UV-induced synthesis,characterization and formation mechanism of silver nanoparticles in alkalic carboxymethylated chitosan solution

The silver nanoparticles (AgNPs) were synthesized in an alkalic aqueous solution of silver nitrate (AgNO₃)/carboxymethylated chitosan (CMCTS) with ultraviolet (UV) light irradiation. CMCTS, a water-soluble and biocompatible chitosan derivative, served simultaneously as a reducing agent for silver cation and a stabilizing agent for AgNPs in this method. UV–vis spectra and transmission electron microscopy (TEM) images analyses showed that the pH of AgNO₃/CMCTS aqueous solutions, the concentrations of AgNO₃ and CMCTS can affect on the size, amount of synthesized AgNPs. Further by polarized optical microscopy it was found that the CMCTS with a high molecular weight leads to a branch-like AgNPs/CMCTS composite morphology. The diameter range of the AgNPs was 2–8 nm and they can be dispersed stably in the alkalic CMCTS solution for more than 6 months. XRD pattern indicated that the AgNPs has cubic crystal structure. The spectra of laser photolysis of AgNO₃/CMCTS aqueous solutions identified the early reduction processes of silver cations (Ag⁺) by hydrated electron formed by photoionization of CMCTS. The rate constant of corresponding reduction reaction was 5.0 × 10⁹ M⁻¹ s⁻¹.     

Rapid extra-/intracellular biosynthesis of gold nanoparticles by the fungus <Emphasis Type="Italic">Penicillium</Emphasis> sp.

In this work, the fungus Penicillium was used for rapid extra-/intracellular biosynthesis of gold nanoparticles. AuCl₄ ⁻ ions reacted with the cell filtrate of Penicillium sp. resulting in extracellular biosynthesis of gold nanoparticles within 1 min. Intracellular biosynthesis of gold nanoparticles was obtained by incubating AuCl₄ ⁻ solution with fungal biomass for 8 h. The gold nanoparticles were characterized by means of visual observation, UV–Vis absorption spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The extracellular nanoparticles exhibited maximum absorbance at 545 nm in UV–Vis spectroscopy. The XRD spectrum showed Bragg reflections corresponding to the gold nanocrystals. TEM exhibited the formed spherical gold nanoparticles in the size range from 30 to 50 nm with an average size of 45 nm. SEM and TEM revealed that the intracellular gold nanoparticles were well dispersed on the cell wall and within the cell, and they are mostly spherical in shape with an average diameter of 50 nm. The presence of gold was confirmed by EDX analysis.     

Nanocrystalline GdAlO3: XPS,EPR and magnetic susceptibility studies

Nanocrystalline gadolinium monoaluminate (GdAlO₃) has been synthesized by sol–gel method after sintering the precursor gel at 950°C. The microstructural features have been proved by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray analysis (EDX). The XRD pattern confirms the formation of single-phase GdAlO₃ while EDX shows that this nanomaterial is stoichiometric; the average size of the nanoparticles is 40 nm. X-ray photoelectron spectroscopy (XPS) has been used to study the chemical composition and bonding in the as-prepared samples. The binding energies of core-level electrons in Gd, Al and O in GdAlO₃ nanopowder have been found slightly shifted compared to the corresponding values of the same elements. The electron paramagnetic resonance (EPR) spectra at 9.23 GHz (X-band) and different temperatures indicate the existence of magnetically concentrated solid containing Gd³⁺ ions. Nèel temperature, T _N =3.993 K, effective Bohr magneton number, μ _eff=8.18, and constant of magnetic exchange interaction, J _ex=−0.069 cm⁻¹, have been determined from DC magnetic susceptibilities measured in the range 2–300 K.     

Synthesis and characterization of ZnCo2O4 nanomaterial for symmetric supercapacitor applications

ZnCo₂O₄ nanomaterial was prepared by co-precipitation method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), and galvanostatic charge–discharge tests at various current densities. It is shown that the crystal structure and surface morphology play an important role in the enhancement of the specific capacitance. The TEM results clearly indicate that the prepared material shows aggregated particles. The particle size powder was about 50 nm, and SEM pictures indicate a porous morphology. The electrochemical behavior of ZnCo₂O₄ was characterized by mixing equal proportion of carbon nanofoam (CNF). From CV, it is concluded that the combination of redox and pseudo-capacitance increases the specific capacitance up to 77 F g⁻¹ at 5 mV s⁻¹ scan rate. The ZnCo₂O₄-based supercapacitor cell has good cyclic stability and high coulombic efficiency.     

Nanosized IrO<Subscript>2</Subscript> electrocatalysts for oxygen evolution reaction in an SPE electrolyzer

Nanosized IrO₂ electrocatalysts (d ~ 7–9 nm) with specific surface area up to 100 m² g⁻¹ were synthesized and characterized for the oxygen evolution reaction in a solid polymer electrolyte (SPE) electrolyzer. The catalysts were prepared by a colloidal method in aqueous solution and a subsequent thermal treatment. An iridium hydroxide hydrate precursor was obtained at ~100 °C, which was, successively, calcined at different temperatures from 200 to 500 °C. The physico-chemical characterization was carried out by X-ray diffraction (XRD), thermogravimetry–differential scanning calorimetry (TG–DSC) and transmission electron microscopy (TEM). IrO₂ catalysts were sprayed onto a Nafion 115 membrane up to a loading of 3 mg cm⁻². A Pt catalyst was used at the cathode compartment with a loading of 0.6 mg cm⁻². The electrochemical activity for water electrolysis of the membrane-electrode assemblies (MEAs) was investigated in a single cell SPE electrolyzer by steady-state polarization curves, impedance spectroscopy and chrono-amperometric measurements. A maximum current density of 1.3 A cm⁻² was obtained at 1.8 V and 80 °C for the IrO₂ catalyst calcined at 400 °C for 1 h. A stable performance was recorded in single cell for this anode catalyst at 80 °C. The suitable catalytic activity and stability of the most performing catalyst were interpreted in terms of proper combination between nanostructure and suitable morphology.     

The direct precipitation of rhabdophane (REEPO<Subscript>4</Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O) nano-rods from acidic aqueous solutions at 5–100 °C

The precipitation of lanthanum and neodymium phosphate phases from supersaturated aqueous solutions at pH ~1.9 was studied at 5, 25, 50, and 100 °C in batch reactors for up to 168 h. Crystalline La and Nd–rhabdophane phases precipitated immediately upon mixing of the initial aqueous La or Nd and PO₄ solutions. Changes in aqueous PO₄ and Rare Earth Element (REE) concentrations during the experiments were determined by ICP-MS and UV–Vis spectrophotometry, while the resulting solids were characterized via powder XRD, SEM, TEM, and FTIR. All precipitated crystals exhibited a nano-rod morphology and their initial size depended on temperature and REE identity. At 5 °C and immediately after mixing the La and Nd–rhabdophane crystals averaged ~44 and 40 nm in length, respectively, while at 100 °C lengths were ~105 and 94 nm. After 168 h of reaction, the average length of the La and Nd rhabdophanes increased by 23 and 53% at 5 °C and 11 and 59% at 100 °C, respectively. The initial reactive solutions in all experiments had activity quotients for rhabdophane precipitation: \textREE ³⁺ + \textPO₄^{3 -} + n\textH₂ \textO = \textREEPO₄ ·  n\textH₂ \textO {\text{REE}}^{ 3+ } + {\text{PO}}_{4}^{3 - } + n{\text{H}}_{2} {\text{O}} = {\text{REEPO}}_{4} \cdot\;n{\text{H}}_{2} {\text{O}} of ~10^−20.5. This activity quotient decreased with time, consistent with rhabdophane precipitation. The rapid equilibration of rhabdophane supersaturated solutions and the progressive rhabdophane crystal growth observed suggests that the REE concentrations of many natural waters may be buffered by rhabdophane precipitation. In addition, this data can be used to guide crystallization reactions in industrial processes where monodisperse and crystalline La or Nd rhabdophane materials are the target.     

Influence of pH on the preparation of dispersed Ag–TiO<Subscript>2</Subscript> nanocomposite

In this paper, data concerning the effect of pH on the morphology of Ag–TiO₂ nanocomposite during photodeposition of Ag on TiO₂ nanoparticles is reported. TiO₂ nanoparticles prepared by sol–gel method were coated with Ag by photodeposition from an aqueous solution of AgNO₃ at various pH levels ranging from 1 to 10 in a titania sol, under UV light. The as-prepared nanocomposite particles were characterized by UV–vis absorption spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂ adsorption/desorption method at liquid nitrogen temperature (−196 °C) from Brunauer–Emmett–Teller (BET) measurements. It is shown that at a Ag loading of 1.25 wt.% on TiO₂, a high-surface area nanocomposite morphology corresponding to an average of one Ag nanoparticle per titania nanoparticle was achieved. The diameter of the titania crystallites/particles were in the range of 10–20 nm while the size of Ag particles attached to the larger titania particles were 3 ± 1 nm as deduced from crystallite size by XRD and particle size by TEM. Ag recovery by photo harvesting from the solution was nearly 100%. TEM micrographs revealed that Ag-coated TiO₂ nanoparticles showed a sharp increase in the degree of agglomeration for nanocomposites prepared at basic pH values, with a corresponding sharp decrease in BET surface area especially at pH > 9. The BET surface area of the Ag–TiO₂ nanoparticles was nearly constant at around a value of 140 m² g⁻¹ at all pH from 1–8 with an anomalous maximum of 164 m² g⁻¹ when prepared from a sol at pH of 4, and a sharp decrease to 78 m² g⁻¹ at pH of 10.     

Luminescent properties of YVO4:Eu/SiO2 core–shell composite particles

We report an efficient process for preparing monodisperse SiO₂@Y_0.95Eu_0.05VO₄ core–shell phosphors using a simple citrate sol–gel method and without the use of surface-coupling silane agents or large stabilizers. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectra were used to characterize the resulting SiO₂@Y_0.95Eu_0.05VO₄ core–shell phosphors. The XRD results demonstrate that the Y_0.95Eu_0.05VO₄ particles crystallization on the surface of SiO₂ annealing at 800 °C is perfectly and the crystallinity increases with raising the annealing temperature. The obtained core–shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 500 nm and an average thickness of ~50 nm), are not agglomerated, and have a smooth surface. The thickness of the YVO₄:Eu³⁺ shells on the SiO₂ cores could be easily tailored by changing the mass ratio of shell to core (W = [YVO₄]/[SiO₂]) (~50 nm for W = 30%). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀ − ⁷F₂ red emission at 618 nm) under the excitation of 320 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the values of W.     

Characterization and photoluminescence studies of Eu<Superscript>2+</Superscript>-doped BaSO<Subscript>4</Subscript> phosphor prepared by the recrystallization method

Eu doped BaSO₄ was prepared by the recrystallization method and characterization of the material was done by using X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. From the XRD pattern of Eu doped BaSO₄ compound, it was found that the prominent phase formed was BaSO₄ and traces of other phases were very weak and the result of FTIR spectrum of BaSO₄:Eu shows that the sulfur-oxygen stretch was found at around 1100 cm⁻¹. The room-temperature PL spectra of the Eu doped BaSO₄ sample showed one peak centered at 374 nm, which is the characteristic emission of Eu²⁺ ion. This emission band at 374 nm corresponds to the 4f⁶ 5d→4f⁷ (⁸S_7/2) transitions of Eu²⁺ ions. The excitation spectrum taken at the wavelength 374 nm extends over a wide range of wavelengths from 220–350 nm with a strong peak at around 260 nm. Furthermore, the present sample shows good crystal quality and high photoluminescence sensitivity. Hence our results suggest possible potential applications of Eu doped BaSO₄ phosphor in optoelectronic devices.     

Facile synthesis of additive-assisted nano goethite powder and its application for fluoride remediation

The present article describes a novel synthesis route for nano-sized goethite (α-FeOOH) using hydrazine sulphate as an additive. The X-ray diffraction (XRD) peaks of synthesized powder matched well with those of α-FeOOH. Transmission electron microscopy (TEM) showed the particles of irregular shape in the range of 1–10 nm. Batch adsorption experiments for fluoride uptake were performed to study the influence of various experimental parameters such as contact time (10 min to 7 h), initial fluoride concentration (10–150 mg L⁻¹), pH (2–11.6) and the presence of competing anions. The time data fitted well to pseudo-second-order kinetic model. The fluoride removal passed through broad maxima in pH ranges of 6–8. High adsorption capacity of 59 mg g⁻¹ goethite was obtained. The isothermic data fitted well to Freundlich model. The presence of other ions namely chloride and sulphate adversely affected fluoride removal. Fluoride from contaminated water sample could be successfully brought down from 10.25 to 0.5 mg L⁻¹.     

Electrical study and dielectric relaxation behavior in?nanocrystalline Ce0.85Gd0.15O2?δ material at intermediate temperatures

The nanocrystalline material of 15 mol% Gd-doped ceria (Ce_0.85Gd_0.15O_2−δ ) was prepared by citrate auto ignition method. The electrical study and dielectric relaxation technique were applied to investigate the ionic transport process in this nanocrystalline material with an average grain size of 13 nm and the dynamic relaxation parameters are deduced in the temperature range of 300–600°C. The ionic transference number in the material is found to be 0.85 at 500°C at ambient conditions. The oxygen ionic conduction in the nanocrystalline Ce_0.85Gd_0.15O_2−δ material follows the hopping mechanism. The grain boundary relaxation is found to be associated with migration of charge carriers. The frequency spectra of modulus M″ exhibited a dielectric relaxation peak corresponding to defect associates (Gd-V_{o^{\blacksquare \blacksquare}})^{_\blacksquare}(\mathrm{Gd}\mbox{-}\mathrm{V}_{\mathrm{o}}^{_{_{{\blacksquare\,\blacksquare}}}})^{_{_{{\blacksquare}}}}. The material exhibits very low values of migration energy and association energy of the oxygen vacancies in the long-range motion, i.e., 0.84 and 0.07 eV, respectively.     

A method to study polydispersity of humic acid from fluorescence quenching by Cu<Superscript>2+</Superscript> ions

The spectral dependence of Stern–Volmer constants (K_SV^lK_{SV}^{\lambda} ) for fluorescence quenching by Cu²⁺ ions in a standard sample of humic acid (HA) (IHSS) with monochromatic excitation (λ_ex = 337.1 nm) conditions has been studied in the spectral range 400–600 nm. This is interpreted within a concept implying that HA macromolecules possess the property of polydispersity, which means that fluorophore-containing sites are different in terms of chemical nature and spatial accessibility. Modeling data show that the minimum number of spectral components required for the simulated spectral dependence of K_SV^lK_{SV}^{\lambda} to agree as closely as possible with that observed experimentally is three.     

Laser-based measurements of line strength, self- and pressure-broadening coefficients of the H35Cl R(3) absorption line in the first overtone region for pressures up to 1 MPa

A high-resolution spectrometer based on a vertical-cavity surface-emitting laser (VCSEL) was developed and used to determine the line strength S(T ₀)=12.53(11)×10⁻²¹ cm⁻¹/(molec cm⁻²) and the self-broadening coefficient g⁰_HCl=0.021787(61)\gamma^{0}_{\mathrm{HCl}}=0.021787(61)  cm⁻¹/atm of the R(3) absorption line in the first rovibrational overtone (2←0) band of H³⁵Cl. Furthermore, the first laser-based high-pressure study on the pressure broadening of HCl by He, N₂ and O₂(g⁰_N2=0.07292(5)\mathrm{O}_{2}(\gamma^{0}_{\mathrm{N}_{2}}=0.07292(5)  cm⁻¹/atm, g⁰_He=0.02113(1)\gamma^{0}_{\mathrm{He}}=0.02113(1)  cm⁻¹/atm, g⁰_O2=0.03978(6)\gamma^{0}_{\mathrm{O}_{2}}=0.03978(6)  cm⁻¹/atm) is presented covering pressures of up to 1 MPa. The results are compared to previously available low-pressure data.     

Preparation and characterization of polyindole–ZnO composite polymer electrolyte with LiClO<Subscript>4</Subscript>

This paper describes the preparation and conductivity studies of polyindole–ZnO composite polymer electrolyte (CPE) with LiClO₄. Polyindole–ZnO-based polymer nanocomposites were prepared by chemical method and characterized by XRD, infrared (IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The IR spectrum confirms the intermolecular interaction between polyindole and ZnO. The significant spectral changes of polyindole and ZnO nancomposites reveal the strong interaction between polyindole and ZnO nanoparticles. The structural morphologies of the ZnO, polyindole, and polyindole–ZnO are obtained from SEM. The TEM image of polyindole nanocomposite shows that ZnO is embedded in polyindole matrix. An enhanced conductivity of 4.405 × 10⁻⁷ S cm⁻¹ at 50 °C for the CPE was determined from impedance studies.     

Hydrothermal synthesis and photoluminescent properties of YV1 − xPxO4:Eu3+ (x = 0–1.0) nanophosphors

A simple hydrothermal process has been proposed to systematically synthesize europium-doped yttrium phosphate-vanadates with general formula YV_1 − xP_xO₄:Eu³⁺ (x = 0–1.0). All the YV_1 − xP_xO₄:Eu³⁺ products were characterized by x-ray diffraction (XRD) and transmission electron microscopy (TEM), the results of which revealed they were single-phase tetragonal-structured nanocrystals with diameter of 20 nm and their cell parameter a exhibited a linear relationship with the x value. Photoluminescence (PL) excitation and emission intensities of the products were sensitive to the x value and the change of the PL intensity with x was a wave-like curve which reached the peak at x = 0.4 and 0.8. In addition, the x value had an obvious influence on the (⁵D⁰–⁷F₂)/(⁵D₀–⁷F₁) intensity ratio of Eu³⁺.     

Plasma with two-negative ions and immobile dust particles: planar and non-planar ion-acoustic wave propagation

By using the hydrodynamic equations of positive and two negative ions, Boltzmann electron density distribution, and Poisson equation with immobile positive/negative dust particles, a cylindrical Korteweg-de Vries (CKdV) equation is derived for small but finite amplitude ion-acoustic waves. At the critical total negative ion concentration and/or the critical density rate of the second-negative ions, the pulses collapse at this limit as nonlinearity fails to balance dispersion. Then the CKdV equation is not appropriate to describe the system. Therefore, the modified CKdV (MCKdV) and extended CKdV (ECKdV) equations are derived at the critical plasma compositions and in the vicinity of the critical plasma compositions, respectively. The physical parameters of two plasma environments (e.g., Xe⁺–F^-–SF₆^-_{6}^{-} and Ar⁺–F^-–SF₆^-_{6}^{-} plasmas) are examined on the wave phase velocity and the nonlinear localized pulse profile. The latter should satisfy necessary condition to exist. The localized pulse of Ar⁺–F^-–SF₆^-_{6}^{-} plasma is much spiky than Xe⁺–F^-–SF₆^-_{6}^{-} plasma. Thus, the mass ratio of the negative-to-positive ions is focused upon and it emphasizes to play an important role on the pulse profile. Dependence of the geometrical divergence on the pulse profile is also investigated, which indicates that the localized pulse damps with time. The implications of our results agrees with the experimental observations.     

Size control synthesis of starch capped-gold nanoparticles

Metallic gold nanoparticles have been synthesized by the reduction of chloroaurate anions [AuCl₄]⁻ solution with hydrazine in the aqueous starch and ethylene glycol solution at room temperature and at atmospheric pressure. The characterization of synthesized gold nanoparticles by UV–vis spectroscopy, high resolution transmission electron microscopy (HRTEM), electron diffraction analysis, X-ray diffraction (XRD), and X-rays photoelectron spectroscopy (XPS) indicate that average size of pure gold nanoparticles is 3.5 nm, they are spherical in shape and are pure metallic gold. The concentration effects of [AuCl₄]⁻ anions, starch, ethylene glycol, and hydrazine, on particle size, were investigated, and the stabilization mechanism of Au nanoparticles by starch polymer molecules was also studied by FT-IR and thermogravimetric analysis (TGA). FT-IR and TGA analysis shows that hydroxyl groups of starch are responsible of capping and stabilizing gold nanoparticles. The UV–vis spectrum of these samples shows that there is blue shift in surface plasmon resonance peak with decrease in particle size due to the quantum confinement effect, a supporting evidence of formation of gold nanoparticles and this shift remains stable even after 3 months.     

An ab initio molecular dynamics study of ionic conductivity in hexagonal lithium lanthanum titanate oxide La0.5Li0.5TiO3

To date, the fastest lithium ion-conducting solid electrolytes known are the perovskite-type ABO₃ oxide, with A = Li, La and B = Ti, lithium lanthanum titanate (LLTO) Li_3x La_{( 2 \mathord}

Optical characterization in Pb(Zr1?xTix)1?yNbyO3 ferroelectric ceramic system

In this work, visible photoluminescence was observed at room temperature in a sintered Pb(Zr_1-xTi_x)_1-y Nb_yO₃\mathrm{Pb}(\mathrm{Zr}_{1-x}\mathrm{Ti}_{x})_{1-y} \mathrm{Nb}_{y}\mathrm{O}_{3} perovskite-type structure system, doped with Nb using the next excitation bands 325, 373 and 457 nm. The intensity and energy of such emissions have been studied by changing the Nb concentration (0<y<0.01) and the Ti content (x), with x=0.20,0.40,0.53,0.60 and 0.80, on both sides of the morphotropic phase boundary (MPB) zone. The principal bands become visible at energies of 1.73, 2.56 and 3.35 eV. The results reveal the role of the Nb⁵⁺ ion substitutions by Zr⁴⁺ or Ti⁴⁺ ions and the symmetry presented in the rhombohedral or tetragonal side of the MPB. Raman spectra which are similar for compositions: 20/80, 40/60 and 53/47 (tetragonal phases) show nine bands, centered around 137, 194, 269, 331, 434, 550, 612, 712 and 750 cm⁻¹. The spectra for samples 60/40 and 80/20, rhombohedral phase, show significant differences, only six bands appear, centered around 124, 209, 234, 330, 549 and 682 cm⁻¹. In addition, optical absorption spectroscopy, structural and micro-structural measurements were carried out by using Uv-vis spectroscopy, X-ray diffraction and scanning electron microscopy techniques, respectively. The experimental results of band gap energy, e.g., in our samples are in accordance with the findings by J. Baedi et al. in the calculations of band structure, energy gap and density of states for different phases of Pb(Zr_1−x Ti _x )O₃ using density functional theory (DFT).     

The effect of sub-band gap photon illumination on the properties of GaN layers grown on Si(111) by MBE

Nanostructured GaN layers are fabricated by laser-induced etching processes based on heterostructure of n-type GaN/AlN/Si grown on n-type Si(111) substrate. The effect of varying laser power density on the morphology of GaN nanostructure layer is observed. The formation of pores over the structure varies in size and shape. The etched samples exhibit dramatic increase in photoluminescence intensity compared to the as-grown samples. The Raman spectra also display strong band at 522 cm⁻¹ for the Si(111) substrate and a small band at 301 cm⁻¹ because of the acoustic phonons of Si. Two Raman active optical phonons are assigned h-GaN at 139 and 568 cm⁻¹ due to E2 (low) and E2 (high), respectively. Surface morphology and structural properties of nanostructures are characterized using scanning electron microscopy and X-ray diffraction. Photoluminance measurement is also taken at room temperature by using He–Cd laser (λ = 325 nm). Raman scattering is investigated using Ar⁺ Laser (λ = 514 nm).