Synthesis and Characterization of Cadmium Selenide (CdSe) Nanoparticles Using Trigonal Selenium (t-Se) Nanorods as Selenium Source

Cadmium selenide (CdSe) nanoparticles were synthesized through colloidal method in aqueous medium using the reaction intermediates selenium nanorods as selenium source. Trigonal selenium nanorods (t-Se) were synthesized in water by the reduction method in the presence of sodium borohydride at 60?°C using sodium selenite (Na₂SeO₃) as selenium source. These selenium nanorods were further utilized to synthesis cadmium selenide nanoparticles at 100?°C in water. The synthesized nanorods and nanoparticles were characterized using XRD, SEM, TEM and XPS analysis. X-ray diffraction (XRD) analysis shown that the nanorods possess trigonal phase while the nanoparticles possess a cubic zinc blende structure. Scanning electron microscope (SEM) analysis of the prepared hexagonal shaped nanorods reveals the diameter of the nanorods are about 150 nm. Transmission electron microscopy (TEM) analysis shows the size of the synthesized CdSe nanoparticles are about 4–8 nm. X-ray photoelectron spectroscopy (XPS) analysis illustrates the presence of respective elements Cd, Se with its corresponding oxidation states. The activity of nano selenium rods in aqueous solution during the conversion of cadmium selenide nanoparticles was discussed.     

Solvent free mechanochemical synthesis of MnO2 for the efficient degradation of Rhodamine-B

MnO₂ nanorods were synthesized by mechanochemical processing with subsequent heat treatment and their photocatalytic activity was studied on the decolourization of aqueous solution of Rhodamine B at different pH levels. A solid state redox reaction 2KMnO₄ + MnCl₂ → 3MnO₂ + 2KCl + O₂ was activated during mechanical milling. Excess KCl salt was added in the starting powder mixture to prevent agglomeration of MnO₂ nanoparticles. The milling resulted in the production of amorphous MnO₂ nanoparticles with a high surface area of 204 m² g^?1. Crystalline MnO₂ nanorods of diameters about 15–20 nm were produced by heating the as-milled powder at 350 °C for 1 h in air. Amorphous MnO₂ nanoparticles showed higher degradation rate of Rhodamine B than crystalline MnO₂ nanorods under simulated sunlight. The degradation rate was higher under acidic conditions. This work demonstrates the potential for cost effective, green and scalable synthesis of MnO₂ nano-catalysts for environmental applications.     

Continuous synthesis of palladium nanorods in oxidative segmented flow

Laminar and segmented flow methods are presented for producing Pd rod‐shaped nanostructures from Na₂PdCl₄ in mixtures of water, ethylene glycol, polyvinyl pyrrolidone, and KBr. Synthesis in laminar flow produced an evolution from Pd nanoparticles to short nanorods with residence time. Use of air as the segmentation gas tuned the oxidative environment promoting anisotropic growth of Pd. Moreover, the elevated temperatures (160°C and 190°C) and pressure (0.8 MPa) reduced the synthesis time from hours for most batch systems to 2 min. The ratio of polyol and Pd precursor metal flow streams controlled the anisotropic growth, obtaining nanorods with a diameter approximately 4 nm and an aspect ratio up to 6. Nanorods were single crystal with the {100} lattice spacing of fcc structure, and without any dislocation, stacking fault, or twin defects. The resulting Pd nanorods had high activity at moderate temperature (40ºC) and pressure (0.2 MPa) in the catalytic hydrogenation of styrene. © 2015 American Institute of Chemical Engineers AIChE J, 62: 373–380, 2016     

Effect of Annealing Temperature on TiO2 Nanorod Films Prepared by dc Reactive Magnetron Sputtering for Dye-Sensitized Solar Cells

Anatase TiO₂ nanorod films have been prepared on ITO coated glass substrates at room temperature by dc reactive magnetron sputtering technique. The nanorods are highly ordered and are perpendicular to the substrate. XRD measurements show that the anatase nanorods have a preferred orientation along the [110] direction. The prepared nanorods were annealed at different temperatures (200?C500 °C) in air for 1 h. The dye-sensitized solar cells (DSSC) have been made using the as-deposited and annealed TiO₂ nanorods as working electrodes. It has been found that annealing improves the efficiency of the DSSC. An optimum conversion efficiency of 2.13%, at 100 mW/cm² light intensity has been achieved with TiO₂ nanorods annealed at 300 °C.     

Synthesis and characterization of some new aromatic polytriazoles as proton conductive membranes

A series of new poly(1,2,4-triazole)s (PTAs) containing pyridine heterocyclic ring, bearing bulky aromatic pendent groups, were synthesized from the reaction of the corresponding polyhydrazides with aniline or 4-aminobenzenesulfonic acid in polyphosphoric acid (PPA) at 175 °C. The non-sulfonated PTAs showed glass transition temperatures (T _gs) of 220–250 °C and inherent viscosities (η _inh) equal to 0.48–0.78 dL/g, and the sulfonated poly(1,2,4-triazole)s (S-PTAs) exhibited T _gs of 235–265 °C and inherent viscosities equal to 0.50–0.83 dL/g. The former polymers were soluble in conc. H₂SO₄ and partially soluble in hot N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), and 1-methyl-2-pyrrolidone (NMP), and the latter were soluble in DMF, NMP, DMSO and DMAc at room temperature. All polymers had useful levels of thermal stability and were stable up to 450 °C in nitrogen. The proton conductivities of undoped sulfonated polytriazole membranes and the acid-doped sulfonated polytriazole membranes lie in the range of 5 × 10^?4–8.1 × 10^?3 and 5 × 10^?3–2.3 × 10^?2 S/cm, respectively, at 90 °C and 100 % relative humidity.     

CONTROLLED GROWTH OF COPPER NANOPARTICLES AND NANORODS IN THE CHANNELS OF SBA-15 BY SUPERCRITICAL FLUID DEPOSITION

Copper nanoparticles and nanorods were prepared in the one-dimensional channels of SBA-15 supported by a modified supercritical fluid deposition (SCFD) method. In this approach, cheap and widely available copper nitrate, which is insoluble in supercritical CO₂ (scCO₂), was used as the copper source and ethanol as the co-solvent, thus avoiding the employment of expensive and less available scCO₂-soluble precursors. The deposition was carried out at the pressure of 21–25 MPa and temperature of 50°C, followed by calcinations at 500°C and H₂ reduction at 500°C. The results showed that highly dispersed Cu nanoparticles or nanorods were obtained controllably just by varying the deposition time, as characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). On the other hand, when Cu(acac)₂ was used as the precursor and without any co-solvent, only nanoparticles were formed in the channels of SBA-15 no matter how long the deposition time.     

VO2(A) nanorods: One-pot synthesis,formation mechanism and thermal transformation to VO2(M)

The monoclinic VO₂(M) has promising applications in intelligent devices but its preparation still requires improvement to permit cost-effective mass production. In this work, we report a 2-stage approach for producing VO₂(M) nanorods by (1) hydrothermal reduction of vanadium pentoxide by sodium bisulfate at 220?°C to form VO₂(A), and (2) subsequent thermal activated phase transformation of VO₂(A) to VO₂(M) at 350–450?°C in vacuum. The obtained VO₂(M) nanorods showed a reversible phase transition temperature at about 62.5?°C and a narrow thermal hysteresis width of 10?°C. The mechanism of the hydrothermal reduction was studied by combined ex situ microscopic and diffraction characterization of cooled samples as well as in situ PXRD experiments, in which the hydrothermal synthesis was monitored in real time by time-resolved diffraction datasets. It was found that the hydrothermal synthesis of VO₂(A) is a 4-step process: (1) reduction of V₂O₅ to form VO₂(B) nanoparticles, (2) oriented attachment of VO₂(B) nanoparticles along the [110] direction, (3) formation of VO₂(B) nanorods as a results of oriented attachments, and (4) hydrothermal transformation of the metastable intermediate VO₂(B) nanorods to VO₂(A) nanorods. This clear understanding of the mechanism will help the further optimization of synthesis temperature and time for preparing VO₂(A). This method provides a low temperature thermal treatment alternative and hence helps the reduction of cost for the production of VO₂(M), bring the mass application of VO₂(M) one step closer.     

Activity and active sites of nitrogen-doped carbon nanotubes for oxygen reduction reaction

Nitrogen-doped carbon (CNx) nanotubes were synthesized by thermal decomposition of ferrocene/ethylenediamine mixture at 600–900 °C. The effect of the temperature on the growth and structure of CNx nanotubes was studied by transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. With increasing growth temperature, the total nitrogen content of CNx nanotubes was decreased from 8.93 to 6.01 at.%. The N configurations were changed from pyrrolic-N to quaternary-N when increasing the temperature. Examination of the catalytic activities of the nanotubes for oxygen reduction reaction by rotating disk electrode measurements and single-cell tests shows that the onset potential for oxygen reduction in 0.5 M H₂SO₄ of the most effective catalyst (CNx nanotubes synthesized at 900 °C) was 0.83 V versus the normal hydrogen electrode. A current density of 0.07 A cm^?2 at 0.6 V was obtained in an H₂/O₂ proton-exchange membrane fuel cell at a cathode catalyst loading of 2 mg cm^?2.     

Novel copolymers of styrene. 1. Alkyl ring-substituted 2-cyano-3-phenyl 2-propenamides

Novel electrophilic trisubstituted ethylene monomers, alkyl ring-substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₄CH=C(CN)CONH₂ (where R is 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-i-propyl, 4-i-butyl, and 4-t-butyl), were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, AIBN at 70 °C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T _g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500 °C range with residue (5–7 wt%), which then decomposed in the 500–800 °C range.     

Structural Evolution of Silicon Carbide Phase from the Polycarbosilane Cured with Iodine: NMR Study

The structural evolution of silicon carbide phase from polycarbosilane fibers cured with iodine in air was investigated using nuclear magnetic resonance (NMR) together with in situ gas analysis up to 1400 °C by thermogravimetry coupled with mass spectroscopy (TG-MS). The investigation with solid-state ¹H, ¹³C, and ²⁹Si NMR analyses showed the influence of the oxygen affinity of Si atoms on the chemical structural changes of the SiOCH system during pyrolysis (up to 800 °C). In particular, the mechanism of phase segregation (SiOC?→?β-SiC?+?SiO₂?+?C) in amorphous SiOC structure at 800–1250 °C was determined. Carbon in the Si–O–C networks is replaced by silicon, forming the Si-O-Si network, while the cleaved carbon atoms, which have unpaired electrons, combine, forming C=C bonds. This mechanism accounts for the structural rearrangement from O₂SiC₂ to O₃SiC to SiO₄ (from the silicon-centered standpoint, i.e., SiO₂ phase), the growth of β-SiC crystallites, and the carbon clustering.     

Colloidal Synthesis of ZnS,CdS and Zn x Cd1−x S Nanoparticles from Zinc and Cadmium Thiobiuret Complexes

ZnS, CdS and Zn _x Cd_1?x S nanoparticles were synthesised from the thermolysis of 1,1,5,5-tetra-iso-propyl-4-thiobiuret complexes of Zn and/or Cd in oleylamine. The influence of the different reaction parameters (precursor concentration, growth temperature, reaction time and injection solvent/capping agent combination) on the size, morphology and optical properties of the produced nanoparticles were studied. ZnS nanoparticles with size smaller than 4.3 nm had the cubic phase whereas the particles with size larger than 4.3 nm had a hexagonal crystal structure as suggested by the selected area electron diffraction. Transmission electron microscopy showed the formation of spherical ZnS nanoparticles in addition to few ZnS nanorods only at growth temperature of 280 °C. Powder X-Ray diffraction (p-XRD) showed that the obtained CdS nanoparticles were cubic under all reaction conditions except when dodecanethiol was used as an injection solvent which produced hexagonal CdS. The change in the crystal structure of the CdS nanoparticles was accompanied with a change in morphology from spherical to triangular. Cubic Zn _x Cd_1?x S nanoparticles were obtained under all reaction conditions. Lattice spacing of the Zn _x Cd_1?x S nanoparticles showed a very good agreement with Vegard’s law. The optical properties of the Zn _x Cd_1?x S nanoparticles were highly dependent on the ZnS to CdS precursor ratio and the solvents/capping agent combinations. This in detail study on the relationship of solvent systems (capping agents), thermolysis temperatures, time of reactions and precursors will help in understanding to control the morphology, size of the crystallites and phase of the materials.     

Nanostructured catalysts for oxygen electroreduction based on bimetallic monoethanolamine complexes of Co(III) and Ni(II)

Oxygen reduction electrocatalysts based on the monoethanolmine complexes {[CoEtm]₂(μ-Etm)₄Ni(NO₃)₂} and {[CoEtm]₂(μ-Etm)₄Ni(NO₃)₂} + activated carbon AG-3 have been obtained by high-temperature synthesis. The nature of active centers on the synthesized electrocatalysts was described. Using potentiostatic and cyclic potentiodynamic voltammetry, the kinetic characteristics of catalysts in the oxygen electroreduction reaction were determined. Thermal decomposition of the thermally unstable complexes was described and character of the active centers formed was discussed. The optimal synthesis temperature of electrocatalysts is 600 °C in an inert atmosphere. The calculated exchange current densities for the oxygen electroreduction reaction at the catalysts in 1 M KOH at 20 °C was j ₀  = 1.01 × 10^?3 A g^?1–3.3 × 10^?3 A g^?1. The Tafel slopes of stationary polarization curves are 0.054–0.063 V for b ₁ and 0.106–0.125 V for b ₂ . The prepared electrocatalysts can be recommended only for electrochemical systems with alkaline electrolyte.     

SURFACE MODIFICATION OF HYDROTHERMALLY GROWN ZnO NANOSTRUCTURES WITH PROCESS PARAMETERS

ZnO nanorods (NRs) were hydrothermally synthesized by using equimolar zinc nitrate hydrate (Zn(NO₃)₂ [sdot] 6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) solutions. The shape of the nanostructures, obtained by aqueous method, was greatly influenced by the growth temperature and the molar concentrations. NRs grown at higher temperature (90°C) have rounded tips, whereas nanostructures of hexagonal flat-end shape were obtained at 75°C. Hardly any nanostructures were observed by further reducing the temperature to 60°C. In addition, solutions with higher molarity favored the appearance of nanoflowers. Scattered ZnO NRs were observed on silicon substrate, whereas aligned ZnO nanowires (NWs) 50–70 nm in diameter were obtained at 75°C by introducing sputtered ZnO film as a seed layer. High-resolution transmission electron microscopy (HRTEM) confirmed the growth of ZnO nanowires along [001] direction. A band-edge luminescence along with a broad visible spectrum was observed for the ZnO nanowires.     

Processing and properties of new heteroaromatic Schiff-base poly(sulfone-ester)s and their blends

A new interesting class of linear Schiff-base poly(sulfone-ester)s has been synthesized by polycondensation of (E)-1-(4,4′-(4-hydroxy-3-chlorobenzylidene)thiocarbamoylaminophenyl-sulfonylphenyl)-3-(4-hydroxy-3-chlorobenzylidene)thiourea with 2,6-pyridinedicarbonyl chloride/thiophene-2,5-dicarbonyl dichloride. The enhancement of physical properties (thermal stability, glass transition temperature, mechanical strength, molar mass, electrical conductivity, etc.) of polymeric materials while maintaining their processability was the foremost aspiration of this research work. The pyridine or thiophene-based heteroaromatic poly(sulfone-ester)s (PSEs) showed ample solubility in amide solvents and good yield. PSEs possessed high inherent viscosity of 1.79–1.93 dL/g and molar mass 125 × 10³–145 × 10³ g mol^?1. The polymers were thermally stable with 10 % weight loss in the range 538–547 °C and glass transition temperature between 293 and 296 °C. Further aim was to obtain novel miscible nano-blends exhibiting good electrical conductivity and heat stability. For this purpose, PAN doped with dodecylbenzenesulfonic acid (PAN/DBSA) was prepared by in situ doping polymerization, and then blended in solution/melt with PSEs. The resulting high performance materials potentially combined the fine thermal properties and processability of poly(sulfone-ester)s with electrical characteristics of polyaniline. FESEM of melt-blended PSEs/PAN/DBSA showed nano-level homogeneity of the microstructure liable for better electrical conductivity (2.7–3.2 S cm^?1). The azomethine and pyridine moieties introduced in the backbone render these polymers thermally and mechanically stable as well as electrically conducting. The miscible blends, exhibited good heat stability (T ₁₀ 520–527 °C, T _g 281–285 °C) and mechanical strength (55.20–57.18 MPa) compared with reported azomethine/polyaniline-based structures. New processable and high-performance engineering plastics, attractive for aerospace applications, can be fabricated using novel blends.     

Thermosensitive folic acid-targeted poly (ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl alcohol) hemisuccinate polymeric nanoparticles for delivery of epirubicin to breast cancer cells

A novel thermosensitive folic acid (FA)-targeted succinylated poly (ethylene-co-vinyl alcohol) (EVOH) (EVOHS-FA) nanocarrier was synthesized for the specific delivery of epirubicin (EPI) to MCF-7 breast cancer cell line. Three different ratios of synthesized EVOH-Suc were reacted with FA. The structure of the desired products (EVOHS₄₀-FA, EVOHS₆₀-FA and EVOHS₈₀-FA) was confirmed by ¹H NMR and FTIR techniques. Nanoparticles were obtained by nano-precipitation procedure using DMSO/H₂O as solvent/anti-solvent. The particle size, zeta potential, entrapment efficacy and in vitro release profile of the final formulations in different temperatures were measured. The optimized nanoparticles had the particle size of 214 ± 8.5 nm, zeta potential of ?29.6 mV, PDI of 0.198 ± 0.04, and a high encapsulation efficiency that released the drug efficiently within 450 h at the temperature of 40 °C compared to 37 °C. The morphology of nanoparticles was studied by scanning electron microscopy. The in vitro cytotoxicity was evaluated using the MTT assay on MCF-7 cell lines in response to temperatures of 37 and 40 °C. The MTT assay indicated that the targeted nanoparticles carrying EPI were significantly more cytotoxic than the non-targeted nanoparticles and the free drug at 40 °C.     

Perturbation-correlation moving-window two-dimensional correlation spectroscopic studies on the heat treatment of poly(vinyl alcohol)/silver nitrate film

In this paper, poly(vinyl alcohol)/silver nitrate (PVA/AgNO₃) films were annealed at 180 °C for 1 h to prepare highly electrically conductive poly(vinyl alcohol)/silver (PVA/Ag) nanohybrids. Ultraviolet (UV)-visible absorption spectra, X-ray diffraction (XRD) scans, and scanning electronic microscopy (SEM) were applied to investigate the structures and morphology of the PVA hybrids. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were employed to study the thermal property of PVA/AgNO₃ films. Furthermore, perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy combined with temperature-dependent Fourier transform infrared (FTIR) spectroscopy was used to investigate the conversion of AgNO₃ into Ag nanoparticles in PVA matrix. The results show that the chelates for AgNO₃ coordinated with hydroxyl groups are primarily decomposed in the temperature regions of 39.7–72.6 °C and 182.7–199.6 °C. AgNO₃ is reduced into Ag⁰ and the hydroxyl groups of PVA are oxidized into carbonyl groups. The PVA-AgNO₃ chelates are very rapidly decomposed in the temperature region of 182.7–199.6 °C. Large amounts of Ag⁰ produced by the reduction of AgNO₃ are aggregated into Ag nanoparticles which are homogeneously dispersed into the PVA matrix. When the temperature increases to 212.7 °C, the unhydrolyzed acetate groups in PVA chains are sharply decomposed.     

Preparation of high surface area mesoporous nickel oxides and catalytic oxidation of toluene and formaldehyde

Mesoporous nickel oxide (NiO) nanoparticles were synthesized by the thermal decomposition reaction of Ni(NO₃)₂·9H₂O using oxalic acid dihydrate as the mesoporous template reagent. The pore structure of nanocrystals could be controlled by the precursor to oxalic acid dihydrate molar ratio, thermal decomposition temperature and thermal decomposition time. The structural characteristic and textural properties of resultant nickel oxide nanocrytals were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N₂ adsorption–desorption isotherm and temperature programmed reduction. The results showed that the most excellently mesoporous nickel oxide particles (m-Ni-1-4) with developed wormlike pores were prepared under the conditions of the mixed equimolar precursor and oxalic acid and calcined for 4 h at 400 °C. The specific surface area and pore volume of m-Ni-1-4 are 236 m² g^?1 and 0.42 cm³ g^?1, respectively. Over m-Ni-1-4 at space velocity = 20,000 mL g^?1 h^?1, the conversions of toluene and formaldehyde achieved 90 % at 242 and 160 °C, respectively. It is concluded that the reactant thermal decomposition with oxalic acid assist is a key step to improve the mesoporous quality of the nickel oxide materials, the developed mesoporous architecture, high surface area, low temperature reducibility and coexistence of multiple oxidation state nickel species for the excellent catalytic performance of m-Ni-1-4.     

Size-Controlled Synthesis of Colloidal Gold Nanoparticles at Room Temperature Under the Influence of Glow Discharge

Highly dispersed colloidal gold (Au) nanoparticles were synthesized at room temperature using glow discharge plasma within only 5 min. The prepared Au colloids were characterized with UV–visible absorption spectra (UV–vis), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) equipped with an energy dispersion X-ray spectrometer (EDX). UV–vis, XPS and EDX results confirmed that Au³⁺ ions in HAuCl₄ solution could be effectively reduced into the metallic state at room temperature with the glow discharge plasma. TEM images showed that Au nanoparticles were highly dispersed. The size of colloidal Au nanoparticles could be easily tuned in the nanometer range by adjusting the initial concentration of HAuCl₄ solution. Moreover, the as-synthesized Au colloids (d _av = 3.64 nm) exhibited good catalytic activity for glucose oxidation. The nucleation and growth of colloidal Au particles under the influence of the plasma was closely related with the high-energy electrons generated by glow discharge plasma.     

Intergrowth Bismuth Layer-Structured Na0.5Bi2.5Nb2O9–Bi4Ti3O12 High Temperature Ferroelectrics Ceramics

Intergrowth superlattice structural Na_0.5Bi_2.5Nb₂O₉–Bi₄Ti₃O₁₂ (NBN–BIT) ceramics were synthesized by solid-state reaction method. In the temperature dependence of dielectric permittivity, two anomalies appeared at 663 and 780 °C, respectively. The dielectric loss tan δ of the NBN–BIT ceramics was very low, especially from room temperature to 400 °C. The ferroelectric hysteresis loop measurement revealed P _r and E _c of NBN–BIT ceramics are 10.5 μC/cm² and 18.5 kV/cm, the P _r nearly as twice as that of the NBN ceramics. The results show that ferroelectric properties of NBN–BIT ceramics increase comparing with pure NBN, and NBN–BIT ceramics are promising candidate materials for high temperature applications.