Hydrothermal Synthesis and Luminescent Properties of Flowerlike Zn2GeO4 and Mn2+-Doped Zn2GeO4 Hierarchical Architectures

Three-dimensional(3D) flowerlike hierarchical Zn₂GeO₄ and Mn²⁺-doped Zn₂GeO₄ microstructures have been prepared by a facile hydrothermal approach. X-Ray diffraction(XRD), field emission scanning electron microscopy(FESEM), transmission electron microscopy(TEM) and photoluminescence(PL) spectrometry were employed to characterize the samples. Such flowerlike hierarchical Zn₂GeO₄ microstructures with an average diameter of 3―4 μm were found to be constructed by abundant single crystalline nanorods of about 90 nm in diameter. The luminescent properties of Zn₂GeO₄:xMn phosphors with different contents of Mn²⁺ as an activator were investigated. The Mn²⁺-doped samples showed green luminescence corresponding to the d-d transition of Mn²⁺ under the irradiation of UV light. The red shift(from 531 nm to 538 nm) in λ_em with increasing Mn²⁺ content was observed in the luminescent spectra, which should be attributed to a weak crystal field because of the substitution of Zn²⁺ by Mn²⁺ at a distorted tetrahedral lattice site.     

Yb3+共掺杂对Zn2GeO4:Mn2+绿色长余辉发光性能增强研究

利用高温固相法合成了Zn2GeO4:Mn2+以及Zn2GeO4:Mn2+,Yb3+绿色发射长余辉发光材料,对样品进行了X射线衍射分析、荧光光谱分析、色坐标、热释发光以及发光寿命测量.分析结果表明,在1050℃下烧结3h的Zn2CeO4为单相产物,所得Zn2GeO4:Mn2+发光材料具有良好的发光性能,在紫外灯激发下发出最强发射位于528 nm的宽带发射并具有优良的长余辉发光特性,其色坐标值分别为x=0.145,y=0.773.Yb3+共掺杂对其长余辉发光性能提高明显.余辉发光在暗场环境下肉眼可观察的持续时间超过2h.通过热释光谱对陷阱进行了分析.对Yb3+共掺杂的长余辉发光增强机理进行了讨论.     

(Zn, Mg)2GeO4:Mn2+ submicrorods as promising green phosphors for field emission displays: hydrothermal synthesis and luminescence properties

(Zn(1-x-y)Mg(y))(2)GeO(4): xMn(2+) (y = 0-0.30; x = 0-0.035) phosphors with uniform submicrorod morphology were synthesized through a facile hydrothermal process. X-Ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photoluminescence (PL), and cathodoluminescence (CL) spectroscopy were utilized to characterize the samples. SEM and TEM images indicate that Zn(2)GeO(4):Mn(2+) samples consist of submicrorods with lengths around 1-2 μm and diameters around 200-250 nm, respectively. The possible formation mechanism for Zn(2)GeO(4) submicrorods has been presented. PL and CL spectroscopic characterizations show that pure Zn(2)GeO(4) sample shows a blue emission due to defects, while Zn(2)GeO(4):Mn(2+) phosphors exhibit a green emission corresponding to the characteristic transition of Mn(2+) ((4)T(1)→(6)A(1)) under the excitation of UV and low-voltage electron beam. Compared with Zn(2)GeO(4):Mn(2+) sample prepared by solid-state reaction, Zn(2)GeO(4):Mn(2+) phosphors obtained by hydrothermal process followed by high temperature annealing show better luminescence properties. In addition, codoping Mg(2+) ions into the lattice to substitute for Zn(2+) ions can enhance both the PL and CL intensity of Zn(2)GeO(4):Mn(2+) phosphors. Furthermore, Zn(2)GeO(4):Mn(2+) phosphors exhibit more saturated green emission than the commercial FEDs phosphor ZnO:Zn, and it is expected that these phosphors are promising for application in field-emission displays.     

Mn4+-, Tb3+,4+-, and Er3+-activated red phosphors in the MgAl2Si2O8 system

Mn⁴⁺ doped and Tb^3+,4+, Er³⁺ co-doped MgAl₂Si₂O₈-based phosphors were prepared by conventional solid-state synthesis at 1,300 °C. They were characterized by thermogravimetry, differential thermal analysis, X-ray powder diffraction, photoluminescence, and scanning electron microscopy. The luminescence mechanism of the phosphors, which showed broad red emission bands in the range of 600–715 nm and had different maximum intensities when activated by UV illumination, was discussed. Such a red emission can be attributed to the intrinsic ²E → ⁴A₂ transitions of Mn⁴⁺.     

A mesoporous template route to the low-temperature preparation of efficient green light emitting Zn2SiO4:Mn phosphors

Green light emitting Zn2SiO4:Mn phosphors have been prepared via a low-temperature solid-state reaction using mesoporous silica SBA-15 template. This mesoporous silica template method features low-temperature formation of phosphors and easy doping. The structure and morphology of the phosphors were characterized by XRD, SEM, TEM, and N2 adsorption/desorption techniques, which confirmed the single crystallinity, ordered mesostructure, closed pore channels, and elongated ropelike morphology. The luminescent properties were examined by photoluminescence spectroscopy at room temperature, and the results of fluorescence decay time measurements show non-single-exponential decay behavior and a decrease of the decay time with an increase of the Mn concentration.     

Controlling Cr3+/Cr4+ concentration in single-phase host toward tailored super-broad near-infrared luminescence for multifunctional applications

Full control on the valence of the active ions in solids to improve properties is the central topic of chemistry and materials. Cr³⁺ and Cr⁴⁺ ions generally emit wavelength-different near-infrared (NIR) light. Here, we have developed a chromium valence-controllable single-phase phosphor, Mg₂GeO₄:Cr³⁺,Cr⁴⁺ to achieve super-broad NIR luminescence. High Li ⁺ content charge compensators can stabilize Cr³⁺, whereas high-temperature sintering tends to facilitate the formation of Cr⁴⁺. Through fine adjusting the synthesis conditions, pure Cr³⁺ or Cr⁴⁺ luminescence can be obtained with peak emission locating at 935 nm and 1190 nm, respectively. Super broad band dual emission spanning from 650 nm to 1600 nm is realized via fully controlling the concentration ratio of Cr³⁺ to Cr⁴⁺ in a single host. By measuring the transmission spectra of several foodstuff illuminated by our phosphors, non-destructive analysis in food safety areas can be realized. This study provides a new strategy for exploiting super broad band NIR luminescent materials.     

Supramolecular structures of Mn2+, Co2+ and Zn2+ complexes containing 1,3-bis(4-pyridyl)propane and aminosalicylate anion

In this study, the synthesis, spectroscopic properties and crystal structures of three new supramolecular compounds named [Mn₂(bpp)₄(H₂O)₄](AS)₄·H₂O (1), [Co₂(bpp)₄(H₂O)₄](AS)₄·H₂O (2) and [Zn(bpp)(AS)₂] (3), have been described, where bpp is 1,3-bis(4-pyridil)propane and AS^?  is aminosalicylate anion. By analysing the similarities between the X-ray powder diffraction results, it has been observed that compounds 1 and 2 are isomorphous, exhibiting an orthorhombic system with space group Pccn; for compound 3, another orthorhombic system was observed, with space group Aba2, which displays coordination between the Zn²⁺ metal ion and the aminosalicylate anion; this can be considered the first case in the literature involving the direct coordination to the metal ion. The vibrational spectra of compounds 1 and 2 are very similar. In the Raman spectra, the main bands are observed at ca. 1625 and 1020 cm^? 1, referring to the ^? O–C = O and CC/CN stretching modes of AS^?  and bpp ligands, respectively.     

Finding an efficient far-red-emitting CaMg2La2W2O12:Mn4+ phosphor toward indoor plant cultivation LED lighting

The development of high-brightness far-red-emitting phosphors with emission wavelength within 650–750 nm is of great significance for indoor plant cultivation light-emitting diode (LED) lighting. Herein, we demonstrate a novel efficient far-red-emitting phosphors CaMg₂La₂W₂O₁₂:Mn⁴⁺ (abbreviated as CMLW:Mn⁴⁺) toward application in plant cultivation LEDs. Interestingly, the CMLW:Mn⁴⁺ phosphors show a broad excitation band in the 250–600 nm spectral range with two peaks at 352 and 479 nm, indicating they could be efficiently excited by near-ultraviolet and blue light. Under 352 nm excitation, the CMLW:Mn⁴⁺ phosphors exhibit an intense far-red emission band in the wavelength range of 650–800 nm peaking at 708 nm, corresponding to the ²E_g → ⁴A_2g transition of Mn⁴⁺ ions. Mn⁴⁺ doping concentration-dependent luminescence properties are studied in detail, and the concentration quenching mechanism is also investigated. Particularly, the internal quantum efficiency of CMLW:Mn⁴⁺ phosphors reaches as high as 44%, and their PL spectra match well with the absorption spectrum of phytochrome P_FR (P_FR stands for far-red-absorbing form of phytochrome). Furthermore, a prototype LED device is fabricated by coating the as-prepared CMLW:0.8%Mn⁴⁺ phosphors on a 460 nm blue LED chip, which produces bright far-red emissions upon 20–300 mA driving currents. This work reveals that the newly discovered far-red-emitting CMLW:Mn⁴⁺ phosphors hold great potential for application in indoor plant cultivation.     

Simultaneous Analysis of Co2+, Cu2+ Mn2+, Ni2+ and Zn2+ in The Ultraviolet Region Using 4-(Pyridil-2-AZO) Resorcinol and Multivariate Calibration

ABSTRACT

A multicomponent spectrophotometric methodology for the simultaneous determination of Co²⁺, Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺ in aqueous solution is reported, using (4-(pyridil-2-azo) resorcinol), a diode array spectrophotometer and multivariate calibration by partial least-squares and principal component regerssions. Spectra are recorded in the UV region. The 225 – 320 nm range is selected as optimal, through a criterion based on tederivatives of the differences between individual spectra, which compares favorably with a genetic algorithm. The methodology is applied to the simultaneous determination of the five than 1.5 mgL^?1. The best result are obtanied at pH 9.0, with average absolute errors of prediction lower than 0.09 mgL^?1     

Optical and Structural Properties of Zn2SiO4:Mn2+ from SLS Waste Bottle Obtained by a Solid State Method

In this studies, 2 wt.% Mn-doped Zn₂SiO₄ were synthesized from SLS waste glass, ZnO and MnO using conventional solid-state method. Structural and optical properties were examined as functions of sintering temperature. Density and linear shrinkage of samples increased with increasing in sintering temperature. X-Ray Diffraction pattern revealed that sintering temperature play an important role in enhancing crystallization of Zn₂SiO₄. It was found that the phase formation changed from amorphous to ȕ- Zn₂SiO₄ and then to α-Zn₂SiO₄ with the unsintered to sinter at 600 °C and 700 °C respectively. The morphology under FESEM characterization shows that the samples become more uniform with rectangular shape like as the sintering temperature increased. From UV-Vis spectroscopy, the results obtained showed that the intensive absorption occurred in the UV region, in the range of 250-γλ0 nm. Prominent green emission colours of α-Zn₂SiO₄ were observed centred at 527 nm while the yellow emission centred at η8η nm resulted from ȕ-Zn₂SiO at an excitation of 260 nm. However, red emission centred at 600 nm was observed for glass samples. These emissions come from the Mn-dopant and correspond to the ⁴T₁ – ⁶A₁ transition.     

Microwave‐Induced In Situ Synthesis of Zn2GeO4/N‐Doped Graphene Nanocomposites and Their Lithium‐Storage Properties

Zn₂GeO₄/N‐doped graphene nanocomposites have been synthesized through a fast microwave‐assisted route on a large scale. The resulting nanohybrids are comprised of Zn₂GeO₄ nanorods that are well‐embedded in N‐doped graphene sheets by in situ reducing and doping. Importantly, the N‐doped graphene sheets serve as elastic networks to disperse and electrically wire together the Zn₂GeO₄ nanorods, thereby effectively relieving the volume‐expansion/contraction and aggregation of the nanoparticles during charge and discharge processes. We demonstrate that an electrode that is made of the as‐formed Zn₂GeO₄/N‐doped graphene nanocomposite exhibits high capacity (1463 mAh g^?1 at a current density of 100 mA g^?1), good cyclability, and excellent rate capability (531 mAh g^?1 at a current density of 3200 mA g^?1). Its superior lithium‐storage performance could be related to a synergistic effect of the unique nanostructured hybrid, in which the Zn₂GeO₄ nanorods are well‐stabilized by the high electronic conduction and flexibility of N‐doped graphene sheets. This work offers an effective strategy for the fabrication of functionalized ternary‐oxide‐based composites as high‐performance electrode materials that involve structural conversion and transformation.     

Constructing novel red-emitting Ba2Y0.8Eu0.2NbO6:Mn4+ phosphors for multi-type luminescent thermometers and high-security anti-counterfeiting films

To date, luminescent materials have been preferably used for non-contact optical thermometers. In this manner, novel red-emitting Ba₂Y_0.8Eu_0.2NbO₆:Mn⁴⁺ (BYEN:Mn⁴⁺) phosphors were designed for multi-type non-contact luminescent thermometers based on the dual-emission states and temperature-dependent lifetime (TDL) models. In the temperature range of 303–483 K, the sensing sensitivities based on the dual-emission states of (⁵D₀→⁷F₂, ²E_g→⁴A_2g) and (⁵D₀→⁷F₁, ²E_g→⁴A_2g) were estimated. Especially, the maximum absolute sensing sensitivity (S_a) was found to be about 0.1558 K^-1 for the BYEN:0.007Mn⁴⁺ phosphor based on the ⁵D₀→⁷F₁ and ²E_g→⁴A_2g positions. This phosphor also exhibited good relative sensing sensitivity (S_r) (0.0186 K^-1) based on the ⁵D₀→⁷F₂ and ²E_g→⁴A_2g states. Besides, the relative sensing sensitivities (S_R) at ⁵D₀→⁷F₁ and ²E_g→⁴A_2g transitions were estimated to be 0.0034 and 0.0194 K^-1, respectively with the help of the TDL technique. In the light of these results, novel red-emitting Ba₂Y_0.8Eu_0.2NbO₆:Mn⁴⁺ phosphors are expected to be a potentially attractive candidate for applications in multi-type luminescent thermometers. Finally, a novel unique polydimethylsiloxane film exhibiting tricolor-luminescent emissions was introduced and further suggested for high-security anti-counterfeiting.     

Investigations on the spin-crossover complex [Fe(bzimpy)2](ClO4)2 and its Mn2+, Co2+, Ni2+ and Zn2+ analogues

Summary A series of transition metal complexes [M(bzimpy)₂](ClO₄)₂ (M=Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺;bzimpy=2,6-bis(benzimidazol-2-yl)pyridine) was synthesized and characterized by elemental analysis, UV-Vis and far-IR spectroscopy. The electronic spectra of [Ni(bzimpy)₂](ClO₄)₂ in solution and solid state reveal a ligand field splitting parameter ₀ in the range of 11470 cm^–1 to 11840 cm^–1. The simultaneous existence of two species with distinct spin state is found for [Fe(bzimpy)₂](ClO₄)₂ by means of variable temperature far-IR measurements. Assignments of the observed far-IR bands are given on the basis of the investigations of the variation of the metal ion in [M(bzimpy)₂](ClO₄)₂.This paper is dedicated to Professor Ulrich Wannagat on the occasion of his 70^th birthday with warmest personal wishes.     

Low-Temperature Synthesis of Nanosize Zn2SiO4:Mn2+ Phosphor from the Precursor Sol in Supercritical Ethanol and its Photoluminescent Properties

Acetylcellulose (AC)/silica and polyvinylpyrrolidone (PVP)/silica composites were prepared by the sol–gel method from Si(OCH₃)₄-AC-HNO₃-H₂O-tetrahydrofuran-CH₃OC₂H₄OH and Si(OCH₃)₄-PVP-(CH₃COOH or NH₃)-H₂O-CH₃OH-CH₃OC₂H₄OH solutions. AC/silica composites were composed of micrometer-sized particles rich in silica and a matrix rich in AC, while PVP/silica composites were single-phase on the SEM length scale. The AC/silica composites exhibited elastic-plastic behavior, and had excellent machinability without chipping on cutting with an electric saw while the PVP/silica composites showed less plasticity and machinability. Youngs modulus and bending strength were increased by post-drying, 1.8–2.8 GPa and 49–88 MPa, respectively, for the AC/silica composites, and 1.0–3.9 GPa and 17–79 MPa, respectively, for the PVP/silica composites.     

Hydrothermal development of magnetic-hydrochar nanocomposite from pineapple leaves and its performance as an adsorbent for the uptake of Mn2+ and reuse of the metal loaded adsorbent in latent fingerprint

Manganese is one of the heavy metals that is a major environmental concern when present in large amount. Manganese is discarded into water systems by numerous industries, including mining, batteries and electroplating etc. Pineapple leaves were applied as a biomass source to produce a magnetic hydrothermal treated hydochar nanocomposite; Fe₃O₄-HC. The BET surface area of Fe₂O₃-HC nanocomposite was 21.27 m²/g. Batch adsorption experiments revealed that the uptake of Mn²⁺ fit well in the pseudo second kinetics model, while the adsorption isotherm best fit the Freundlich model, with a maximum adsorption capacity of 2.99 mg/g at 25 °C and a pH of 5. The obtained thermodynamic parameters demonstrated that Mn²⁺ ion adsorption using the Fe₂O₃-HC nanocomposite was endothermic and nonspontaneous. Additionally, Fe₂O₃-HC nanocomposite demonstrated to be highly selective towards Mn²⁺ ions in the presence of other ions. The removal percentage of Mn²⁺ from a real water sample spiked with 50 mg/L Mn²⁺ was reported to be 53.2%. The spent adsorbent was then used to detect latent fingerprints, which revealed that Mn²⁺-Fe₂O₃-HC nanocomposite generated better and clear latent fingerprints than Fe₂O₃-HC nanocomposite.     

Photo and Thermo‐luminescence Properties of Mn4+, Ce4+ and Sm3+ in MgAl2Si2O8 Phosphor

Mn⁴⁺, Ce⁴⁺ and Sm³⁺ doped MgAl₂Si₂O₈‐based phosphors were synthesized at 1300 °C by solid state reaction and characterized by thermogravimetry (TG), differential thermal analysis (DTA), X‐ray powder diffraction (XRD), photoluminescence (PL), thermoluminescence (TL) and scanning electron microscopy (SEM). The phosphors showed broad red emission bands in the range of 610–715 nm and different maximum intensity when activated by UV illumination. Such a red emission can be attributed to the intrinsic ²E→⁴A₂ transitions of Mn⁴⁺.     

New garnet compounds A 3 2+ B 2 2+ C4+V 2 5+ O12(A = Ca,Cd; B = Mg,Zn, Co,Ni, Cu,Mn, Cd; C = Ge,Si)

Garnet compounds A ₃ ²⁺ B ₂ ²⁺ C⁴⁺V ₂ ⁵⁺ O₁₂ (A = Ca, Cd; B = Mg, Zn, Co, Ni, Cu, Mn, Cd; C = Ge, Si) (space group \(Ia\bar 3d\) , Z = 8) have been prepared by solid-phase synthesis in air at 900–1250°C. Most of these compounds melt incongruently or decompose in the solid phase. The isomorphic capacity of garnets and their homogeneity fields are discussed. The structures of Ca₃Zn₂GeV₂O₁₂ and Ca₃Cu₂GeV₂O₁₂ have been refined by the Rietveld method.