Sn<Superscript>4+</Superscript> and La<Superscript>3+</Superscript> co doped TiO<Subscript>2</Subscript> nanoparticles and their optical,photocatalytic and antibacterial properties under visible light

Sn⁴⁺ and La³⁺ co-doped TiO₂ photocatalytic material with nanoparticle structure have been successfully prepared using SnCl₂·2H₂O and La(NO₃)₃·6H₂O as precursors. Scanning electron microscopy, X-ray diffraction, transmission electron microscopy and UV–visible spectroscopy have been used to for the characterization of the morphology, crystal structure, particle size and optical properties of the samples. The photocatalytic properties of sample with various amount of La doped TiO₂ have been studied by photo degradation of methyl orange (MO) in water under visible light. XRD patterns showed both rutile and anatase phases for 5 mol% of Sn and 5–10 mol% of La. But anatase phase with a little rutile phase was formed for 5 mol%Sn and 10 mol%La. The prepared Sn and La co doped TiO₂ photo-catalyst showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of MO solution under visible irradiation. Antibacterial behavior towards E. coli was then studied under visible irradiation. The synthesized T-5%Sn-10%La powder exhibited superior antibacterial activity under visible irradiation compared to the pure TiO₂.     

Electrochemically induced Ti<Superscript>3+</Superscript> self-doping of TiO<Subscript>2</Subscript> nanotube arrays for improved photoelectrochemical water splitting

We report a facile electrochemical reduction method to synthesize Ti³⁺-self-doped TiO₂ nanotube arrays (TNTs), where the effects of reduction duration and potential on the photoelectrochemical performance were systematically investigated. The X-ray photoelectron spectroscopy and electron paramagnetic resonance spectra confirmed the presence of Ti³⁺ in the TNTs. Under the optimum reduction condition, the Ti³⁺-self-doped TNTs exhibited remarkably enhanced photocurrent density and photoconversion efficiency, which were nearly 3.1 and 1.75 times that of pristine TNTs, respectively. The enhancement of PEC performance is due to the improved electrical conductivity, accelerated charge transfer rate at the TNTs/electrolyte interface, as well as the improved visible light response, which is elucidated by electrochemical impedance spectra, Mott–Schottky, and UV–Vis diffuse reflection spectra.     

Synthesis of PANI/TiO<Subscript>2</Subscript>–Fe<Superscript>3+</Superscript> nanocomposite and its photocatalytic property

A convenient method for synthesizing highly photocatalytic activity PANI/TiO₂–Fe³⁺ nanocomposite was developed. The effect of calcination temperature on the phase composition of TiO₂ nanopowder was investigated. It was found that higher temperature could promote the formation of rutile phase. The nanocomposite was characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM), infrared spectroscopy (IR) and X-ray diffraction (XRD). The results indicated that the nanohybrid was composed of TiO₂, Fe³⁺ and PANI. The photocatalytic property of the nanocomposite was evaluated by the degradation of methyl orange. In the presence of this catalyst, the degradation rate of methyl orange of 95.2% and 70.3% could be obtained under the UV and sunlight irradiation within 30 min, respectively. The apparent rate constant was 5.64 × 10⁻² which is better than that of the Degussa P25.     

Synthesis and properties of AgTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based NASICON-type phosphates doped with Nb<Superscript>5+</Superscript>, Zr<Superscript>4+</Superscript>, and Ga<Superscript>3+</Superscript>

We have synthesized materials based on a silver titanium phosphate with partial substitution of tri-, tetra-, or pentavalent cations for titanium: Ag_1±x Ti_2−x M _x (PO₄)₃ (M = Nb⁵⁺, Ga³⁺) and AgTi_2−x Zr _x (PO₄)₃. The materials have been characterized by X-ray diffraction and impedance spectroscopy and have been shown to have small thermal expansion coefficients. Their ionic conductivity has been determined. Silver ions in these materials are difficult to replace with protons.     

Persistent luminescence of Zn<Subscript>2</Subscript>GeO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>/Pr<Superscript>3+</Superscript> phosphors

Zn₂GeO₄, Zn₂GeO₄:Mn²⁺, Zn₂GeO₄:Pr³⁺ and Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors were fabricated by a solid state reaction. The phase and luminescent properties of the fabricated phosphors were investigated. The XRD patterns show that all of the fabricated phosphors have an orthorhombic structure. The fabricated Zn₂GeO₄ shows an emission band in the range of 350–550 nm. The fabricated Zn₂GeO₄:Mn²⁺ and Zn₂GeO₄:Pr³⁺ phosphors show emission bands corresponding to Mn²⁺ and Pr³⁺ ions, respectively. The fabricated Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor shows the emission band results from Mn²⁺ and the codoped Pr³⁺ enhances the emission intensity of Mn²⁺. Moreover, Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor exhibits longer decay time than that of Zn₂GeO₄:Mn²⁺. The higher intensity and longer lifetime of Mn²⁺ emission are induced by the energy transfer from Pr³⁺ of various vacancies to Mn²⁺ in Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors.     

TiO<Subscript>2</Subscript> nanocrystals grown on graphene as advanced photocatalytic hybrid materials

A graphene/TiO₂ nanocrystals hybrid has been successfully prepared by directly growing TiO₂ nanocrystals on graphene oxide (GO) sheets. The direct growth of the nanocrystals on GO sheets was achieved by a two-step method, in which TiO₂ was first coated on GO sheets by hydrolysis and crystallized into anatase nanocrystals by hydrothermal treatment in the second step. Slow hydrolysis induced by the use of EtOH/H₂O mixed solvent and addition of H₂SO₄ facilitates the selective growth of TiO₂ on GO and suppresses growth of free TiO₂ in solution. The method offers easy access to the GO/TiO₂ nanocrystals hybrid with a uniform coating and strong interactions between TiO₂ and the underlying GO sheets. The strong coupling gives advanced hybrid materials with various applications including photocatalysis. The prepared graphene/TiO₂ nanocrystals hybrid has superior photocatalytic activity to other TiO₂ materials in the degradation of rhodamine B, showing an impressive three-fold photocatalytic enhancement over P25. It is expected that the hybrid material could also be promising for various other applications including lithium ion batteries, where strong electrical coupling to TiO₂ nanoparticles is essential.     

Strong up-conversion luminescence and electrical properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> multifunctional ceramics by Er<Superscript>3+</Superscript> doping

Novel green-emitting piezoelectric ceramics of SrBi_4?x Er _x Ti₄O₁₅ (SBT-xEr) were prepared. Strong up-conversion with bright green (524 and 548 nm) and a relatively weak red (660 nm) emission bands were obtained under 980 nm excitation at room temperature, which is attributed to the intra 4f–4f electronic transition of (²H_11/2, ⁴S_3/2)–⁴I_15/2 and the transition from ⁴F_9/2 to ⁴I_15/2 of Er³⁺ ions, respectively. Simultaneously, Er³⁺ doping promotes the electrical properties. At 0.8 mol%Er, the optimal electric properties with high Curie temperature of T _c?~527?°C, large remanent polarization of 2P _r?~14.92 μC/cm² and piezoelectric constant of d ₃₃?~17 pC/N was achieved. As a multifunctional material, Er³⁺ doped SBT showed a great potential to be used in 3D-display, bio-imaging, solid state laser and optical temperature sensor.     

Synthesis and luminescence properties of Eu<Superscript>2+</Superscript>-doped Li<Subscript>2</Subscript>SrSiO<Subscript>4</Subscript>

We have studied the luminescence spectra of Li₂Sr_{1 − x} Eu _x SiO₄ (x = 0.0001–0.01) solid solutions prepared by solid-state reactions and a sol-gel process in a reducing atmosphere. The spectra show a broad band in the range 500–700 nm, centered at 578 nm, which is due to the 4f ⁶5d → 4f ⁷ transition. The luminescence excitation spectrum shows, in addition to bands due to Eu²⁺ 4f ⁷ → 4f ⁶5d transitions, a strong band centered at 174 nm, attributable to absorption in the SiO₄⁴⁻ group.     

Phase conversion and spectral properties of long lasting phosphor Zn<Subscript>3</Subscript> (PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Mn<Superscript>2+</Superscript>, Ga<Superscript>3+</Superscript>

A red long lasting phosphor Zn₃(PO₄)₂:Mn²⁺,Ga³⁺ (ZPMG) was prepared by ceramic method, and phase conversion and spectral properties were investigated. Results indicated that the phase conversion from α-Zn₃(PO₄)₂, β-Zn₃(PO₄)₂ toγ-Zn₃(PO₄)₂ occurs with different manganese concentration incorporated and sinter process. The structural change induced by the phase transformation results in a remarkable difference in the spectral properties. The possible luminescence mechanism for this red LLP with different forms has been illustrated.     

Tunable luminescence properties and energy transfer of single-phase Ca<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>O: Dy<Superscript>3+</Superscript>, Eu<Superscript>2+</Superscript> multi-color phosphors for warm white light

The novel Ca_4?x(PO₄)₂O: xDy³⁺ and Ca_4?x?y(PO₄)₂O: xDy³⁺, yEu²⁺ multi-color phosphors were synthesized by traditional solid-state reaction. The crystal structure, particle morphology, photoluminescence properties and energy transfer process were investigated in detail. The X-ray diffraction (XRD) results demonstrate that the products showed pure monoclinic phase of Ca₄(PO₄)₂O when x < 0.1. The scanning electron microscopy (SEM) indicated that the phosphors were grain-like morphologies with diameters of ~ 3.7–7.0 μm. Under excitation of 345 nm, Dy³⁺-doped Ca₄(PO₄)₂O phosphors showed multi-color emission bands at 410, 481 and 580 nm originated from oxygen vacancies and Dy³⁺. Interestingly, Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors exhibited blue emission band at 481 nm and broad emission band from 530 to 670 nm covering green to red regions. The energy transfer process from Dy³⁺ to Eu²⁺ was observed for the co-doped samples, and the energy transfer efficiency reached to 60% when Eu²⁺ molar concentration was 8%. In particular, warm/cool/day white light with adjustable CCT (2800–6700 K) and high CRI (R_a > 85) can be obtained by changing the Eu²⁺ co-doping contents in Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors. The optimized Ca_3.952(PO₄)₂O: 0.04Dy³⁺, 0.008Eu²⁺ phosphor can achieve the typical white light with CCT of 4735 K and CRI of 87.     

Influence of Mn<Superscript>2+</Superscript> on the up-conversion emission performance of Mn<Superscript>2+</Superscript>, Yb<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>: ZnWO<Subscript>4</Subscript> green phosphors

The Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors are synthesized successfully through the high temperature solid state reaction method. The micro-structure and morphology have been investigated by means of XRD and EDS. The doped concentrations of Mn²⁺, Yb³⁺, Er³⁺ are measured by ICP. The absorption spectra and emission spectra with different doped concentrations of Mn²⁺ are presented to reveal the influence of Mn²⁺ on the green up-conversion performance. Excited with 970 nm LED, the up-conversion emission peak at 547 nm is obtained and the CIE spectra as well as the green light photo are also presented. The results indicate that the Mn²⁺ ions play the role of the luminescence adjustment in the up-conversion process, which can improve the up-conversion green emission intensity effectively. The luminescence adjustment mechanism of Mn²⁺ ions in Mn²⁺, Yb³⁺, Er³⁺: ZnWO₄ green phosphors has been discussed. The crystal parameters of Dq, B and C are calculated to evaluate the energy level split effect.     

Electrical Conductivity of Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> Crystals Doped with Ca<Superscript>2+</Superscript>, Pb<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, and Ba<Superscript>2+</Superscript>

Single crystals of Bi₂WO₆ (a layered perovskite-like compound) doped with Ca²⁺, Pb²⁺, Sr²⁺, and Ba²⁺ on the Bi³⁺ site are grown, and their oxygen ionic conductivity is measured along the polar axis. The intrinsic conductivity of the doped crystals differs insignificantly from the conductivity of undoped Bi₂WO₆, indicating that the oxygen ions in the Bi₂O₂ layers contribute little to the oxygen ionic conductivity of the crystals. The sharp change in the activation energy for conduction at 600°C attests to a transition from one conduction mechanism to another in going from low to high temperatures.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 863–865.Original Russian Text Copyright © 2005 by Kharitonova, Voronkova, Yanovskii.     

Synthesis and thermoluminescence properties of CdB<Subscript>4</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript> and CdB<Subscript>4</Subscript>O<Subscript>7</Subscript>:Mn<Superscript>2+</Superscript>

Polycrystalline samples of undoped, terbium-doped (CdB₄O₇:Tb³⁺), and manganese-doped (CdB₄O₇:Mn²⁺) cadmium tetraborate have been prepared by solid-state reactions at 850°C. Using differential scanning calorimetry and X-ray diffraction, we have determined the melting point of CdB₄O₇ (t _m = 976°C) and shown that this compound melts incongruently. The observed monotonic decrease in the orthorhombic cell parameters of the doped materials indicates the formation of substitutional solid solutions (sp. gr. Pbca). The thermoluminescence intensity of the doped materials has been shown to depend on the nature and concentration of the activators and the irradiation time.     

Morphology and luminescent properties of Al<Superscript>3+</Superscript>/Mg<Superscript>2+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Al³⁺/Mg²⁺ doped Y₂O₃:Eu phosphor was synthesized by the glycine-nitrate solution combustion method. In contrast to Y₂O₃:Eu which showed an irregular shape of agglomerated particles (the mean particle size >10 μm), the morphology of Al³⁺/Mg²⁺ doped Y₂O₃:Eu crystals was quite regular. Al³⁺/Mg²⁺ substituting Y³⁺ in Y₂O₃:Eu resulted in an obvious decrease of the particle size. Meanwhile, higher the Al³⁺/Mg²⁺ concentration, smaller the particle size. In particular, the introduction of Al³⁺ ion into Y₂O₃ lattice induced a remarkable increase of PL and CL intensity. While, for Mg²⁺ doped Y₂O₃:Eu samples, their PL and CL intensities decreased. The reason that causes the variation of PL and CL properties for Al³⁺ and Mg²⁺ doped Y₂O₃:Eu crystals was concluded to be related to sites of Al³⁺ and Mg²⁺ ions inclined to take and the difference of ion charge.     

Luminescent properties of Pb<Superscript>2+</Superscript>- and Mn<Superscript>2+</Superscript>-activated CdI<Subscript>2</Subscript> crystals

The luminescent properties of CdI₂, CdI₂:Pb²⁺, CdI₂:Mn²⁺, and CdI₂:Pb²⁺,Mn²⁺) crystals have been studied at temperatures from 85 to 295 K under optical and x-ray excitation. Analysis of new and earlier spectroscopic data suggests that the 560-nm luminescence of CdI₂:Pb²⁺ and CdI₂:(Pb²⁺,Mn²⁺) crystals under excitation on the long-wavelength component of the A absorption band of Pb²⁺ centers is due to Pb²⁺-bound anion excitons. The 640-to 660-nm emission of these crystals is attributable to α centers. The manganese luminescence in the codoped material originates from both intracenter Mn²⁺ excitations and a sensitized process due to energy transfer from the host and Pb²⁺-related centers. The mechanisms of recombination and energy transfer processes in cadmium iodide crystals codoped with Pb²⁺ and Mn²⁺ are discussed.     

Synthesis,structural characterization,and photocatalytic properties of iron-doped TiO<Subscript>2</Subscript> aerogels

Fe(III)-doped TiO₂ aerogels are prepared by acid catalyzed sol–gel method followed by supercritical drying, and then heat treatment. Raman spectra together with X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns of the iron-doped TiO₂ aerogel samples revealed the existence of both anatase and brookite crystalline phases. It was found that the brookite phase formation is favored by the increase of the iron content in the dried samples. XRD measurements show that the lattice constant c of anatase phase decreases with the dopant addition, while the value of a remains essentially unchanged. The microstructure of the investigated samples is relatively compact with small mesopores as revealed from transmission electron microscopy (TEM). The most enhanced photocatalytic activity was exhibited by the TiO₂ aerogel sample with 1.8 at.% Fe(III) whose apparent rate constant of the salicylic acid photodegradation was found to be of almost six times higher than that of Degussa P25.     

Structure and luminescent properties of Cs<Subscript>2</Subscript>Sr(VO<Subscript>3</Subscript>)<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>

We have developed a procedure for thermally stimulated synthesis of a cesium strontium metavanadate, Cs₂Sr(VO₃)₄:Mn²⁺ (0.01, 0.50, 1.00, 5.00 at % Mn²⁺), using MnO-containing starting mixtures. The EPR spectrum of the material containing 0.01 at % Mn²⁺ shows a hyperfine structure due to the incorporation of a small amount of manganese into the diamagnetic double metavanadate host. The luminescent and optical properties of Cs₂Sr(VO₃)₄:Mn²⁺ depend on manganese content. In contrast to higher doping levels, doping with 0.01 at % Mn²⁺ increases the integrated emission intensity of the vanadate by 10% and improves its chromaticity characteristics (approaching them to those of white light). We assume that this is due to the reduction in the density of vacancy-type growth defects, such as oxygen vacancies.     

Synthesis,structural, photoluminescence and mechanoluminescence properties of Tb<Superscript>3+</Superscript>: Ca<Subscript>2</Subscript>Gd<Subscript>2</Subscript>W<Subscript>3</Subscript>O<Subscript>14</Subscript> novel green nanophosphors

Novel green nanophosphors Ca₂Gd₂W₃O₁₄: Tb³⁺ were synthesized by solid state reaction method. From the X-ray diffraction profiles it is observed that Tb³⁺: Ca₂Gd₂W₃O₁₄ phosphors were crystallized in the form of tetragonal structure. The scanning electron microscopy (SEM) image shows that the particle size is at around 300 nm. In addition to these the prepared powder phosphors were also examined by the energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL) and mechanoluminescence (ML) spectra. Emission spectra of Tb³⁺: Ca₂Gd₂W₃O₁₄ nanophosphors have shown bright green emission at 545 nm (⁵D₄ → ⁷F₅) with an excitation wavelength λ_exci = 374 nm (⁷F₆ → ⁵G₆). ML spectra shows the radiation effect on the Ca₂Gd₂W₃O₁₄: Tb³⁺ nanophosphors and from that it was observed that these phosphors are very less sensitive for lower exposure.     

Synthesis and properties of laser-active liquids POCl<Subscript>3</Subscript>-SbCl<Subscript>5</Subscript>-<Superscript>235</Superscript>UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack>-Nd<Superscript>3+</Superscript>

The effect of the synthesis conditions on the properties of inorganic laser-active liquids POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ is considered. The kinetic dependences of the U(IV) content and decay time of the Nd³⁺ luminescence in POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions for various synthesis procedures at 380 K have been obtained. In POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions, nonradiative energy transfer Nd³⁺ → U⁴⁺ is observed, and quenching of the Nd³⁺ luminescence is described by the Stern-Volmer law: k _q = (6.4 ± 0.6) × 10⁵ l mol^?1 s^?1. Laser liquids POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ with neodymium concentration of up to 0.7 M, uranyl concentration of up to 0.1 M, and decay time of the Nd³⁺ luminescence of up to 220 μs have been prepared for the first time.     

Color-tunable luminescence properties of Sm<Superscript>3+</Superscript>/Dy<Superscript>3+</Superscript> co-doped NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> phosphors and their energy transfer mechanism

The Sm³⁺, Dy³⁺ doped and Sm³⁺/Dy³⁺ co-doped NaLa(MoO₄)₂ spherical phosphors were hydrothermally synthesized by the EDTA-2Na mediated method. Under the excitation of 297 nm, the quenching concentration of Sm³⁺ in NaLa(MoO₄)₂ host was determined to be 13%, and the concentration quenching mechanism was discussed to be the electric quadrupole–quadrupole interaction. After Sm³⁺ and Dy³⁺ ions were co-doped into the NaLa(MoO₄)₂ host, the energy transfer behaviors resulted from Dy³⁺ to Sm³⁺ ions were investigated by the help of the luminescent spectra of the obtained phosphors. By varying co-doping concentrations of Sm³⁺/Dy³⁺ ions, the emission color of NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ can be tuned from reddish-orange, pink and white to bluish-green. The CIE chromaticity coordinate, the correlated color temperature and the quantum efficiency of NaLa_0.87(MoO₄)₂:1%Sm³⁺, 12%Dy³⁺ were calculated to be (0.356, 0.320), 4353 K and 20%, respectively. Furthermore, in the temperature-dependent analysis, it presented good thermal stability, which can become a promising single-phased white-emitting phosphor for white LEDs devices. Based on these results, the possible energy transfer mechanism between Dy³⁺ and Sm³⁺ in NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ was also proposed.