Highly efficient photocatalytic activity and mechanism of novel Er3+ and Tb3+ co-doped BiOBr/ g-C3N5 towards sulfamethoxazole degradation

Bismuth oxyhalides (BiOX (X = Cl, Br, I) are considered to be an important p-type semiconductors in the photocatalysis applications. In particular, tetragonal BiOBr is considered as a stable photocatalyst due to its resilient absorption in the visible region with an band gap energy of 2.8 eV. In the meantime, lanthanide ions (with 3+ oxidation state) implies as conversion catalyst gained huge impact and remain a serious topic in materials chemistry. Here we synthesized upconversion photocatalyst mainly consists of BiOBr with the Er ³⁺ and Tb ³⁺ ions along with low band gap g-C₃N₅ for the improved photocatalytic performances. The synthesized Er³⁺/Tb³⁺@BiOBr-g-C₃N₅ heterojunction was systematically characterized by XRD, and FT-IR for the confirmation of the composite and their morphology were analysed with FESEM and HR-TEM analysis which revealed that the sheets of g-C₃N₅ were decorated by Er³⁺/Tb³⁺ loaded BiOBr microspheres. The XPS analysis confirmed the suitable oxidation state of all the individual elements existing in the composite. As the UV-DRS analysis showed that the band gap of the Er³⁺/Tb³⁺ BiOBr-gC₃N₅ heterojunction was narrowed to 2.64 eV. To evaluate the photocatalytic efficiency of the synthesized g-C₃N₅, Er³⁺/Tb³⁺@BiOBr and Er³⁺/Tb³⁺@BiOBr-gC₃N₅ heterojunction under the simulated visible light irradiation source towards the aqueous sulfamethoxazole degradation. The Er³⁺/Tb³⁺@BiOBr-gC₃N₅ heterojunction shows maximum degradation efficiency of 94.2% after 60 min of visible light irradiation whereas the pure g-C₃N₅ provided about 43.8% and Er³⁺/Tb³⁺@BiOBr implies 55.2% degradation efficiency. The plausible degradation mechanism of pollutant removal was proposed.     

Effect of silica coating on the structural and luminescent properties of Sm3+/Yb3+ or Tm3+/Yb3+ co-doped TiO2 nanoparticles

The luminescent characteristics of spherical titanium dioxide (TiO₂) nanoparticles (NP's) doped with Sm³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ with and without a silica coating were analyzed. These nanoparticles were synthesized using the spray pyrolysis technique and coated with silica through a wet chemical process. The Sm³⁺/Tm³⁺ and Yb³⁺ doping induces a triphasic poly-crystalline structure of rutile and anatase TiO₂ and a Sm₂Ti₂O₇/Tm₂Ti₂O₇ cubic phase. A Williamson-Hall analysis was used to monitor the tensions of the NP's crystallites at the various doping concentrations and with addition of the silica shell. The luminescent spectra presented the characteristic emission peaks for the electronic energy levels transitions of the Sm³⁺/Tm³⁺ and Yb³⁺ ions. The Sm³⁺/Yb³⁺ co-doped NP's showed a maximum emission peak in the visible region at 612 nm, associated with ⁴G_5/2 → ⁶H_7/2 transitions of the Sm³⁺ ions. The IR emission peak at 973 nm (²F_5/2 → ²F_7/2) pertaining to Yb³⁺. For the combination of Tm³⁺/Yb³⁺, two emissions associated with Tm³⁺ ions were observed at 440 nm (¹D₂ → ³F₄) and 806 nm (³H₄ → ³H₆). The emission at 973 nm (²F_5/2 → ²F_7/2) is correlated to the Yb³⁺ ions. Silica coating of the NP's resulted in luminescence emission intensity increase of about 4 times.     

Difference in the Nature of Eu3+ Environment in Eu3+‐Doped BaTiO3 and BaSnO3

BaTiO₃ and BaSnO₃ samples doped with Eu³⁺ ions were prepared using glycine‐nitrate gel combustion method. Relative intensities and line shapes of magnetic dipole allowed ⁵D₀ → ⁷F₁ and electric dipole allowed ⁵D₀ → ⁷F₂ transitions of Eu³⁺ from the hosts, BaTiO₃ and BaSnO₃, are significantly different. Based on detailed structural investigations, it is confirmed that synthesizedBaTiO₃ sample is tetragonal with no center of symmetry around Ba²⁺ ions. Unlike this BaSnO₃ is cubic with centrosymmetric Ba²⁺ site. From X‐ray diffraction and experimentally obtained Judd–Ofelt parameters (Ω₂ and Ω₄ values), it is confirmed that in BaTiO₃ there is a decrease in the average Ba–O and Ba–Ba distances compared with that in BaSnO₃. This leads to higher Eu–O bond polarizability and adds to the distortion in its environment around Eu³⁺ in BaTiO₃:Eu compared with BaSnO₃:Eu. This is responsible for the observed difference in the luminescence properties.     

Bright White‐Emitting Phosphors Ba2Gd(BO3)2Cl: Dy3+/Dy3+‐Tm3+ for Hg‐Free Lamps and White LEDs Applications

Spectroscopic properties of Ba₂Gd(BO₃)₂Cl: Dy³⁺ and Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ under vacuum ultraviolet (VUV) and ultraviolet (UV) light excitations were investigated. Dy³⁺ single‐doped Ba₂Gd(BO₃)₂Cl showed broad absorption band in the VUV region, and bright warm white light with chromaticity coordinates (CIE) of (0.340, 0.381) upon VUV excitation at 172 nm, demonstrating this phosphor's applicability in mercury free lamps. Upon direct excitation Tm³⁺ from its ⁶F₆ level to ¹D₂ level, the decrease of emission intensity and lifetime of Tm^{3+ 1}D₂–³F₄ emission with increasing concentration of Dy³⁺ in Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ confirmed the occurrence of energy transfer from Tm³⁺ to Dy³⁺. In addition, Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ could be efficiently excited by 358 nm UV light and its emission color could be tuned from blue to yellow by codoping Tm³⁺. When 1% Tm³⁺ and 5% Dy³⁺ were codoped in the Ba₂Gd(BO₃)₂Cl, intensive white‐emitting light with CIE of (0.352, 0.328) and correlated color temperature of 4589 K was achieved upon 358 nm excitation, revealing the potential application of Ba₂Gd(BO₃)₂Cl: Dy³⁺, Tm³⁺ for white light‐emitting diodes (LEDs).     

Synthesis and photoluminescence enhancement of Ca3Sr3(VO4)4:Eu3+ red phosphors by co-doping with La3+

In this study, a series of red-emitting Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphors co-doped with La³⁺ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca₃Sr₃(VO₄)₄. Furthermore, the Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the ⁷F₀→⁵D₂ electron transition of Eu³⁺. The strong emission peak observed at 619 nm corresponded to the ⁵D₀→⁷F₂ electron transition of Eu³⁺. Co-doping with La³⁺ significantly improved the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺ red phosphors. The optimum luminescence of the phosphor was observed at Eu³⁺ and La³⁺ concentrations of 5% and 6%, respectively. Moreover, co-doping with La³⁺ also improved the fluorescence lifetime and thermal stability of the Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphor. The CIE chromaticity coordinate of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ at 619 nm was ~1.53 times that of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺ and 2.63 times that of SrS:Eu²⁺. The introduction of charge compensators could further increase the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.     

Influence of Bi3+ as a sensitizer and SiO2 shell coating as a protecting layer towards the enhancement of red emission in LnVO4: Bi3+, Eu3+ @ SiO2 (Ln=Gd,Y and Gd/Y) powder phosphors for optical display devices

Enhanced red luminescence in LnVO₄: Bi³⁺, Eu³⁺ @ SiO₂ phosphors has been improved mainly in three stages by investigating the effects of: (i) host composition (Gd, Y and Gd/Y), (ii) co-doping Bi³⁺ as a sensitizer and finally (iii) SiO₂ shell coating. XRD data revealed that the produced phosphors possess crystalline, pure phase with tetragonal structure. Silica coating on phosphor particles have been characterized by SEM/EDAX, TEM, PL and with the presence Si–O–Si, Si–O vibrational modes from the FT-IR spectra. Absorption band edges due to VO₄^3?, shifted to higher wavelength with Bi-concentration, owing to the presence of Bi–O bond in addition to V–O. The emission intensities of ⁵D₀→⁷F₂ transition are stronger than ⁵D₀→⁷F₁; indicating the lower inversion symmetry near Eu³⁺, ions. Red emission intensity due to the efficient energy transfer from VO₄^3? to Eu³⁺ via Bi³⁺ ions in Y_0.949VO₄: Bi³⁺_0.001, Eu³⁺_0.05 phosphor was improved significantly, i.e. 1.6 times compared to Y_0.95VO₄: Eu³⁺_0.05. This was further enhanced 2.25 times by SiO₂ shell coating. Thus, Y_0.949VO₄: Bi³⁺_0.001, Eu³⁺_0.05 @ SiO₂ are suggested to be a promising red phosphor for application in display devices or lighting.     

Preparation,Structure, and Up‐Conversion Luminescence of Yb3+/Er3+ Codoped SrIn2O4 Phosphors

SrIn₂O₄, which shows lower phonon energy than CaIn₂O₄, is not only a good photocatalyst but also can be an excellent up‐conversion (UC) host to exhibits UC luminescence. In this work, Yb³⁺ and/or Er³⁺ doped SrIn₂O₄ phosphors were synthesized, and their UC luminescence properties were studied and compared with those in the CaIn₂O₄ host. The structure of SrIn₂O₄: 0.01Er³⁺ and SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ samples were refined by the Rietveld method and found to that SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ showed increasing unit cell parameters and cell volume, indicating In³⁺ sites were substituted successfully by Yb³⁺ and/or Er³⁺ ions. From the UC luminescence spectra and diffuse reflection spectra, Er³⁺‐doped SrIn₂O₄ showed very weak luminescence due to ground state absorption of Er³⁺; Yb³⁺/Er³⁺ codoped SrIn₂O₄ presented strong green (550 nm) and red (663 nm) UC emissions which were assigned to energy transfer from Yb³⁺ transition ²F_7/2→²F_5/2 to the Er³⁺ transition ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2. Comparing with CaIn₂O₄, Yb³⁺/Er³⁺ codoped SrIn₂O₄ showed obvious advantages with higher UC luminescent intensity. The pumping powers study showed that UC emissions in Yb³⁺/Er³⁺ codoped SrIn₂O₄ were attributed to energy transfer of Yb³⁺→Er³⁺ with a two‐photon process. The possible UC luminescent mechanism of Yb³⁺/Er³⁺‐doped SrIn₂O₄ was discussed.     

Lu3+/Yb3+ and Lu3+/Er3+ co-doped antimony selenide nanomaterials: synthesis,characterization, and electrical,thermoelectrical, and optical properties

Lu³⁺/Yb³⁺ and Lu³⁺/Er³⁺ co-doped Sb₂Se₃ nanomaterials were synthesized by co-reduction method in hydrothermal condition. Powder X-ray diffraction patterns indicate that the Ln_xLn^′_xSb_2−2xSe₃ Ln: Lu³⁺/Yb³⁺ and Lu³⁺/Er³⁺ crystals (x = 0.00 − 0.04) are isostructural with Sb₂Se₃. The cell parameters were increased for compounds upon increasing the dopant content (x). Scanning electron microscopy and transmission electron microscopy images show that co-doping of Lu³⁺/Yb³⁺ ions in the lattice of Sb₂Se₃ produces nanorods, while that in Lu³⁺/Er³⁺ produces nanoparticles, respectively. The electrical conductivity of co-doped Sb₂Se₃ is higher than that of the pure Sb₂Se₃ and increases with temperature. By increasing the concentration of Ln³⁺ions, the absorption spectrum of Sb₂Se₃ shows red shifts and some intensity changes. In addition to the characteristic red emission peaks of Sb₂Se₃, emission spectra of co-doped materials show other emission bands originating from f-f transitions of the Yb³⁺ ions.     

Control of Oxidation State of Eu Ions in Na2O–Al2O3–SiO2 Glasses

Glasses doped with well‐controlled Eu³⁺ and Eu²⁺ ions have attracted considerable interest due to the possibility of tuning the wavelength range of the emitted light from violet to red by using their ⁵D₀→⁷F_j and 5d–4f electron transitions. Glasses were prepared to dope Eu³⁺ ions in a Na₂O–Al₂O₃–SiO₂ system, and the changes in the valence state of Eu³⁺ ions and the glass structure surrounding the Eu atoms during heating under H₂ atmosphere were investigated using fluorescence spectroscopy, X‐ray absorption fine‐structure spectroscopy, and ²⁷Al magic‐angle spinning solid‐state nuclear magnetic resonance spectroscopy. The reduction behavior of Eu³⁺ ions was dependent on the Al/Na molar ratio of the glass. For Al/Na < 1, the Al³⁺ ions formed the AlO₄ network structure accompanied by the Na⁺ ions as charge compensators; the Eu³⁺ ions occupied the interstitial positions in the SiO₄ network structure and were not reduced even under heating in H₂ gas. On the other hand, in the glasses containing Al₂O₃ with the Al/Na ratio exceeding unity, the Eu³⁺ ions commenced to be coordinated by the AlO₄ units in addition to the SiO₄ network structure. When heated in H₂ gas, H₂ gas molecules reacted with the AlO₄ units surrounding Eu³⁺ ions to form AlO₆ units terminated with OH bonds, and reduced Eu³⁺ ions to Eu²⁺ via the extracted electrons.     

Synthesis and photoluminescence properties of Eu2+/Eu3+ or Ce3+/Eu3+ co-doped Sr5(BO3)3F compounds

The synthesis and photo-luminescence properties of Eu²⁺/Eu³⁺ or Ce³⁺/Eu³⁺ co-doped Sr₅(BO₃)₃F compounds are reported. Using the Sr₅(BO₃)₃F as the host, through the solid state reaction under the reductive atmosphere, Eu²⁺/Eu³⁺ and Ce³⁺/Eu³⁺co-doped samples were prepared. These compounds exhibit good photo-luminescence properties. Under the excitation of 376 nm, an unusual red orange emission coming from the Eu²⁺ ions can be obtained in Eu ions doped Sr₅(BO₃)₃F, which exhibits a broadband emission in the range of 450–800 nm with the peak at around 600 nm. At the same time, the characteristic f-f excitation and emission of Eu³⁺ can improve and adjust the Eu²⁺ emission in Eu³⁺/Eu²⁺ codoped Sr₅(BO₃)₃F. In addition, the adjustable luminescence properties from blue to white of Sr₅(BO₃)₃F:Ce³⁺, Eu³⁺ are investigated. The energy transfer behavior from Ce³⁺ to Eu³⁺ was confirmed. In the spectra of the co-doped samples, we can hardly observe the characteristic peak of Eu²⁺, because Ce⁴⁺ can oxidize Eu²⁺ to Eu³⁺, and Ce⁴⁺ itself is reduced to Ce³⁺. The CIE coordinates from (0.2758, 0.2420) to (0.3857, 0.3015) show Sr₅(BO₃)₃F:3%Ce³⁺, x%Eu³⁺ (x = 1,3,5,7,9) are in the white light emission region. All results demonstrate that the Sr₅(BO₃)₃F:Eu³⁺/Eu²⁺ and Sr₅(BO₃)₃F:Ce³⁺/Eu³⁺ phosphors have good application prospects for LED plant growth and white LED, respectively. The bond energy method was used to explain the reason why the Eu²⁺/Eu³⁺ ion instead of only Eu²⁺ and Ce³⁺/Eu³⁺ instead of Ce³⁺/Eu³⁺/Eu²⁺ can exist in the host Sr₅(BO₃)₃F. The theoretical analysis agree well with the experimental result.     

Simultaneous sulfide and acetate oxidation under denitrifying conditions using an inverse fluidized bed reactor

BACKGROUND: Simultaneous removal of sulfur, nitrogen and carbon compounds from wastewaters is a commercially important biological process. The objective was to evaluate the influence of the CH₃COO^?/NO₃^? molar ratio on the sulfide oxidation process using an inverse fluidized bed reactor (IFBR). RESULTS: Three molar ratios of CH₃COO^?/NO₃^? (0.85, 0.72 and 0.62) with a constant S^2?/NO₃^? molar ratio of 0.13 were evaluated. At a CH₃COO^?/NO₃^? molar ratio of 0.85, the nitrate, acetate and sulfide removal efficiencies were approximately 100%. The N₂ yield (g N₂ g^?1 NO₃^?‐N consumed) was 0.81. Acetate was mineralized, resulting in a yield of 0.65 g inorganic‐C g^?1 CH₃COO^?‐C consumed. Sulfide was partially oxidized to S⁰, and 71% of the S^2? consumed was recovered as elemental sulfur by a settler installed in the IFBR. At a CH₃COO^?/NO₃^? molar ratio of 0.72, the efficiencies of nitrate, acetate and sulfide consumption were of 100%, with N₂ and inorganic‐C yields of 0.84 and 0.69, respectively. The sulfide was recovered as sulfate instead of S⁰, with a yield of 0.92 g SO₄^2?‐S g^?1 S^2? consumed. CONCLUSIONS: The CH₃COO^?/NO₃^? molar ratio was shown to be an important parameter that can be used to control the fate of sulfide oxidation to either S⁰ or sulfate. In this study, the potential of denitrification for the simultaneous removal of organic matter, sulfide and nitrate from wastewaters was demonstrated, obtaining CO₂, S⁰ and N₂ as the major end products. Copyright © 2008 Society of Chemical Industry     

Conversion of two-micron radiation into visible light using glass and ceramics based on ZBLAN: Но<Superscript>3+</Superscript> and ZBLAN: Ho<Superscript>3+</Superscript> + Yb<Superscript>3+</Superscript>

Visualization of infrared radiation of Tm:YLF-laser at the wavelength of 1908 nm has been investigated in the glass and ceramics samples with compositions of 53ZrF₄ · 20 BaF₂ · 1HoF₃ · 3YbF₃ · 3AlF₃ · 20NaF and 53ZrF₄ · 20BaF₂ · 3LaF₃ · 1HoF₃ · 3AlF₃ · 20NaF (mol %). In luminescence spectra of ZBLAN samples doped with Но³⁺, the bands at the wavelengths of 480, 540, and 650 nm were observed, which correspond to ⁵ F ₃ → ⁵ I ₈, ⁵ S ₂, ⁵ F ₄ → ⁵ I ₈, and ⁵ F ₅ → ⁵ I ₈ electron transitions in Но³⁺ ions with the maximum intensity of the red band (650 nm). Occupancy of the ⁵ S ₂ and ⁵ F ₄ levels in the ZBLAN: 1% Но³⁺ samples is related to the sequential absorption of the exciting radiation quanta. The level of ⁵ F ₅ is filled mainly due to the ionic interaction. Additional doping with the Yb³⁺ ions led to the change of the luminescence color to green and a decrease in the threshold radiation power density of the Tm:YLF-laser in ceramic samples up to 2 W/cm².     

Luminescence and Quantum Efficiencies of Eu3+‐Doped Vanadate Garnets

Nondoped and 5.0 mol% Eu³⁺‐doped vanadate garnets Ca₅Mg₄(VO₄)₆, NaCa₂Mg₂[VO₄]₃, KCa₂Mg₂[VO₄]₃, and NaSr₂Mg₂[VO₄]₃ were synthesized by solid‐state reactions. The formation of single‐phase compound with garnet structure is confirmed by X‐ray diffraction. The photoluminescence (PL) and PL excitation (PLE) spectra are investigated together with color coordinates. The luminescence process is discussed on the charge‐transfer transitions in [VO₄]^3? ions and the crystal structure. The PL quantum efficiencies (QE) are measured for nondoped and Eu³⁺‐doped samples. The Eu³⁺‐doped samples have higher QEs than the corresponding nondoped ones although the energy transfer occurs from [VO₄]^3? to Eu³⁺. Broad emission band due to [VO₄]^3? with intense sharp lines due to Eu³⁺, which gives white color, is observed in Eu³⁺‐doped NaCa₂Mg₂[VO₄]₃ and NaSr₂Mg₂[VO₄]₃ under excitation with UV light. These materials are suggested to be useful for lighting under the excitation with near‐UV LED.     

Synthesis and characterization of monodispersed BaSO4/Y2O3:Eu3+ core–shell submicrospheres

Spherical BaSO₄ particles have been coated with Y₂O₃:Eu³⁺ phosphor layers (BaSO₄/Y₂O₃:Eu³⁺) by the wet chemical method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dipersive spectroscopy (EDS), photoluminescence spectra were utilized to characterize the BaSO₄/Y₂O₃:Eu³⁺ core–shell-structured phosphor particles. The obtained core–shell phosphors consist of well dispersed submicron spherical particles with narrow size distribution. XRD result shows that no reaction occurred between the BaSO₄ cores and the Y₂O₃:Eu³⁺ shells even after annealing at 1400 °C. TEM and EDS results show that BaSO₄ particles are well coated with the shell of Y₂O₃:Eu³⁺. The BaSO₄/Y₂O₃:Eu³⁺ core–shell particles show a red emission corresponding to ⁵D₀?⁷F₂ of Eu³⁺ under the excitation of ultraviolet.     

White‐emitting phosphor Ba2B2O5:Ce3+, Tb3+, Sm3+: Luminescence,energy transfer,and thermal stability

A series of Ba₂B₂O₅: RE (RE=Ce³⁺/Tb³⁺/Sm³⁺) phosphors were synthesized using high‐temperature solid‐state reaction. The X‐ray diffraction (XRD), luminescent properties, and decay lifetimes are utilized to characterize the properties of the phosphors. The obtained phosphors can emit blue, green, and orange‐red light when single‐doped Ce³⁺, Tb³⁺, and Sm³⁺. The energy can transfer from Ce³⁺ to Tb³⁺ and Tb³⁺ to Sm³⁺ in Ba₂B₂O₅, but not from Ce³⁺ to Sm³⁺ in Ce³⁺ and Sm³⁺ codoped in Ba₂B₂O₅. However, the energy can transfer from Ce³⁺ to Sm³⁺ through the bridge role of Tb³⁺. We obtain white emission based on energy transfer of Ce³⁺→Tb³⁺→Sm³⁺ ions. These results reveal that Ce³⁺/Tb³⁺/Sm³⁺ can interact with each other in Ba₂B₂O₅, and Ba₂B₂O₅ may be a potential candidate host for white‐light‐emitting phosphors.     

Photoluminescence Properties of Color‐Tunable Ca3La6(SiO4)6: Ce3+, Tb3+ Phosphors

A series of newly developed color‐tunable Ca₃La₆(SiO₄)₆: Ce³⁺, Tb³⁺ phosphors were successfully prepared in this study. The crystal structures of the prepared phosphors were revealed to be hexagonal with space group P6₃/m, and the lattice parameters were evaluated via utilizing the Rietveld refinement method. Upon excitation at 288 nm, the emission spectra of Ce³⁺and Tb³⁺ ions co‐doped Ca₃La₆(SiO₄)₆ phosphors included a blue emission band and several emission lines. The blue emission band with a peak at 420 nm originated in the f–d transitions of Ce³⁺ ions, and the emission lines in the range of 450–650 nm were assigned to the ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions of Tb³⁺ ions. Increasing the doping content of Tb³⁺ ions considerably strengthened Tb³⁺ emission and reduced Ce³⁺ emission owing to the energy transfer from Ce³⁺ to Tb³⁺ ions. The mechanism of the energy transfer was confirmed to be a dipole–dipole interaction. The effective energy transfer from Ce³⁺ to Tb³⁺ ions caused a color shift from purplish‐blue to yellowish‐green. Color‐tunable Ca₃La₆(SiO₄)₆: Ce³⁺, Tb³⁺ phosphors have the potential to be utilized in light‐emitting diodes with proper modulation of the amount of Tb³⁺ ions.     

A broadband-sensitive upconverter: Garnet-type Ca3Ga2Ge3O12 codoped with Er3+, Y3+, Li+, Ni2+, and Nb5+

We have developed a new broadband-sensitive photon upconversion (UC) material that can be used for transparent ceramic plates mounted on the rear faces of crystalline silicon solar cells. We selected the host material of a cubic crystal structure codoped with Er³⁺ and Ni²⁺ so that the Ni²⁺ dopants were fully activated to sensitize the Er³⁺ emitters. In garnet-type Ca₃Ga₂Ge₃O₁₂ with additional codopants of Nb⁵⁺ and Li⁺ for charge compensation, all the Ni²⁺ dopants occupied the six-coordinated Ga³⁺ sites, leading to highly efficient energy transfer from the Ni²⁺ to the Er³⁺. Formation of four-coordinated Ni²⁺ that quenches the UC emission of the Er³⁺ was prevented, because Ni²⁺ cannot substitute the four-coordinated Ge⁴⁺ much smaller than Ni²⁺. Consequently, energy dissipation from the Er³⁺ to the Ni²⁺ was well reduced compared with the previously developed Gd₃Ga₅O₁₂:Er,Ni,Nb in which the Ni²⁺ dopants partially occupied the four-coordinated Ga³⁺ sites. Additional introduction of Y³⁺ and Li⁺ enhanced optical transitions and improved the UC performance, owing to more enhanced lattice distortion, along with eliminating different phases. The optimal composition (Ca_0.6Er_0.1Y_0.1Li_0.2)₃(Ga_0.98Ni_0.01Nb_0.01)₂Ge₃O₁₂ exhibited a broadband sensitivity ranging from 1.1 μm (the absorption edge of silicon) to 1.6 μm for the UC emission at 0.98 μm.     

Role of Li+ ion in improved crystallization and the luminescence enhancement of up and down conversion process in Er3+/Yb3+ doped in Y4O(OH)9NO3 and Y2O3 nanoparticles

Here, the up-and down-conversion emissions enhancement in Er³⁺/Yb³⁺/Li⁺ co-doped Y₄O(OH)₉NO₃ and Y₂O₃ nanoparticles was studied in function of the calcination temperature. Tri-doped Y₄O(OH)₉NO₃ nanophosphors were synthesized by the hydrothermal method and then calcined to yield Y₂O₃ nanocrystalline structures. The phase evolution from Y₄O(OH)₉NO₃ to Y₂O₃ was investigated by XRD analysis, and the quantification of Li ⁺ species in the nanoparticles lattice was done by FTIR. Both techniques allow explaining the photoluminescence enhancement in terms of the calcination temperature required to achieve optimum lithium incorporation. SEM analysis was used to monitor changes in the morphology with the thermal treatment temperature. The resulting photoluminescence emission spectra of the Er³⁺/Yb³⁺ doped Y₄O(OH)₉NO₃ and Y₂O₃ nanocrystals were composed of emission bands associated with the Er^{3+ 2}H_11/2, ⁴S_3/2 → ⁴I_15/2 (green), ⁴F_9/2 → ⁴I_15/2 (red), and ⁴I_13/2 → ⁴I_15/2 (infrared) intraelectronic transitions, and its relative contribution was found to be sensitive to the calcination temperature. Thus, tunable color emission from yellowish-orange to yellow-green light with a color temperature of 2581–4433 K upon 980 nm excitation, respectively, was observed.     

Preparation of environmentally friendly high-emissivity Ca2+-Fe3+ co-doped LaAlO3 ceramic

Ca²⁺-Cr³⁺ co-doped LaAlO₃ is an excellent ceramic material with high emissivity; however, it is harmful to the environment because of the presence of Cr³⁺ ions. In this study, Ca²⁺-Fe³⁺ co-doped LaAlO₃ ceramic materials were successfully prepared via a high-temperature solid-state reaction. The emissivity of Ca²⁺-Fe³⁺ co-doped LaAlO₃ was 0.91, which is approximately equal to that of Ca²⁺-Cr³⁺ co-doped LaAlO₃. To compensate for the lack of data on the thermophysical properties of doped LaAlO₃ high-emissivity ceramics, the thermal expansion coefficients and thermal conductivities of LaAlO₃ doped with Ca²⁺-Fe³⁺ or Ca²⁺-Cr³⁺ were investigated. The thermal conductivities of La_0.9Ca_0.1Al_0.9Fe_0.1O₃ and La_0.9Ca_0.1Al_0.9Cr_0.1O₃ at 1200°C were 3.802 and 3.707 W·m⁻¹·K⁻¹, respectively. The thermal expansion coefficients of La_0.9Ca_0.1Al_0.9Fe_0.1O₃ and La_0.9Ca_0.1Al_0.9Cr_0.1O₃ at 1200°C were 11.49×10⁻⁶ and 11.41×10⁻⁶ K⁻¹, respectively. These results indicate that Ca²⁺-Fe³⁺ co-doped LaAlO₃ exhibits great potential as a new generation of environmentally friendly near-infrared radiating materials in the field of energy efficiency.     

Enhanced photocatalytic activity of La1-xSrxCoO3/Ag3PO4 induced by the synergistic effect of doping and heterojunction

This study sought to design and synthesize a series of perovskite-based La_1-xSr_xCoO₃/Ag₃PO₄ (with x = 0–1) heterojunction photocatalysts with different Strontium (Sr) doping contents by a simple sol-gel method and properties of the material were comprehensively characterized. Moreover, tetracycline (TC) was chosen as the target pollutant to assess the effect of Sr doping on the catalytic performance of LaCoO₃/Ag₃PO₄. Our results demonstrated that the partial replacement of La³⁺ with Sr²⁺ coupled with shifting Co³⁺ to the mixed-valence state of Co³⁺-Co⁴⁺ led to the formation of substantially more oxygen vacancies in the crystal lattice of La_1-xSr_xCoO₃/Ag₃PO₄. Therefore, the doped catalyst La_1-xSr_xCoO₃/Ag₃PO₄ exhibited enhanced photocatalytic performance. When x = 0.9, the obtained La_0·1Sr_0·9CoO₃/Ag₃PO₄ exhibit an optimal performance for TC degradation. Kinetic analyses demonstrated that the degradation rate constant of TC in La_0·1Sr_0·9CoO₃/Ag₃PO₄ system was 0.0098 min^?1, which is 1.78 times that of LaCoO₃/Ag₃PO₄, and 2.45 times that of SrCoO₃/Ag₃PO₄. Additionally, free radical sequestration experiments indicated that OH^?, h⁺, and O₂^?? all participated in the degradation of TC in the following order: h⁺>O₂^??>OH^?. Finally, analyses of photocatalytic mechanisms suggested that the enhanced photocatalytic activity of La_0·1Sr_0·9CoO₃/Ag₃PO₄ was due to its strong electron transfer properties and the formation of substantially more surface oxygen vacancies in Sr-doped La_0·1Sr_0·9CoO₃.