污水处理厂尾水的电化学脱氮技术

污水处理厂尾水中因可生物降解的有机物含量较低,无法实现生物深度脱氮,外排仍含有较高浓度的总氮,若排入河流会引起富营养化,因此深入研究尾水的深度脱氮技术具有重要意义。采用催化电氧化技术,以污水处理厂尾水为研究对象,研究了在电流密度、水力停留时间(HRT)、进水pH值等因素的影响下,尾水中总氮的去除。结果表明,催化电氧化技术在电流密度为32.67 mA·cm^-2、进水pH值为6.25～7.02、HRT为30 min时,总氮(TN)从26.40 mg·L^-1降至11.91 mg·L^-1,NO₃^--N从18.03 mg·L^-1降至4.90 mg·L^-1,去除率分别可达到54.9%和72.8%;TN的脱除主要以硝氮(NO₃^--N)的去除为主。催化电氧化技术能高效去除污水厂尾水中的总氮,且具有运行稳定和抗冲击等优点。为污水处理厂尾水的电化学深度脱氮提供了理论基础。     

Importance of soil type on the release of nonexchangeable NH 4 + and availability of fertilizer NH 4 + and fertilizer NO 3 -

Nitrogen uptake from non-exchangeable NH ₄ ⁺ byLolium multiflorum and availability of fertilizer NH ₄ ⁺ and fertilizer NO ₃ ^- were studied in pot experiments with three different soil types. The luvisol derived from loess released considerable amounts of non-exchangeable NH ₄ ⁺ when cropped. In this soil fertilizer NH ₄ ⁺ was only weakly fixed and was as available to the crop as fertilizer NO ₃ ^- . The recovery of fertilizer NH ₄ ⁺ was even higher than the recovery of fertilizer NO ₃ ^- . In the fluvisol (alluvial soil) and in the cambisol (brown earth from basalt) N recovery was higher from NO ₃ ^- fertilizer than from NH ₄ ⁺ fertilizer. In these soils NH ₄ ⁺ fertilizer was strongly fixed by 2:1 clay minerals and thus less available to the grass. Particularly in the basaltic soil the content of non-exchangeable NH ₄ ⁺ was low and so was the release of nonexchangeable NH ₄ ⁺ . At the same time this soil showed the strongest fixation of fertilizer NH ₄ ⁺ . Release and refixation of fertilizer NH ₄ ⁺ in the loess soil appears to be an important feature of this soil type with a beneficial effect on soil nitrogen turnover and availability.     

Detectability of15N-depleted fertilizer N in soil and plant tissue during a corn-rye crop rotation

Use of¹⁵N-depleted fertilizer materials have been primarily limited to fertilizer recovery studies of short duration. The objective of this study was to determine if¹⁵N-depleted fertilizer N could be satisfactorily used as a tracer of residual fertilizer N in plant tissue and various soil N fractions through a corn (Zea mays L.) -winter rye (Secale cereale L.) crop rotation. Nitrogen as¹⁵N-depleted (NH₄)₂SO₄ was applied at five rates (0, 84, 168, 252, and 336 kg N ha^–1) to corn. Immediately following corn harvest a winter rye cover crop treatment was initiated. Residual fertilizer N was easily detected in the soil NO ₃ ^- -N fraction following corn harvest (140-d after application). Low levels of exchangeable NH ₄ ⁺ -N (<2.5 mg kg^–1) did not permit accurate isotope-ratio analysis. Fertilizer-derived N recovered in the soil total N fraction following corn harvest was detectable in the 0 to 30-cm depth at each N rate and in the 30 to 60 and 60 to 90-cm depths at the 336 kg ha^–1 N rate. Atom %¹⁵N concentrations in the nonexchangeable NH ₄ ⁺ -N fraction did not differ from the control at each N rate. Nitrogen recovery by the winter rye cover crop reduced residual soil NO ₃ ^- -N levels below the 10 kg ha^–1 level needed for accurate isotope-ratio analysis. Atom %¹⁵N concentrations in the soil total N fraction (approximately one yr after application) were indistinguishable from the control plots below the 168, 252, and 336 kg ha^–1 N rate at the 0 to 30, 30 to 60, and 60 to 90-cm depths, respectively. Recovery of residual fertilizer N by the winter rye cover crop was verified by measuring significant decreases in atom %¹⁵N concentrations in rye tissue with increasing N rates. The greatest limitation to the use of¹⁵N-depleted fertilizer N as a tracer of residual fertilizer N in a corn-rye crop rotation appears to be its detectibility from native soil N in the total N pool.Research partially supported by grants from the National Fertilizer and Environmental Research Center/TVA and the Virginia Division of Soil and Water Conservation.     

ESR of Gd3+: a surrogate for the study of lanthanide dispersion in zeolitic and amorphous catalysts

Gd³⁺-ESR spectroscopy can be used as a sensitive method for the study of lanthanide additives in catalysts. Here we present the results of a comparative study of Gd/SiO₂-Al₂O₃ and Gd/HZSM-5. ESR gives evidence of rigid bonding of isolated Gd³⁺ ions into both amorphous silica-alumina and into HZSM-5. In addition, the zeolitic matrix stabilizes very small Gd³⁺-clusters (containing only a few ions) capable of interacting with water molecules. Excess Gd is present as non-dispersed, particulate oxide. Strong bonding of PO₃^3- anionic ligands irreversibly changes the local environment and reactivity towards H₂O of the Gd³⁺-clusters in HZSM-5. The Gd³⁺ ions do not block the cationic positions of HZSM-5 from further interaction with paramagnetic Cu²⁺ or Rh²⁺ cations. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ternary adsorbent photocatalyst hybrid (APH) nanomaterials for improved abstraction of tetracycline from water

ABSTRACT

Current health situations have instigated increased frequency of taking antibiotics for cure of infections but this amplified use is posing threats to environment. This research is focused to remove Tetracycline (TC), an antibiotic from water, using an advanced nanohybrid that compact the properties of adsorbent and photocatalyst. Compared to conventional methods for remediation of TC, large surface area (452 m²g^?1) adsorbent photocatalyst hybrid (APH) g-C₃N₄/α-MoO₃/ZIF-67 (CMZ) have found much effective as 97% degradation of TC is observed in 110 min with 0.1 g of APH. Increasing g-C₃N₄ in the hybrids has improved percent degradation of TC molecules. CMZ-3 is found as a potential candidate for water treatment.     

Luminescent properties of a novel afterglow phosphor Sr3Al2O5Cl2:Eu,Ce

A series of Eu²⁺ and Ce³⁺ doped/co-doped Sr₃Al₂O₅Cl₂ afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P2₁2₁2₁. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f⁶5d–4f⁷/5d¹–4f¹ transitions of Eu²⁺/Ce³⁺, could be observed in phosphors of Sr₃Al₂O₅Cl₂:Eu²⁺/Sr₃Al₂O₅Cl₂:Ce³⁺, respectively. Because of the overlap spectral range between the Sr₃Al₂O₅Cl₂:Eu²⁺ and Sr₃Al₂O₅Cl₂:Ce³⁺ phosphors, the energy transfer (ET) from Ce³⁺ to Eu²⁺ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce³⁺ could significantly prolong the afterglow duration of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr₃Al₂O₅Cl₂:1.0%Eu²⁺, 0.5%Ce³⁺ sample, exhibiting much longer than that of Sr₃Al₂O₅Cl₂: 1.0%Eu²⁺ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce³⁺ for the enhanced afterglow property was experimentally determined to be 0.5%.     

Surface characterization of sulfated zirconia and its catalytic activity for epoxidation reaction of castor oil

The solid acid catalysts SO₄^2?/ZrO₂ were prepared by impregnation technique at different calcination temperatures. The surface characterizations were carried out by using scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), temperature programed desorption of NH₃ (NH₃-TPD), and N₂-BET. The SEM results showed that the size of the SO₄^2?/ZrO₂ was not uniform and varied from about 1 to 20?µm. The characteristic peaks in FTIR spectra were essentially the same within the calcination temperature range of 400–700?°C. The XRD results indicated that the transition temperature from amorphous to tetragonal phase was up to 500?°C. The strong acid and superacid sites of the samples could be observed by the NH₃-TPD results. The largest BET surface area was 140 m²/g, when the calcination temperature was at 500?°C, and all the pore size distributions belong to mesoporous range. The solid acid SO₄^2?/ZrO₂ was used for the epoxidation of castor oil. When the calcination temperature of SO₄^2?/ZrO₂ was 600?°C, reaction temperature 45?°C, and reaction time 8?h, the reaction effect was better with an iodine value of 33.0?±?1.6?g/100?g and an epoxy value of 2.45?±?0.11?mol/100?g.     

Photoluminescence properties of Eu3+-doped stalk-like Al2O3 via a hydrothermal route followed by heat treatment

ABSTRACT

Uniform Al₂O₃:Eu³⁺ samples were successfully fabricated via a hydrothermal method and subsequent thermal decomposition of Eu³⁺-doped precursors. The sample characterisations were carried out by means of X-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence spectra. XRD results revealed Eu³⁺-doped samples were a pure γ-Al₂O₃ phase after being calcined at 1173?K. SEM results showed that these Eu³⁺-doped Al₂O₃ samples were stalk-like, with an average length of 1.5?μm. Upon excitation at 394?nm, the orange–red emission bands, having wavelengths longer than 580?nm, were to be from ⁵D₀→⁷F_J (J?=?1, 2) transitions. The asymmetry ratio of (⁵D₀→⁷F₂)/(⁵D₀→⁷F₁) intensity is about 0.54, 2.76, 3.29, 2.86, 3.36, 3.13 for Eu³⁺ concentrations of 0.1, 0.4, 0.7, 1.0, 1.5 and 2.0?mol-%, respectively. The optimal doping concentration of Eu³⁺ ions in Al₂O₃ is 1.5?mol-%. According to Dexter's theory, the critical distance between Eu³⁺ ions for energy transfer was determined to be 14?Å.     

水热一步法合成SO42-/Zr-PHTS及其催化性能

在低酸度硫酸体系中,以P123(EO₂₀PO₇₀EO₂₀)为模板剂水热法一步合成硫酸化锆掺杂PHTS固体酸催化剂(SO₄^2-/Zr-PHTS),利用XRD、TEM、N₂吸附-脱附以及NH₃-TPD、Py-FTIR等手段对其进行表征。结果表明,SO₄^2-/Zr-PHTS具有有序的六方相介孔结构,具有以L酸为主的弱、中强度的酸性中心;随着硅锆摩尔比的增加,其酸量逐渐减少,比表面积逐渐增加,孔容、孔径无显著变化。SO₄^2-/Zr-PHTS在催化四氢呋喃聚合中表现出良好的反应性能,推测固体酸的表面酸性和孔结构决定着催化四氢呋喃聚合的反应性能。     

Characterization of Copper–Cobalt Ores and Quantification of Cu2+, Co2+, Co3+, and Fe3+ in Aqueous Leachates Using UV/Visible Spectrophotometry

Ultraviolet/visible (UV/vis) spectroscopy was used to determine qualitatively and quantitatively Cu²⁺, Co²⁺, Co³⁺, and Fe³⁺ in oxidized Cu–Co ore leachates. The mineralogical and chemical characteristics of the three oxidized Cu–Co ore samples considered were determined using Fourier transform infrared spectroscopy (FTIR), X-ray powder diffractometry (XRD), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and X-ray fluorescence spectrometry (XRF). The results showed that Cu and Co in the samples were in the form of carrollite (Co₂CuS₄), malachite (Cu₂CO₃(OH)₂, and heterogenite (CoO(OH)). The samples contained (2.73% Cu and 0.19% Co), (2.82% Cu and 0.07% Co), and (0.03% Cu and 0.05% Co), respectively. Gangues were mainly constituted of quartz, goethite, and hematite. The ultraviolet/visible (UV/vis) results indicated that the wavelengths of absorbance of the metal ions in dilute ethylenediaminetetraacetic acid aqueous solution (pH ≈ 3.5) were Fe³⁺ (293 nm), Cu²⁺ (821 nm), Co³⁺ (344 nm), and Co²⁺ (512 nm). The molar concentrations of the metal ions obtained using the UV/vis method compared well with the results obtained using the atomic absorption spectroscopy (AAS) method. UV/vis spectroscopy was also used to monitor the conversion of Co³⁺ into Co²⁺ using different reducing agents. The results showed that the molar concentration of Co²⁺ in the aqueous solutions increased with the addition of reducing agents, of about 80.95% (copper foil), 61.22% (ferrous sulfate), and 20.35% (sodium sulfite), respectively.     

Influence of Co3O4, Fe2O3 and SiC on microstructure and properties of glass foam from waste cathode ray tube display panel (CRT)

Abstract

In the present study, the effect of temperature and oxidising agents such as Fe₂O₃ and Co₃O₄ on physical and mechanical properties of glass foam is investigated. The glass foam is made of panel glass from dismantled cathode ray tubes and SiC as a foaming agent. In the process, powdered waste glass (mean particle size below 63 μm) in addition to 4 wt-% SiC powder (mean particle size below 45 μm) are combined with Fe₂O₃ and Co₃O₄ (0·4, 0·8 and 1·2 wt-%) have been sintered at 950 and 1050°C. The glass foamed containing 1·2 wt-% Co₃O₄ has good physical properties, with porosity more than 80% and bending strength more than 1·57±0·12 MPa. However, by adding different amounts of Fe₂O₃ in comparison with samples without iron oxide, little changes in porosity and strength are obtained.     

A reddish orange stoichiometric phosphor LiEu(PO3)4 for white light-emitting diodes

Stoichiometric phosphors LiGd_1−xEu_x(PO₃)₄(x=0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via traditional solid state reactions. The X-ray powder diffraction measurements show that all prepared samples are isostructural with LiNd(PO₃)₄. Eu³⁺ doped phosphors can emit intense reddish orange light under the excitation of near ultraviolet light from 370 to 410 nm. The strongest two at 591 and 613 nm can be attributed to the transitions from excited state ⁵D₀ to ground states ⁷F₁ and ⁷F₂, respectively. The typical chromaticity coordinates (x=0.620, y=0.368) of Eu³⁺ doped phosphors are in red area. The recorded absorbance spectra indicate that there is effective absorbance in the near UV region for all Eu³⁺ doped samples. Present research indicates that LiGd_1–xEu_x(PO₃)₄ is a promising phosphor for white light-emitting diodes.     

Influence of precursor Bi/Fe ion concentration on hydrothermal synthesis of BiFeO3 crystallites

In this study we investigated the effect of precursor Bi³⁺/Fe³⁺ ion concentration on the hydrothermal synthesis of BiFeO₃ crystallites. It is demonstrated that the phase-purity and morphology of the products is highly dependent on the metal ion concentration. Phase-pure BiFeO₃ crystals can be prepared at the Bi³⁺/Fe³⁺ ion concentration ranging from 0.025 to 0.0625 M. The samples prepared at n(Bi³⁺/Fe³⁺)=0.025, 0.0375, 0.05, and 0.0625 M, are composed, respectively, of cuboid-like particles (100–200 nm), regular spherical agglomerates (30–40 μm) made up of irregular grains with size about several hundred nanometers, irregular flower-like clusters formed from irregular grains of several hundred nanometers in size, and octahedron-shaped particles (500–600 nm). These samples have a similar bandgap energy of 2.20 eV and exhibit a typical antiferromagnetic behavior at room temperature.     

In situ synthesis,mechanical and cyclic oxidation properties of Ti3AlC2/Al2O3 composites

ABSTRACT

Ti₃AlC₂/Al₂O₃ composite materials were successfully fabricated from TiO₂/TiC/Ti/Al powders by the in situ reactive hot pressed technique. The microstructure, mechanical and oxidation properties of the composites were investigated in the paper. Vickers hardness increased with the Al₂O₃ content. The relative density of Ti₃AlC₂/Al₂O₃ composites exhibits a declining tendency with Al₂O₃ content especially exceeds 10 vol.?%. The Ti₃AlC₂/Al₂O₃ composites show excellent electrical conductivity. The flexural strength and fracture toughness of Ti₃AlC₂/10 vol. % Al₂O₃ are 461 ± 20?MPa and 6.2?±?0.2?MPa m^1/2, respectively. The cyclic oxidation behaviour of resistance of Ti₃AlC₂/10 vol. % Al₂O₃ composites at 800–1000°C generally obeys a parabolic law. The oxide scale of sample consists of a mass of α-Al₂O₃ and TiO₂, forming a dense and adhesive protect layer. The result indicates that the Al₂O₃ can greatly improve the oxidation resistance of Ti₃AlC₂.     

Efficiency and Mechanism of Ciprofloxacin Hydrochloride Degradation in Wastewater by Fe3o4/Na2S2O8

ABSTRACT

The nanosized Fe₃O₄ catalyst was synthesized via a modified reverse coprecipitation method and characterized by means of a scanning electron microscope (SEM) and an X-ray diffraction (XRD) analysis instrument. The degradation efficiency and reaction rate of Fe₃O₄ in activating sodium persulfate used to degrade ciprofloxacin were determined from the catalyst dosage, oxidant concentration, and initial pH. The results showed that under the optimum conditions of a catalyst dosage of 2.0 g·L^?1, a sodium persulfate concentration of 1.0 g·L^?1, and an initial pH of 7, the degradation rate of ciprofloxacin was 93.73%, the removal rate of total organic carbon was 78%, and the first-order reaction constant was 0.06907 min^?1 within 40 min. It was also demonstrated that the reactive oxygen species in the Fe₃O₄/sodium persulfate catalytic system were mainly composed of SO₄^– and supplemented by OH· and HO₂· using probe compounds such as ethanol, tertiary butanol, and benzoquinone.     

NO reduction by CH4over La2O3: temperature‐programmed reaction and in situ DRIFTS studies

The chemistry between NO _x species adsorbed on La₂O₃ and CH₄ was probed by temperature‐programmed reaction (TPR) as well as in situ DRIFTS. During NO reduction by CH₄ in the presence of O₂, NO ₃ ^- does not appear to activate CH₄, thus either an adsorbed O species or an NO ₂ ^- species is more likely to activate CH₄. In the absence of O₂, a different reaction pathway occurs and NO^- or (N₂O₂)^2- species adsorbed on oxygen vacancy sites seem to be active intermediates, and during NO reduction with CH₄ unidentate NO ₃ ^- , which desorbs at high temperature, behaves as a spectator species and is not directly involved in the catalytic sequence. Because reaction products such as CO₂ or H₂O as well as adsorbed oxygen cannot be effectively removed from the surface at lower temperatures, steady‐state catalytic reactions can only be achieved at temperatures above 800 K, even though formation of N₂ and N₂O from NO was observed at much lower temperature during the TPR experiments. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and luminescent properties of Tb3+ doped Y2O2SO4 microflakes

Abstract

Tb³⁺ doped Y₂O₂SO₄ (Y₂O₂SO₄:Tb³⁺) microflakes were prepared by a combination method of electrospinning and calcination. The two-dimensional microflakes had smooth surface and high radial/axial ratio. Crystal structures of the Y₂O₂SO₄:Tb³⁺ microflakes resulted in layer by layer growth in axial direction. A possible formation mechanism was proposed on the basis of experimental results, which indicated that poly(vinyl pyrrolidone) played the role of the nanostructure directing template and revealed the growth priority in radial direction. The microflakes showed a favourable fluorescent property symbolised by the characteristic green emission (541 nm) resulting from the ⁵D₄→⁷F₅ transition of Tb³⁺ ions under 229 nm ultraviolet excitation. The maximum intensity of Tb³⁺ emission of the Y₂O₂SO₄:Tb³⁺ microflakes was 2·3 times stronger than that of the Y₂O₂SO₄:Tb³⁺ bulk powders with the same doping concentration.     

Solvent-Free Selective Oxidation of Benzyl Alcohol and Benzaldehyde by tert-Butyl Hydroperoxide Using MnO- 4-Exchanged Mg–Al–Hydrotalcite Catalysts

MnO^- ₄ (0.4 mmol/g)-exchanged Mg-Al-hydrotalcite is an active and highly selective catalyst for the oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide under reflux in the absence of solvent. It also shows high activity for the oxidation of benzaldehyde to benzoic acid. The higher the Mg/Al ratio, the higher is the catalytic activity (in both the reactions) and basicity of the hydrotalcite catalyst.     

Structural characterization of maleic anhydride grafted polyethylene by C NMR spectroscopy

Maleic anhydride grafted polyethylene, [2,3-¹³C₂] MA-g-PE, which was synthesized with ¹³C labeled maleic anhydride [2,3-¹³C₂] MA in solution, was characterized by ¹³C NMR spectroscopy in order to make clear the structure of graft groups. The results reveal that [2,3-¹³C₂] MA-g-PE has succinic anhydride oligomeric grafts with a terminal unsaturated MA ring in addition to well-known saturated succinic anhydride oligomeric grafts and that the former grafts are longer but fewer than the latter.     

Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu,Mn phosphors via Dy addition and their color-tunable properties

A series of novel single-phase white phosphors Ba_1.3Ca_0.69−x−ySiO₄:0.01Eu²⁺,xMn²⁺, yDy³⁺ were synthesized by the solid-state method. The excitation spectra of these phosphors exhibit a broad band in the range of 260–410 nm, which can meet the application requirements for near-UV LED chips (excited at 350–410 nm). The emission spectra consist of two broad bands positioned around 455 nm and 596 nm, which are assigned to 5d→4f transition of Eu²⁺, and ⁴T₁→⁶A₁ transition of Mn²⁺, respectively. The luminescence intensity of phosphors enhances obviously by doping Dy³⁺ ions, and the intensity of two bands reaches an optimum when Dy³⁺ amounts to 2 mol%. In addition, thermoluminescence investigation of phosphor was conducted, getting two shallow trap defects with activation energy of 0.43 eV and 0.45 eV, which demonstrates the energy transfer mechanism of Dy–Eu through the process of hole and electron traps. By precisely tuning the Mn²⁺ content, an optimized white light with color rendering index (CRI) of R_a=84.3%, correlated color temperature (CCT) of T_c=8416 K and CIE chromaticity coordinates of (0.2941, 0.2937) is generated. The phosphor could be a potential white phosphors for near-UV light emitting diodes.