers, and propose that controlled carbon activation of lead oxide by copper oxide modifies the burn rate in double base propellants.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Nurunnisa Atceken, Jack Hemingway, Craig L. Bull, Xiaojiao Liu, Adam A. L. Michalchuk, Sumit Konar, Carole A. Morrison, Colin R. Pulham
Summary: In this study, the high-pressure behavior of 3,4,5-TNP was investigated using neutron powder diffraction and single-crystal X-ray diffraction. A new high-pressure phase was identified and the compound was found to be sensitive to initiation under pressure.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Edmund Morris, Colin R. Pulham, Carole A. Morrison
Summary: This review summarizes almost 200 years of research on the structure of nitrocellulose, covering its production to its application in composite materials. Despite the emergence of synthetic plastics, nitrocellulose still has wide practical applications as a moldable plastic, energetic rocket propellant, and biomolecular binding membrane. The influence of cellulose source materials and nitration conditions on the structure and properties of nitrocellulose is discussed, along with the need for further understanding and research in this area. The review also highlights the opportunities to control and improve the material properties of nitrocellulose through its structural manipulation.