Nanophotocatalysis using immobilized titanium dioxide nanoparticle: Degradation and mineralization of water containing organic pollutant: Case study of Butachlor

In this paper, the degradation and mineralization of Butachlor in aqueous solution by nanophotocatalysis using immobilized TiO₂ nanoparticles were investigated. Butachlor (N-butoxymethyl-2-chloro-2′,6′-diethylacetanilide) is a persistent organic pollutant in agricultural soil and watercourses. A simple and effective method was used for immobilization of titanium dioxide nanoparticles. UV-vis and Ion Chromatography (IC) analyses were employed to obtain the details of the photocatalytic degradation and mineralization of Butachlor. The effects of operational parameters such as H₂O₂, inorganic anions (NO₃⁻, Cl⁻ and SO₄²⁻) and pH were investigated. The lack of any absorbance in 254 nm was indicative of the complete degradation of aromatic intermediates. The mineralization of Butachlor was evaluated by monitoring of the formed inorganic anions (NO₃⁻ and Cl⁻). Butachlor is effectively degraded following first order kinetics model. Results show that the immobilized titanium dioxide nanoparticle photocatalysis is an effective method for treatment Butachlor from contaminated water.     

Synthesis and optical properties of (Gd1−x,Eux)2O2SO4 nano-phosphors by a novel co-precipitation method

(Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphors were synthesized by a novel co-precipitation method from commercially available Gd₂O₃, Eu₂O₃, H₂SO₄ and NaOH starting materials. Composition of the precursor is greatly influenced by the molar ratio of NaOH to (Gd_1−x,Eu_x)₂(SO₄)₃ (the m value), and the optimal m value was found to be 4. Fourier transform infrared spectrum (FT-IR) and thermal analysis show that the precursor (m = 4) can be transformed into pure (Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphor by calcining at 900 °C for 2 h in air. Transmission electron microscope (TEM) observation shows that the Gd₂O₂SO₄ phosphor particles (m = 4) are quasi-spherical in shape and well dispersed, with a mean particle size of about 30-50 nm. Photoluminescence (PL) spectroscopy reveals that the strongest emission peak is located at 617 nm under 271 nm light excitation, which corresponds to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 10 mol% and the concentration quenching mechanism is exchange interaction among the Eu³⁺ ions. Decay study reveals that the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions has a single exponential decay behavior.     

Effect of ZnO doping on morphology and electrochemical properties of sub-micron RuO2 sensing electrode of DO sensor

Thick-film 20 mol% ZnO-doped RuO₂ sensing electrodes (SEs) were fabricated by screen-printing technique on the platinised alumina substrate of the planar electrochemical dissolved oxygen (DO) sensor. The effect of ZnO doping on morphology, electrochemical properties and sensing characteristics of the sensor was investigated. It was found that ZnO doping has not only improved the SE structure, but has also enhanced selectivity of the DO sensor. Selectivity testing exhibited that the presence of Cl⁻, Li⁺, SO₄²⁻, NO³⁻, Ca²⁺, PO₄³⁻, Mg²⁺, Na⁺ and K⁺ with a concentration range of 10⁻⁷ to 10⁻¹ mol/L in the solution had practically no effect on the sensor's emf. The reason in enhancement of the sensor characteristics could be related to the establishment of the better structured SE as more advanced crystallization is achieved for the doped RuO₂-SE.     

Synthesis,characterization and photoluminescence properties of (Gd1−x,Eux)2O2SO4 sub-microphosphors by homogeneous precipitation method

(Gd_1−x,Eu_x)₂O₂SO₄ sub-microphosphors were synthesized by homogeneous precipitation method from commercially available Gd₂O₃, Eu₂O₃, H₂SO₄ and (NH₂)₂CO (urea) starting materials. Fourier transform infrared spectra show that the precursors with different molar ratios of (NH₂)₂CO to Gd₂(SO₄)₃ (the m value) are mostly composed of gadolinium hydroxyl, carbonate and sulfate groups with some crystal water. X-ray diffraction indicated that the precursor (m = 5) can be transformed into pure Gd₂O₂SO₄ phase after heat treated at 900 °C for 2 h in air. Field emission scanning electron microscope micrographs illustrate that the Gd₂O₂SO₄ phosphor particles (m = 5) are quasi-spherical in shape and well dispersed, with a mean particle size of about 300–500 nm. Photoluminescence spectroscopy reveals that the strongest emission peak for (Gd_1−x,Eu_x)₂O₂SO₄ sub-microphosphors is located at 618 nm under 270 nm light excitation, which corresponds to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 5 mol% and the concentration quenching mechanism is due to the electric dipole–dipole interaction. Decay study reveals that the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions fits with a mono exponential function.     

Corrosion and impedance studies on magnesium alloy in oxalate solution

Corrosion behavior of AZ91E alloy was investigated in oxalate solution using potentiodynamic polarization and electrochemical impedance measurements (EIS). The effect of oxalate concentration was studied, where the corrosion rate increases with increasing oxalate concentration. The effect of added ions (Br⁻, Cl⁻ or SiO₃²⁻) on the electrochemical behavior of magnesium alloy in 0.1 M Na₂C₂O₄ solution at 298 K, was investigated. It was found that the corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na₂C₂O₄). This was confirmed by scanning electron microscope (SEM) observations. However, for the other added ions Br⁻ or Cl⁻, the corrosion rate is higher than the blank.     

Visible light absorption ability and photocatalytic oxidation activity of various interstitial N-doped TiO2 prepared from different nitrogen dopants

Nitrogen-doped TiO₂ was developed to enable photocatalytic reactions using the visible range of the solar spectrum. This work reports on the synthesis, characterisation and kinetic study of interstitial N-doped TiO₂ prepared by the sol–gel method using three different types of nitrogen dopants: diethanolamine, triethylamine and urea. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and UV–visible spectroscopy were used to analyse the titania. Different interstitial N-doped TiO₂ properties, such as absorption ability in the UV–visible light region, redshift in adsorption edge, good crystallisation and composition ratio of titania structures (anatase and rutile) could be obtained from different nitrogen dopants. Amongst investigated nitrogen precursors, diethanolamine provided the highest visible light absorption ability of interstitial N-doped TiO₂ with the smallest energy bandgap and the smallest anatase crystal size, resulting in the highest efficiency in 2-chlorophenol degradation. The photocatalytic activity of all N-doped TiO₂ can be arranged in the following order: TiO₂/diethanolamine > TiO₂/triethylamine > TiO₂/urea > un-doped TiO₂. The initial rate of 2-chlorophenol degradation using the interstitial N-doped TiO₂ with diethanolamine was 0.59 mg/L-min and the kinetic constant was 2.34 × 10⁻² min⁻¹ with a half-life of 98 min. In all cases, hydroquinone was detected as a major intermediate in the degradation of 2-chlorophenol.     

Luminescence excitation spectra of TbX3 (X = Cl, Br, I)

A systematic study of the excitation spectrum of TbX₃ (X = Cl⁻, Br⁻, I⁻) is presented in this work. In general, the excitation spectra of TbX₃ can be divided into three major regions: (1) the short-wave host lattice absorption region, (2) the intermediate absorption region where the Tb³⁺ 4f⁸ → 4f⁷5d¹ interconfigurational excitation transition are located, and (3) the long-wave excitation region where the Tb³⁺ 4f⁸ → 4f⁸ intraconfigurational excitation transition are located. The high spin and the low spin components of the Tb³⁺ interconfigurational excitation transition are clearly identified in the case of TbCl₃. The luminescence of TbX₃ (X = Cl⁻, Br⁻, I⁻) is dominated by emission transitions emanating from the Tb³⁺⁵D₄ state. A comparative study of the optical properties of TbX₃ (X = Cl⁻, Br⁻, I⁻) with the properties of the Tb³⁺ ion in several halide host lattices is presented. Further, a comparative study of the fundamental host lattice optical transitions in terbium halides and other halide materials is also presented.     

Electrochemical degradation of a real textile effluent using boron-doped diamond or β-PbO2 as anode

Constant current electrolyses are carried out in a filter-press reactor using a boron-doped diamond (Nb/BDD) or a Ti-Pt/β-PbO₂ anode, varying current density (j) and temperature. The degradation of the real textile effluent is followed by its decolorization and chemical oxygen demand (COD) abatement. The effect of adding NaCl (1.5 g L⁻¹) on the degradation of the effluent is also investigated. The Nb/BDD anode yields much higher decolorization (attaining the DFZ limit) and COD-abatement rates than the Ti-Pt/β-PbO₂ anode, at any experimental condition. The best conditions are j = 5 mA cm⁻² and 55 °C, for the system's optimized hydrodynamic conditions. The addition of chloride ions significantly increases the decolorization rate; thus a decrease of more than 90% of the effluent relative absorbance is attained using an applied electric charge per unit volume of the electrolyzed effluent (Q_ap) of only about 2 kA h m⁻³. Practically total abatement of the effluent COD is attained with the Nb/BDD anode using a Q_ap value of only 7 kA h m⁻³, with an energy consumption of about 30 kW h m⁻³. This result allows to conclude that the Nb/BDD electrode might be an excellent option for the remediation of textile effluents.     

Low-temperature synthesis of δ-MnO2 with large surface area and its capacitance

δ-MnO₂ was synthesized by a facile low-temperature hydrothermal method with a mixed system of KMnO₄ and CO(NH₂)₂ at 90 °C for 24 h. The obtained product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and N₂ adsorption-desorption. Results showed that the as-synthesized product had a layered structure and a high specific surface area of 230 m² g^− 1. Electrochemical characterization indicated that the prepared material exhibited an ideal capacitive behavior with the initial capacitance value of 265 F g^− 1 in 1 mol L^− 1 Na₂SO₄ aqueous solution at a scan rate of 5 mV s^− 1 and excellent cycling behavior.     

Ethanol-thermal synthesis of Cd1−xZnxS nanoparticles with enhanced photodegradation of 4-chlorophenol

Cd_1−xZn_xS nanoparticles were prepared by a one-pot solvothermal process from Zn(CH₃COO)₂, Cd(CH₃COO)₂ and NaS₂CNEt₂·3H₂O (sodium diethyldithiocarbamate, DDTC). The Cd_1−xZn_xS nanoparticles were characterized by X-ray powder diffraction, transmission electron microscope and high-resolution transmission electron microscope equipped with an energy-dispersive X-ray spectrometer. The absorption spectra of the Cd_1−xZn_xS nanoparticles can be tuned into visible region by modulating stoichiometric ratio between Zn and Cd. With the increase of Zn content, the Cd_1−xZn_xS nanoparticles showed an enhanced photocatalytic activity on degradation of 4-chlorophenol. The Cd_1−xZn_xS prepared under the optimal experimental condition (initial Zn/Cd = 3:1, 210 °C, 24 h, in ethanol) possessed the best photocatalytic activity. The conversion ratio could reach up to 84% after 12 h under irradiation of visible light for Cd_1−xZn_xS prepared in ethanol, which was obviously superior to those of products prepared in water. These results showed that both crystallinity and synthetic medium were responsible for the enhanced photocatalytic activity for 4-chlorophenol.     

Low-energy electron interaction with nitrobenzene: C6H5NO2

Low-energy electron attachment to C₆H₅NO₂ (nitrobenzene) in the gas phase is reported in the electron energy range from about 0 up to 10 eV with an energy resolution of 120 meV. Dissociative and nondissociative electron attachment to nitrobenzene were observed. From the numerous ions observed, the two most abundant were NO₂⁻ and C₆H₅NO₂⁻. Based on comparison of the abundance of studied ions with Cl⁻ in the dissociative electron attachment to CCl₄ at 0.8 eV, estimates of cross sections for the all observed ions were obtained for the first time (e.g. σ(NO₂⁻)=4.6×10⁻²⁰ m² and σ(C₆H₅NO₂⁻)=3.8×10⁻²¹ m²).     

Absorption and emission properties of Ho doped lead-zinc-borate glasses

This paper reports on the affect of lead content on the absorption and emission spectra of the Ho³⁺ ion doped lead-zinc-borate glasses in the composition (mol%) of (20 − x)PbO-20ZnO-(59 + x)B₂O₃-1.0Ho₂O₃ where x = 0, 5,10,15 of PbO content with λ_exc = 405 nm. The experimental absorption band energies have satisfactorily been correlated with the theoretical results with an r.m.s deviation of zero with the following correction factors obtained by a least square fit analysis: ΔE¹ = 348.495936 cm^− 1, ΔE² = 1.436043 cm^− 1, ΔE³ =  46.481575 cm^− 1, Δξ_4f = − 28.512979 cm^− 1, Δα = 55.508936 cm^− 1, Δβ = − 1394.339908 cm^− 1 and Δγ = 1208.424336 cm^− 1. By applying the Judd-Ofelt intensity parameter Ω₂ has been found to be linearly decreasing with the PbO content from 5 to 10 mol% and then increasing. And also radiative (A, A_T, β, τ_r) characteristic factors of the luminescent transitions (⁵I₈ ← ⁵F_3,4,5 and ⁵S₂) of the glasses have been evaluated. Stimulated emission cross-sections (σ_p^E) of the measured emission transitions of holmium glasses have also been computed.     

Characterization and photocatalytic activity of nanostructured indium tin oxide thin-film electrode for azo-dye degradation

Photocatalytically active indium tin oxide thin film electrodes were prepared by electron beam evaporation technique onto a glass substrate having thickness 120 nm. Degradation of reactive dye yellow direct 42 has been performed using photoeletrocatalysis. A biased potential is applied across indium tin oxide photoelectrode illuminated by UV light. The best experimental conditions were found to be dye concentration 1.0 × 10^− 5 mol L^− 1, pH 5.25 and 0.5 mol L^− 1 NaCl as supporting electrolyte when the photoelectrode was biased at + 0.5 V versus saturated calomel electrode. The effects of other electrolytes, dye concentration, pH solution, electrode annealing temperature and applied potentials have been also investigated and are discussed. Several common inorganic salts Na₂SO₄, Na₂CO₃, NaNO₃ and NaCl were chosen to act as supporting electrolytes, which was added into the dye solution. It is shown that the charge-transfer resistance of photoanode can be calculated by the analysis of its electrochemical impedance spectroscopy, and the photoelectrocatalytic degradation rate of yellow direct 42 was inversely proportional to the value of charge-transfer resistance of photoelectrodes at different pH. The value of charge-transfer resistance is smaller, the higher its photoelectro-activity is.     

Synthesis and characterization of a new layered magnesium zinc phosphate hydrate

A new layered magnesium zinc phosphate hydrate, MgZn(HPO₄)₂·H₂O, with a zinc phosphate framework isostructural with the one of Na₂Zn(HPO₄)₂·4H₂O, was prepared by the direct ambient pressure and temperature reaction between zinc 2,4-pentanedionate, phosphoric acid and hexahydrated magnesium chloride. The as-prepared sample is monoclinic (a = 8.780(7) Å, b = 13.240(7) Å, c = 11.123(0) Å and β = 116.21(2)°). The prepared solid undergoes two thermal transformations when it is heated from 110 to 600 °C. The first transformation is due to the release of intercalated water molecules and the second one is due to the HPO₄²⁻ → P₂O₇⁴⁻ transition.     

Oxidation of triclosan by ferrate: Reaction kinetics,products identification and toxicity evaluation

The oxidation of triclosan by commercial grade aqueous ferrate (Fe(VI)) was investigated and the reaction kinetics as a function of pH (7.0–10.0) were experimentally determined. Intermediate products of the oxidation process were characterized using both GC–MS and RRLC–MS/MS techniques. Changes in toxicity during the oxidation process of triclosan using Fe(VI) were investigated using Pseudokirchneriella subcapitata growth inhibition tests. The results show that triclosan reacted rapidly with Fe(VI), with the apparent second-order rate constant, k_app, being 754.7 M⁻¹ s⁻¹ at pH 7. At a stoichiometric ratio of 10:1 (Fe(VI):triclosan), complete removal of triclosan was achieved. Species-specific rate constants, k, were determined for reaction of Fe(VI) with both the protonated and deprotonated triclosan species. The value of k determined for neutral triclosan was 6.7(±1.9) × 10² M⁻¹ s⁻¹, while that measured for anionic triclosan was 7.6(±0.6) × 10³ M⁻¹ s⁻¹. The proposed mechanism for the oxidation of triclosan by the Fe(VI) involves the scission of ether bond and phenoxy radical addition reaction. Coupling reaction may also occur during Fe(VI) degradation of triclosan. Overall, the degradation processes of triclosan resulted in a significant decrease in algal toxicity. The toxicity tests showed that Fe(VI) itself dosed in the reaction did not inhibit green algae growth.     

(WO3)x–(TiO2)1−x nano-structured porous catalysts grown by micro-arc oxidation method: Characterization and formation mechanism

Very recently, we fabricated (WO₃)_x–(TiO₂)_1−x layers via micro-arc oxidation process under different applied voltages. Morphological and topographical studies, accomplished by SEM and AFM techniques, revealed that the pores size as well as the surface roughness increased with the voltage. Phase structure and chemical composition of the layers were also investigated by XRD and XPS and the results showed the grown layers consisted of titanium and tungsten oxides. It was found that WO₃ dispersed in the TiO₂ matrix and also doped into the TiO₂ lattice. In addition, optical properties of the synthesized layers were studied employing a UV–vis spectrophotometer. Band gap energy of the layers was approximately determined as 2.87 eV. Finally, methylene blue was selected as a model material and its degradation rate on the surface of the layers was measured to determine the photocatalytic efficiency. The degradation rate constants were measured as 2.2 × 10⁻² and 0.9 × 10⁻² min⁻¹ under ultraviolet and visible irradiations.     

Ca3Al2(SiO4)3−δCl4δ:Eu, Mn: A potential phosphor with energy transfer for near-UV pumped white-LEDs

A series of Eu²⁺ and Mn²⁺ coactivated Ca₃Al₂(SiO₄)_3−δCl_4δ phosphors have been synthesized by solid state reactions and their luminescence properties have been investigated by means of powder diffuse reflection, photoluminescence excitation and emission spectra, and lifetimes. The phosphor Ca₃Al₂(SiO₄)_3−δCl_4δ:Eu²⁺, Mn²⁺ exhibits two dominating bands situated at 460 and 550 nm, originate from the allowed 5d → 4f transition of the Eu²⁺ ion and the ⁴T_1g(4G) → ⁶A_1g(6S) transition of the Mn²⁺ ion, respectively. We have discovered that energy transfers from Eu²⁺ to Mn²⁺ by directly observing significant overlap of the excitation spectrum of Mn²⁺ and the emission spectrum of Eu²⁺ as well as the decline of lifetimes of Eu²⁺. By utilizing the principle of energy transfer, we have demonstrated that with appropriate tuning of activator content Ca₃Al₂(SiO₄)_3−δCl_4δ:Eu²⁺, Mn²⁺ phosphors exhibit potential to act as a phosphor for near ultraviolet light-emitting diodes.     

Crystal structure and spectroscopic investigations of an organic monophosphate

Single crystals of (p-ClC₆H₄NH₃)H₂PO₄ are synthesized in water by interaction of H₃PO₄ and (p-ClC₆H₄NH₂). This compound crystallizes in the orthorhombic system with the Pbca space group. Its unit-cell parameters are a = 9.724(3), b = 7.861(1), c = 25.078(6) Å, V = 1917.1(6) Å³ and Z = 8. The crystal structure has been solved and refined to R = 0.039, using 4298 independent reflections. The atomic arrangement can be described by inorganic layers parallel to ab plane, between which the organic cations are located. This compound exhibits a reversible phase transition at 403 K. The electrical conductivity measurements show that the (p-ClC₆H₄NH₃)H₂PO₄ has a conductivity value which goes from σ = 0.88 × 10⁻⁶ Ω⁻¹ cm⁻¹ at room temperature (293 K) to 3.31 × 10⁻⁴ Ω⁻¹ cm⁻¹ at 433 K. Its characterisation by TA, NMR and IR is reported too.     

Interfacial reactions in Nb/NbSi2 and Nb/NbSi2-B systems

For the use of Nb-based alloys at high temperatures, a high oxidation resistant coating such as NbSi₂ coating is required. In the present study, to clarify the physico-chemical compatibility between Nb and NbSi₂, the extent of the interfacial reaction and the reaction products were studied at temperatures ranging from 1573 to 1773 K. Growth of the reaction layer formed in the interfacial reactions was caused by the preferential diffusion of Si toward to the Nb side, leading to the formation of a Nb₅Si₃ layer. The growth followed a parabolic rate law, and the growth rate constant was expressed by k_p (m² s⁻¹) = 7.98 × 10⁻¹⁰ exp(−131.84 kJ mol⁻¹/RT). In addition, behavior of boron in the Nb/NbSi₂ interfacial reaction was clarified.