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JOURNAL OF MOLECULAR LIQUIDS · 2023 · IF 6

Highly efficient and selective separation of dysprosium and neodymium from polyethylene glycol 200 solution by non-aqueous solvent extraction with P350

Zhenyu Zhang,Juan Liu,Ting Li,Zhikai Fu,Jinshui Mao,Xiaocheng Li,Sili Ren

Recycling of Nd(III) and Dy(III) from waste NdFeB magnets is increasingly critical in the sustainable development of rare-earth elements (REEs) industry. The efficient separation of Nd(III) and Dy(III) from conventional aqueous solution by solvent extraction (SX) is facing huge challenge due to the high activity, high interfacial tension and the high dielectric constants of water that affect the coordination of REEs with the extractant. Herein, a novel non-aqueous solvent extraction (NASX) system based on neutral extractant P350 was developed to extract Nd(III) and Dy(III) with high extraction efficiency and separation factor. In this extraction system, the majority of water in the aqueous phase was replaced by different low-dielectric-constant polar molecular organic solvents (PMOSs) to reduce the influence of water during extraction. The effect of the type and content of PMOSs, P350 concentration, extract equilibration time and temperature on the separation performance were systematically investigated. It was encouraging to find that the favorable separation factor of Nd(III) and Dy(III) elements ( β Nd/Dy ) was determined to be 201 when extracted from 70 vol% PEG 200 with 0.2 mol/L P350, which was higher than that in traditional extraction from aqueous phase. Slope analysis method was used to determine the extractant stoichiometry and the main species of extraction complex was identified as DyCl 3 ·2L which was verified by Fourier infrared spectroscopy (FT-IR). Furthermore, in the simulation of recovery of NdFeB magnetic immersion solution experiment, the extraction efficiency (E%) of Dy(III) can reach 85 %, while co-extraction of Nd(III) was only 6 % and the β Dy/Nd was as high as 83.4. According to the McCabe-Thiele diagram, 3-stages counter-current solvent extraction was needed to completely extract Dy(III). Moreover, 97.11 % of Nd(III) and 98.5 % of Dy(III) in the loaded organic phase can be sequentially stripped by 0.04 mol/L and 0.4 mol/L HCl, respectively. These results indicated that the developed processes in this work have superior extraction efficiency, large separation factors and excellent stripping stability. Eventually, a P350-PEG 200 extraction system-based separation process was proposed in the hope of providing a novel and low-cost alternative to the efficient recycle of Nd(III) and Dy(III) from end-of-life NdFeB.

研究领域: 化学工程 · 材料科学 · 环境科学
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Journal of Water Process Engineering · 2025 · IF 6.7

Ultrafast separation of Nd and Dy from Co by modified mesoporous silica with a novel phosphate group ligand

Yilai Zhong,Zengyuan Li,Jianchun Qin,Wenlong Li,Chunlin He,Lifeng Chen,Xiangbiao Yin,Mohammed F. Hamza,Yuezhou Wei,Shunyan Ning

Recycling rare earth elements (REEs) from NdFeB magnets alleviates the growing demand for these resources and contributes to environmental protection. Phosphate groups are known for their high adsorption selectivity for rare and precious metals. In this study, a novel phosphorus-functionalized silicon-based adsorption material (PPA@APTES/SBA-15) was synthesized using poly (ethylene glycol)- block -poly (propylene glycol)- block -poly (ethylene glycol) copolymer (P123) as a template, tetraethyl orthosilicate (TEOS) as a silicon source, (3-amino-propyl) trimethoxysilane (APTES) as a coupling agent, and phosphite ester as a functional ligand. This material was designed for the adsorption and separation of Nd and Dy from NdFeB leaching simulants. The batch experiments revealed that PPA@APTES/SBA-15 achieved equilibrium separation of Co and REEs within 10 s, with SF REE/Co  ≥ 2018.76. The material exhibited near 100 % adsorption efficiency for Nd and Dy in 6 M HCl solution, along with excellent reusability. Notably, column experiments also demonstrated near complete adsorption efficiency for Nd and Dy. SEM-EDS, TEM, XRD, and N 2 adsorption-desorption isotherms confirmed that PPA@APTES/SBA-15 possessed a uniform hexagonal mesoporous structure and a high specific surface area. TG-DSC analysis demonstrated that the organic loading of PPA@APTES/SBA-15 was 9 %. FT-IR, XPS, and DFT analysis suggested that PPA@APTES/SBA-15 bond metal ions via P OH (P O) groups.

CAS / MDL: 78-10-4
研究领域: 材料科学 · 环境科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2023 · IF 4.2

Solvent Extraction of Dy(III) and Nd(III) with an Unsymmetrical Pentanediamide Extractant

Zhenfeng Xiong,Ying Huang,Nan Li,Chaozhi Zhang,Yonghua Li,Zhuo Yang,Weidong Zhou,Kemei Zhou,Rong Zha,Changdong Sheng

Recovery of rare-earth elements (REEs), especially those of Dy and Nd, from Nd–Fe–B permanent magnets is crucial for sustainable development. Herein, an unsymmetrical pentanediamide extractant, N,N′-dimethyl-N,N′-didecyl-3-oxapentanediamide (DMDDOPDA), was synthesized and characterized for the effective extraction of Dy(III) and Nd(III). DMDDOPDA can form coordination bonds with metal ions because of the strong electron-donating abilities of the N and O atoms. The coordination sites might be inclined toward one side during the extraction. DMDDOPDA exhibited superior extraction performance in the HNO3 system than it did in the HCl system. The highest extraction efficiencies of Dy(III) and Nd(III) under optimal conditions were 99.9% and 99.5%, respectively, while their optimum stripping efficiencies were 100% and 85.3%, respectively. DMDDOPDA extraction of Dy(III) and Nd(III) in the four investigated diluents involved the formation of a neutral coordination complex. This study provides new insights into REE extraction using pentanediamide extractants.

CAS / MDL: 7757-82-6 108-88-3
研究领域: 化学工程 · 材料科学
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OPTICAL MATERIALS · 2023 · IF 3.9

Energy transfer behavior and tunable spectroscopic properties of Ba3Lu4O9:Dy3+,Eu3+ phosphors for white LEDs

Hui Li,Ziyao Wang

Ba 3 Lu 4 O 9 :Dy 3+ ,Eu 3+ phosphors were developed through the conventional solid-state reaction. Luminescent performance including the energy transfer from dysprosium to europium , spectral tunability, fluorescent lifetime and thermal quenching behavior of the as-studied phosphors was studied. The characteristic emission of Dy 3+ and Eu 3+ were detected in Ba 3 Lu 4 O 9 :Dy 3+ ,Eu 3+ upon the excitation at various ultraviolet–visible wavelengths. The critical distance between dysprosium and europium ions was evaluated to be about 16.05 Å. The energy transfer from dysprosium to europium in Ba 3 Lu 4 O 9 can be attributed to the dipole-quadruple mechanism, and the efficiency was evaluated to be 81.8% for Ba 3 Lu 3.52 O 9 :0.16Dy 3+ ,0.32Eu 3+ . The tunable warm-white emission and high thermal stability reveal that the as-studied phosphor can be an auspicious alternative for white LEDs application.

研究领域: 材料科学 · 光学
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2024 ·Vol. 26 ·期 46 ·28971-28979 · IF 2.9

Molten salt synthesized Tb3+, Pr3+ or Dy3+ single doped CaTa4O11 with persistent luminescence

Yuhan Fan,Yongze Cao,Meiling Li,Sai Xu,Yichao Wang,Xizhen Zhang,Jinsu Zhang,Baojiu Chen

A series of Tb3+, Pr3+ and Dy3+ monodoped CaTa4O11(CTO) persistent luminescence (PersL) phosphors have been successfully synthesized using the molten salt method with KCl flux. The PersL color is green and orange for Tb3+ and Pr3+ or Dy3+ doped samples, respectively. The trap depth of Tb3+, Pr3+ and Dy3+ monodoped CTO is 0.33, 0.31 and 0.30 eV, respectively. The PersL time of 3 mol% Tb3+, 1 mol% Pr3+ and 1 mol% Dy3+ monodoped samples is 52.20, 35.00 and 59.46 s, respectively. Tb3+, Pr3+ and Dy3+ monodoped CTO phosphors can be used in luminescence displays and anti-counterfeit labels under commercial 254 nm UV light.

研究领域: 材料科学 · 光学
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JOURNAL OF NON-CRYSTALLINE SOLIDS · 2024 · IF 3.2

Luminescence and spectroscopic studies on Dy3+-Eu3+ doped SiO2-B2O3-ZnO-La2O3-BaO glass for WLED

Zhichao Jin,Zhongli Zhu

A series of SiO 2 -B 2 O 3 -ZnO-La 2 O 3 -BaO (SBZLBa) glasses doped with Dy 3+ and Eu 3+ were synthesized using the melt-quenching technique. Their optical characteristics and potential applications in W-LED devices were investigated. The structural effects resulting from doping the glass with Dy 3+ and Eu 3+ ions were elucidated through infrared spectroscopy and an examination of the physical properties. The variations in emission intensity within the fluorescence spectrum validated the sensitizing effect of Dy 3+ on Eu 3+ within the glass matrix. By manipulating the transitions of both Dy 3+ and Eu 3+ , the excitation wavelength was altered, enabling the realization of cool white, neutral white, and warm white luminescence, thus accommodating the diverse requirements for white light emission in lighting applications. After incorporating 1.0 mol% of Dy 2 O 3 and 0.8 mol% of Eu 2 O 3 , respectively, the glass exhibited CIE coordinates of (0.3332, 0.3535), positioning it within the white light spectrum and in close proximity to the ideal white light coordinates of (0.33, 0.33). The SBZLBa-Dy 2 O 3 –0.8Eu 2 O 3 glass exhibited a quantum yield of 5.98 %. It has been demonstrated through acid and alkali resistance tests that this glass possesses excellent chemical stability. Additionally, temperature-dependent emission spectra have revealed that the luminous intensity of the glass maintains over 85 % of its room temperature value at 185 °C, with Eα determined to be 0.2387 eV.

研究领域: 材料科学 · 光学工程
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2024 ·Vol. 35 ·期 16 ·1-14 · IF 2.8

Color-tunable photoluminescence and energy transfer properties of single-phase Sr2MgSi2O7:Eu3+, Dy3+

Cao Renping,Cao Ya,Rong Yongtong,Lan Bang,Nie Jingheng,Zhang Lei,Chen Yuyu,Wang Jing

Eu 3+ and Dy 3+ as activators in luminescence materials have been widely investigated because of their superior luminous properties. In this work, we synthesize Sr 2 MgSi 2 O 7 :Dy 3+ , Sr 2 MgSi 2 O 7 :Eu 3+ , and Sr 2 MgSi 2 O 7 :Eu 3+ , Dy 3+ in air via the solid-state reaction method. We research crystal phase and purity of all samples via XRD, discern their crystal structure and space-group, and investigate their luminescence properties. The yellow emission of Sr 2 MgSi 2 O 7 :Dy 3+ with emission spectrum in the range of 450–775 nm can be observed due to the 4 F 9/2  →  6 H 15/2 , 6 H 13/2 , 6 H 11/2 , and 6 H 9/2 transitions of Dy 3+ ion. The red emission of Sr 2 MgSi 2 O 7 :Eu 3+ in the range of 550–725 nm is shown owing to the 5 D 0  →  7 F 1 , 7 F 2 , 7 F 3 , and 7 F 4 transitions of Eu 3+ ion. Sr 2 MgSi 2 O 7 :Eu 3+ , Dy 3+ under excitation 388 nm shows yellow emission with chromaticity coordinates (0.3578, 0.3911) and glows red–orange light with chromaticity coordinates (0.5753, 0.3863) under excitation 394 nm. Sr 2 MgSi 2 O 7 :Eu 3+ , Dy 3+ can shows tunable emission when the ratio between Eu 3+ and Dy 3+ ions is changed. The energy transfer from Dy 3+ to Eu 3+ ions are known via the spectral features. Sr 2 MgSi 2 O 7 :Eu 3+ , Dy 3+ has a good thermal stability. Luminous mechanisms and energy transfer process of samples are analyzed by the energy level diagrams of Dy 3+ and Eu 3+ ions.

研究领域: 材料科学 · 光学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Insights into the mechanism of separation of Co, Nd, and Dy by different crystal structures of zirconium phosphate in bead form

Zhongyan Luo,Jukka Kuva,Jan Luyten,Risto Koivula,Małgorzata Szlachta,Hongli Bao,Junhua Xu

The increasing demand for Co, Nd, and Dy, particularly in neodymium iron boron (NdFeB) magnets, has heightened concerns over their supply risks. Developing efficient, environmentally friendly methods to recover Co, Nd, and Dy from spent NdFeB magnets is therefore critical. This study presents the synthesis of two types of crystalline zirconium phosphate (ZrP) encapsulated in polyacrylonitrile (PAN) composite beads. The structure, morphology, and chemical properties were analyzed using X-ray diffraction (XRD), thermogravimetry (TG), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray computed tomography (XCT), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), and 31 P nuclear magnetic resonance (NMR). The intercalation of dimethylformamide (DMF) enlarged the interlayer spacing of α-ZrP and γ-ZrP, thereby enhancing their ion exchange properties. Batch sorption experiments revealed that α-ZrP/PAN outperformed γ-ZrP/PAN in both sorption and separation efficiency. α-ZrP/PAN beads exhibited high selectivity for Nd 3 + and Dy 3 + , with minimal Co 2 + sorption (8.57 %). Stepwise elution studies on α-ZrP/PAN demonstrated the obtained metal purities to be ∼100 wt% for Co, 64.1 wt% for Nd, and 96.5 wt% for Dy. Sorbent regeneration was investigated over ten sorption–desorption cycles, which revealed that α-ZrP/PAN retained 72.72 % of its sorption capacity, demonstrating excellent reusability and stability, while γ-ZrP/PAN’s capacity declined to 68.95 % after five cycles. The ion-exchange reaction accompanied by shrinking of the interlayer space was illustrated by combining the batch sorption experiments, column operations, and analyses from XRD, FT-IR, and X-ray photoelectron spectroscopy (XPS). Overall, α-ZrP/PAN shows promise for Co, Nd, and Dy separation from NdFeB magnets, although further optimization of sorbents and elution agents is necessary.

研究领域: 材料科学 · 环境工程 · 化学工程
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JOURNAL OF LUMINESCENCE · 2023 · IF 3.6

Synthesis and luminescence properties of Eu3+, Dy3+ co-doped Ca3Bi(PO4)3 single-phase phosphor

Renping Cao,Caiping Chen,Fangrui Cheng,Ting Chen,Bang Lan,Lan Li,Ru Liu,Jing Wang

In this work, we synthesize Ca 3 Bi(PO 4 ) 3 :Dy 3+ , Ca 3 Bi(PO 4 ) 3 :Eu 3+ , and Ca 3 Bi(PO 4 ) 3 :Eu 3+ , Dy 3+ . The crystal structure, phase purity, and the luminescence properties of samples are investigated, respectively. Ca 3 Bi(PO 4 ) 3 :Dy 3+ under excitation at 350 nm shows yellow emission because of the 4 F 9/2  →  6 H 15/2 , 6 H 13/2 , 6 H 11/2 , and 6 H 9/2 transitions of Dy 3+ . Ca 3 Bi(PO 4 ) 3 :Eu 3+ with excitation at 394 nm emits red-orange emission due to the 5 D 0 → 7 F 1 , 7 F 2 , 7 F 3 , and 7 F 4 transitions of Eu 3+ ion. Ca 3 Bi(PO 4 ) 3 :Dy 3+ , Eu 3+ with excitation at 394 nm mainly shows the emission of Eu 3+ , however, that with excitation at 350 nm mainly derive from Dy 3+ ion. We investigate the effects of the ratio between Dy 3+ and Eu 3+ in Ca 3 Bi(PO 4 ) 3 :Eu 3+ , Dy 3+ on the luminescence properties. The energy transfer from Dy 3+ to Eu 3+ in Ca 3 Bi(PO 4 ) 3 :Eu 3+ , Dy 3+ is found. We analyze the luminous mechanism of samples by energy level diagrams of Dy 3+ and Eu 3+ ions. The results are helpful for the research of other Dy 3+ and Eu 3+ co-doped luminescence materials.

研究领域: 材料科学 · 光学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2019 · IF 4.175

Tunable luminescence and energy transfer from Ce3+ to Dy3+ in Ca3Al2O6 host matrix prepared via a facile sol-gel process

Qinjiang He,Renli Fu,Xiufeng Song,Haitao Zhu,Xinqing Su,Chaoqun You

Herein, Ce 3+ and Ce 3+ /Dy 3+ co-doped Ca 3 Al 2 O 6 phosphors have been designed and synthesized via a facile citrate-based sol-gel technique, and their structural, photoluminescence properties and energy transfer phenomenon were investigated comprehensively. The XRD analysis indicated that pure Ca 3 Al 2 O 6 phase can be synthesized at low temperature (1000 °C) for merely 2 h. The photoluminescence spectra showed the dominant emission of Ce 3+ singly doped phosphors is located in the blue region even at low Ce 3+ doping level, which indeed favors the energy transfer from Ce 3+ to other luminescent centers. When Dy 3+ is co-doped into Ca 3 Al 2 O 6 :Ce 3+ phosphors, the remarkable sensitizing effect of Ce 3+ on Dy 3+ is validated by comparatively analyzing the excitation, emission spectra and average lifetimes of the series of samples. Through the concentration quenching theory, the critical distance between Ce 3+ and Dy 3+ is calculated to be 13.50 Å. Furthermore, the energy transfer mechanism between them is most likely ascribed to electric dipole-dipole interaction. In virtue of the variation of the emission intensities of Ce 3+ and Dy 3+ , the emitting colors of Ca 3 Al 2 O 6 :Ce 3+ , Dy 3+ phosphors can realize tunable luminescence from deep blue to bluish-white region through controlling the Dy 3+ content. Based on these analysis, Ca 3 Al 2 O 6 :Ce 3+ , Dy 3+ phosphors could potentially be applied as a single-phase color-tunable phosphors pumped by near-ultraviolet (n-UV) radiation.

CAS / MDL: 77-92-9 5949-29-1
研究领域: 材料科学 · 光学
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Analytical Methods · 2022 ·Vol. 14 ·期 41 ·4077-4084 · IF 3.532

Dy(III)-coordination imprinted self-assembly microspheres based on a silica core for highly sensitive and selective detection of two carbamate pesticides

Zerong Long,Shilin Shen,Hui Yuan

Carbamate (CB) pesticides possess potential carcinogenic and mutagenic activities towards humans even at very low dosages. Thus, broad-specificity probes with high sensitivity and speed are needed for multiple CB determination. This study is the first to focus on Dy3+ ions-coordinated self-assembly on a silica core using a surface imprinting procedure, for the simultaneous fluorometric detection of residues of metolcarb (MC) and pirimicarb (PC) insecticides. A simple and mild solvothermal method was applied for the preparation of fluorescent imprinted microspheres starting from 1,10-phenanthroline (Phen)-ligated Dy3+ ions to guide imprinted self-assembly of chitosan (CTS), glutaraldehyde (GA), and two carbamate pesticides (MC and PC) on the silica surface by means of coordinate bonds and hydrogen bonds. The as-prepared microspheres displayed strong fluorescence emissions via the antenna effect derived from the Phen ligand and the Schiff base oligomers for sensitizing the Dy3+ ions. An expanded in-depth mechanism study was performed on the fluorescence enhancement involving Förster resonance energy transfer (FRET) from the pesticides (donor) to the acceptor. A linear increase in fluorescence at 483 nm for MC and 574 nm for PC upon the imprinted microspheres was observed under the same 350 nm excitation wavelength. Moreover, the quantitative recognition process could be carried out simultaneously and tolerate strong distractions both from five other similar carbamate insecticides and from complicated matrices (e.g., an extract of Chrysanthemum morifolium Ramat). The detection limit was 4 ng mL−1 with a range of 10–60 ng mL−1 for MC and 0.4 ng mL−1 with a range of 1–30 ng mL−1 for PC. Further characterization of the material, including TEM, SEM, XPS, and FTIR, Raman, and fluorescence spectra, verified that the Dy3+ ions play a decisive role in promoting imprinted self-assembly around the silica core. Hence, a novel polynuclear Ln–organic imprinted probe having high selectivity, stability, and sensitivity for the detection of two carbamate insecticides is presented in this study.

研究领域: 分析化学 · 环境科学 · 食品科学
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JOURNAL OF THE AMERICAN CERAMIC SOCIETY · 2020 ·Vol. 103 ·期 12 ·6847-6859 · IF 3.502

Visible emission and energy transfer in Tb3+/Dy3+ co-doped phosphate glasses

Yan Sun,Fei Yu,Meisong Liao,Juping Ma,Xin Wang,Dongbing He,Weiqing Gao,Jonathan Knight,Lili Hu

In this work, we systematically study the spectroscopic properties of Tb 3+ /Dy 3+ co-doped phosphate glasses in the visible spectral region and explore the sensitization role of Dy 3+ in the enhancement of visible fluorescence of Tb 3+ ions. Judd-Ofelt parameters Ω 2 and Ω 4 /Ω 6 of the phosphate glass as host for Tb 3+ are calculated as 21.60 × 10 -20 cm 2 and 0.73, respectively, based on the measured spectral absorption. Multiple energy transfer (ET) routes from Dy 3+ to Tb 3+ and their efficiencies are characterized, and the enhanced fluorescence properties of Tb 3+ are investigated, including the emission spectral strength and the spontaneous emission lifetime as functions of Dy 3+ doping concentration. The efficient nonradiative ET processes between Dy 3+ and Tb 3+ allow a moderate concentration level of Tb 3+ to achieve favorably stronger spectral absorption at blue and ultraviolet wavelengths. Tb 3+ /Dy 3+ co-doped phosphate glass shows promising potential for phosphors and lasing operation at visible wavelengths.

研究领域: 材料科学 · 光学
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