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JOURNAL OF ALLOYS AND COMPOUNDS · 2025 · IF 6.3

Supercritical Hydrothermal Synthesis, Magnetism, and Rotating Magnetocaloric Effect of Fluorocarbonates K4RE2(CO3)3F4 (RE = Ce, Pr, Nd, Sm, Eu, Tb, and Dy) with Rare-earth Dimers RE2O12F4

Jingfang Tong,Weijie Lin,Ruixin Guo,Zhongzheng Deng,Haitao Zhou,Shu Guo,Xiaojun Kuang

Strong magnetic anisotropy in low-dimensional magnets leads to a significant rotating magnetocaloric effect, presenting new opportunities for the exploration of more efficient and streamlined refrigeration systems. In this study, we have successfully synthesized a series of centimeter-scale rare-earth-containing fluorocarbonates, K 4 RE 2 (CO 3 ) 3 F 4 ( RE = Ce, Pr, Nd, Sm, Eu, Tb, and Dy) through a supercritical hydrothermal method, featuring unique RE 2 O 12 F 4 magnetic dimers. The above materials' fundamental magnetism has been systematically investigated, and no long-range magnetic transitions were captured above 1.8   K. Based on the low-temperature specific heat results, the long-range magnetic ordering was found around 0.84   K and 0.97   K for K 4 Tb 2 (CO 3 ) 3 F 4 and K 4 Dy 2 (CO 3 ) 3 F 4 , respectively. Furthermore, the anisotropic magnetism of K 4 Tb 2 (CO 3 ) 3 F 4 and K 4 Dy 2 (CO 3 ) 3 F 4 reveals significant magneto-crystalline anisotropy, with the magnetic field ( B ) aligned along the RE 2 O 12 F 4 magnetic dimer, which acts as the easy magnetic axis. The maximum rotating field entropy change, − Δ S R max for K 4 Tb 2 (CO 3 ) 3 F 4 reaches approximately 9   J   kg -1 K -1 around 17   K, while for K 4 Dy 2 (CO 3 ) 3 F 4 , it is approximately 5.5   J   kg -1 K -1 near 11   K, both under a 7   T field applied along the c -axis. These findings highlight the potential of these compounds for magnetic refrigeration applications through a rotating crystallographic direction.

研究领域: 材料科学 · 物理学
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Materials Chemistry Frontiers · 2022 ·Vol. 7 ·期 1 ·168-182 · IF 8.683

High charge carrier storage capacity and wide range X-rays to infrared photon sensing in LiLuGeO4:Bi3+,Ln3+ (Ln = Pr, Tb, or Dy) for anti-counterfeiting and information storage applications

Peiran Huang,Zuhui Wen,Yue Yu,Jingyi Xiao,Zhanhua Wei,Tianshuai Lyu

X-Ray or 254 nm UV-light charged storage phosphors have various promising applications such as in anti-counterfeiting and information storage. However, developing such storage phosphors with high charge carrier storage capacity remains challenging. In this work, photoluminescence spectroscopy, thermoluminescence (TL), and vacuum-referred binding energy (VRBE) diagram were combined to study the trapping and liberation processes of charge carriers in Bi3+ and/or Ln3+ (Ln = Tb, Pr, or Dy) doped LiLuGeO4. Unintended defects act as good electron trapping centers, while Bi3+, Tb3+, and Pr3+ act as hole-capturing and recombination centers. Dy3+ does not act as an electron trapping center but as a luminescence center by energy transfer from Bi3+ → Dy3+. The ratios of the integrated TL intensities between 303 K and 650 K for LiLuGeO4:0.005Bi3+, LiLuGeO4:0.005Bi3+,0.005Tb3+, or LiLuGeO4:0.005Bi3+,0.005Dy3+ after X-ray charging to that of the state-of-the-art BaFBr(I):Eu2+ is about 1.24, 0.59, and 0.90, respectively. More than 10 h or 40 h afterglow was measurable in both LiLuGeO4:0.005Bi3+ and LiLuGeO4:0.005Bi3+,0.005Tb3+ after X-ray or 254 nm UV-light charging. The stored charge carriers stored can be efficiently excited to produce optically stimulated luminescence with a wide range 365 nm UV-light to 850 nm infrared laser beam. Proof-of-concept colour-tailorable afterglow, X-ray irradiation time or sample mass-dependent dosimetry, and optically-stimulated luminescence with a wide range of 365 nm UV-light to 850 nm infrared laser stimulation will be demonstrated for anti-counterfeiting, information storage, and display applications in the developed Bi3+ and/or Ln3+-doped LiLuGeO4. This work not only reports Bi3+ and/or Ln3+ doped LiLuGeO4 storage phosphors with excellent charge carrier storage capacity but also deepens our understanding of the afterglow and storage phosphors and luminescence mechanisms, which can guide us to explore new afterglow and storage phosphors for multimode applications.

研究领域: 材料科学 · 光学
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OPTICAL MATERIALS · 2024 · IF 3.8

Multicolor luminescence and energy transfer of KSrGd(PO4)2:Ln3+ (Ln = Ce, Sm, Eu, Tb, Dy, Dy/Eu, Yb/Ho, Yb/Er, Yb/Tm) phosphors for WLED and multiple anti-counterfeiting

Mengran Ouyang,Huimin Du,Jiahao Wu,Shanshan Hu,Jun Yang

KSrGd(PO 4 ) 2 :Ln 3+ (Ln = Ce, Sm, Eu, Tb, Dy, Dy/Eu, Yb/Ho, Yb/Er, Yb/Tm) phosphors were synthesized by high temperature solid state method. Doping the KSrGd(PO 4 ) 2 matrix with 5%Dy 3+ ions resulted in white light emission under 345 nm excitation. The calculated color temperature (CCT) of this white light is 5523 K, indicating as positive white light. It was found that the luminous intensity of the obtained KSrGd(PO 4 ) 2 :5%Dy 3+ at 200 °C was 76.80 % of that at room temperature, showing good thermal stability as well as possibility of application in white LED. Under the excitation at 392 nm, the fluorescence quantum yield of KSrGd(PO 4 ) 2 :10%Eu 3+ is 79.92 %. Energy transfer between Dy 3+ and Eu 3+ is observed in KSrGd(PO 4 ) 2 :Dy 3+ /Eu 3+ samples, with identified mechanism as the quadrupole-quadrupole interaction. Tunable luminescence ranging from white to yellow then to orange-red is achieved by adjusting the doping concentration of Eu 3+ in KSrGd(PO 4 ) 2 :5%Dy 3+ , x%Eu 3+ . Under the excitation of 980 nm near-infrared light, the prepared KSrGd(PO 4 ) 2 :Yb 3+ /Ho 3+ , KSrGd(PO 4 ) 2 :Yb 3+ /Er 3+ and KSrGd(PO 4 ) 2 :Yb 3+ /Tm 3+ samples showed up-conversion emissions of red, yellow and blue, respectively, with two-photon processes. In KSrGd(PO 4 ) 2 matrix, multi-color and multi-security marks were successfully prepared by utilizing up/down conversion luminescence characteristics, which obtained good anti-counterfeiting effect and improved anti-counterfeiting security. Therefore, the obtained KSrGd(PO 4 ) 2 : Ln 3+ phosphors exhibit promising application prospects in the fields of WLED and multiple anti-counterfeiting.

研究领域: 材料科学 · 光学
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JOURNAL OF CHEMICAL THERMODYNAMICS · 2019 · IF 2.29

Phase equilibria in Mg(NO3)2–Ln(NO3)3 (Ln = Nd, Sm, Eu, Tb)–HNO3 (∼20%)–H2O systems at 298.15 K and thermodynamic properties of Mg3Ln2(NO3)12·24H2O (Ln = Nd, Sm)

Zhan-Ping Qiao,Meng-Yao Su,Yuan-Lin Dang,Qi-Chao Yang

The phase diagrams of the Mg(NO 3 ) 2 –Ln(NO 3 ) 3 (Ln = Nd, Sm, Eu, Tb)–HNO 3 –H 2 O systems in the (∼20%) HNO 3 regions at T  = 298.15 K were determined by using an isothermal solution saturation method. The Schreinemaker’s wet residues method was used to determine the compositions of solid-phases. Both Mg(NO 3 ) 2 –Nd(NO 3 ) 3 –HNO 3 –H 2 O and Mg(NO 3 ) 2 –Sm(NO 3 ) 3 –HNO 3 –H 2 O systems are complicated with three equilibrium solid phases Mg(NO 3 ) 2 ·6H 2 O, Mg 3 Ln 2 (NO 3 ) 12 ·24H 2 O and Ln(NO 3 ) 3 ·6H 2 O (Ln = Nd, Sm). But the systems Mg(NO 3 ) 2 –Eu(NO 3 ) 3 –HNO 3 –H 2 O and Mg(NO 3 ) 2 –Tb(NO 3 ) 3 Tb–HNO 3 –H 2 O are simple eutonic type. The two new solid-phase compounds Mg 3 Nd 2 (NO 3 ) 12 ·24H 2 O and Mg 3 Sm 2 (NO 3 ) 12 ·24H 2 O are congruently soluble in an average medium of ∼20 mass % HNO 3 , and they were identified and characterized by the methods of powder X-ray diffraction, X–ray diffraction single crystal structure analysis, and thermogravimetric/differential thermogravimetric. The XRD diffraction patterns for the two new solid-phase compounds are identical due to their isomorphic structure. They belong to hexagonal systems, with space group R 3 . For Mg 3 Nd 2 (NO 3 ) 12 ·24H 2 O, a  =  b  = (1.0993 ± 0.0005) nm, c  = (1.7211 ± 0.0007) nm, V  = (1.8012 ± 0.0013) nm 3 , D c  = (4.2532 ± 0.0024) g·cm −3 , Z  = 3; for Mg 3 Sm 2 (NO 3 ) 12 ·24H 2 O, ( a  =  b  = 1.1198 ± 0.0004) nm, c  = (1.7257 ± 0.0006) nm, V  = (1.8742 ± 0.0011) nm 3 , D c  = (4.1201 ± 0.0012) g cm −3 , Z  = 3. The standard molar enthalpies of solution of the compounds Mg 3 Nd 2 (NO 3 ) 12 ·24H 2 O and Mg 3 Sm 2 (NO 3 ) 12 ·24H 2 O in water (aq) were measured to be (101.26 ± 0.77) kJ mol −1 and (80.27 ± 0.81) kJ mol −1 , and their standard molar enthalpies of formation were calculated to be – (12214.13 ± 2.5) kJ mol −1 and – (12183.6 ± 2.5) kJ mol −1 , respectively.

研究领域: 化学 · 物理化学 · 材料科学
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Journal of Cleaner Production · 2023 · IF 11.1

Promoting vivianite recovery: Crucial role of tightly-bound extracellular polymeric substances

Shu Wang,Nanqi Ren,Danhui Liang,Jifei Chang,Xin Wang,Jiaguo Yan,Xiang Cheng,Lili Dong,Nan Li

Vivianite is an important bio-induced product of dissimilated iron reduction (DIR), which exists widely in activated sludge and digested sludge of wastewater treatment plants (WWTPs). Extracellular polymeric substances (EPS) surrounding dissimilatory iron-reducing bacteria (DIRB) were reported to be transient media for microbial extracellular electron transfer (EET) and DIR. However, what happens when a layer of EPS envelops microbial cells during vivianite recovery? This study tried to assess the relationship between iron reduction and electron transfer by stripping EPS layer-by-layer, then clarified the delamination of different EPS layers on the performance of vivianite recovery. After stripping total EPS (PC-EPS batches) of DIRB, the Fe (III) reduction efficiencies ( R Fe ), Fe (III) reduction rate ( V Fe ), and vivianite formation efficiency ( R V ) decreased by 33%, 37%, and 30%, respectively. Tightly bound-EPS (TB-EPS) was confirmed to play a crucial role in vivianite formation, which contributed 28–51% to vivianite recovery and 34–55% to iron reduction. Electronic shuttle substances were contained in TB-EPS, which enhanced the EET rate and efficiency between cells and Fe (III). The polysaccharide content of TB-EPS was positively related to adhesiveness between cells and mineral, as well as the iron reduction efficiency. Furthermore, redox proteins (PpcA, OmcB) were embedded in EPS, which shortened the distance of electron hopping to across the EPS layer and further accelerated vivianite recovery from wastewater. Long-term operation of anaerobic reactors confirmed that TB-EPS played critical roles in bio-induced vivianite formation.

研究领域: 环境科学 · 微生物学 · 污水处理 · 生物地球化学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Multicolor fluorescent cellulose hydrogels actuators: Lanthanide-ligand metal coordination, synergetic color-changing and shape-morphing, and antibacterial activity

Xuezhen Feng,Chao Wang,Shibin Shang,He Liu,Xujuan Huang,Jianxin Jiang,Haibo Zhang

The development of stimulus-responsive materials with multifunctionality is important for achieving bionic artificial intelligence. However, stimulus-responsive cellulose hydrogels that simultaneously change their shape and fluorescent color under a single stimulus are difficult to fabricate. Here smart, multicolor fluorescent cellulose hydrogels were prepared from cellulose, levofloxacin, epichlorohydrin, and lanthanide ions (Eu 3+ or Tb 3+ ). The hydrogels were incorporated with pan paper into synergetic color-changing and shape-morphing actuators (Eu-CLF and Tb-CLF actuators). Besides fluorescing with the metal ligands, levofloxacin possesses antibacterial activity. The fluorescence color of Eu-CLF hydrogel in Tb 3+ solution changed from red to yellow, whereas that of Tb-CLF hydrogel in Eu 3+ solution changed from green to red. Both the Eu-CLF and Tb-CLF hydrogels fluoresced blue and green in alkali and acid solution, respectively. The actuator thus achieves synergetic color-changing and shape-morphing under a single external stimulus (acidic/alkaline switching). Such an activator shaped like a bionic flower and an intelligent octopus-type soft robot with camouflaging ability were then prepared. This study provides an elegant strategy for developing advanced multi-responsive multicolor tunable behaviors for bionic soft robots, biosensors , and camouflaged robots.

研究领域: 材料科学 · 仿生学 · 人工智能 · 机器人技术 · 生物传感器
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2025 · IF 4.6

Magnetically recyclable hyper-cross-linked porous polymer as adsorbent combined with LC/MS for effective enrichment and detection of some endocrine disruptors in shrimp samples

Cong Liu,Yanli Dong,Junmin Wang,Qianqian Wang,Chun Wang,Qiuhua Wu

Phenolic environmental endocrine disruptors (EEDs) pose significant risks to the reproductive and nervous systems. Herein, we synthesized a magnetic OH-anchored porous polymer (M-Pue@TB-HCP2) by linking natural puerarin with 1,3,5-tris(bromomethyl)benzene for the first time. M-Pue@TB-HCP2 showed high extraction recovery (94 %-99 %) for phenolic EEDs (bisphenol S, bisphenol A, bisphenol B and p -tert-butylphenol) thanks to its amphiphilic sites supplying hydrogen bonding and π conjugation interaction. Moreover, M-Pue@TB-HCP2 displayed excellent reusability and long service life. Using M-Pue@TB-HCP2 as magnetic solid-phase extraction adsorbent, coupled with high-performance liquid chromatography-mass spectrometry, a novel method was established for detecting trace EEDs from shrimps, achieving low detection limit (0.80–5.50 ng g −1 for green shrimp, 1.00–4.00 ng g −1 for white shrimp), good spiked recovery of 80.3 %-117 %, relative standard deviation less than 5.7 %. The method has the merits of high sensitivity, good accuracy and excellent reproducibility, making it suitable for the trace analysis of EEDs in shrimps. This work not only provides a new option for rapid and accurate detection of trace EEDs in shrimps but also explores a new strategy for the preparation of efficacious adsorbents by utilizing sustainable raw materials.

研究领域: 环境科学 · 高分子化学 · 分析化学 · 食品安全 · 内分泌学 · 纳米技术 · 吸附技术
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