Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Synthesis and optical properties of tetragonal KTa0.6Nb0.4O3 nanoparticles

Tetragonal phase KTa_0.6Nb_0.4O₃ (KTN) nanoparticles have been prepared by hydrothermal method. The obtained particles were characterized by X-ray powder diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy and UV-vis absorption spectrum techniques. A systematic change in crystal structure from cubic to tetragonal is observed with the increase of reaction temperature and KOH concentration. Room temperature UV-vis absorption spectrums of KTN particles show that the band gap changes from 3.24 to 3.34 eV with grain size diminished, which reveals the existence of blue-shift phenomenon of absorption bands.     

Surface-functionalization of spherical silver nanoparticles with macrocyclic polyammonium cations and their potential for sensing phosphates

The synthesis of aqueous dispersion of spherical, underivatized silver nanoparticles (Ag-NPs) stabilized by macrocyclic polyammonium chlorides (MCPAC), [28]ane-(NH₂ ⁺)₆O₂·6Cl⁻ (28-MCPAC) and [32]ane-(NH₂ ⁺)₈·8Cl⁻ (32-MCPAC), which are evidently anion receptors, is reported. As-synthesized Ag-NPs are characterized by UV-vis spectroscopy and transmission electron microscopy (TEM). The 28/32-MCPAC-stabilized Ag-NPs show the surface plasmon band around 400 nm. The TEM-images show that the particles are spherical and well-dispersed. By tuning the 28/32-MCPAC:Ag-OAc (silver acetate) ratio, nanoparticles with different core diameters ranging from 13 to 8 nm for 28-MCPAC and from 10 to 6 nm for 32-MCPAC can be obtained. The advantage of using MCPAC as stabilizers is that they make the particles functionalized for sensing anions. Thus, the potential of the as-synthesized Ag-NPs for sensing phosphates: H₂PO₄ ⁻ (monobasic phosphate, MBP), HPO₄ ²⁻ (dibasic phosphate, DBP) and PO₄ ³⁻ (tribasic phosphate, TBP) is investigated spectroscopically. Interaction of phosphate ions with macrocyclic polyammonium cations makes the Ag-NPs bare, leading agglomeration. The phosphate-assisted agglomeration of 32-MCPAC-Ag-NPs follow the order TBP > DBP ≫ MBP. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Real-time SAXS and ultraviolet-visible spectral studies on size and shape evolution of gold nanoparticles in aqueous solution

Gold nanoparticles were synthesized with seed mediated wet growth method. A coexistent system with gold nanorods and nanospheres was prepared. In-situ real-time small angle X-ray scattering (SAXS) and ultraviolet-visible (UV-vis) absorption were used to monitor the growth process of Au nanoparticles in the aqueous solution. Combining SAXS measurement and UV-vis spectra, the contribution of gold nanorods was separated from that of gold nanospheres. The growth behavior of the gold nanorods and the gold nanospheres was studied. The size and shape evolution of both gold nanoparticles as well as their volume fractions were obtained. After adding the seed-solution into the growth solution to form a particle suspension, within the first 18 min, a mutual competitive growth occurred between the gold nanorods and nanospheres. And their average particle sizes always increased with growth time. 18-min later, the evolution of size and shape of gold nanoparticles was almost stopped. The results demonstrate that the aspect ratio of gold nanorods in the particle suspension follows an exponential decay change after the initial 5-min growth. The evolution process of size and shape of gold nanoparticles in the particle suspension has been discussed.     

Spectroscopic characterization approach to study surfactants effect on ZnO2 nanoparticles synthesis by laser ablation process

Zinc peroxide nanoparticles having grain size less than 5 nm were synthesized using pulsed laser ablation in aqueous solution in the presence of different surfactants and solid zinc target in 3% H₂O₂. The effect of surfactants on the optical and structure of ZnO₂ was studied by applying different spectroscopic techniques. Structural properties and grain size of the synthesized nanoparticles were studied using XRD method. The presence of the cubic phase of zinc peroxide in all samples was confirmed with XRD, and the grain sizes were 4.7, 3.7, 3.3 and 2.8 nm in pure H₂O₂, and H₂O₂ mixed with SDS, CTAB and OGM respectively. For optical characterization, FTIR transmittance spectra of ZnO₂ nanoparticles prepared with and without surfactants show a characteristic ZnO₂ absorption at 435-445 cm⁻¹. FTIR spectrum revealed that the adsorbed surfactants on zinc peroxide disappeared in case of CTAB and OGM while it appears in case of SDS. This could be due to high critical micelles SDS concentration comparing with others which is attributed to the adsorption anionic nature of this surfactant. Both FTIR and UV-vis spectra show a red shift in the presence of SDS and blue shift in the presence of CTAB and OGM. The blue shift in the absorption edge indicates the quantum confinement property of nanoparticles. The zinc peroxide nanoparticles prepared in additives-free media was also characterized by Raman spectra which show the characteristic peaks at 830-840 and 420-440 cm⁻¹.     

Effect of melt compounding temperature on dielectric relaxation and ionic conduction in PEO–NaClO<Subscript>4</Subscript>–MMT nanocomposite electrolytes

Polymer nanocomposite electrolytes (PNCEs) of poly(ethylene oxide) and sodium perchlorate monohydrate complexes with montmorillonite (MMT) clay up to 20 wt.% MMT concentration of poly(ethylene oxide) (PEO) are synthesized by melt compounding technique at melting temperature of PEO (∼70 °C) and NaClO₄ monohydrate (∼140 °C). Complex dielectric function, electric modulus, alternating current (ac) electrical conductivity, and impedance properties of these PNCEs films are investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The direct current conductivity of these materials was determined by fitting the frequency-dependent ac conductivity spectra to the Jonscher power law. The PNCEs films synthesized at melting temperature of NaClO₄ monohydrate have conductivity values lower than that of synthesized at PEO melting temperature. The complex impedance plane plots of these PNCEs films have a semicircular arc in upper frequency region corresponding to the bulk material properties and are followed by a spike in the lower frequency range owing to the electrode polarization phenomena. Relaxation times of electrode polarization and ionic conduction relaxation processes are determined from the frequency values corresponding to peaks in loss tangent and electric modulus loss spectra, respectively. A correlation is observed between the ionic conductivity and dielectric relaxation processes in the investigated PNCEs materials of varying MMT clay concentration. The scaled ac conductivity spectra of these PNCEs materials also obey the ac universality law.     

Ultrasonic investigation of magnetic nanoparticles suspension with PEG biocompatible coating

Water suspension of nanoparticles was studied by ultrasound spectroscopy. Nanoparticles have a core-shell structure with magnetic core Fe₃O₄ and surfactant shells. The surface of magnetic particles was coated with oleate sodium as the primary layer and polyethylene glycol as the secondary layer. The acoustic properties of suspensions, such as velocity and attenuation of ultrasonic waves, have been measured. From experimental data mechanical properties have been determined. Adiabatic compressibility of nanoparticles suspension decreased with increase of temperature. The changes of ultrasonic wave attenuation under the influence of the external magnetic field, show that magnetic liquids with high concentration of magnetic material (despite two surfactant shells) show tendency to aggregate.     

Dielectric spectroscopy and confirmation of ion conduction mechanism in direct melt compounded hot-press polymer nanocomposite electrolytes

Solid-type polymer nanocomposite electrolyte (PNCE) comprising poly(ethylene oxide) (PEO), lithium perchlorate (LiClO₄) and montmorillonite (MMT) nano-platelets were synthesized by direct melt compounded hot-press technique at 70 °C under 3 tons of pressure. The spectra of complex dielectric function, electric modulus and alternating current (ac) electrical conductivity, and complex impedance plane plots of these materials were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. The variation of electrode polarization and ionic conduction relaxation times with MMT concentration up to 20 wt.% confirms their strong correlation with direct current ionic conductivity. The predominance of exfoliated MMT structures in PEO matrix and their effect on cation conduction mechanism and ion pairing were discussed by considering a supramolecular transient cross-linked structure. The normalized ac conductivity as a function of scaled frequency of these PNCE materials obey the universal time–concentration superposition behaviour alike the disordered solid ionic conductors.     

Preparation and Properties of Novel Modified Humidity Control Composite Materials

Montmorillonite /polyacrylamide (MMT/PAM) humidity control materials, with the MMT modified separatly by argent-ammonium complex ions ([Ag(NH₃)₂]⁺) and copper ions (Cu²⁺) (Ag-MMT/PAM, Cu-MMT/PAM) were prepared. The structures of the Ag-MMT/PAM and Cu-MMT/PAM were characterized with X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR) and scanning electron microscopy (SEM). The humidity control property was examined by a desiccator method. Antibacterial properties were tested with an inhibition zone method. The results showed that the structures of Ag-MMT/PAM and Cu-MMT/PAM were loose and porous. Polyacrylamide was intercalated into the layers of the MMT. The increasing interlayer spacings of Ag-MMT/PAM and Cu-MMT/PAM were from 1.51 nm for the original MMT to 2.04 nm and 2.11 nm, respectively. Both Ag-MMT/PAM and Cu-MMT/PAM presented good humidity control and antibacterial properties.     

Synthesis and structural properties of polypyrrole/nano-Y2O3 conducting composite

In this work, polypyrrole/nano-Y₂O₃ conducting composite was synthesized by chemical oxidative polymerization. The composite was characterized using transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectra, UV-vis absorption spectra, X-ray photoelectron spectroscopy and electrical conductivity measurements. The results indicate that Y₂O₃ nanoparticles are almost enwrapped by polypyrrole. The addition of Y₂O₃ nanoparticles results in changes in the surface structure and conductivity of the composite. Thermogravimetric analysis shows that composite has better thermal stability than that of pure polypyrrole.     

Formation of ZnO@Cd(OH)2 core-shell nanoparticles by sol-gel method: An approach to modify surface chemistry for stable and enhanced green emission

We report the formation of highly stable and luminescent ZnO@Cd(OH)₂ core-shell nanoparticles by simple introduction of cadmium salt in the initial precursor solution, used to synthesize ZnO nanoparticles by sol-gel route. The cadmium to zinc salt concentration ratio has been also varied to control the growth of ZnO nanoparticles at the smaller particle size. Formation of ZnO@Cd(OH)₂ core-shell nanostructure has been confirmed by X-ray diffraction (XRD), energy dispersive analysis of X-rays (EDAX) and X-ray photoelectron spectroscopy (XPS). UV-vis absorption spectroscopy exhibits blue-shift in absorption edge on increasing cadmium concentrations. The photoluminescence emission spectra showed the remarkably stable and enhanced visible (green) emission from suspended ZnO@Cd(OH)₂ nanoparticles in comparison to bare ZnO nanoparticles. It is postulated that Cd(OH)₂ layer at the surface of ZnO nanoparticles prevents the agglomeration of nanoparticles and efficiently assists the trapping of hole at the surface site, a first step necessary for visible emission. The Fourier transform infrared spectroscopy (FTIR) also supports our assumption about surface chemistry.     

Carbonization of Chitosan in Palladium-Chitosan/ Montmorillonite Composites to Prepare Novel Heterogeneous Catalysts for Heck Reactions

Palladium-carbon/montmorillonite (Pd-C/MMT) heterogeneous catalysts were prepared by carbonization of chitosan in palladium-chitosan/montmorillonite (Pd-CS/MMT) composites under a N₂ atmosphere. The main purpose of this study was to determine the effects of the carbonization temperature (250, 450, and 650°C) on the material microstructure and its catalytic performance. X-ray diffraction patterns revealed that the formation of an intercalation of the carbonaceous material between the clay mineral layers which was also confirmed by Fourier transform infrared spectra results. The N content of the Pd-C/MMT catalyst decreased as the carbonization temperature was increased. Thermogravimetry curves revealed that the thermal stability of the Pd-C/MMT catalyst increased obviously as the carbonization temperature was increased. Pd nanoparticles, sized at about 20 nm, were mainly dispersed on the surface of the MMT, as observed by high-resolution transmission electron microscopy (HR-TEM). The prepared Pd-C/MMT catalysts had good catalytic activity when applied in Heck coupling reactions of aromatic halides and alkenes to produce aryl olefins. The relations between the recyclability and the material composition are discussed.     

Synthesis and photophysical properties of novel polymeric Eu(III) complex with bicoordination ligand

A novel complex of Eu(III) with bicoordination ligand: 4,4′-bis[2-(2′-pyridyl) benzimidazol-yl]-biphenyl (Bmbp) has been synthesized. The structure of the ligand was characterized by ¹H NMR, FT-IR and UV-vis; Eu(III) complex was characterized by FT-IR, UV-vis, elemental analysis, conductivity measurements and gel-permeation chromatography (GPC). The luminescence properties were investigated by UV-vis and fluorescence spectra. The experimental results show that the complex contain more than one Eu(III) ion, the emission at 614 nm from the ⁵D₀→⁷F₂ electronic dipole transition is large enhanced, and the complex is excellent energy transfer from ligand to Eu³⁺in the solid state. Thermal property measurement and analysis show that it has a good thermal stability.     

银纳米粒子自组织二维有序阵列

采用液液二相转移方法合成出颗粒直径为(4.18±0.5)nm的银纳米粒子溶胶,并用紫外可见光谱对所制得的银纳米粒子溶胶的单分散性和稳定性进行了研究.结果表明,所得到的溶胶相为稳定的、粒径分布窄的单分散体系.红外光谱的分析结果表明,稳定剂1壬基硫醇包缚在银纳米粒子表面.并且,通过自组织方法获得了二维有序的银纳米粒子阵列 关键词： 银纳米粒子 液液二相转移方法 自组织 二维有序阵列     

Synthesis and characterization of CdS/PVA nanocomposite films

A series CdS/PVA nanocomposite films with different amount of Cd salt have been prepared by means of the in situ synthesis method via the reaction of Cd²⁺-dispersed poly vinyl-alcohol (PVA) with H₂S. The as-prepared films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) spectra, Fourier transform infrared spectroscope (FTIR) and thermogravimetric analysis (TGA). The XRD results indicated the formation of CdS nanoparticles with hexagonal phase in the PVA matrix. The primary FTIR spectra of CdS/PVA nanocomposite in different processing stages have been discussed. The vibrational absorption peak of CdS bond at 405 cm⁻¹ was observed, which further testified the generation of CdS nanoparticles. The TGA results showed incorporation of CdS nanoparticles significantly altered the thermal properties of PVA matrix. The photoluminescence and UV-vis spectroscopy revealed that the CdS/PVA films showed quantum confinement effect.     

Enhanced magnetic and optical properties of pure and (Mn,Sr) doped BiFeO3 nanocrystals

Pure and (Mn, Sr) doped BiFeO₃ nanoparticles with the diameter in the range of 30–100 nm were controllably synthesized by a soft chemical method at a relatively low temperature. The diameter of the product was well controlled by adjusting the concentration of tartaric acid. Vibrating sample magnetometer (VSM) measurements verified that great enhancement of ferromagnetic property could be achieved either by decreasing their diameter or adding doping ions (Mn, Sr). Having suppressed the spiral spin structure, BiFeO₃ nanoparticles with perfect ferroelectric and ferromagnetic properties were excellent in ferroelectromagnet applications. The photoluminescent property of BiFeO₃ nanoparticles was also investigated in order to exploiting their possible application in nanoscale optoelectronic devices.     

Preparation of magnetite aqueous dispersion for magnetic fluid hyperthermia

An aqueous magnetic suspension was prepared by dispersing amphiphilic co-polymer-coated monodispersed magnetite nanoparticles synthesized through thermal decomposition of iron acetylacetonate (Fe(acac)₃) in a mixture of oleic acid and oleylamine. The average diameter of narrow-size-distributed magnetite nanoparticles varied between 5 and 12 nm depending on the experimental parameters such as reaction temperature, metal salt concentration and oleic acid/oleylamine ratio. Though the as-synthesized particles were coated with oleate and were dispersible in organic solvent, their surfaces were modified using amphiphilic co-polymers composed of poly(maleic anhydride-alt-1-octadecene) and polyethylene glycol-methyl ether and made dispersible in water. Infrared spectra of the sample indicated the existence of −COOH groups on the surface for further conjugation with biomolecules for targeted cancer therapy.     

Photo- and cathodoluminescence of the cetylpyridinium chloride: ZnO nanocomposites

The cathodoluminescence and photoluminescence (PL) spectra of ZnO nanoparticles (NPs) embedded into the cetylpyridinium chloride (CPCL) matrix were studied. The composites were obtained by drying an aqueous suspension of CPCL and ZnO NPs, with NaCl and with NaOH additives. We observed that only NaOH addition lead to a significant increase in the PL intensity which we attribute to the surface chemistry of the ZnO NPs. We propose that thin ZnOH₂ and Na₂ZnO₂ layers form on the surface of the NPs; these layers present an increased number of oxygen vacancies, which act as emitting centres.     

Preparation and characterization of graphene/CdS nanocomposites

Graphene-based nanocomposites are emerging as a new class of materials that hold promise for many applications. In this paper, we present a facile approach for the preparation of graphene/CdS nanocomposites through simple reflux processes, in which thiourea (CS(NH₂)₂) and thioacetamide (C₂H₅NS) act as a sulphide source, respectively. The samples were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrum (FT-IR), ultraviolet-visible (UV-vis) spectroscopy and thermogravimetry analysis. It was shown that in the nanocomposites, the CdS nanoparticles were densely and uniformly deposited on the graphene sheets, and the sulphide source used has a great influence on the morphology, structure and property of the graphene/CdS nanocomposites. The good distribution of CdS nanoparticles on graphene sheets guarantees the efficient optoelectronic properties of graphene/CdS and would be promising for practical applications in future nanotechnology.     

Constructing amorphous RuxOy on CuO/Cu2O nanowire arrays for improved oxygen evolution

More than 50% of engineered nanomaterials released into the environment contain silver nanoparticles (Ag-NPs). The mobility, bioavailability, and toxicity of engineered Ag-NPs are known to depend on their properties and the environmental conditions. However, almost nothing is known about the fate of naturally occurring Ag-NPs, which are formed during the reduction of Ag⁺ by natural organic matter, primarily humic substances (HSs). The aim of this work was to study the interaction of soils and plants with simulated natural Ag-NPs, i.e., Ag-NPs stabilized with HSs (Ag-HS-NPs). To reach this goal, Ag-HS-NPs were synthesized, and their sorption-desorption behavior on two contrasting soils (a mineral soil and one rich in organic matter) was evaluated, including alterations in the mineral composition of the soil solution. In parallel, the influence of Ag-HS-NPs on wheat seedling growth was estimated. Introduction of Ag-HS-NPs into the soils resulted in a 1.3- to 2-fold or greater increase in the concentration of many elements in the soil solution (Al, Cr, Cu, Fe, etc.), and this effect was more pronounced for the organic soil than for the mineral soil. To explain this effect, we hypothesized that this phenomenon was due to the partial dissolution of Ag-HS-NPs leading to the production of Ag⁺ that could be further reduced by soil organic matter, which was correspondingly oxidized. Therefore, the partial breaking of soil aggregates because of the decomposition of soil organic matter in the presence of Ag-HS-NPs could be expected. Plants treated with Ag-HS-NPs demonstrated a lower rate of water uptake, which decreased by over 81%. The shoot and root biomass decreased by 15–17% and by 13–15%, respectively. This study clearly demonstrates an underestimated hazard of Ag-NPs formed in nature in terms of their ability to adversely affect the environment.