A stable and efficient La-doped MIL-53(Al)/ZnO photocatalyst for sulfamethazine degradation

Photocatalytic technology can solve various environmental pollution problems, especially antibiotic pollution. A novel La-doped MIL-53(Al)/ZnO composite material was successfully synthesized by a combination of hydrothermal method and calcination, showing high photocatalytic degradation percent of sulfamethazine (SMT). The 2 mol% La MIL-53(Al)/ZnO photocatalyst shows the highest degradation efficiency toward SMT (92%) within 120 min, which is 4.1 times higher than pure ZnO (increased from 18% to 92%). In addition, the degradation analysis of SMT by high performance liquid chromatography proves that the products are CO₂ and H₂O. The improved photocatalytic activity is mostly caused by the following factors. (1) Doping La ions can decrease the band gap of ZnO, enhance light response, and effectively enhance the separation rate of photo-generated holes and electrons. (2) MIL-53(Al) can adsorb SMT and promote the separation of electron. This work shows that the synthesized La-doped MIL-53(Al)/ZnO photocatalyst is expected to be used as a green and effective method for treatment of environment water pollution.     

Synthesis of yttrium and cerium doped ZnO nanoparticles as highly inexpensive and stable photocatalysts for hydrogen evolution

Yttrium and cerium co-doped ZnO nanoparticles were synthesized by combustion route and characterized using X-ray diffraction(XRD),scanning electron microscopy(SEM),Brunauer-Emmett-Teller(BET),energy dispersive spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS),UV-visible diffuse reflectance spectroscopy(UV-vis DRS),photoluminescence(PL)and electrochemical impedance spectroscopy(EIS)techniques.The introduction of yttrium ions has efficiently increased the relative percentage of Ce³⁺ions in ZnO.Yttrium and cerium co-doped ZnO shows efficient photo activity for hydrogen evolution(10.61 mmol/((g·h))higher than previously reported optimal value for rare earth codoped ZnO photocatalysts.This remarkably increased hydrogen evolution can be ascribed to the synergy between electronic anchoring effect of Y³⁺/Y²⁺and Ce⁴⁺/Ce³⁺redox couples.This report presents new idea for the synthesis of efficient photocatalyst using economical route and ion anchoring effect.The hydrogen evolution was also tested using Na₂S and Na₂SO₃as electron donors under visible light illumination.The synthesized photocatalysts also exhibit high stability.     

Enhanced photodegradation activity of ZnO:Eu~(3+)and ZnO:Eu~(3+)@Au 3D hierarchical structures

In this work the flower-like hierarchical structures(HS) based on 3 D pristine ZnO,ZnO:Eu~(3+)and ZnO:Eu~(3+)@Au were successfully obtained by a template-free solvothermal and deposition-precipitation method.The decolorization/photodegradation of these structures towards model organic dye(rhodamine 6 G) was studied.The synthesized ZnO-based HS were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),UV-vis and photoluminescence(PL) spectroscopies.The proposed synthesis approaches allow to obtain highly crystalline 3 D ZnO,ZnO:Eu~(3+) and ZnO:Eu~(3+)@Au composites.Results of scanning microscopy show that ZnO flower-like HS are assemblies from smaller components,forming larger ones,the whole ZnO structure was approximately 3 μm.Au nanoparticles(size～10 nm)are successfully deposited on ZnO HS surface.Luminescent studies show that ZnO is an ideal matrix for incorporation of Eu~(3+)ions in broad concentration range(Eu~(3+)=1.0 at%-5.0 at%) with an efficient red luminescence.The strong UV emission in ZnO,as well as ZnO;Eu~(3+)HS is observed under 325 nm excitation.Doping of ZnO HS matrix by Eu~(3+)ions leads to the red shift of deep level emission peak(DLE).The PL intensity reaches the maximum up to 5 at% Eu~(3+).The photocatalytic properties of ZnO and ZnO:Eu~(3+)@Au HS were investigated under UV-Vis light irradiation towards rhodamine 6 G.The obtained results demonstrate the synergetic effect of the deposited gold nanoparticles and Eu~(3+)doping on photocatalytic activity of ZnO:Eu~(3+)@Au HS in comparison to pristine ZnO and ZnO:Eu~(3+)HS.     

La-doped SnO2 synthesis and its electrochemical property

Tin dioxide (SnO₂) and La-doped (1%, 5%, 10% in mass ratio) SnO₂ samples were prepared via a hydrothermal method. The as-prepared powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results showed that the particle size of SnO₂ decreased gradually with the increase of the doped La element. When used as anode materials of Li ion battery, the La-doped samples exhibited better cycling performance than the pure SnO₂, and the cycling performance of the La-doped samples got better and better with the increase of the doped La. The better electrochemical performance of the doped material could be attributed to the doping of La element, which not only enabled SnO₂ powders to have a good dispersivity but also reduced their particle size.     

Aluminium and cerium co-doped ZnO nanoparticles:Facile and inexpensive synthesis and visible light photocatalytic performances

Facile combustion route synthesized Al and Ce co-doped ZnO nanoparticles photocatalysts were characterized using XRD,SEM,BET,EDS,UV-visible DRS,PL,photocurrent and EIS techniques.XRD and SEM analyses identify that crystallite and particle size is reduced from 13.26 to 11.88 nm with introduction of Al and Ce into ZnO which assists inhibiting the recombination of photo generated charge carriers.UVvisible DRS spectra indicate that optical assimilation of ZnO is significantly increased to visible region(-406 nm)and band gap reduces from 3.18 to 3.06 eV with introduction of Al and Ce co-dopants.Electrochemical impedance spectroscopy analysis under visible light illumination confirms the enhancement in visible light activity of Al and Ce co-doped ZnO nanoparticles as photocatalysts.The enhanced activity of Al and Ce co-doped ZnO photocatalyst can be ascribed to enhanced light assimilation,high surface area and efficient charge transfer process.Our results reveal that by incorporating precise amount of Al(~2%)and Ce(~2%)into ZnO,a highly efficient catalyst can be synthesized that have degraded almost 95%methyl orange(MO)dye in just 45 min.Further,the influence of various operational parameters such as solution pH,catalyst dose,dye concentration,airflow rate and light intensity on photodecomposition of MO was evaluated.Furthe rmore,a possible mechanism for Al and Ce modified ZnO was proposed and designed photocatalysts demonstrates good stability in aqueous medium.     

Cryoscopic studies in fluoride-oxide-silica systems: Part I. systems containing Li+, Na+ and K+

The depressions of the freezing temperatures of NaF and KF by additions of 3M₂O · 2SiO₂, M₂O -SiO₂, M₂O · 2SiO₂ and SiO₂ (where M = Li, Na and K) have been measured and the variations of the activities of NaF and KF with liquidus composition have been calculated. These activities are shown to be in good agreement with a proposed theoretical model of the anionic constitutions of these melts. In melts of M₂O/SiO₂ > 1 linear chain silicate ions and free F⁻ ions are postulated and in melts of M₂O/SiO₂ < 1 reaction between F⁻ and silicate ions to produce polyfluorosilicate anions is postulated. The effect of alkali cation type on the deviation of the liquidus activities from the proposed ideal behavior in melts of M₂O/SiO₂ > 1 and the degrees of polymerization of the fluorosilicate ions in melts of M₂O/SiO₂ < 1 are explained in terms of coulombic interactions and the effects of cation size on the polarization behavior. In the reciprocal systems MF-M₂ ^′O · SiO₂ and MF-M₂ ^′O · 2SiO₂ deviations from proposed ideality are correlated with the signs and magnitudes of the standard free energy changes for the exchange reactions. The conclusions as to the dependency of solution mechanism of fluorides in their alkali silicates on M₂O/ SiO₂ ratio are in agreement with conclusions drawn from studies of infrared absorption in these systems.     

GASEOUS REDUCTION BEHAVIOR OF IRON OXIDE IN MINERAL PHASES AND IN CaO-SiO2-FeO SLAG POWDER

To elucidate the gaseous reduction behavior of iron ore sinter, it is necessary to know the effect of SiO₂, which is contained in the ore as a gangue mineral, and to know the reducibility of FeO in solidified CaO-SiO₂-FeO slag. In the present study, the gaseous reduction behavior of the CaO-SiO₂-FeO slag, 2FeO·SiO₂, and CaO·FeO·SiO₂ powder has been investigated, and the rate constants of hydrogen reduction are derived to be about 0.4 and 0.6?mol/(s·m³·atm) for 2FeO·SiO₂ and CaO·FeO·SiO₂, respectively. The rate constants for the reduction of 2FeO·SiO₂ and CaO·FeO·SiO₂ with CO are one order of magnitude smaller than with H₂.     

Cryoscopic studies in fluoride-Oxide-Silica systems: Part II. systems containing Mg2+, Ca2+, Ba2+ and Pb2+

The depressions of the freezing temperatures of MgF₂, CaF₂, and BaF₂ by adding 2MO · SiO₂, 3MO · 2SiO₂, MO · SiO₂, 2MO · 3SiO₂, and MO · 2SiO₂ where M = Mg, Ca and Ba, have been measured, as have the depressions of the freezing temperature of PbF₂ resulting from additions of 2Pb · SiO₂, 3PbO · 2SiO₂ and PbO · SiO₂. The variations of the activities of the fluorides with liquidus composition have been calculated. These are shown to be in good agreement with a proposed theoretical model of the constitutions of these melts. In the alkaline earth systems with MO/SiO₂ > 1.5 linear chain silicate ions and free F⁻ ions are postulated and in melts of MO/SiO₂ < 1.5 reaction between F⁻ and silicate ions to form polyfluorosilicate anions is postulated. These conclusions are in agreement with those drawn from infrared absorption studies of CaF₂-CaO-SiO₂ glasses. The activity behavior in the reciprocal systems MF₂-M′O · SiO₂ and M′F₂-MO · SiO₂ is explained in terms of polymerization and preferred ionic association effects within the melts. In the lead fluoride-silicate systems fluorination of the silicate ions occurs at PbO/SiO₂ = 2 and, in contrast with the alkali and alkaline earth systems, it appears that polyfluorosilicate anions and free O²⁻ anions can coexist in lead fluorosilicate melts.     

First-principles study of electronic structure and optical properties of Er:Lu2O3

In the present computational study,we found that Er:Lu₂O₃materials have promise for application in laser applications.The crystal structure and the electronic and optical properties of Er:Lu₂O₃materials were studied using first-principle calculations under the framework of density functional theory.Based on the experimental and calculated results,the structure of Lu₂O₃was established.The calculated results show that doping by Er³⁺can effectively improve its absorption coefficient in the ultraviolet region and improve the static dielectric constant of Lu₂O₃.As the doping concentration of Er³⁺increases,the energy of the valence band electrons excited to the conduction band decreases,and the transition is more likely to occur.The absorption coefficient,reflectance,and electron energy loss spectroscopy are bathochromic shifted.The Lu_2-xEr_xO₃(02O₃.     

Existence form of lathanum and its improving mechanism of visible-light-driven La-F co-doped TiO_2

The existence form and effect of La on the phase composition,morphology,recombination of photocarriers,and optical absorptivity of La-F codoped TiO_2 were investigated.Experimental results indicate that all the phase composition of samples is anatase TiO_2,the grain sizes decrease with the increasing of La content The catalysts have a well-defined spherical structure with an average size of 12-14 nm,and the doping elements are uniformly dispersed.Compared with pure TiO_2,the absorption edge of La_(1.5)F_5-TiO_2 red shifts from 388 to 437 nm,accordingly the energy gap(E_g) reduces from 32 to 2.84 eV,Besides,the recombination rate of electron-holes in La_(1.5)F_5-TiO_2 is the weakest among the prepared samples,and the specific surface area of La_(1.5)F_5-TiO_2 reaches 105.27 m~2/g.The apparent reaction rate constant k of La_(1.5)F_5-TiO_2 for methylene blue(MB) degradation under visible light obtained from the apparent first-order model achieves 0.0166±0.52 min~(-1),which is greater than 0.0033±0.09 min 1 of TiO_2.Moreover,high-resolution transmission electron microscopy(HRTEM) observation reveals that there coexist La_2O_3 particles in the co-doped TiO_2.     

Selective separation of iron and scandium from Bayer Sc-bearing red mud

In this study, we investigated the separation of iron and scandium from Sc-bearing red mud. The red mud object of our study contained 31.11 wt% total iron (TFe), 0.0045 wt% Sc, hematite (Fe₂O₃) and ferrosilite (FeO·SiO₂) as the main Fe-bearing minerals. The Sc-bearing red mud was treated by a novel deep reduction roasting and magnetic separation process that includes the addition of coke and CaO to extract Fe and enriching Sc from the Sc-bearing red mud. The addition of coke and CaO enhances the transformation of hematite (Fe₂O₃) to metallic iron (Fe⁰) and magnetite (Fe₃O₄) as well as the transformation of ferrosilite into metallic iron (Fe⁰). The test results show that utilizing the new process a Fe concentrate with a TFe content of 81.22 wt% and Fe recovery of 92.96% was obtained. Furthermore, magnetic separation tailings with Sc content of 0.0062 wt% and Sc recovery of 98.65% were also obtained. The test results were achieved under the following process conditions: roasting temperature of 1373 K, roasting time of 45 min, calcium oxide dosage of 20 wt%, coke dosage of 25 wt%, grinding fineness of 90% < 0.04 mm, and magnetic field intensity of 0.24 T. The major minerals in the Fe concentrate are metallic iron (Fe⁰) and magnetite (Fe₃O₄). The main minerals in the magnetic separation tailings with a low TFe content of 2.62% are CaO·SiO₂, Na₂O·SiO₂, FeO·SiO₂, Ca₃Fe₂Si₃O₁₂, CaAl₂SiO₆ and CaFe(SiO₃)₂.     

Luminescence properties of composite material Sr2MgSi2O7:Eu2+,Dy3+/light conversion agent with multilayer structure

In order to improve the red luminescent properties,Sr₂ MgSi₂ O₇:Eu²⁺,Dy³⁺was selected as a blue persistent luminescent donor phosphor,while light conversion agent was utilized to tune the persistent luminescent spectra from blue to red.Composite red luminescent material Sr₂ MgSi₂ O₇:Eu²⁺,Dy³⁺/light conversion agent(SMED/LCA) was fabricated with light conversion agent and Sr₂ M...     

Photocatalytic reduction of CO2 over Sm-doped TiO2 nanoparticles

Highly efficient photocatalytic reduction of CO₂ is essential for solving the greenhouse effect and energy crisis. In this paper, the Sm-TiO₂ nanocomposites were successfully prepared via sol-gel method. The CO₂ photoreduction activities of synthesized samples were tested under irradiation for 6 h and the results indicate that the 0.5% Sm-TiO₂ catalyst has superior performance and stability. The CO and CH₄ yields of 0.5% Sm-TiO₂ catalyst are 55.47 and 3.82 μmol/g·cat respectively, which are 5.02 and 2.67 times the yield of TiO₂. The possible mechanism of Sm doped TiO₂ was investigated through comprehensive characterization and photoelectrochemical analysis. After the Sm doping, the photo-generated electrons in TiO₂ could migrate to Sm 4f, and some of them can be captured by reducing Sm³⁺ to Sm²⁺, which can lower the recombination rate of electron and hole pairs. Therefore, the enhanced photocatalytic performance could be ascribed to large specific surface area, fast separation rate of electron–hole pairs and high visible light response. This report provides some meaningful attempts in researching the CO₂ photocatalytic reduction.     

Samarium doped apatite-type orange-red emitting phosphor Ca_5(PO_4)_2SiO_4 with satisfactory thermal properties for n-UV w-LEDs

A novel single-phase Sm~(3+) activated Ca_5(PO_4)_2SiO_4 phosphor was successfully fabricated via a conventional solid-state method, which can be e fficie ntly excited by near ultraviolet(n-UV) light-emitting chips.The crystal structure and luminescence properties were characterized and analyzed systematically by using relevant instruments. The Ca_5(PO_4)_2SiO_4:Sm~(3+) phosphor shows an orange-red emission peaking at600 nm under the excitation of 403 nm and the optimal doping concentration of Sm~(3+) is determined to be 0.08, The critical distance of Ca_5(PO_4)_2SiO_4:0.08 Sm~(3+) is calculated to be 1.849 nm and concentration quenching mechanism of the Sm~(3+) in Ca_5(PO_4)_2SiO_4 host is ascribed to energy transfer between nearestneighbor activators. The decay time of Ca_5(PO_4)_2 SiO_4: 0,08 Sm~(3+) is determined to be 1.1957 ms. In addition, the effect of temperature on the emission intensity was also studied, 72.4% of the initial intensity is still preserved at 250 ℃, better thermal stability compared to commercial phosphor YAG:Ce~(3+) indicates that Ca_5(PO_4)_2SiO_4:0.08 Sm3+ has excellent thermal stability and active energy is deduced to be 0.130 eV.All the results demonstrate that orange-red emitting Ca_5(PO_4)_2SiO_4:0.08 Sm~(3+) phosphor exhibits good luminescent properties. Owing to the excellent thermal quenching luminescence property,Ca_5(PO4)_2SiO_4:0.08 Sm~(3+) phosphor can be applied in n-UV white light emitting diodes and serve as the warm part of white light.     

Effect of TiO2 on equilibrium phase sinter at oxygen partial pressure of 5×10−3 atm

Abstract

The effect of TiO₂ content on the phase compositions of sinter was conducted under reaction equilibrium at oxygen partial pressure of 5×10^?3 atm. The results showed that TiO₂ mainly existed in the phase of perovskite. With the increase in TiO₂ content, the content of secondary hematite phase increased and the ratio of hematite and magnetite in the sinter phase decreased. Meanwhile, the ratio of perovskite and Ca₂SiO₄ increased and the increased level of perovskite was larger than that of the Ca₂SiO₄ phase. The volume fraction of the phase silico-ferrite of calcia and alumina decreased from 44·9 to 41·5%, and the chemical formula of silico-ferrite of calcia and alumina changed from 4·7CaO.9·2Fe₂O₃.Al₂O₃.2·3SiO₂ to 1·6CaO.4·9Fe₂O₃.Al₂O₃.1·8SiO₂ when the percentage of TiO₂ was from 0 to 12 mass-% in the sinter.     

Photocatalytic degradation of imidacloprid by composite catalysts H3PW12O40/La-TiO2

A series of La-doped TiO2 with different mass fractions were prepared by sol-gel method. Composite catalysts H3PW12O40/La-TiO2 with different loading levels were synthesized using impregnation method. The prepared samples were characterized by fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis diffuse reflectance spectroscopy (DRS) and nitrogen adsorption-desorption analysis. The Keggin structure of H3PW12O40 (HPW) remained intact on the surface of the composites, they had relatively uniform spherical grains of diameter less than 20 nm. The visible light activity of prepared composites were improved by loading HPW and doping La. The prepared composites were used as photocatalysts in degradation of pesticide imidacloprid. Results revealed that 20%H3PW12O40/0.3%La-TiO2 possessed the best photocatalytic activity. Thus, the degradation conversion of imidacloprid reached 98.17% after 60 min irradiation when 20%H3PW12O40/0.3% La-TiO2 was used as catalysts. The degradation of imidacloprid corresponded with first-order kinetic reaction, and the half life of the degradation of imidacloprid was 9.35 min in the optimal conditions.     

Fine controllable blue emission and its mechanism in Ce3+-doped orthosilicate solid solution phosphors for different plant growths

The designed Ce~(3+)-doped alkaline-earth silicate phosphors Ca_mSr_(2-m-n)Ba_nSiO_4:Ce~(3+),Li~+(CSBS:Ce~(3+))were synthesized by a high temperature solid-state reaction. The crystal field splitting and the centroid shift from the free ion energy of 5 d configuration were approximated from the spectrum for Ca_2SiO_4,Sr_2SiO_4 and Ba_2SiO_4 phosphors. The single-phase purity was checked by means of X-ray diffraction. Here,when the doped concentration of Ca~(2+) is less than 80%(m ≤1.6), we report the structural phase transformation from monoclinic system β-Ca_2SiO_4 to orthorhombic system α-Ca_2SiO_4. The phosphors excited by near-ultraviolet(NUV) light at wavelengths ranging from 200 to 400 nm demonstrate a broad asymmetric blue emission band. The emission peak wavelength redshifts firstly from 417 nm of Ca_2SiO_4 to 438 nm of Sr_(0.3)Ca_(1.6)SiO_4, and then blueshifts to 411 nm of Sr_2SiO_4, and the end of 401 nm of Ba_2SiO_4.These results indicate that the tunable blue-emission of the phosphors can be realized through changing the solid solution components, which has a potential use as a blue component for fabricated precision modulation LEDs light sources and auxiliaries of SSC plastics films for different plant growths.We discuss in detail the possible mechanism and energy diagram of the tunable blue luminescence in Ca_mSr_(2-m-n)Ba_nSiO_4:Ce~(3+),Li~+ phosphors.     

Phase Relationship of CaO-SiO2-FeO-5 mass pct P2O5 System with Low Oxygen Partial Pressure at 1673?K (1400?°C)

Dephosphorization by using multiphase flux could considerably decrease the consumption of CaO and prevent the addition of fluorite. However, the equilibrium phase relationship within this system, which is of significant importance for understanding the formation mechanism of multiphase flux, remains unclear. Thus, it is required to provide reliable phase diagrams of the basic slag system of multiphase flux. In this research, the phase relationship of the CaO-SiO₂-FeO-5 mass pct P₂O₅ system at 1673?K (1400?°C) with $ {P}_{{{\text{O}}_{2} }} $ of 9.24?×?10^?11 atm has been studied by using the chemical equilibration method. It has been found that solid solution consists mainly of 2CaO·SiO₂-3CaO·P₂O₅, but occasionally it contains 3CaO·SiO₂. Liquidus saturated with solid solution shrinks toward the FeO corner compared with the isothermal at 1673?K (1400?°C) of the CaO-SiO₂-FeO system equilibrated with metallic iron. Thermodynamically stable CaO-FeO phase is confirmed, which could promote the condensation of 3CaO·P₂O₅ into the solid solution and increase the phosphorus partition ratio between the solid solution and molten slag. Based on the regular solution model, the effect of T.Fe and CaO content in the liquid phase on the phosphorus partition ratio between the solid solution and molten slag is discussed.     

Formation and Evolution Mechanism of the Inclusions of Al2O3·SiO2·CaO and Al2O3·SiO2·CaO·MgO in Seamless Steel Tube Steel

Herein, the formation and evolution mechanism of inclusions of Al₂O₃·SiO₂·CaO and Al₂O₃·SiO₂·CaO·MgO in seamless steel tube steel are investigated. In the long strip defects on the longitudinal cross section of the steel tube after the rolling bar piercing, the defect is mainly formed by Al₂O₃·SiO₂·CaO·MgO inclusions and Al₂O₃·SiO₂·CaO·inclusions dotted with·CaS inclusions after the rolling. The typical inclusions in the different steelmaking stages are mainly composed of CaS, Al₂O₃·(SiO₂), CaO·(SiO₂), MnS·(TiN), Al₂O₃·SiO₂·CaO·(CaS)·(MnS), Al₂O₃·SiO₂·CaO·MgO·(MnO), Al₂O₃·SiO₂·CaO·MgO·(CaS)·(MnS), etc. In the billet, the average sizes of Al₂O₃·SiO₂·CaO-based and Al₂O₃·SiO₂·CaO·MgO-based inclusions are much larger than those of the other types of inclusions. Part of SiO₂ in the deoxidized products SiO₂ can be reduced by [Al], resulting in the formation of the Al₂O₃·SiO₂ composite inclusions. The SiO₂ in Al₂O₃·SiO₂ inclusions can continuously be reduced by the dissolved [Ca] to form the Al₂O₃·SiO₂·CaO composite inclusions. The SiO₂ in the Al₂O₃·SiO₂·CaO inclusions can be reduced by the dissolved [Mg] to form the Al₂O₃·SiO₂·CaO·MgO composite inclusions. Another formation process of Al₂O₃·SiO₂·CaO·MgO inclusions is the entrapment of ladle slag in the vacuum degassing (VD) stage, due to the strong agitation of the rising Ar bubbles in the vacuum condition of the VD stage.