Synthesis and characterization of MoO<Subscript>3</Subscript> nanostructures by solution combustion method employing morphology and size control

Molybdenum oxide nanostructures were synthesized utilizing the solution combustion method where the ammonium molybdate powder and an organic additive were used as precursors. Different organic additives including ethylene diamine tetra-acetic acid (EDTA), polyethylene glycol 200 (PEG 200), sorbitol and urea were used as surfactants in order to investigate the effect of additive structure on morphology and particle size of products. Also various reaction parameters such as the additive/Mo molar ratio, concentration of metal ion in solution, pH of the reaction, and temperature of the synthesis media were changed to study effects on product morphology and size. Outcomes were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction, and Transmission Electron Microscopy (TEM) techniques. Results show a variety of MoO₃ nanoparticles and nanorods produced within the size range of 10–80 nm. Furthermore, microrods and microsheets were also obtained through this method whose length varied in the order of microns.     

Sonochemical synthesis of silver vanadium oxide micro/nanorods: Solvent and surfactant effects

In this investigation, a facile sonochemical route has been developed for the preparation of silver vanadium oxide (SVO) micro/nanorods by using silver salicylate and ammonium metavanadate as silver and vanadate precursor, respectively. Here, silver salicylate, [Ag(HSal)], is introduced as a new silver precursor to fabricate AgVO₃ nanorods. The effect of numerous solvents and surfactants on the morphology and sonochemical formation mechanism of AgVO₃ nanorods was studied. AgVO₃ nanorods were characterized by SEM and TEM images, XRD patterns, FT-IR, XPS, and EDS spectroscopy. SEM, TEM, and XRD results showed that AgO nanoparticles were formed onto AgVO₃ nanorods in the presence of ethanol, cyclohexanol, dimethylsulfoxide (DMSO), and acetone. By using polyethylene glycol (PEG-6000) and N,N-dimethylformamide (DMF) as organic additives, the thickness of AgVO₃ nanorods decreased.     

Phase-controlled preparation of iron (oxyhydr)oxide nanocrystallines for heavy metal removal

Obtaining cost-effective iron (oxyhydr)oxide nanocrystallines is the essential prerequisite for their future extensive applications in environmental remediation, such as the removal of heavy metals from contaminated waters. Here, various phases of iron (oxyhydr)oxide nanocrystallines were simply synthesized from the phase-controlled transformation of amorphous hydrous ferric- or ferrous-oxide in thermal solution with a certain ethanol/water ratio and with the presence of oleic acid. According to this method, goethite nanorods in diameter of 3–4 nm, hematite nanocubes sized 20–30 nm, and magnetite nanoparticles in diameter of 6–7 nm were successfully obtained. The final products of this transformation can be conveniently controlled by adjusting the reaction parameters, such as pH, temperature, and ethanol/water ratio. Due to the enhanced specific surface area and probably the modifications of the surface structure of nanocrystallines, the as-synthesized goethite nanorods and magnetite nanoparticles demonstrated extremely strong As(III) affinity, with 5.8 and 54 times of As(III) adsorption, respectively, higher than the micron-sized relatives. The cost-effective feature of as-synthesized nanocrystallines and their remarkably enhanced affinity toward arsenic made them potentially applicable for the removal of arsenic and such like heavy metals from the contaminated environment.     

Solvothermal synthesis and characterization of CdSe nanocrystals with controllable phase and morphology

Zinc blende (ZB) CdSe hollow nanospheres were solvothermally synthesized from the reaction of Cd(NO₃)₂·4H₂O with a homogeneously secondary Se source, which was first prepared by dissolving Se powder in the mixture of ethanol and oleic acid at 205 °C. As Se power directly reacted with Cd(NO₃)₂·4H₂O in the above mixed solvents, wurtzite (W) CdSe solid nanoparticles were produced. Time-dependent experiments suggested that the formation of CdSe hollow nanospheres was attributed to an inside-out Ostwald ripening process. The influences of reaction time, temperature and ethanol/oleic acid volume ratio on the morphology, phase and size of the hollow nanospheres were also studied. Infrared (IR) spectroscopy investigations revealed that oleic acid with long alkene chains behaved as a reducing agent to reduce Se powder to Se²⁻ in the synthesis. Photoluminescence (PL) measurements showed that the ZB CdSe hollow nanospheres presented an obvious blue-shifted emission by 42 nm, and the W CdSe solid nanoparticles exhibited a band gap emission of bulk counterpart.     

Morphology development and oriented growth of single crystalline ZnO nanorod

Single crystalline ZnO nanorods were achieved by the assembly of nanocrystallines in tens of nanometer under hydrothermal conditions with the assistance of surfactant cetyltrimethylammonium bromide (CTAB). The obtained nanorod has rough surface as a result of oriented attachment growth. Transmission electron microscope (TEM) images showed the morphology evolution of the nanorod at different reaction time. Defects were observed and porous structure was left after the assembly of hundreds of nanocrystalline building blocks. Effect of pH condition on the morphology of the nanorod was also investigated.     

LaF3:Yb3+/Tm3+纳米棒的制备与上转换发光

在乙醇-油酸混合体系中,以溶剂热方法成功制备了Yb3+/Tm3+离子双掺杂的LaF3发光纳米棒。XRD表征结果表明所合成的材料为LaF3:Yb3+/Tm3+(JCPDS卡号:72-1435),SEM扫描结果表明LaF3纳米棒的尺寸大约为0.1μm,室温下以980nm红外半导体激光器激发,纳米晶在可见光区(700nm)和近红外区(804nm)有较强上转换发光。通过发光机理的讨论,本文中纳米晶强的近红外和红色上转换发光分别是双光子及三光子反斯托克斯(Anti-stokes)发光。     

Direct monitoring of gold nanorod growth

The seed-mediated growth of gold nanorods is shown to be strongly dependent on the reaction time and chemical environment of the reaction solution. The versatile seed-mediated approach in aqueous surfactant solutions has been used in this study for the synthesis of gold nanorods. Changes in the aspect ratio of gold nanorods were reflected in shifts of the plasmon resonance peaks and were monitored using UV-Visible absorption spectroscopy (UV-Vis) to follow the different stages of gold nanorod formation as a function of time and varying amounts of silver ion. Unlike the use of strong reducing agents to make spherical gold nanoparticles, the growth of gold nanorods requires weak reducing conditions, leading to an unknown degree of gold reduction. Therefore, cyclic voltammetry was used to electrochemically interrogate the entire reaction from gold seed to gold nanorod as a function of time. Data obtained revealed that time-dependent gold species are involved in gold nanorod formation.     

Preparation and Characterization of Hyaluronic Acid Hydrogel Blends with Gelatin

Porous hydrogel blends composed of various weight ratios of hyaluronic acid (HA) and gelatin (Gel) were fabricated by a freeze-drying method. The 1-ethyl-3(3-dimethylaminopropyl) carbodiimide (EDC) was used as a crosslinker to improve their biostability. The effect of the component and crosslinker content on the morphology, swelling ratio (SR), and mechanical properties were investigated. The results indicated that after chemical crosslinking the hydrogel showed a smoother and denser surface with less pores and a crosssection with smaller pores than that without crosslinking. The crosssection morphologies of the HA/Gel hydrogels changed from a sheet-like appearance to a fiber-like appearance with increasing HA content. The addition of HA improved the swelling property, but reduced the compressive strength. As the crosslinker content increased, the SR decreased; however, the compressive strength of the HA/Gel hydrogels increased. All these results suggest that HA/Gel hydrogel crosslinked by EDC is a potential candidate for tissue engineering scaffolds.     

Synthesis and characterization of PbS nanorods and nanowires

 A surfactant assisted solvotermal approach for the controllable synthesis of PbS nanowires and nanorods is applied. The synthesis is based on decomposition of lead thiocyanate in boiling benzyl alcohol with Cetyl trimethyl ammonium bromide used as a surfactant. Nanowires of PbS (about 2–3 μm with an average diameter of 30–50 nm) and nanorods (200–300 nm in length with an axial ratio of 4–5) were synthesised. The nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED) and X-ray diffraction analysis. The experimental results indicate that the reaction duration and concentration of surfactant play key roles in determining the final morphologies of PbS blocks building and also in their crystallinity. A possible mechanism for creation of PbS nanowires and nanorods is discussed.     

Preparation of nano-hydroxyapatite particles with different morphology and their response to highly malignant melanoma cells in vitro

To investigate the effects of nano-hydroxyapatite (HA) particles with different morphology on highly malignant melanoma cells, three kinds of HA particles with different morphology were synthesized and co-cultured with highly malignant melanoma cells using phosphate-buffered saline (PBS) as control. A precipitation method with or without citric acid addition as surfactant was used to produce rod-like hydroxyapatite (HA) particles with nano- and micron size, respectively, and a novel oil-in-water emulsion method was employed to prepare ellipse-like nano-HA particles. Particle morphology and size distribution of the as prepared HA powders were characterized by transmission electron microscope (TEM) and dynamic light scattering technique. The nano- and micron HA particles with different morphology were co-cultured with highly malignant melanoma cells. Immunofluorescence analysis and MTT assay were employed to evaluate morphological change of nucleolus and proliferation of tumour cells, respectively. To compare the effects of HA particles on cell response, the PBS without HA particles was used as control. The experiment results indicated that particle nanoscale effect rather than particle morphology of HA was more effective for the inhibition on highly malignant melanoma cells proliferation.     

Shape control of CdTe nanocrystals synthesized in presence of in situ formed CdO particles

The shape of semiconductor nanocrystals synthesized with wet-chemical approaches in many cases can be controlled by the concentration and the activity of the precursors. In this study, we introduce a possibility to influence these two factors in the colloidal synthesis of cadmium telluride nanoparticles synthesized in the presence of in situ generated cadmium oxide particles. By changing the composition of the solvent (a mixture of oleylamine and octadecene), different shapes of CdTe nanocrystals can be synthesized. In reactions with higher oleylamine concentration, we observed the formation of elongated nanoparticles: nanorods (~14?nm length) and nanowires (several hundred nm long), while CdTe nanodots formed, if octadecene was used in excess. Formation of CdTe in octadecene and oleylamine as solvent was studied by nuclear magnetic resonance (NMR) spectroscopy. Based on these results, the influence of the solvent composition on the shape of the nanocrystals was attributed to the interplay of several factors, such as enhancement of the carboxylate precursor activity in the presence of an amine and the possibility of the formation of additional Cd monomers by the dissolution of CdO. At later stages of the reaction with high oleylamine content, also oleic acid depletion, leading to a destabilization of the particles, influences the shape of the resulting nanocrystals and lead to the formation of nanowires.     

Enhanced photocatalytic activity of Cu-doped ZnO nanorods

Cu-doped ZnO nanorods with different Cu concentrations were synthesized through the vapor transport method. The synthesized nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and UV–vis spectroscopy. The XRD results revealed that Cu was successfully doped into ZnO lattice. The FE-SEM images showed that the undoped ZnO has needle like morphology whereas Cu-doped ZnO samples have rod like morphology with an average diameter and length of 60–90 nm and 1.5–3 μm respectively. The red shift in band edge absorption peak in UV-vis absorbance spectrum with increasing Cu content also confirm the doping of Cu in ZnO nanorods. The photocatalytic activity of pure and Cu-doped ZnO samples was studied by the photodegradation of resazurin (Rz) dye. Both pure ZnO and the Cu-doped ZnO nanorods effectively removed the Rz in a short time. This photodegradation of Rz followed the pseudo-first-order reaction kinetics. ZnO nanorods with increasing Cu doping exhibit enhanced photocatalytic activity. The pseudo-first-order reaction rate constant for 15 % Cu-doped ZnO is equal to 10.17×10^?2min^?1 about double of that with pure ZnO. The increased photocatalytic activity of Cu-doped ZnO is attributed to intrinsic oxygen vacancies due to high surface to volume ratio in nanorods and extrinsic defect due to Cu doping.     

简单溶液法制备氧化锌纳米棒及光学性质

以水合醋酸锌(ZnAc₂·2H₂O)和水合肼(N₂H₄·H₂O)为反应物,在未使用任何表面活性剂的简单反应体系中制得了ZnO纳米棒。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)和室温荧光光谱对产物的晶体结构、形貌和发光性质进行了表征和分析。测试结果表明,所得产物为六方纤锌矿结构ZnO纳米棒,平均直径为120 nm,产物结晶完整,尺寸均匀。这种简单溶液法制备的ZnO纳米棒在386 nm处具有一个尖锐的紫外发光峰,发射光谱的半峰全宽仅为18 nm,在可见光区有一个较弱的宽频发光带。在该反应体系中通过调控混合溶剂的配比,不使用任何表面活性剂的条件下,为ZnO一维纳米棒的形核和生长提供了微型反应空间。     

Morphology control of KDP crystallites

The actual crystal morphology is synergistically determined by atomic interactions between the crystal surface, growth units and additives in the mother solution. Our present results microscopically show that the ideal crystal morphology is greatly determined by intrinsic characteristics such as the bond number, direction and strength in the crystallographic frame, while ethanol molecules in the mother solution can intensively affect the crystal size and aspect ratio of potassium dihydrogen phosphate (KDP). Some quantitative analyses concerning the addition of ethanol to the KDP solution are also described.     

Effects of organic modifiers on the size-controlled synthesis of hydroxyapatite nanorods

Size-controlled synthesis of hydroxyapatite nanorods were carried out by chemical precipitation method using polyethylene glycol (MW 600), Tween 20, trisodium citrate, and d-sorbitol as organic modifiers and starting from calcium nitrate, phosphoric acid, and ammonia solution. The influence of the organic modifiers on the sizes of the resultant HAP nanorods was investigated under different synthesis temperatures. It was found that polyethylene glycol was beneficial to the formation of HAP nanorods with a larger aspect ratio (average length/average diameter) at high synthesis temperature, Tween 20 and trisodium citrate favored the formation of small-sized HAP nanorods, and d-sorbitol helped the formation of HAP nanorods with long length at low synthesis temperatures.     

不同比例有机无机肥配施土壤腐殖质组分的光谱学特征

以16年长期定位试验为基础,探讨不同比例有机无机肥配施对土壤腐殖质特征的影响。通过分离纯化腐殖质中的胡敏酸（HA）和富里酸（FA）组分,并利用元素分析、红外光谱和核磁共振研究分析了F1（70%化肥+30%有机肥）、F2（50%有机肥+50%化肥）和F3（100%有机肥）三种施肥方式下的HA和FA含量及结构变化。结果表明,F3对于提升HA和FA含量的效果优于F1和F2处理,说明有机肥的施用量越高,土壤腐殖质组分的含量就越高。元素分析表明,不同配比的有机无机肥对HA和FA各元素含量及原子比影响不同。F2和F3都提高了HA的缩合度,降低了氧化度和极性,其中F3的效果更加明显;有机肥的施用还能促进HA中含氮化合物的形成,并且在F2中的效果最好;有机肥的施用同样提高了FA的缩合度而降低了氧化度和极性并促进了含氮化合物的形成,尤其在F2处理中尤为明显。腐殖质红外光谱分析表明,与F1相比,F2和F3提高了HA中脂肪族化合物、碳水化合物物质的含量,FA的羧基基团、脂肪基团含量也增加,且在F3处理中表现最为显著;F2处理则降低了HA中脂肪烃物质的含量,FA中的碳水化合物则达到最高。13C核磁共振波谱分析显示,在三种处理中,有机肥的施用提高了HA和FA的脂化度而降低其芳化度,其中F2处理中HA官能团变化更加显著,FA在F3处理中则变化更加明显。综上所述,有机肥显著提高了土壤腐殖质组分含量,并且提高了HA和FA的脂化度降低其芳化度,但是不同用量有机肥下HA和FA的形成机制不同。     

Enrichment of surfactant from its aqueous solution using ultrasonic atomization

Dilute aqueous solutions of dodecyl-benzenesulfonic acid sodium salt (DBS-Na) and polyoxyethylenenonylphenyl ethers (PONPEs) were ultrasonically atomized. The surfactants were concentrated in collected mist droplets. The enrichment ratio increased with decreasing surfactant concentration. Depending on the surfactant’s molecular weight and affinity to water, different enrichment ratio was observed in the range of low feed concentrations. For anionic surfactant, DBS-Na, the enrichment ratio was significantly improved by KCl addition and a peak appeared on the plot of the ratio against KCl concentration. Addition of NaCl or CaCl₂ · 2H₂O to the surfactant solution also enhanced the enrichment ratio; however, the effect was relatively small. Such behaviors of the ratio were interpreted as enhanced interfacial adsorption of the surfactant and a lack of supply of surfactant monomers from liquid bulk because of slow breaking of surfactant micelles. Time required for collecting an amount of mist was also observed. Among the three salt systems, the time for KCl system was twice as long as others. This fact suggested that the formation of smaller droplets in KCl system.     

Self-assembled monolayers formed on AZ31 Mg alloy

Self-assembled monolayer (SAM) was successfully adsorbed on the AZ31 Mg alloy surface using oleic acid and stearic acid with various organic solvents, such as acetone, ethanol, and hexane. The surface monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS) and anodic polarization test. It was shown that the higher contact angle and the best anti-corrosion property were obtained with treatment in oleic acid with ethanol solution.     

Magnetic fluids with excesses of a surfactant according to the data of small-angle neutron scattering

Magnetic fluids (magnetite/oleic acid/benzene) with excesses of a surfactant (oleic acid) are studied using small-angle neutron scattering. Solutions of oleic acid in benzene are also studied to reveal whether an aggregation of acid molecules can occur. It is shown that oleic acid does not form micelles in benzene in the range of concentrations under study (up to volume fractions of 35%). It follows from our results that the excess of a surfactant (less than a volume fraction of 25%) in a magnetic fluid does not lead to a noticeable aggregation of its particles. At the same time, an increase in the attraction between free surfactant molecules in the magnetic fluid (compared to pure solutions of oleic acid in benzene) is observed. If the excess of a surfactant is greater than 25%, then the stability of the magnetic fluid is sharply violated, which leads to the aggregation of magnetic particles.     

Enhanced mechanical strength of hydroxyapatite nanorods reinforced with polyethylene

Hydroxyapatite (HAp) nanostructures may be an advanced candidate in biomedical applications for an apatite substitute of bone and teeth than other form of HAp. In contrast, well-defined size and shape control in synthesizing HAp nanostructures is always difficult. In this study, hydroxyapatite nanorods (HAp NRs) were prepared by simple hydrothermal method with controlling the reaction time without using any surfactant or templating agents. The nanostructure clearly depicts the growth stages of the HAp NRs by increasing the reaction time. The synthesized HAp has the rod like morphology with uniform size distribution with the aspect ratio of about 8–10. Transmission electron microscopic (TEM) and high resolution TEM (HRTEM) images show that the growth direction of the HAp is parallel to the (001) plane. The interplanar distances measured in segments (fringes) of the HRTEM micrograph were ~0.35 nm, corresponding to the interplanar spacing of the (002) plane of the hexagonal HAp. X-ray diffraction (XRD) measurements indicate that the improved crystallinity of the HAp by increasing the reaction time. The mechanical studies reveal that the improved tensile strength and the abrasion resistance are observed for the HAp nanorods reinforcing with high molecular weight polyethylene (HMWPE).