Rare-earth,nitrogen-rich,oxygen heterocyclic supramolecular compounds (Nd,Sm, and Eu): Synthesis,structure, and catalysis for ammonium perchlorate

Three novel rare-earth, nitrogen-rich and oxygen heterocyclic supramolecular complexes, namely [Nd (BTF)₂(H₂O)₅]_n, [Sm(BTF)₂(H₂O)₅]_n, and [Eu(BTF)₂(H₂O)₅]_n, were synthesized. A single crystal was obtained by the solvent evaporation method, and the structure and coordination mode of metal complexes were determined by single crystal X-ray diffraction. Results show that the supramolecular complexes contain many hydrogen bonds and thus have good thermal stability (T_dec > 540 K). The thermal decomposition of ammonium perchlorate (AP) catalyzed by the complexes was investigated by differential thermal analysis, which reveals a pre-eminent catalytic effect on AP. The high temperature decomposition peak of AP can be advanced by nearly 90 K at the amount of added complexes of 10 wt%, and the activation energy of AP descent range is from 70 to 150 kJ/mol. The other properties were fully characterized through elemental analysis and Fourier transform infrared spectroscopy.     

Magnetic properties and magnetization mechanism of anisotropic NdFeB/SmFeN hybrid bonded magnets prepared with different coercivity NdFeB powders

Anisotropic NdFeB/SmFeN hybrid bonded magnets were prepared by warm compaction process under an orientation magnetic field of 22 kOe,mixing with anisotropic SmFeN powders in different addition and HDDR-NdFeB powders in different coercivity.With the addition of 20 wt% SmFeN,the density and remanence of hybrid magnets increase from 5.58 g/cm³,8.4 kGs to 6.02 g/cm³,9.0 kGs,respectively.And as the addition amount of SmFeN powders varies from 20 wt% to 40 wt%,the maximum energy ...     

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6（COO）6] （H2O）6} and {Ho2[C6（COO）6]（H2O）6}

Two novel 3-D coordination compounds, Nd2[C6（COO）6]（H2O）6 （1）and Ho2[C6（COO）6]（H2O）6 （2）, were hydrothermaily synthesized from mellitic acid and neodymium perchlorate （or holmium perchlorate） in the alkaline aqueous solution and characterized with elemental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the orthorhombic system, space group Pnnm, with a=1.3531 （4） nm, b=0.6687 （2） nm, c=1.0224（3） nm, V=0.92523（5） nm^3, Z=4, D=2.630 g/cm^3, F（000）=696.0, Goof=1.052. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0195, wR2=0.0382 for 1; a=1.3411 （2） nm, b=0.6586（1） nm, c=1.0116（2） nm, V=0.8935（3） nm^3, Z=4, D=2.877 g/cm^3, F（000）=724.0, Goof=1.061. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.     

Synthesis of two lanthanide clusters LnIII4 (Gd4 and Dy4) with [2 × 2] square grid shape: Magnetocaloric effect and slow magnetic relaxation behaviors

Two isostructural tetranuclear lanthanide clusters named [Ln₄(L)₄(CH₃O)₄]·CH₃OH (Ln = Gd(III) for 1, Dy(III) for 2, H₂L = N′-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide) were successfully isolated by using a polydentate Schiff based ligand and Ln(III) nitrate salts. The structures of 1 and 2 were characterized by X-ray structural analyses, they are held by four double deprotonated ligands L²⁻. In them all the lanthanide ions are eight-coordinated and distributed over four vertices of a parallelogram, presenting a Ln₄ cluster with a strict [2 × 2] square grid pattern. The details of magnetic analysis show that 1 displays weak anti-ferromagnetic exchange between neighboring Gd(III) ions through carboxylate oxygen and methanol oxygen ligand atoms. Furthermore, 1 exhibits significant magnetocaloric effect with the maximum entropy change –ΔS_m value of 28.5 J/(kg·K) for ΔH = 7.0 T at 2.0 K. For compound 2, remarkable slow magnetic relaxation behaviors are observed in the presence of zero magnetic field with τ₀ = 1.02 × 10⁻⁶ s and energy barrier ΔE/k_B = 43.24 K.     

Association of a terpyridine ligand with lanthanide and copper(II) nitrates

Reactions between the 1,3-bis(6-methylpyridin-2-yl)pyridine ligand L, C₁₇H₁₅N₃ and Ln^III (1a, 1b, 1c, 1d) or a mixture of Ln^III and Cu^II nitrates (2a, 2b, 2c, 2d) resulted in a series of respectively novel mono- and heterodinuclear complexes, where Ln^III=Sm (a), Eu (b), Tb (c), Dy (d). The compounds were characterized by elemental analysis, ESI-MS and IR spectra, furthermore we obtained crystals of [H₂L][Eu(NO₃)₅] (1b) and [CuL₂][Eu(NO₃)₅] (2b) suitable for XRD characterization. In the crystal structures the Eu ions are 10-coordinated with quite a narrow range of Eu-O distances which are between 0.2436 and 0.2556 nm. In 1b the ligand molecule is protonated in both terminal rings, and the N-H groups are involved in the N-H···O hydrogen bonds with the same oxygen atom of one of the nitro groups. These hydrogen bonds connect the ions in 1b into the complex which is the principal building block of the structure. In 2b the [CuL₂]²⁺ counterions are present; the Cu is octahedrally coordinated by all nitrogen iatoms of two L molecules which are therefore almost perpendicular to each other. The electrostatic interactions between the charged species are in both cases the main driving force of the crystal packing.     

Synthesis of Nano-sized Yttria via a Sol-Gel Process Based on Hydrated Yttrium Nitrate and Ethylene Glycol and Its Catalytic Performance for Thermal Decomposition of NH4ClO4

Nano-sized yttria particles were synthesized via a non-aqueous sol-gel process based on hydrated yttrium nitrate and ethylene glycol. The effects of the molar ratio of ethylene glycol to yttrium ion and calcination temperature on crystallite size of the products were studied. The catalytic performance of the as-prepared yttria for the ammonium perchlorate (AP) decomposition was investigated by differential scanning calorimetry (DSC). The results indicate that the nano-sized cubic yttria particles with less than 20 nm in average crystallite size can be obtained after 2 h reflux at 70 ℃, dried at 90 ℃, forming xerogel, and followed by annealing of xerogel for 2 h, and that the addition of the nano-sized yttria to AP incorporates two small exothermic peaks of AP in the temperature ranges of 310 ～ 350 ℃ and 400 ～ 470 ℃ into a strong exothermic peak of AP and increases the apparent decomposition heat from 515 to over 1110 J·g-1. It is also clear that the temperature of AP decomposition exothermic peak decreases and the apparent decomposition heat of AP increases with the increase of the amount of nano-sized yttria. The fact that the addition of the 5 % nano-sized yttria to AP decreases the temperature of AP exothermic peak to 337.7 ℃ by reduction of 114.6 ℃ and increases the apparent decomposition heat from 515 to 1240 J·g-1, reveals that nano-sized yttria shows strong catalytic property for AP thermal decomposition.     

Novel lanthanide coordination polymers based on mixed N,O-donor ligands and their visible-light-driven photocatalytic performance

In the present work,we prepared three isostructural lanthanide(Ln) coordination polymers(CPs).namely [Ln(Hhpc)(phen)(NO₃)](Ln=Gd(1),La(2),Y(3),H₃ hpc=5-hydroxy-1 H-pyrazole-3-carboxyIic acid,phen=1,10-phenanthroline) by hydrothermal method.Their structures were characterized by single crystal X-ray diffraction,Fourier transform infrared spectrum,elemental analysis,powder X-ray diffraction and thermal gravimetric analysis.CPs 1-3 are isostrutural and exhibit two-dimensional(...     

Fabrication of wide temperature lanthanum and cerium doped Cu/TNU-9 catalyst with excellent NH3-SCR performance and outstanding SO2+H2O tolerance

The effects of La on the catalytic performance,SO₂ and H2O resistance of Cu-Ce/TNU-9 catalyst were studied in the selective catalytic reduction of NO_x via ammonia(NH₃-SCR).The results show that the La doped Ce-Cu/TNU-9(CCL/T9) catalyst exhibits better SCR performance than Ce-Cu/TNU-9(CC/T9) and Cu/TNU-9(C/T9) in the wide temperature window(200-450 ℃) due to La benefiting from enhancing Cu⁺+Ce⁴⁺?Cu²⁺-+Ce³⁺ to facilitate ...     

A downshifting Eu3+ doped glass embedded with concave pyramid microstructure to improve the efficiency of silicon solar cell

The average photoelectric conversion efficiency (PCE) of a bare mono crystalline silicon solar cell is 14.71% ± 0.03% under AM1.5. It decreases to 14.20% ± 0.005% when covering an un-doped flat glass on the solar cell, and it goes down to 14.10% ± 0.005% by using a 5 wt% Eu³⁺ doped glass. The absorptions of the Eu³⁺ doped CPM glass one-to-one match the excitation spectra at 362, 381, 393, 400, 413 and 464 nm, which are related to the transitions of ⁷F₀→(⁵D₄, ⁵G₂, ⁵L₆, ⁵D₃), ⁷F₁→⁵D₃, and ⁷F₀→⁵D₂, respectively. In addition, a concave pyramid microstructure (CPM) is embedded in the glass surface to increase light transmittance. The average PCE increases to 14.61% ± 0.07% when a 5 wt% Eu³⁺ doped CPM glass covers on the silicon solar cell. Compared with the un-doped flat glass, a net increase of the PCE is 0.41%, where the 0.16% increment of PCE is from the lighting trapping of the CPM structure, and the downshifting of near ultraviolet (NUV) light by Eu³⁺ ion donates the other 0.25% increment. It confirms that the as-prepared Eu³⁺ doped CPM glass has a good downshifting and antireflection function.     

White up-conversion luminescence and highly-sensitive optical temperature sensing in Na3La(VO4)2:Yb,Er,Tm,Ho phosphors

In this work,tunable white up-conversion luminescence was achieved in the Yb³⁺,Er³⁺,Tm³⁺,Ho³⁺ codoped Na₃La(VO₄)₂ phosphors under 980 nm excitation.The emissions of three primary colors are mainly attributed to the ²H_11/2/⁴S_3/2→⁴I_15/2 transitions of Er³⁺,¹G₄→³H₆ transition of Tm³⁺,and_5...     

Synthesis of NaYF4:20% Yb3+,2% Er3+,2% Ce3+@NaYF4 nanorods and their size dependent uptake efficiency under flow condition

Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications. However, the low uptake efficiency of nanoparticles by cells has limited their applications. In this work, we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions. Using the same size NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺ (the contents of rare earths elements are in molar fraction) nanoparticles as core, NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺@NaYF₄ core–shell structured nanorods (NRs) with different sizes of 60–224 nm were synthesized by thermal decomposition and hot injection method. Under excitation at 980 nm, a strong upconversion green emission (541 nm, ²H_11/2 → ⁴I_15/2 of Er³⁺) is observed for all samples. The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs. Under flow conditions, the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells. This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.     

Preparation of hybrid perovskite-type Li0.33La0.56TiO3 by adding ionic liquids

Perovskite-type Li_0.33La_0.56TiO₃ (LLTO) shows greater advantages than organic liquid electrolytes to be used in all-solid-state lithium-ion batteries with high energy densities. Ionic liquid [BMIM][BF₄] was used to improve the properties of Li_0.33La_0.56TiO₃ by attrition milling in this study. The microstructure, crystallinity and lithium-ion conductivity of the samples were measured by scanning electron microscopy (SEM), X-ray diffraction (XRD), and impedance spectroscopy (IS). The total ionic conductivities of the samples LLTO + x wt% [BMIM][BF₄] increase upon adding [BMIM][BF₄] and the maximum conductivity reaches 4.71 × 10⁻⁴ S/cm when x = 12.5 wt%. The enhancement of the total conductivity is ascribed to the bridging role of the ionic liquid among grains, as evidenced by the low activation energy of 0.17–0.25 eV and the SEM observation. The Li⁺ transference numbers of the hybrid samples are all lower than that of the pure LLTO, indicating the existence of electronic conductions. The hybrid material with a mixed conductivity and good stability in the atmosphere can find uses in all-solid-state lithium-ion batteries to improve the interface contact between electrolytes and electrodes.     

Synthesis, Characterization, and Reactivity of Amine Bis（phenolato） Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.     

Application of three Ln(Ⅲ)-coordination polymers in fields of luminescence,antibacteria and detection of Fe3+ and 4-nitrophenol

Three lanthanide-based coordination polymers(Ln-CPs) with layered structure,{[La₂(L)₃(DMF)(H₂O)₃]·H₂O}_n(1),{[Eu₂(L)₃(DMF)₂(H₂O)]·(H₂O)}_n(2){Tb₂(L)₃(DMF)₂(H₂O)]·H₂O}n(3) were successfully synthesized from H₂L(N,N’-bis(4-carbozylbenzyl)aniline).Remarkably,compound 3 has extremely high sensitivity to 4-n...     

A NIR to NIR rechargeable long persistent luminescence phosphor Ca2Ga2GeO7:Yb3+,Tb3+

Near infrared to near infrared (NIR–NIR) photo-stimulated persistent luminescence (PSPL) has shown excellent potential in high-resolution bioimaging for deep tissues. However, the PSPL in NIR-Ⅱ region (900–1700 nm) is still lacking. In this work, Ca₂Ga₂GeO₇:Yb³⁺,Tb³⁺ (CGGYT) phosphor with unique low-dimensional crystal structure was synthesized by high-temperature solid–state reaction. Thanks to the carriers transferring from deep traps to shallow ones induced by low energy light, the 978 nm PSPL originating from ²F_5/2 to ²F_7/2 transition of Yb³⁺ induced by multimode stimulating (980 nm or WLED) is successfully realized after pre-excited by UV lamp. The NIR PSPL of the specimen can be repeatedly stimulated after placed in dark for 12 h. Moreover, the results indicate that codoping with Tb³⁺ can significantly enhance the NIR-II PSPL owing to the quantum cutting persistent energy transfer (QC PET) from Tb³⁺ to Yb³⁺. Our study points to a new direction for the future development of multimode PSPL materials for bioimaging or multimode optical storage applications.     

Energy transfer process of Nd3+/Ho3+ co-doped fluoride halide glasses with anion substituted multi-wavelength tunable mid-infrared luminescence

Ho³⁺ doped ZBLAN glass with 2.0 and 2.9 μm emission was prepared. In order to further improve the luminescence of Ho³⁺, halogen ions (Cl, Br, I) were introduced to reduce the maximum phonon energy and phonon state density of the sample. At the same time, Nd³⁺ was introduced to transfer the energy to Ho³⁺ pumped with a 793 nm laser (Nd³⁺:⁴F_5/2,⁴F_3/2→Ho³⁺:⁵I₆). The effect of different halogen ion on the luminescent properties of the fluoride halide glass was compared. The results show that the luminescent intensity of infrared increases with the introduction of different halogen ions. By comparison, it is found that the sample with I^– has the strongest luminescence of 1064 nm, 2.0 μm and 2.9 μm. This is consistent with the calculated J-O intensity parameters. In addition, the 2.0 and 2.9 μm emission of Ho³⁺ pumped with a 450 nm laser will not disappear. A mid-infrared sample with multi-wavelength excitation and multi-wavelength emission can be obtained. Nd³⁺/Ho³⁺ co-doped fluoride halide glasses with 1064 nm, 2.0 μm and 2.9 μm luminescence were prepared by melt quenching method. The luminescent mechanism and the energy transfer process between the two ions of Nd³⁺/Ho³⁺ co-doped fluoride halide glass were studied. The J-O parameters, luminescence lifetime and absorption emission cross-sectional area of Ho³⁺ and Nd³⁺ were calculated, respectively. It is found that the value of Ω₂ in the glass matrix increases with the introduction of different halogen ions, while Ω₄ and Ω₆ do not change obviously in different glass compositions. This is because the environment of the crystal field around the rare earth ions changes. The crystal phase and phonon energy of the sample were analyzed by X-ray diffraction pattern and a Fourier transform infrared spectrometer, respectively. Based on the above spectra and data (phonon energy is 634.71 cm⁻¹), it can be predicted that Nd³⁺/Ho³⁺ co-doped fluoride halide glass is a potential mid-infrared luminescent material.     

Hydroxyl-and-carboxyl ligand concatenating multi-lanthanide substituted tellurotungstates and electrochemical detection of noradrenaline

Developing and exploring organic–inorganic hybrid multi-lanthanide (Ln) implanted heteropolyoxometalates (HPOMs) has bloomed into an emerging research field. In this article, two neoteric d-gluconic acids (H₆GA) concatenating multi-Ln^III implanted heteropolytungstates K₁₄H₁₀[Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂(B-α-TeW₉O₃₃)₄]·60H₂O (Ln = La³⁺ (1), Pr³⁺ (2)) were obtained in acidic aqueous system. Attractively, in the polyanion structure of 1 and 2, six W^VI and four Ln^III centers are connected by four flexible H₂GA^4? ligands via carboxyl and hydroxyl groups, resulting in the heterometallic [Ln₄(H₂O)₄W₆(H₂GA)₄O₁₂]⁸⁺ cluster and then the heterometallic cluster is surrounded by four [B-α-TeW₉O₃₃]^8– segments. Electrochemical measurements for the 1@CFMCN/GCE sensor (CFMCN = carboxyl-functionalized multiwalled carbon nanotube; GCE = glass carbon electrode) demonstrate that 1@CFMCN/GCE shows benign recognition response to detecting noradrenaline (NDA). This research expands the structural diversity of Ln-implanted HPOMs and presents an electrochemical platform of recognizing NDA in the field of biosensors.     

Physicochemical properties of Li3Ba2La3(MoO4)8:Eu,Tb red-emitting phosphor for solid state white lamps

In this work,combustion synthesis was used for the first time to fabricate a phosphor material with red emission for applications in solid-state white-light lamps.We synthesized a material with emission wavelength at λ_em=617 nm,excited under long UV-blue wavelength based on Eu³⁺,Tb³⁺-activated molybdates Li₃Ba₂(La_1-x-yEu_xTb_y)₃(MoO₄)₈ with 0 ≤ x ≤1 and 0 ≤ y ≤ 1.A series of pow...