氧化铜纳米晶的合成及其丙酮气敏性能研究

本文通过水热的方法,合成CuO纳米材料.利用广角X射线衍射(Wide-angle XRD),透射电子显微镜(TEM),并结合氮气吸附(N2 adsorption measurement)等手段,证实这是一种高度结晶的单分散纳米CuO材料.气敏测试表明,CuO纳米晶是一种优异的丙酮气体敏感材料,具有较低的工作温度和较高的丙酮敏感性能.本文中,我们对该现象进行了分析,并提出其可能的机理.     

Uniform dispersion of CuO nanoparticles on mesoporous TiO2 networks promotes visible light photocatalysis

Here, we focus our efforts on synthesizing a uniform dispersion of CuO nanoparticles on mesoporous TiO₂ networks for the first time. H₂PtCl₆ was added through a photocatalytic reaction to produce 0.5% Pt/CuO–TiO₂ nanocomposites. XRD patterns confirmed that the prepared TiO₂ formed the anatase phase. TEM images showed close contacts between CuO and TiO₂ with 5–10 nm particle sizes. One of the advantages of the synthesized mesoporous CuO–TiO₂ nanocomposites was the high pore volume (0.540 cm³ g⁻¹) and large surface area (300 m² g⁻¹). The H₂ evolution over the mesoporous 3 wt% CuO–TiO₂ nanocomposites using a glucose hole scavenger [10 vol%] was determined to be ~13000 μmol/g, a value that was 1300 times greater than that of mesoporous TiO₂. The H₂ evolution rate was increased by up to 1300 and 20 times for 3 wt% CuO–TiO₂ and 0.1 wt% CuO–TiO₂ nanocomposites, respectively, compared with that of mesoporous TiO₂. The increase in H₂ evolution over mesoporous CuO–TiO₂ nanocomposites was explained by the increased light harvesting capacity, high glucose molecule diffusion and efficient charge carrier separation. Moreover, the construction of a heterostructure with a p–n CuO–TiO₂ heterojunction expedited the separation of charge carriers and promoted the evolution of H₂. In addition, H₂ evolution was substantially increased by the synergistic effects of Pt and CuO on the mesoporous TiO₂ networks. Photoelectrochemical and photoluminescence measurements were employed to prove the H₂ evolution mechanism over the CuO nanoparticles deposited on the mesoporous TiO₂ networks.     

Controlled synthesis of CuO nanoparticles using TritonX-100-based water-in-oil reverse micelles

CuO nanoparticles were synthesized by TritonX-100 based water-in-oil reverse micelles system, and characterized by X-ray diffractometer (XRD) and transmission electron microscopy (TEM), respectively. The results indicated that the grain size, morphology and distribution were highly dependent on the ratio of water to surfactant (R). The control effect of water content dissolved in reverse micelles was attributed to the enhancement of the exchange rate of reactants among micelles and the relevant change in the interfacial film flexibility of reverse micelles with the increasing amount of water in the microemulsion.     

Structural,magnetic and electric properties of ZrO2 tapes decorated with magnetic nanoparticles

We produced ZrO₂ ceramic tape decorated with magnetic nanoparticles through tape casting technique. The green and sintered magnetic tapes were characterized by XRD, SEM, EDS, magnetic measurements, and I–V curves. We investigated the changes in the structural, magnetic and electrical properties, after the sintering process, and discussed the connections between them. The magnetic properties, performed in a wide range of external magnetic field and temperature, show magnetite phase for the magnetic nanoparticles governing the magnetic and electric properties of the green tape. On the other hand, for the sintered tape, the increase in the hematite phase led to remarkable changes in the magnetic and electrical properties. The electrical characterization reflects the observed changes in the structural properties after the sintering process. Additionally, the main advantages of the ceramic tapes decorated with magnetic nanoparticles reside in the possibility of producing functional thin ceramic materials that are easily moldable for electronic devices applications.     

Synthesis,characterization and alcohol sensing property of Zn-doped SnO2 nanoparticles

The Zn-doped SnO₂ nanoparticles synthesized by the chemical co-precipitation route and having dopant concentration varying from 0 to 4 at%, were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) for structural and morphological studies. XRD analyses reveal that all the samples are polycrystalline SnO₂ having tetragonal rutile structure with nanocrystallites in the range 10–25 nm. The TEM images show agglomeration of grains (cluster of primary crystallites). A corresponding selected area electron diffraction pattern reveals the different Debye rings of SnO₂, as analyzed in XRD. Alcohol sensing properties of all the Zn-doped samples were investigated for various concentrations of methanol, ethanol and propan-2-ol in air at different operating temperatures. Among all the samples examined, the 4 at% Zn-doped sample exhibits the best response to different alcohol vapors at the operating temperature of 250 °C. For a concentration of 50 ppm, the 4 at% Zn-doped sample shows the maximum response 85.6% to methanol, 87.5% to ethanol and 94.5% to propan-2-ol respectively at the operating temperature of 250 °C. A possible reaction mechanism of alcohol sensing has been proposed.     

Structural,magnetic, thermal and optical properties of Sn2+ cation doped magnetite nanoparticles

Tin doped nanomagnetites, Sn_xFe_3-xO₄, were synthesized with various concentrations of Sn²⁺ ion (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) by co-precipitation method. XRD, VSM, TG-DTA, SEM-EDX and UV–Vis were used to characterize and study the structural, magnetic, thermal, and optical properties of Sn_xFe_3-xO₄ nanoparticles. XRD confirmed the presence of cubic structure and spinel phase of tin doped magnetites. The d-spacing, lattice parameter, density, crystallite size and cation distribution were derived from the XRD analysis. The M − H curves exhibited changes in saturation magnetization (M_s), coercive field (H_c), remanent magnetization (M_r) and susceptibility (χ), with increasing concentration of non-magnetic Sn²⁺ ions. Differential thermal analysis was used to study the thermal stability of Sn_xFe_3-xO₄ nanoparticles. The SEM images revealed the surface morphology of the nanoparticles and the EDX spectra showed an increase in the Sn content and a corresponding decrease in the Fe content for the tin doped samples. The optical bandgap was found to be centered at 3.9 eV for the synthesized materials. This systematic study may be the first comprehensive report on synthesis and characterization of tin doped magnetites.     

Gadolinium ferrite nanoparticles: Synthesis and morphological,structural and magnetic properties

In this study we report on the successful synthesis of Gd_xFe_3−xO₄ nanoparticles with nominal Gd-content (x) in the range 0.00≤x≤0.50. The effect of the nominal Gd-content on morphological, structural and magnetic properties was investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy and Mössbauer spectroscopy. We found the actual inclusion of Gd³⁺ ions into cubic ferrite structure lower than the nominal values, though no extra phase was observed in the whole range of our investigation. Moreover, from Mössbauer data we found evidences of Gd³⁺ ions replacing both Fe³⁺ and Fe²⁺ ions, the latter leading to iron vacancies in the cubic ferrite crystal structure. As the nominal Gd-content, the lattice parameter and the average crystallite size increases monotonically. We found that in the same range of nominal Gd-content the lattice parameter decreases with the increase of iron vacancy content.     

Structural and dielectric properties of CuO nanoparticles

The DC conduction and dielectric behaviour of copper oxide nanoparticles prepared by sol-gel method and sintered at 950 °C were studied in the temperature range of 200–526 K. The formation of single phase monoclinic CuO was confirmed by x-ray diffraction. Chemical composition of the CuO ceramic was investigated with X-ray photoelectron spectroscopy (XPS) technique. Although XRD analysis shows the formation of single phase CuO, XPS spectra revealed the presence of Cu³⁺ and Cu²⁺. Deviation from linearity ln (σ_DC) vs. 1/T plot at ~390 K was observed, which indicates that DC conduction in the CuO pellet is dominated by two different conduction mechanisms. The results obtained on AC conductivity indicate that AC conduction mechanism could be well explained by the multihopping model at low frequencies, while high frequency AC conductivity data can be described by small polaron tunnelling model. The dielectric relaxation mechanism in the CuO pellet was studied by impedance spectroscopy. It was found that while dielectric constant is an increasing function of temperature, it decreases with increasing frequency. The obtained impedance spectra indicated that the grain boundary effects and intergranular activities play a crucial role on the dielectric relaxation processes.     

Doped Poly(m-phenylenediamine-co-aniline) (P(mPD-co-ANI)): Synthesis,Characterization, Physical Properties,and Precursor for CuO Nanoparticles

Poly(m-phenylenediamine-co-aniline) P(mPD-co-ANI) and Mn-, Ni-, and Cu-doped poly(m-phenylenediamine-co-aniline) (M-P(mPD-co-ANI)) have been synthesized and characterized. Cu-P(mPD-co-ANI) has been used as a molecular precursor of CuO nanoparticles. The spectral, optical, refractive index, solubility, and thermal properties of the synthesized polymers have been measured and discussed. The optical bandgap (E_g) measurements indicated that Ni(P(mPD-co-ANI)) has wider optical band than the pure (P(mPD-co-ANI)). Calcination of Cu-P(mPD-co-ANI) at 600°C produced (CuO) nanoparticles. The obtained nanoparticles have been characterized by XRD and TEM. The average size of CuO nanoparticles was found to be 42?nm. The refractive index measurements indicate slight change in the refractive index values of the polymer solution than that of pure solvent. The solubility of the synthesized polymers in ethanol, dimethyl formamide (DMF)–aqueous mixed solvents was found to increase as the mole fractions of both ethanol and DMF increase. The UV spectra of the synthesized polymers in ethanol, DMF–aqueous mixed solvents indicate blueshift and hyperchromic effect.     

Analysis and characterization of structural,morphological, thermal properties and colloidal stability of CuO nanoparticles for various natural fuels

CuO nanoparticles were made quickly from natural macromolecules using the combustion process, and their structural, morphological, thermal, and particle stability properties were examined. All samples were monoclinic polycrystalline by XRD. Tea extract, wine, honey, and cow urine-assisted nanoparticles had crystallite sizes of 25.82, 26.18, 27.69, and 25.32 nm, respectively, according to the WH plot. FESEM and EDAX analysis verifies leaf, pollen grain, disc, and rice-like morphologies and stoichiometric products. Crystallite size correlates with TEM mean particle size. The parameters of the XRD pattern, which was matched with the standard data, reveal the presence of a pure monoclinic CuO phase with only substantial vibrations at 430 cm^-1 to 603 cm^-1. Thermal investigations (TG-DTA) demonstrate that particles are stable at 896°C-960°C before sublimating. Tea extract, wine, honey, and cow urine have been shown to affect CuO weight reduction. Anti-microbial study of the organic fueled CuO was made with Staphylococcus aureus (Gram-positive) and Pseudomonas aeruginosa (Gram-negative) bacteria, also Candida albicans and Aspergillus niger fungi. It is found that CuO nanoparticles effectively inhibit fungal growth more than bacterial growth.     

纳米TiO_2、NiO和CuO的制备、表征及催化苯酚羟基化反应研究

分别采用均匀沉淀法和固相法合成纳米级的TiO2,NiO和CuO颗粒,用XRD,TEM等对其结构和形貌进行了表征,用纳米TiO2,NiO和CuO为催化剂,对苯酚羟基化反应的活性进行研究。结果表明,纳米TiO2,NiO和CuO颗粒催化苯酚羟基化反应具有较好的催化活性,苯酚的转化率分别达到25.3%,28.3%和27.5%。     

Synthesis, characterization and catalytic property of CuO and Ag/CuO nanoparticles for the epoxidation of styrene

CuO nanorodes, CuO nanoplates and Ag/CuO nanoparticles were synthesized in the presence of polyethylene glycol by depositional in alkaline environment. Oxide nanoparticles were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared absorption spectra (FT-IR). CuO and Ag/CuO nanoparticles show high catalytic activity for the selective epoxidation of styrene to styrene oxide by TBHP. Under the optimized reaction condition, the oxidation of styrene catalyzed by CuO nanorods gave 100% conversion with 60 and 35% styrene oxide and benzaldehyde, respectively. Ag/CuO gave 99% conversion and styrene oxide (71%) and benzaldehyde (12%) being the major product.     

Synthesis, surface modification and photocatalytic property of ZnO nanoparticles

ZnO nanoparticles were synthesized by calcination of precursor prepared by the precipitation method. Polystyrene was grafted onto the surface of ZnO nanoparticles to improve the dispersion of the particles and to reduce their photocatalytic activity. The obtained particles were characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction, and transmission electron microscopy. The photocatalytic activity of bare and modified ZnO nanoparticles was studied. The influence of surface modification on the photocatalytic degradation of methyl orange has been analyzed. The composition of residual solution was determined through high performance liquid chromatography. Experimental results show that well dispersed ZnO nanoparticles were obtained after surface modification. ZnO nanoparticles possess high photocatalytic activity, whereas the photocatalytic activity can be significantly reduced when polystyrene was grafted onto the particle surface.     

Synthesis and functionalization of magnetic nanoparticles with covalently bound electroactive compound doxorubicin

We report here on covalent functionalization of magnetic nanoparticle colloidal suspension (ferrofluid) with doxorubicin. Since doxorubicin (adriamycin) is a potent anti-cancer drug, such particles can be guided with external magnetic field to a target tissue, a carrier process that may overcome the non-specificity and efficiency of adriamycin as a drug. The nanoferrite functionalization was effected by means of acid chloride chemistry leading to the formation of covalent bond between the hydroxyl groups at the nanoparticle surface and acid chloride molecules. This procedure can be easily tailored to provide the nanoferrites with various functionalities capable of further modifications with, e.g., drug molecules. Thus, we used such modified nanoferrites to covalently attach molecules of anti-tumor drug—doxorubicin. The attachment was verified by means of FTIR and cyclic voltammetry. Mean size of nanoferrites was evaluated by powder X-ray diffraction (PXRD) technique and high-resolution field emission scanning electron microscope (HR-FESEM). The amount of doxorubicin attached to nanoparticles was assessed by means of quartz crystal microbalance combined with cyclic voltammetry.     

Synthesis,structural and morphological characteristics,magnetic and optical properties of Co doped ZnO nanoparticles

Zn_1−xCo_xO (x==0.05, 0.10, 0.15) nanoparticles have been synthesized by an alternative wet-chemical synthesis route using the SimAdd technique. The as-obtained powders were investigated by FT-IR spectroscopy, X-ray diffraction and thermal analysis correlated with evolved gas analysis (TG–DTA–FT-IR) in order to determine their chemical nature, crystalline structure and to establish the decomposition sequences. The precipitates are generally amorphous, but low-intensity reflection peaks assigned both to the zinc oxalate dihydrate, and zinc hydroxide can be observed in the recorded patterns, indicating that hydroxy-oxalate precipitates were obtained. The structure, morphology and magnetic properties of the thermally treated samples have been investigated by X-ray diffraction, FT-IR, HRTEM, SAED, UV–vis and EPR. XRD studies reveal a hexagonal wurtzite-type structure for all Zn_1−xCo_xO samples. TEM investigations show particle size between 28 and 37 nm, with spherical and polyhedral shapes and with tendency to form aggregates. The presence of a Co₃O₄ secondary phase was evidenced by XRD, UV–vis and EPR for the Zn_0.85Co_0.15O sample. The ferromagnetic behavior of the samples was revealed. The paper highlights that by varying the cobalt concentration it is possible to modulate the structural, morphological, optical and magnetic properties.     

PtO2-nanoparticles functionalized CuO polyhedrons for n-butanol gas sensor application

The CuO polyhedrons functionalized with different amounts of PtO₂ nanoparticles were synthesized by simple two-step method. The gas sensing properties of the sensors prepared by PtO₂ functionalized CuO polyhedron were studied and compared with pure CuO sensors. The electrical sensitivity values show that the response of S2-CuO (3.5%_wt PtO₂-CuO) polyhedron is higher than that of pure CuO polyhedron in n-butanol/air atmosphere. The sensor showed excellent reproducibility and good selectivity to n-butanol gas, and its working temperature was relatively low (180?°C), and the reaction time quickly reached 2.4?s. The enhanced properties are attributed to the structure of the CuO polyhedron and the synergistic effect of CuO and PtO_2.     

Fabrication and NO2 gas sensing performance of TeO2-core/CuO-shell heterostructure nanorod sensors

TeO₂-nanostructured sensors are seldom reported compared to other metal oxide semiconductor materials such as ZnO, In₂O₃, TiO₂, Ga₂O₃, etc. TeO₂/CuO core-shell nanorods were fabricated by thermal evaporation of Te powder followed by sputter deposition of CuO. Scanning electron microscopy and X-ray diffraction showed that each nanorod consisted of a single crystal TeO₂ core and a polycrystalline CuO shell with a thickness of approximately 7 nm. The TeO₂/CuO core-shell one-dimensional (1D) nanostructures exhibited a bamboo leaf-like morphology. The core-shell nanorods were 100 to 300 nm in diameter and up to 30 μm in length. The multiple networked TeO₂/CuO core-shell nanorod sensor showed responses of 142% to 425% to 0.5- to 10-ppm NO₂ at 150°C. These responses were stronger than or comparable to those of many other metal oxide nanostructures, suggesting that TeO₂ is also a promising sensor material. The responses of the core-shell nanorods were 1.2 to 2.1 times higher than those of pristine TeO₂ nanorods over the same NO₂ concentration range. The underlying mechanism for the enhanced NO₂ sensing properties of the core-shell nanorod sensor can be explained by the potential barrier-controlled carrier transport mechanism.

PACS

61.46. + w; 07.07.Df; 73.22.-f     

Size-regulated group separation of CoFe2O4 nanoparticles using centrifuge and their magnetic resonance contrast properties

Magnetic nanoparticle (MNP)-based magnetic resonance imaging (MRI) contrast agents (CAs) have been the subject of extensive research over recent decades. The particle size of MNPs varies widely and is known to influence their physicochemical and pharmacokinetic properties. There are two commonly used methods for synthesizing MNPs, organometallic and aqueous solution coprecipitation. The former has the advantage of being able to control the particle size more effectively; however, the resulting particles require a hydrophilic coating in order to be rendered water soluble. The MNPs produced using the latter method are intrinsically water soluble, but they have a relatively wide particle size distribution. Size-controlled water-soluble MNPs have great potential as MRI CAs and in cell sorting and labeling applications. In the present study, we synthesized CoFe₂O₄ MNPs using an aqueous solution coprecipitation method. The MNPs were subsequently separated into four groups depending on size, by the use of centrifugation at different speeds. The crystal shapes and size distributions of the particles in the four groups were measured and confirmed by transmission electron microscopy and dynamic light scattering. Using X-ray diffraction analysis, the MNPs were found to have an inverse spinel structure. Four MNP groups with well-selected semi-Gaussian-like diameter distributions were obtained, with measured T₂ relaxivities (r₂) at 4.7 T and room temperature in the range of 60 to 300 mM⁻¹s⁻¹, depending on the particle size. This size regulation method has great promise for applications that require homogeneous-sized MNPs made by an aqueous solution coprecipitation method. Any group of the CoFe₂O₄ MNPs could be used as initial base cores of MRI T₂ CAs, with almost unique T₂ relaxivity owing to size regulation. The methodology reported here opens up many possibilities for biosensing applications and disease diagnosis.

PACS

75.75.Fk, 78.67.Bf, 61.46.Df