Photoelectrocatalytic activity of immobilized Yb doped WO_3 photocatalyst for degradation of methyl orange dye

Pure WO_3 and Yb:WO_3 thin films have been synthesized by spray pyrolysis technique. Effect of Yb doping concentration on photoelectrochemical, structural, morphological and optical properties of thin films are studied. X-ray diffraction analysis shows that all thin films are polycrystalline nature and exhibit monoclinic crystal structure. The 3 at% Yb:WO_3 film shows superior photoelectrochemical(PEC) performance than that of pure WO_3 film and it shows maximum photocurrent density(Iph= 1090 μA/cm~2) having onset potentials around +0.3 V/SCE in 0.01 M HClO_4. The photoelectrocatalytic process is more effective than that of the photocatalytic process for degradation of methyl orange(MO) dye. Yb doping in WO_3 photocatalyst is greatly effective to degrade MO dye. The enhancement in photoelectrocatalytic activity is mainly due to the suppressing the recombination rate of photogenerated electron-hole pairs. The mineralization of MO dye in aqueous solution is studied by measuring chemical oxygen demand(COD) values.     

Crystal growth,spectroscopic, second and third order nonlinear optical spectroscopic studies of L-phenylalanine doped ammonium dihydrogen phosphate single crystals

The frequency doubling and tripling can be reached for Nd:YAG laser beam using the single crystal of ammonium dihydrogen phosphate (ADP). The growth and characterization of pure and L-phenylalanine doped ADP crystals are considered in the present contribution. The transparent good quality single crystals are grown using low temperature solution growth technique. The functional group alteration is studied using FT-IR spectroscopy. The larger improvement is observed in linear and nonlinear optical properties of ADP crystals on doping by L-phenylalanine. The reduction in charge carrier density is observed in photoconductivity spectra of all the grown crystals.     

Growth of gamma glycine crystal and its characterisation

Single crystal of γ-glycine, an organic nonlinear optical material, has been grown by solvent evaporation technique from a mixture of aqueous solutions of glycine and potassium nitrate, lithium nitrate at room temperature. Gamma glycine crystals have been grown up to the dimension of 20 mm × 15 mm × 12 mm. Powder X-ray diffraction of the grown crystal was recorded and indexed. Single crystal X-ray diffraction studies were carried out and the unit cell parameters were compared with the literature values. The γ-phase of glycine is confirmed by single crystal XRD and FTIR spectral analysis. The crystals were characterised by UV–vis–NIR transmission spectrum in the range 200–1100 nm. The second harmonic generation conversion efficiency of γ-glycine crystal was twice the efficiency of KDP crystal. Thermal characteristics of γ-glycine crystals were determined by thermogravimetric analysis (TGA) and differential thermal analysis, which shows the thermal stability of the grown crystals. Dielectric constant and dielectric loss measurements were carried out at different temperatures and frequencies. The microhardness of the grown crystals has been studied using Vicker's microhardness tester.     

Spectroscopic and thermal studies of γ-glycine crystal grown from potassium bromide for optoelectronic applications

Single crystals of an organic nonlinear optical material γ-glycine have been synthesized by slow evaporation technique from aqueous solutions of α-glycine and potassium bromide at room temperature. Single crystal X-ray diffraction analysis confirmed the growth of γ phase of glycine. The powder X-ray diffraction of the grown crystal was recorded and indexed. Functional groups present in the sample were identified by FTIR spectral analysis. The optical absorption studies show that the UV cut-off wavelength of γ-glycine is at 238 nm and has a wide transparency window. The thermal characteristics of the grown crystal were determined by thermogravimetric and differential thermal analysis (TG/DTA), which show the thermal stability of the grown crystals. The powder second harmonic generation (SHG) efficiency of γ-glycine crystals was measured by Kurtz and Perry powder technique using Nd:YAG laser and it was found to be 2.56 times that of potassium dihydrogen phosphate (KDP) crystals.     

Semiorganic nonlinear optical l-lysine sulphate growth and characterization

l-Lysine sulphate (LLS), a semiorganic nonlinear optical (NLO) material useful for frequency doubling in the IR region, has been synthesized. The solubility studies have been carried out in the temperature range 30–50 °C. Single crystals have been grown by slow evaporation method from an aqueous acetone solution of l-lysine and sulphuric acid. The grown crystals were bulk, bright and transparent. These crystals were characterized by X-ray and FTIR studies. Powder X-ray pattern indicates that LLS crystallizes in orthorhombic space group P2₁2₁2₁ with four unit cells. FTIR spectral studies were performed for the conformation of the l-lysine molecule and hydrogen bonds. The optical transmission spectra of the grown crystal are tested by UV–vis spectrophotometer and found that the crystal was transparent over entire visible region. The second harmonic generation test of the LLS revealed the nonlinear nature of the crystal.     

Growth and characterization of 2-amino-4-picolinium 4-aminobenzoate single crystals

The organic material of 2-amino-4-picolinium 4-aminobenzoate (C₆H₉N₂⁺·C₇H₆NO₂^?) was synthesized and grown as single crystals at room temperature by slow evaporation solution growth technique in the constant temperature bath (±0.01 °C) using ethanol as solvent. The grown crystals were characterized by XRD and FT-IR spectral analyses. The melting point, density, UV–visible spectral studies were carried out for the grown crystals. The theoretical factor group analysis predicts 372 internal modes of vibration and optical modes in the grown title compound. The second harmonic generation (SHG) output of 2-amino-4-picolinium 4-aminobenzoate was recorded by Kurtz–Perry powder technique and it is found to be 355 mV at a given pulse energy of 1.45 mJ/s and for urea the SHG output was 525 mV. The dielectric behaviour of 2-amino-4-picolinium 4-aminobenzoate was investigated with different frequencies and temperatures.     

A comparative study of key properties of glycine glycinium picrate (GGP) and glycinium picrate (GP): A combined experimental and quantum chemical approach

Using experimental and computational techniques, a comparative study of electro-optical properties for glycine glycinium picrate (GGP) and glycinium picrate (GP) compounds has been performed. The single crystal of GGP has been grown using slow evaporation technique that was further subjected to experimental characterization of its electro-optical properties. The good optical transparency and mechanical strength at micro level was confirmed from optical and nanoindentation measurements using the Oliver–Pharr method of the grown single crystals. Differential scanning calorimetric (DSC) analysis was done to probe the thermal stability of the grown single crystals. Using the density functional theory (DFT) methods, we have not only investigated the GGP but also proposed GP molecule. Additionally, we have shed light on the molecular geometries, infrared and Raman spectra, linear and nonlinear optical properties of both GGP and GP at molecular level. The time dependent DFT (TD-DFT) approach was adopted to calculate the excitation energies of the molecules in different phases including gas, water, acetone, cyclohexane and chloroform as well. For GGP, its wavelength of maximum absorption is calculated to be ～390 nm at B3LYP/6-31G¹ level of theory. The calculated amplitudes of first hyperpolarizability (β_tot) for GGP and GP are found to be 712 and 970 a. u., respectively, which are about 16 and 23 times larger than that of the urea molecule (a prototype NLO molecule). Thus the present study not only brings to limelight the optical and nonlinear optical properties of GGP but also sheds light on the possible potential of GP as new NLO molecule.     

Photocatalytic activity of nitrogen and copper doped TiO2 nanoparticles prepared by microwave-assisted sol-gel process

Cu and N-doped TiO₂ photocatalysts were synthesized from titanium (IV) isopropoxide via a microwave-assisted sol-gel method. The synthesized materials were characterized by X-ray diffraction, UV-vis diffuse reflectance, photoluminescence (PL) spectroscopy, SEM, TEM, FT-IR, Raman spectroscopy, photocurrent measurement technique, and nitrogen adsorption–desorption isotherms. Raman spectra and XRD showed an anatase phase structure. The SEM and TEM images revealed the formation of an almost spheroid mono disperse TiO₂ with particle sizes in the range of 9-17 nm. Analysis of N₂ isotherm measurements showed that all investigated TiO₂ samples have mesoporous structures with high surface areas. The optical absorption edge for the doped TiO₂ was significantly shifted to the visible light region. The photocurrent and photocatalytic activity of pure and doped TiO₂ were evaluated with the degradation of methyl orange (MO) and methylene blue (MB) solution under both UV and visible light illumination. The doped TiO₂ nanoparticles exhibit higher catalytic activity under each of visible light and UV irradiation in contrast to pure TiO₂. The photocatalytic activity and photocurrent ability of TiO₂ have been enhanced by doping of the titania in the following order: (Cu, N) - codoped TiO₂ > N-doped TiO₂ > Cu-doped TiO₂ > TiO₂. COD result for (Cu, N)-codoped TiO₂ reveals ∼92% mineralization of the MO dye on six h of visible light irradiation.     

Impact of Fe3+ on UV absorption of K2Al2B2O7 crystals

K₂Al₂B₂O₇ (KABO) is a new nonlinear optical crystal capable of laser harmonic generation in the UV range. However, abnormal UV absorption prevents its application in effectively generating UV light with wavelength shorter than 300 nm. The transmittance spectra of the grown crystals show distinct absorption bands at 216 nm and 264 nm. It is observed that the UV absorption is strongly correlated with iron impurity at a parts per million (ppm) level. Furthermore, electron paramagnetic resonance (EPR) spectra of the absorbing crystals show a strong signal at g = 2.00 position corresponding to a Fe³⁺ center. A new crystal growth method which reduces the iron content has been proposed and results show that the new KABO crystal is free from the Fe³⁺ UV absorptions.     

Sensitivity and stability of the Fricke–gelatin–xylenol orange gel dosimeter

Spectrophotometric measurements of the Fricke–gelatin–xylenol orange (FGX) gel dosimeter demonstrated reproducible linear dose response up to 25 Gy. However, oxidation processes continue post-irradiation, affecting the response of this dosimetry system. Additional oxygenation during preparation increases the sensitivity of the gel but does not improve the auto-oxidation stability of the dosimeter post-irradiation. A suitably stable gel composition that is recommended for radiotherapy dosimetry measurements contains 0.5 mM ferrous ammonium sulphate, 50 mM sulphuric acid, 0.15 mM xylenol orange and 3.0% by weight gelatin.     

Effect of sunset yellow dye on morphological,optical, dielectric,thermal and mechanical properties of KDP crystal

Herein, we describe the growth and morphology of well-defined dyed crystals of KH₂PO₄ (potassium dihydrogen orthophosphate; KDP) containing organic azo (sunset yellow; SSY) dye in the {1 0 1} & {0 0 1} pyramidal growth sectors. An understanding on selective dye inclusion in various growth sector of host crystal is proposed, which will help in designing novel tailor-made dyed photonic crystals. The structural analysis and the identification of various functional groups present in as grown KDP crystals were carried out using powder XRD, FTIR and Raman studies. Solid state transmittance spectra for dyed KDP crystals displayed three absorption peaks at 230 nm, 311 nm and 477 nm, which were blue shifted for SSY dye in KDP crystal relative to neutral aqueous solution of SSY dye. These blue shifts in the absorption maxima confirm the successful incorporation of sunset yellow dye into the pyramidal growth sectors of dyed KDP crystals. The band around 409 nm in the photoluminescence emission spectrum indicates a violet emission. SSY dye doped KDP crystals showed enhanced dielectric properties and thermal stability as compared to pure KDP crystal. The mechanical strength of the KDP crystals estimated using Vickers microhardness test was found to decrease with the increase in SSY dye doping.     

UV–vis,IR and 1H NMR spectroscopic studies and characterization of ionic-pair crystal violet–oxytetracycline

The present study shows the formation and characterization of the ionic-pair between the antibiotic oxytetracycline and the dye crystal violet in ammonia solution pH 9.0 ± 0.2 extracted into chloroform. The characterization was demonstrated using UV–vis spectrophotometry, ¹H NMR, measurement of relaxation times T₁ and IR spectroscopy, using a comparison between the signals of individual pure compounds with the signals with the mixture CV–OTC in different alkaline media. The formation of ionic-pair was also corroborated by new signals and chemical shifts. (2D) NMR spectroscopy experiments show that the interaction is electrostatic.     

Optical, dielectric and microhardness studies on 1 0 0 directed ADP crystal

1 0 0 directed ammonium dihydrogen phosphate single crystal has been grown using the uniaxially solution-crystallization method of Sankaranarayanan–Ramasamy (SR). The size of the grown crystal is 40 mm in diameter and 50 mm in thickness. The grown crystals were characterized by UV–vis spectroscopy, Vickers hardness and dielectric studies. Comparing the 1 0 0 plane of the conventional method grown ADP crystal with 1 0 0 directed SR method grown ADP crystal, optical transparency, dielectric constant and Vickers hardness number are increased and dielectric loss is decreased in SR method grown crystal.     

Spectrophotometric and titrimetric methods for the determination of nordiazepam in pure and pharmaceutical dosage form

A spectrophotometric method and two titrimetric methods for the determination of nordiazepam via its iodobismuthate complex are described. These methods depend on the reaction of nordiazepam with potassium bismuth iodide which give an orange precipitate. Determination of nordiazepam in the precipitated complex is done iodometrically using standard potassium iodate solution or complexometrically using standard EDTA solution and xylenol orange indicator. Alternatively, the complex is dissolved in ethanol and its absorbance is measured at 323 nm. The three methods were applied for the determination of reference samples of nordiazepam in the concentration range of 1–30 mg ml^?1 (for the iodometric method) and of 5–30 mg ml^?1(for the complexometric method) and of 0.04–3.2 mg ml^?1 (for the spectrophotometric method). The proposed methods were applied for the determination of nordiazepam in madar tablets and the validity of the proposed methods was assessed by applying the standard addition technique.     

Temperature dependence on the dose response of the Fricke–gelatin–xylenol orange gel dosimeter

The effect of temperature during optical absorbance measurements and irradiation on the values of the molar absorption coefficient, (ε_m)_t, and radiation chemical yield, G_t^′, respectively, for the Fricke–gelatin–xylenol orange (FGX) gel dosimeter were investigated. At 20 °C, the product (ε_m)_tG_t^′ was found to be 6.76×10^?3 m² J^?1. While an irradiation temperature coefficient, k₂, was evident (?0.53% °C^?1), no temperature effect was found during measurement in the range 16–25 °C.     

A new class of proton-conducting ionic plastic crystals based on organic cations and dihydrogen phosphate

Choline dihydrogen phosphate ([N_1.1.1.2OH]DHP) and 1-butyl-3-methylimidazolium dihydrogen phosphate ([C₄mim]DHP) were synthesized as a new class of proton-conducting ionic plastic crystals. Both [N_1.1.1.2OH]DHP and [C₄mim]DHP showed solid–solid phase transition(s) and showed a final entropy of fusion lower than 20 J K⁻¹ mol⁻¹ which is consistent with Timmerman’s criterion for molecular plastic crystals. The ionic conductivity of [N_1.1.1.2OH]DHP was in the range of 10⁻⁶ S cm⁻¹–10⁻³ S cm⁻¹ in the plastic crystalline phase. On the other hand, the ionic conductivity of [C₄mim]DHP showed about 10⁻⁵ S cm⁻¹ in the plastic crystalline phase. [N_1.1.1.2OH]DHP showed one order of magnitude higher ionic conductivity than [C₄mim]DHP in the temperature range where the plastic phase is stable.     

Nonlinear optical crystal BiAlGa2(BO3)4

The new nonlinear optical crystals BiAlGa₂(BO₃)₄ have been grown by spontaneous crystallization with molten flux based on a Bi₂O₃–B₂O₃ solvent. From single crystal X-ray diffraction measurement, BiAlGa₂(BO₃)₄ has been found to crystallize in the trigonal huntite structure type, space group R32, with cell dimensions a = 9.4433(9) and c = 7.4130(10) Å. The diffuse reflectance spectrum on a powder sample indicated that the short-wavelength absorption edge of BiAlGa₂(BO₃)₄ extends to approximately 271 nm. Second-harmonic generation (SHG) on powder samples has been measured using Kurtz and Perry technique, which indicated that BiAlGa₂(BO₃)₄ is a phase-matchable material, and its SHG coefficient is measured to be four times as large as that of KDP.     

Synthesis,growth, and characterization of a new NLO material 3-(2,3-dimethoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one

3-(2,3-Dimethoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (DMPP) a potential second harmonic generating (SHG) has been synthesized and grown as a single crystal by the slow evaporation technique at ambient temperature. The structure determination of the grown crystal was done by single crystal X-ray diffraction study. DMPP crystallizes with orthorhombic system with cell parameters a = 20.3106(8) Å, b = 4.9574(2) Å, c = 13.4863(5) Å, α = 90°, β = 90°, γ = 90° and space group Pca2₁. The crystals were characterized by FT-IR, thermal analysis, UV–vis–NIR spectroscopy and SHG measurements. Various functional groups present in DMPP were ascertained by FTIR analysis. DMPP is thermally stable up to 80 °C and optically transparent in the visible region. The crystal exhibits SHG efficiency comparable to that of KDP.     

Mesoporous TiO2−xAy (A = N,S) as a visible-light-response photocatalyst

Mesoporous TiO_2?xA_y (A = N, S) thin films were fabricated using thiourea as a doping resource by a combination of sol-gel and evaporation-induced self-assembly (EISA) processes. The results showed that thiourea could serve two functions of co-doping nitrogen and sulfur and changing the mesoporous structure of TiO₂ thin films. The resultant mesoporous TiO_2?xA_y (A = N, S) exhibited anatase framework with a high porosity and a narrow pore distribution. The formation of the O–Ti–N and O–Ti–S bonds in the mesoporous TiO_2?xA_y (A = N, S) were substantiated by the XPS spectra. A new bandgap in visible light region (520 nm) corresponding to 2.38 eV could be formed by the co-doping. After being illuminated for 3 h, methyl orange could be degraded nearly completely by the co-doped sample under both ultraviolet irradiation and visible light illumination. While pure mesoporous TiO₂ could only degrade 60% methyl orange under UV illumination and showed negligible photodegradation capability in the visible light range. Furthermore, the photo-induced hydrophilic activity of TiO₂ film was improved by the co-doping. The mesoporous microstructure and high visible light absorption could be attributed to their good photocatalytic acitivity and hydrophilicity.     

Growth and characterization of naphthalene single crystals grown by modified vertical Bridgman method

The large size 20 mm diameter naphthalene single crystals were grown by modified vertical Bridgman method. The optical quality of the grown crystal was analyzed by photoluminescence and ultraviolet visible absorption spectral measurements. Photoluminescence spectrum indicated violet emission at 410 nm. The UV–vis absorption spectrum shows the maximum at 219.32 nm. The microhardness measurements and differential thermal analysis performed to analyze the mechanical and thermal stability of the as grown crystals. The dielectric measurements were carried out at five frequencies, viz., 100 Hz, 1 kHz, 10 kHz, 100 kHz and 1 MHz and at various temperatures, ranging from 308 K to 348 K indicate an increase of the dielectric parameters with the increase of temperature at all the five frequencies. The conductivity of the material is understood to be more of electronic in nature. Also, the increase in the dielectric parameters with that of temperature is due to the temperature variation of electronic polarizability.