多元醇还原法制备FePt纳米颗粒

以乙酰丙酮铁和氯铂酸作为Fe源和Pt源,1,2-十二烷二醇为还原剂,通过多元醇还原法制备出单分散的FePt纳米颗粒,研究了表面活性剂油酸和油胺对FePt纳米颗粒形貌和分散性的影响。结果显示,未使用表面活性剂制得的FePt纳米颗粒粒度范围是1.0～6.0 nm,平均粒径为3.4 nm;使用油酸和油胺制得的FePt纳米颗粒粒度范围是2.5～5.5 nm,平均粒径4.1 nm。通过XRD、TEM和VSM分析表明,油酸和油胺修饰的FePt纳米颗粒为面心立方结构,形状近似球形,分散性良好,粒径分布较未使用表面活性剂时变窄;VSM显示其矫顽力趋近于0,呈现超顺磁性。     

Magnetic Properties of FePt Nanoparticles Prepared by a Micellar Method

FePt nanoparticles with average size of 9 nm were synthesized using a diblock polymer micellar method combined with plasma treatment. To prevent from oxidation under ambient conditions, immediately after plasma treatment, the FePt nanoparticle arrays were in situ transferred into the film-growth chamber where they were covered by an SiO₂ overlayer. A nearly complete transformation of L1₀ FePt was achieved for samples annealed at temperatures above 700 °C. The well control on the FePt stoichiometry and avoidance from surface oxidation largely enhanced the coercivity, and a value as high as 10 kOe was obtained in this study. An evaluation of magnetic interactions was made using the so-called isothermal remanence (IRM) and dc-demagnetization (DCD) remanence curves and Kelly–Henkel plots (ΔM measurement). The ΔM measurement reveals that the resultant FePt nanoparticles exhibit a rather weak interparticle dipolar coupling, and the absence of interparticle exchange interaction suggests no significant particle agglomeration occurred during the post-annealing. Additionally, a slight parallel magnetic anisotropy was also observed. The results indicate the micellar method has a high potential in preparing FePt nanoparticle arrays used for ultrahigh density recording media.     

L10 FePt Nanoparticles Processing with Applied Magnetic Field

Due to the strong magnetic anisotropy energy, the L1₀ FePt nanocrystals are considered as one of promising candidates for magnetic recording media with ultrahigh densities. The surfaces of Si and SiO₂ wafers have been covered by FePt nanoparticles (NPs) and heated at 600 °C for 1 h to form the L1₀ phase. Bonding of NPs with the SiO₂ surface in the presence of magnetic field during annealing process controls the L1₀ FePt NPs size and their uniform surface distribution. In the presence of perpendicular magnetic field to the surface, the size of NPs obtains up to 30 nm with coercivity of 5.8 kOe and in parallel magnetic field, the NPs size reaches to 45 nm with coercivity of 2.9 kOe. These results and the easy axis ordering of samples have been determined by energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometer analyses.     

Size Controlling of L1<Subscript>0</Subscript>-FePt Nanoparticles During High Temperature Annealing on the Surface of Carbon Nanotubes

Mono-size FePt nanoparticles with particles size about 2.5 nm have been prepared by polyol method on the surface of carbon nanotubes (CNTs). The CNTs functinalization time and the mass ratio of nanoparticles to CNTs affects on the CNTs surface coating. The as-synthesis nanocomposites have a superparamagnetic behavior with chemically disordered fcc structure at room temperature and they can be transformed into chemically ordered fct structure after thermal annealing above 600 °C. Their magnetic behavior changes from the superparamagnetic to the ferromagnetic with a large coercivity up to 0.83 T for the nanocomposites which annealed at 800 °C. The CNTs surfaces as a substrate prevent the agglomeration of nanoparticles during high temperature annealing and the FePt nanoparticles after annealing at 800 °C have finite size with an average about 10 nm. The structure, composition and magnetic properties of nanocomposite were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometer.     

Radiation synthesis and characterization of poly(vinyl alcohol)/poly(N-vinyl-2-pyrrolidone) based hydrogels containing silver nanoparticles

A series of PVA/PVP based hydrogels at different compositions were prepared by gamma irradiation. The gel fraction degree of swelling were investigated. Highly stable and uniformly distributed silver nanoparticles have been obtained onto hydrogel networks. The morphology and structure of (PVA/PVP) hydrogel and dispersion of the silver nanoparticles in the polymeric matrix were examined by scanning electron microscopy (SEM) and infrared spectroscopy (FT-IR), respectively. The formation of silver nanoparticles has been confirmed by ultraviolet visible (UV–vis) spectroscopy. A strong characteristic absorption peak was found to be around 420 nm for the silver nanoparticles in the hydrogel nanocomposite. The X-ray diffraction pattern confirmed the formation of silver nanoparticles with average particle size of 12 nm. The diameter distribution of silver nanoparticles was determined by dynamic light scattering DLS. Transmission electron microscope (TEM) showed almost spherical and uniform distribution of silver nanoparticles through the hydrogel network and the mean size of silver nanoparticles ranging is 23 nm. The good swelling properties and antibacterial of PVA/PVP-Ag hydrogel suggest that it can be a good candidate as wound dressing.     

Formation of FePt intermetallic compound nanoparticles by plasma-induced cathodic discharge electrolysis

Magnetic nanoparticles of FePt intermetallic compound were formed in molten LiCl-KCl-CsCl electrolyte under 1 atm of Ar atmosphere by plasma-induced cathodic discharge electrolysis. By utilizing the displacement reaction between the Fe(0) and Pt(II), FePt intermetallic compound nanoparticles were obtained from the melt. The displacement reaction produced small primary particles that considerably aggregated to form larger secondary particles. The coercivity of the obtained FePt intermetallic compound nanoparticle increased with a longer residence time in the melt. The coercivity of the FePt intermetallic compound nanoparticle obtained after a residence time of 3 h was measured to be 199 mA m⁻¹. FePt intermetallic compound nanoparticles could also be obtained by the co-depositing Fe and Pt from Fe(II) and Pt(II) in the melt. In this case, the primary particle size distribution became broader, but the aggregation of primary particles was suppressed. The coercivity of the obtained FePt intermetallic compound nanoparticles showed a quite high value of 245 mA m⁻¹ that did not depend on the residence time.     

Volumetric distribution of Pt nanoparticles supported on mesoporous carbon substrates studied by X-ray photoelectron spectroscopy depth profiling

We present an X-ray photoelectron spectroscopy depth profiling study of the size and volumetric distributions of Pt nanoparticles supported on two mesoporous carbons. Based on the analysis of the chemical shift of the Pt4f peaks, we found the one with a mesopore diameter of ∼5 nm has a uniform distribution of crystalline Pt nanoparticles throughout the porous body. In contrast, the other with a mesopore diameter of ∼3 nm has a distinct distribution of crystalline Pt nanoparticles on the outermost surfaces of the porous material and extremely small (<1 nm) Pt nanoparticles in the interior region. The small Pt particle size in the interior represents the effect of pore entrance blockage of those mesopore channels with diameter less than 3 nm. Such blockage gives rise to the encapsulation of very small amounts of Pt precursors inside the nanospace of the porous matrix, with the result that the particles grown in the interior region of the support are less than 1 nm in size.     

Aerosol sample preparation methods for X-ray diffractive imaging: Size-selected spherical nanoparticles on silicon nitride foils

We are developing aerosol generating and processing methods for X-ray analyses of nanoscale materials using conventional synchrotron radiation sources and using the newly operational soft X-ray free-electron laser in Hamburg (FLASH) at the Deutsches Elektronen Synchrotron. Charge-reduced electrospray, differential mobility analysis and an electrostatic precipitator were used to prepare samples consisting of size-monodisperse spherical nanoparticles deposited on 20 nm thick silicon nitride foils supported by silicon frames. Ninety-seven and 102 nm diameter spheres were selected from a broader distribution of 98 nm spheres using differential mobility. We measured the size distribution of the spheres using forward scattering from 1.65 nm light at the Advanced Light Source (ALS) in Lawrence Berkeley National Laboratory and scanning electron microscopy (SEM). The full-width half maximum (FWHM) of the size distribution of the size-selected spheres was as narrow as 5.4 nm when measured by SEM, as compared to 16 nm for the non-size-selected distribution. Forward scattering measurements of the 97 nm diameter size-selected spheres fit a size distribution with a FWHM of 4 nm and allowed us to validate the methodology for use in future diffraction imaging experiments at FLASH.     

Preparation of silver nanoparticles using chitosan suspensions

Silver/chitosan nanocomposites were prepared by using basic chitosan suspension as a stabilizer and as a reductant in the absence of other chemicals. The size and distribution of the resulting nanocomposite were strongly dependent on the concentration of chitosan and sodium hydroxide. UV-vis spectra and analytical electron microscopy (AEM) revealed the presence of silver/chitosan nanocomposites. In addition, Ag nanoparticles were obtained by annealing silver/composites at 600 °C. These nanoparticles were characterized by field emission scanning electron microscopy (FESEM) and energy dispersive X-ray spectrometry (EDS). The FESEM indicated that the size of a majority of the Ag nanoparticles ranged between 10 and 150 nm. A change in the nanoparticles to porous-like nanostructures was observed when the composite feeding amount was increased, the annealing time prolonged, and the reaction temperature elevated.     

Chemical synthesis of FePt nanoparticles with high alternate current magnetic susceptibility for biomedical applications

The present paper describes ordered alloy FePt nanoparticles with high magnetic susceptibility to alternate current (ac) fields at around room temperature for biomedical applications such as magnetic sensing devices for diagnostics and magnetic hyperthermia for cancer therapy. Since ac magnetic susceptibility takes the maximum value at a temperature near the blocking temperature of magnetic nanoparticles, the blocking temperature of the FePt nanoparticles is required to be adjusted at around room temperature to improve biomedical performances. Ordered alloy FePt has much higher magnetic anisotropy than iron oxides, and it can be the best candidate in the case of their particle size less than 10 nm. The ordered alloy FePt nanoparticles are synthesized by reduction of Fe and Pt organo-metallic compounds with tetraethylene glycol using poly(N-vinyl-2-pyrrolidone) (PVP) as a protective agent. PVP is a water-soluble polymer, and is proper to obtain dispersion into water. Influences of reaction temperature on crystallite size (particle size) and blocking temperature and the relationship between the blocking temperature and the value of ac magnetic susceptibility at around room temperature are investigated. Furthermore, PVP concentration at the synthesis to obtain well dispersed nanoparticle-suspension is examined.     

Silver/Polyaniline Nanocomposite for the Electrocatalytic Hydrazine Oxidation

Silver/polyaniline (Ag-PANi) nanocomposites were prepared via in situ reduction of silver in aniline by mild photolysis performed with short wavelength (365 nm) radiation from UV lamp for 12 h. Reduction of the silver in aqueous aniline leads to the formation of silver nanoparticles which in turn catalyze oxidation of aniline into polyaniline. A slightly broadened X-ray diffraction (XRD) pattern suggests small particle which was size consistent with cubic silver nanoparticles. The UV–Vis absorption revealed that the bands at about 400–420 nm due to benzonoid ring of the polyaniline are overlapped and blue-shifted due to the presence of silver nanoparticles in powdered state. Scanning electron microscopy (SEM) of the silver/polyaniline (Ag-PANi) nanocomposite showed a size distribution with nanofibers and granular morphology of silver nanoparticles. Our findings are not only the promising approach for electro-catalytic hydrazine oxidation but also utilized in the other bio-sensing applications.     

Structural,optical, morphological properties of silver doped cobalt oxide nanoparticles by microwave irradiation method

The synthesis of silver doped cobalt oxide nanoparticles by microwave-assisted method and their structural, optical, antibacterial activities are presented in this study. The doping concentrations were chosen as 5, 10, 15, and 20 wt percentages. The sample was undergone powder X-ray diffraction studies and the result shows the good crystalline nature of the sample. Also, the average crystallite size increases from 13.95 nm, 21.26 nm, 26.13 nm, and 28.35 nm with different doping concentrations. The transmission electron microscopy image shows cubic and spherical morphology. The optical properties were tested by UV–vis–NIR absorption spectrum. It indicates the decrease of band gap value. From the antibacterial activity studies, the 20 wt % Ag doped nanoparticles exhibit better activity.     

Facile corrosion synthesis and sintering of disperse pure tetragonal zirconia nanoparticles

Disperse pure tetragonal zirconia (t-ZrO₂) nanoparticles smaller than 10 nm are essential for preparation of structural and functional zirconia materials, but syntheses of t-ZrO₂ nanoparticles using inorganic zirconium salts usually result in severe agglomeration. In this paper, we report a hydrothermal corrosion approach for improving the dispersity of t-ZrO₂ nanoparticles synthesized by precipitation using zirconium oxychloride without any surfactants. Disperse pure t-ZrO₂ nanoparticles with average sizes of 4.5 and 6 nm and size distributions of 2–11 and 3–12 nm were obtained by calcining precipitates at 400 °C for 2 h and 500 °C for 0.5 h followed by HCl corrosion at 120 °C for 75 h, respectively. Disperse t-ZrO₂ nanoparticles with an average size of 6 nm and a size distribution of 3–12 nm were pressed into green compacts at 500 MPa and sintered by two-step sintering (heating to 1150 °C without hold and decreasing to 1000 °C with a 10 h hold). The sintered bodies are dense pure monoclinic ZrO₂ nanocrystalline ceramic with a relative density of 99.9% and an average grain size of 110 nm.     

Preparation,characterization, and in vitro release of folic acid-conjugated chitosan nanoparticles loaded with methotrexate for targeted delivery

To reduce the toxicity of methotrexate (MTX) and increase the targeting of nanoparticles, the MTX-loaded chitosan (CS) covalently bonded with folic acid (FA) nanoparticles were prepared, and sodium tripolyphosphate was used as the cross-linking agent. FA was successfully conjugated to CS confirmed by ¹H-NMR and Fourier transform infrared spectrometer (FT-IR). The prepared FA–CS nanoparticles were characterized by FT-IR spectroscopy to confirm the cross-linking reaction between FA–CS and cross-linking agent. X-ray diffraction was performed to reveal the crystalline nature of the drug after encapsulation. The average diameters of the nanoparticles ranged from 293.9 ± 24.2 to 401.5 ± 20.4 nm with a narrow particle size distribution. In vitro release pattern in phosphate buffer saline (pH 6.8) indicated that the characteristics of the MTX-loaded nanoparticles appeared to have an initial burst effect and followed by a slow, sustained drug release. FA or low molecular weight FA conjugate fragments were also released from the nanoparticles, which might have potential to reduce toxic effects of MTX within the body.     

Synthesis of vertically aligned single-walled carbon nanotubes with metallic chirality through facet control of catalysts

For nanotube synthesis, iron platinum (FePt) alloy particles have been prepared on a single crystalline magnesium oxide (MgO) substrate by alternate sputter deposition of FePt and MgO. Partially facetted {1 1 1}-nano particles of FePt have been epitaxially formed on the substrate and periodically exposed on the surface. The particles of FePt were half-buried between deposited MgO showed superior thermal stability and microparticulations were also achieved by optimization of film layer thickness. By using the substrates for growth of carbon nanotubes, vertically aligned single-walled carbon nanotubes (forest) have been successfully grown on the substrate containing the faceted FePt nanoparticles. Raman spectra of the forest have revealed prominent features of metallic nanotubes in the radial breathing-mode region.     

Single-step polyol synthesis of alloy Pt<Subscript>7</Subscript>Sn<Subscript>3</Subscript> versus bi-phase Pt/SnO<Subscript>x</Subscript> nano-catalysts of controlled size for ethanol electro-oxidation

Disordered alloy and bi-phase PtSn nanoparticles of nominal Pt:Sn ratio of 70:30 atomic % with controlled size and narrow size distribution were synthesized using a single-step polyol method. By adjusting the solution pH it was possible to obtain Pt₇Sn₃ nanoparticles of various sizes from 2.8 to 6.5 nm. We found that the presence of NaOH in the synthesis solution not only influenced the nanoparticle size, but as it was revealed by XRD, it apparently also dictated the degree of Pt and Sn alloying. Three catalysts prepared at lower NaOH concentrations (C_NaOH < 0.15 M) showed disordered alloy structure of the nominal composition, while the other three catalysts synthesized at higher NaOH concentrations (C_NaOH > 0.15 M) consisted of bi-phase nanoparticles comprising a crystalline phase close to that of pure Pt together with an amorphous Sn phase. These observations are plausibly due to the phase separation and formation of monometallic Pt and amorphous SnO_x phases. A proposed reaction mechanism of Pt₇Sn₃ nanoparticle formation is presented to explain these observations along with the catalytic activities measured for the six synthesized carbon-supported Pt₇Sn₃ catalysts. The highest catalytic activity towards ethanol electro-oxidation was found for the carbon-supported bi-phase catalyst that formed the largest Pt (6.5 nm) nanoparticles and SnO_x phase. The second best catalyst was a disordered alloy Pt₇Sn₃ catalyst with the second largest nanoparticle size (5 nm), while catalysts of smaller size (4.5–4.6 nm) but different structure (disordered alloy vs. bi-phase) showed similar catalytic performance inferior to that of the 5 nm disordered alloy Pt₇Sn₃ catalyst. This work demonstrated the importance of producing bi-metallic PtSn catalysts with large Pt surfaces in order to efficiently electro-oxidize ethanol.     

Sulfur Nanoparticles Synthesis and Characterization from H2S Gas, Using Novel Biodegradable Iron Chelates in W/O Microemulsion

Sulfur nanoparticles were synthesized from hazardous H₂S gas using novel biodegradable iron chelates in w/o microemulsion system. Fe³⁺–malic acid chelate (0.05 M aqueous solution) was studied in w/o microemulsion containing cyclohexane, Triton X-100 and n-hexanol as oil phase, surfactant, co-surfactant, respectively, for catalytic oxidation of H₂S gas at ambient conditions of temperature, pressure, and neutral pH. The structural features of sulfur nanoparticles have been characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive spectroscopy (EDS), diffused reflectance infra-red Fourier transform technique, and BET surface area measurements. XRD analysis indicates the presence of α-sulfur. TEM analysis shows that the morphology of sulfur nanoparticles synthesized in w/o microemulsion system is nearly uniform in size (average particle size 10 nm) and narrow particle size distribution (in range of 5–15 nm) as compared to that in aqueous surfactant systems. The EDS analysis indicated high purity of sulfur (>99%). Moreover, sulfur nanoparticles synthesized in w/o microemulsion system exhibit higher antimicrobial activity (against bacteria, yeast, and fungi) than that of colloidal sulfur.     

Fabrication and optical characterizations of Yb,Er codoped CaF2 transparent ceramic

Nanoparticles of Yb, Er codoped calcium fluoride were obtained by a co-precipitation method. Scanning electron microscope (SEM) and X-ray powder diffraction (XRD) analysis showed that the obtained nanoparticles were single fluorite phase with grains size around 30–50 nm. Yb, Er:CaF₂ transparent ceramics were fabricated by hot pressing (HP) the nanoparticles at a temperature of 800 °C in a vacuum environment. For a 2 mm thickness ceramic sample, the transmittance at 1200 nm reached about 83%. Microstructures were characterized using SEM analysis, and the average grain size was about 700 nm. Grain boundaries of the ceramic sample were clean and no impurities were detected. The absorption, upconversion and infrared emission spectra of transparent ceramic sample under 978 nm excitation were measured and discussed.     

Size-Selected Ag Nanoparticles with Five-Fold Symmetry

Silver nanoparticles were synthesized using the inert gas aggregation technique. We found the optimal experimental conditions to synthesize nanoparticles at different sizes: 1.3 ± 0.2, 1.7 ± 0.3, 2.5 ± 0.4, 3.7 ± 0.4, 4.5 ± 0.9, and 5.5 ± 0.3 nm. We were able to investigate the dependence of the size of the nanoparticles on the synthesis parameters. Our data suggest that the aggregation of clusters (dimers, trimer, etc.) into the active zone of the nanocluster source is the predominant physical mechanism for the formation of the nanoparticles. Our experiments were carried out in conditions that kept the density of nanoparticles low, and the formation of larges nanoparticles by coalescence processes was avoided. In order to preserve the structural and morphological properties, the impact energy of the clusters landing into the substrate was controlled, such that the acceleration energy of the nanoparticles was around 0.1 eV/atom, assuring a soft landing deposition. High-resolution transmission electron microscopy images showed that the nanoparticles were icosahedral in shape, preferentially oriented with a five-fold axis perpendicular to the substrate surface. Our results show that the synthesis by inert gas aggregation technique is a very promising alternative to produce metal nanoparticles when the control of both size and shape are critical for the development of practical applications.     

Natural citric acid assisted synthesis of CuO nanoparticles: Evaluation of structural,optical, morphological properties and colloidal stability for gas sensor applications

In the present research, natural ingredient lemon juice was selected as a fuel to prepare nanoparticles under combustion method. The structural properties of nanophase copper oxide nanoparticles (CuO NPs) synthesized by a natural citric acid aided combustion process were studied using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). According to the SEM and TEM images, the manufactured product is made up of spherical nanoparticles with a limited size distribution. According to the XRD pattern, the average crystallite size of monoclinic structured CuO nanoparticles was 10.4 nm for as-prepared samples and 20.5 nm for annealed samples. The zeta potential value confirms the negative surface charge of the samples and the values show the excellent stability (-58.1 mV) for as-prepared sample and the good particles stability (-38.3 mV) was exhibited for heat treated sample. The optical band gap of CuO nanoparticles is 2.01 eV and it decreases to 1.28 eV under heat treatment. The sensitivity and selectivity of the samples were tested under different operating temperatures (OT) and different gas concentrations (GC). Recovery-response time plots confirm that the CuO nanoparticles are promising materials for gas sensor fabrications.