Review
Chemistry, Analytical
Swadesh Mandal, Susanta Lahiri
Summary: Cloud point extraction (CPE) is a greener alternative to conventional separation techniques in the field of analytical chemistry. This article provides an overview of various aspects of CPE and its recent developments, focusing on the extraction and speciation of metal ions and anionic species. The article also briefly discusses the extraction and determination of nanoparticles by CPE.
MICROCHEMICAL JOURNAL
(2022)
Review
Chemistry, Inorganic & Nuclear
Julia Torres, Carlos Kremer
Summary: This review focuses on the coordination chemistry of Ln ions with Oxydiacetate, iminodiacetate, and thiodiacetate, which are flexible dicarboxylates used as chelating agents. The study analyzes the stability of resulting complexes in solution and explores the synthesis of new materials by combining different coordination modes and the fluxional geometry of these ligands. It also discusses the luminescent properties and examines the potential applications, such as white-light emitters and catalysts in organic processes, of these compounds and complexes.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Haifeng Zheng, Yanling Li, Xuyi Zhang, Jinglu Han, Songsong Li, Guolong Wu, Qingshi Liu, Xiaojuan Liu, Wuping Liao
Summary: This paper analyzes the complexation differences between four phosphoric acid extractants and rare earth elements through theoretical calculations. The results show that P204 has the strongest extraction ability. This study provides a foundation for the design of extractants.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Rayco Lommelen, Koen Binnemans
Summary: Solvent extraction is a challenging method to separate and purify metals on an industrial scale due to the complex chemistry involved. The efficiency of metal extraction is related to its hydration in the aqueous phase and the strength of metal-anion bonds in the organic phase.
Article
Chemistry, Multidisciplinary
Faiza Nazir, Ahsan Nazir, Sonia Javed, Hafiz Affan Abid
Summary: The application of principles of Green Chemistry is important in eliminating the risk of environmental pollution and ensuring a sustainable and cleaner environment. This study focuses on the synthesis of sustainable green solvents for extracting phytochemicals from plants, and the comparison with traditional organic solvents. The results show that the NADES extracts have higher concentrations of bioactive components and demonstrate potential for biomedical applications in drug delivery systems by eliminating toxic solvents.
SUSTAINABLE CHEMISTRY AND PHARMACY
(2023)
Article
Chemistry, Inorganic & Nuclear
Chenglong Liang, Shiyi Tan, Lixiong Shao, Xinxin Xue, Jiahao Liu, Nannan Liu, Weibing Zhang, Qian Shi
Summary: A novel Yb-based three-dimensional metal-organic framework (ACBP-6) with free Lewis basic sites was synthesized and used to construct a sensitive current sensor. The sensor exhibited high selectivity and signal-to-noise ratio for Cu2+ detection with a detection limit of 1 μM.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Seraj A. Ansari, Amey P. Wadawale, Willem Verboom, Prasanta K. Mohapatra
Summary: The complexation and structural analysis of the solid complex of UO22+ ions and N,N,N ',N '-tetramethyl diglycolamide isolated from a room temperature ionic liquid show that its nature and structural features are identical to those of the complex isolated from an aqueous medium.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Analytical
Shekhar Kumar
Summary: In this study, the generation and characterization of nitric acid third phase were investigated. The results showed the presence of chain-linked nitric acid dimer to a single molecule of TBP in the generated nitric acid third phase, while the speciation in the light phase was similar to unpartitioned organic phase.
JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY
(2023)
Article
Chemistry, Analytical
Deborah V. A. de Aguiar, Gesiane da S. Lima, Jussara Roque, Joao V. A. Oliveira, Iris Medeiros Junior, Alexandre de O. Gomes, Luiz A. N. Mendes, Boniek G. Vaz
Summary: This study provides a direct flow injection electrospray ionization (ESI) (-) Orbitrap mass spectrometry method for the quantitative analysis of non-basic nitrogen-containing compounds (NCCs) in petroleum-derived samples, without the need for fractionation steps. The method was validated by quantifying benzocarbazole (BC) using the standard addition method, and demonstrated satisfactory results in the matrix-mix.
ANALYTICAL CHEMISTRY
(2023)
Article
Engineering, Chemical
Nagaphani Kumar Batchu, Zheng Li, Bram Verbelen, Koen Binnemans
Summary: The extraction efficiency of rare-earth elements is related to the basicity of the extractant molecules; extractants with longer alkyl chains exhibit higher metal extraction efficiencies; extraction from ethylene glycol solutions is more effective than from aqueous solutions.
SEPARATION AND PURIFICATION TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Alexandru Topor, Daniel Avram, Radu Dascalu, Catalin Maxim, Carmen Tiseanu, Marius Andruh
Summary: Three 1D coordination polymers with benzoate bridges were assembled with the presence of 18-crown-6-ether, where crown ether molecules played an important role in the supramolecular architecture. A molecular alloy was prepared by substituting Tb-III ions with Eu-III ions in the host lattice. Luminescence thermometry performance of the Tb0.95Eu0.05 system showed a maximum S-r value of 1.88% K-1 at 80 K and decreased to 1.60% K-1 at 313 K. Time-gated emission spectroscopy successfully reduced the spectral overlap of Tb and Eu emissions in the 610 to 625 nm range by 100% at 80 K. Compound 1 and the molecular alloy Tb0.95Eu0.05 exhibited X-ray induced luminescence.
DALTON TRANSACTIONS
(2021)
Article
Polymer Science
Tong Chen, Sanping Zhao
Summary: An effective strategy was developed to fabricate novel lanthanide ions-pyromellitic acid-methoxy poly(ethylene glycol) (Ln-PMA-MPEG) nano-assemblies via biomimetic mineralization. These nano-assemblies showed potential applications as ratiometric fluorescent nanosensors for solvent recognition and metal ion detection.
Article
Chemistry, Multidisciplinary
Liming Deng, Huihui Zhao, Kang Liu, Dingxuan Ma
Summary: The synthesis of two new three-dimensional lanthanide metal-organic frameworks with rich uncoordinated nitrogen or oxygen atoms that can be used as Lewis basic sites for high sensitivity to metal ions and solvent molecules. The compounds show promise as bifunctional luminescence sensors for detecting Fe3+ ions and nitrobenzene. The quenching mechanism for Fe3+ ions has been discussed in detail, demonstrating the potential of these probes for environmental contaminant detection.
Article
Chemistry, Analytical
Yihuan Song, Qingfang Ma, Heyong Cheng, Jinhua Liu, Yuanchao Wang
Summary: A method utilizing online solid-phase extraction coupled with high performance liquid chromatography and inductively coupled plasma mass spectrometry was developed for simultaneous enrichment and analysis of ultra-trace lead and mercury species in water. This method allows for efficient and accurate determination of lead and mercury species in water samples, with high enrichment factors and low LODs and LOQs. The method was successfully applied to analyze trace lead and mercury species in various types of water samples, showing promising results for unstable sample analysis.
ANALYTICA CHIMICA ACTA
(2021)
Article
Chemistry, Analytical
Yuan-Jun Tong, Lu-Dan Yu, Yanjun Huang, Qi Fu, Nan Li, Sheng Peng, Sai Ouyang, Yu-Xin Ye, Jianqiao Xu, Fang Zhu, Janusz Pawliszyn, Gangfeng Ouyang
Summary: A new strategy utilizing polymeric ligands to enhance the sensitivity of a lanthanide metal-organic framework (Ln-MOF) to UO22+ was proposed in this study. The resulting fluorescent composite, PVTPcTb-TBT, showed improved detection sensitivity and selectivity to UO22+ compared to Tb-TBT, with a low limit of detection of 0.75 nm. Additionally, the strategy was successfully applied to on-site analysis of real water samples, showcasing its potential for practical applications.
ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bart Verlinden, Andreas Wilden, Karen Van Hecke, Richard J. M. Egberink, Jurriaan Huskens, Willem Verboom, Michelle Hupert, Patrik Wessling, Andreas Geist, Petra J. Panak, Rainier Hermans, Marc Verwerft, Giuseppe Modolo, Koen Binnemans, Thomas Cardinaels
Summary: This study investigated the solvent optimization, radiolysis behavior, and solvent extraction characteristics of the diglycolamide mTDDGA. It was found that the two diastereomers of mTDDGA exhibited significant differences in extraction, and the main degradation compound showed good ability to extract uranium.
SOLVENT EXTRACTION AND ION EXCHANGE
(2023)
Article
Green & Sustainable Science & Technology
Koen Binnemans, Peter Tom Jones
Summary: This academic position paper proposes the 12 Principles of circular hydrometallurgy, a novel and sustainable approach. It aims to guide future research in the field and provide a benchmark for assessing existing processes. Circular hydrometallurgy focuses on energy and resource efficiency, minimal reagent consumption, and waste reduction. The paper presents the principles that promote sustainability, such as reagent regeneration, water loop closure, waste prevention, and integration of materials and energy flows.
JOURNAL OF SUSTAINABLE METALLURGY
(2023)
Review
Green & Sustainable Science & Technology
Koen Binnemans, Peter Tom Jones
Summary: This paper reviews the properties of methanesulfonic acid (MSA) and its potential for use in hydrometallurgy. MSA is a very strong acid with high solubility of its salts in water and low toxicity. It offers more environment-friendly alternatives to traditional acids in lead hydrometallurgy and can be adopted in all hydrometallurgical processes that require strong acids. The global production of MSA is expected to increase rapidly in the future.
JOURNAL OF SUSTAINABLE METALLURGY
(2023)
Article
Green & Sustainable Science & Technology
Viet Tu Nguyen, Clio Deferm, Ward Caytan, Sofia Riano, Peter Tom Jones, Koen Binnemans
Summary: A hydrometallurgical process has been developed to convert lithium chloride solution to lithium hydroxide solution by a chloride/hydroxide anion exchange reaction using solvent extraction. The organic phase, composed of a quaternary ammonium chloride and a hydrophobic phenol in a diluent, showed the best results. The process involves two steps: contacting the organic phase with sodium hydroxide solution and then with lithium chloride solution, resulting in the transformation of lithium chloride solution into lithium hydroxide solution. The process has been successfully demonstrated in continuous counter-current mode.
JOURNAL OF SUSTAINABLE METALLURGY
(2023)
Article
Engineering, Environmental
Hongshan Zhu, Stephan Heinitz, Samuel Eyley, Wim Thielemans, Koen Binnemans, Steven Mullens, Thomas Cardinaels
Summary: 213Bi is a promising candidate for targeted alpha therapy, but finding suitable materials to separate it from its parent 225Ac is an ongoing challenge. This study evaluates sulfonated activated carbon (SNCAs) as alternative sorbents for use in radionuclide generators and finds that SNCAs have high and selective uptake of Bi3+. Different elution solutions can efficiently extract Bi3+ from SNCAs. This research suggests that SNCAs with sufficient oxygen-containing groups are promising sorbents for the separation of 213Bi in an inverse 225Ac/213Bi radionuclide generator.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Stijn Raiguel, Viet Tu Nguyen, Isadora Reis Rodrigues, Clio Deferm, Sofia Riano, Koen Binnemans
Summary: The world's seas and oceans have a large amount of lithium, but the low concentration makes solvent extraction impractical for recovery. However, seawater desalination brine, after nanofiltration treatment, has a much higher concentration of lithium. Therefore, a solvent extraction process can effectively recover lithium from such streams. The proposed process involves removal of magnesium and calcium, followed by lithium extraction, scrubbing, stripping, removal of residual alkaline earth metals, and precipitation of lithium. The process has a yield of 74% and produces lithium carbonate with a purity of 97 wt%.
SOLVENT EXTRACTION AND ION EXCHANGE
(2023)
Article
Green & Sustainable Science & Technology
Koen Binnemans, Peter Tom Jones
Summary: Over the past 10-20 years, many academic papers have described the benefits of ionic liquids (ILs) and deep-eutectic solvents (DESs) in extractive metallurgy processes. However, despite being hailed as game-changers, these neoteric solvents have not made significant commercial breakthroughs. This paper reflects on the reasons for their lack of impact, including issues with viscosity, chemical stability, recycling, and cost, and suggests that a deeper understanding of hydrometallurgical processes at the molecular level is more likely to lead to innovation.
JOURNAL OF SUSTAINABLE METALLURGY
(2023)
Article
Engineering, Environmental
Hongshan Zhu, Stephan Heinitz, Samuel Eyley, Wim Thielemans, Koen Binnemans, Steven Mullens, Thomas Cardinaels
Summary: 213Bi-labeled radiopharmaceuticals for cancer treatment are of great interest, and finding a suitable sorbent material for separating 213Bi from its parent radionuclide 225Ac is challenging. This study reports on the synthesis and evaluation of sulfonated carbon materials (SCMs) as sorbents in inverse 225Ac/213Bi generators. The sulfonation of carbon materials prepared at 500 degrees C (SCM-500) showed promising results, with high selectivity for Bi3+ over La3+ and high chemical 213Bi yield in column tests.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Engineering, Chemical
Joren van Stee, Filip Keppens, Jinu Joseph John, Koen Binnemans, Tom Van Gerven
Summary: This study presents a reproducible production method for microreactor manifolds using commercially available and 3D printed parts. It was found that tubes and fittings alone cannot produce reliable and reproducible manifolds. However, a hybrid manifold consisting of a 3D printed distributor and commercial tubes and fittings showed a significant reduction in maldistribution for both single- and two-phase flow. Furthermore, the surface tension of the applied liquid was shown to have a significant effect on maldistribution, possibly due to the presence of air bubbles.
CHEMICAL ENGINEERING RESEARCH & DESIGN
(2023)
Article
Environmental Sciences
Dzenita Avdibegovic, Elke Barbier, Blaz Jaklic, Sreco Davor Skapin, Matjaz Spreitzer, Koen Binnemans
Summary: In the present study, strong cation and anion exchange resins were used to recover non-rare earth constituents from end-of-life rare-earth magnets. The results showed that the cation exchange resin was effective in recovering metal ions from both aqueous and ethanolic solutions, while the anion exchange resin selectively recovered copper and iron from ethanolic solutions. The ion exchange mechanism involved the formation of chloro complexes of copper and their exchange with sulfate counter ions of the resin.
Article
Chemistry, Inorganic & Nuclear
Bart Verlinden, Karen Van Hecke, Andreas Wilden, Giuseppe Modolo, Koen Binnemans, Thomas Cardinaels, Piotr M. Kowalski
Summary: In this paper, the radiolytic degradation of diglycolamides was analyzed using computational chemistry methods, focusing on structural and thermodynamic aspects. The most vulnerable parts of the organic ligands prone to attack and degradation by radicals were identified through electronic density and bond strength analysis. By computing free energy, a possible degradation path involving the breaking of the C-O bond by H radical attack was obtained. Solvation effects, including solvation entropy effects, were taken into account to investigate realistic reaction conditions. The resulting degradation mechanism is consistent with experimentally observed degradation products.
Article
Chemistry, Multidisciplinary
Dominic Maertens, Koen Binnemans, Thomas Cardinaels
Summary: Annular centrifugal contactors (ACCs) are efficient in counter-current multistage solvent extraction (SX) due to their high throughput, short residence times, and small footprint. However, the availability of commercial laboratory-scale ACCs is limited, and their designs lack flexibility. In this study, customized transparent ACCs were used to monitor the process and identify operational issues. The modified ACCs demonstrated improved performance in a uranium-TBP SX process.
SOLVENT EXTRACTION AND ION EXCHANGE
(2023)
Article
Chemistry, Physical
Pieter Geysens, Da Tie, Alexandru Vlad, Jan Fransaer, Koen Binnemans
Summary: Electrowinning is a clean process for neodymium metal recovery, but the current methods are limited by high energy consumption or high costs and environmental impact. In this study, new fluorine-free organic electrolytes were developed, enabling the electrodeposition of neodymium metal at room temperature. These electrolytes consist of solvated neodymium borohydride dissolved in ether solvents, prepared from non-fluorinated precursors. The electrodeposition of neodymium in these electrolytes demonstrated higher stability and was characterized to confirm the presence of neodymium metal.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Filip Kolesar, Karen Van Hecke, Peter Zsabka, Ken Verguts, Koen Binnemans, Thomas Cardinaels
Summary: A new variant of the AmSel system using Aliquat-336 nitrate as the diluent was tested for the separation of Am(iii) from a PUREX raffinate. The introduction of Aliquat-336 nitrate improved the separation between Am(iii) and fission products, especially for light lanthanides and strontium. The Am/Cm separation factors remained similar to the original AmSel process. Slower stripping kinetics and extraction of the SO3-Ph-BTBP complexant occurred at low HNO3 concentrations during the stripping step, but mitigation actions were implemented to counteract these issues.
Article
Chemistry, Multidisciplinary
Hongshan Zhu, Stephan Heinitz, Samuel Eyley, Wim Thielemans, Elien Derveaux, Peter Adriaensens, Koen Binnemans, Steven Mullens, Thomas Cardinaels
Summary: In this study, the effects of gamma radiation on AG MP-50 cation exchange resin and sulfonated activated carbon (SAC) were investigated. It was found that the surface sulfonic acid groups of AG MP-50 resin suffered severe radiation-induced degradation, while no apparent changes in acquired morphological characteristics were observed for SAC. The sorption performance of both materials for La3+ and Bi3+ remained generally the same.
