Preparation and electrochemical capacitance of cobalt oxide (Co3O4) nanotubes as supercapacitor material

Cobalt oxide (Co₃O₄) nanotubes have been successfully synthesized by chemically depositing cobalt hydroxide in anodic aluminum oxide (AAO) templates and thermally annealing at 500 °C. The synthesized nanotubes have been characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrochemical capacitance behavior of the Co₃O₄ nanotubes electrode was investigated by cyclic voltammetry, galvanostatic charge-discharge studies and electrochemical impedance spectroscopy in 6 mol L⁻¹ KOH solution. The electrochemical data demonstrate that the Co₃O₄ nanotubes display good capacitive behavior with a specific capacitance of 574 F g⁻¹ at a current density of 0.1 A g⁻¹ and a good specific capacitance retention of ca. 95% after 1000 continuous charge-discharge cycles, indicating that the Co₃O₄ nanotubes can be promising electroactive materials for supercapacitor.     

Zirconium nitride (ZrN) fibers prepared by carbothermal reduction and nitridation of electrospun PVP/zirconium oxychloride composite fibers

Zirconium nitride (ZrN) fibers were synthesized by carbothermal reduction and nitridation of composite fibers obtained by electrospinning. The structure and morphology of ZrN fibers were characterized by the scanning electron microscopy (SEM) and transmission electron microscopy (TEM). After calcinations at 1600 °C, the surface of ZrN fibers with average diameter about 500 nm is rough but the continuous microstructure was still maintained by the connection of irregular fine particles. The diameter of ZrN crystalline was in the range of 100–500 nm. Both X-ray diffraction (XRD) and Raman spectroscopy analysis indicated that the zirconium nitride fibers have a NaCl-structure cubic cell and the better crystallinity of grains.     

合成工艺对氮化硼纳米管显微结构和性能的影响

采用无定型B粉为原料,在催化剂Fe2O3和CaO辅助作用下,控制反应气氛氨气的流量(150~200 mL/min),在1200℃下于真空管式炉中保温4 h,制备氮化硼纳米管(BNNTs)。采用透射电子显微镜(TEM)、X射线衍射(XRD)和傅里叶转换红外光谱分析(FTIR)等手段对产物的结构和形貌进行了表征,结果表明:所得产物为竹节状氮化硼纳米管(BNNTs),其晶体结构为六方氮化硼,外径约为35~100 nm,长度为数微米至数十微米。     

Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source

Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl₄ and PdCl₂ on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.     

Heteroepitaxial growth of TiN film on MgO (100) by reactive magnetron sputtering

TiN thin films were deposited on MgO (100) substrates at different substrate temperatures using rf sputtering with Ar/N₂ ratio of about 10. At 700°C, the growth rate of TiN was approximately 0.05 μm/h. The structural and electrical properties of TiN thin films were characterized with x-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Hall measurements. For all deposition conditions, XRD results show that the TiN films can be in an epitaxy with MgO with cube-on-cube orientation relationship of (001)_TiN // (001)_MgO and [100]_TiN // [100]_MgO. TEM with selected-area electron diffraction pattern verifies the epitaxial growth of the TiN films on MgO. SEM and AFM show that the surface of the TiN film is very smooth with roughness approximately 0.26 nm. The minimum resistivity of the films can be as low as 45 μΩ cm.     

Morphology and Microstructure of As-Synthesized Anodic TiO2 Nanotube Arrays

The as-grown structure of electrochemically synthesized titania nanotube arrays is investigated by scanning electron microscope (SEM) in combination with transmission electron microscope (TEM) as well as X-ray diffraction (XRD). The analysis reveals a preferred growth direction of the nanotubes relative to the substrate surface and the well control on the nanotube arrays morphology. The crystal structure of the anatase phase is detected and exists in the tube walls without any thermal treatment, which makes it possible to realize the application of as-formed TiO₂ nanotubes avoiding the degradation of the nanotube structures when sintering. In addition, a new growth, layered model of the anodic TiO₂ nanotubes is presented to obtain further understanding of the growth mechanism.     

银纳米线的光吸收性能研究

结合晶种法和光化学还原法成功制备出银纳米线,其直径在50nm左右,长度为4～5μm。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见光谱(UV-vis)、红外光谱(FT-IR)对产物的结构进行了表征,并对银纳米线的光吸收性能及生长机理进行了初步探讨。结果表明,所制得的银纳米线具有面心立方结构,沿着(111)晶面生长;紫外-可见光谱显示在350nm和416nm处存在吸收峰。     

Microstructure and optical properties of nanocrystalline Cu2O thin films prepared by electrodeposition

Cuprous oxide (Cu₂O) thin films were prepared by using electrodeposition technique at different applied potentials (−0.1, −0.3, −0.5, −0.7, and −0.9 V) and were annealed in vacuum at a temperature of 100°C for 1 h. Microstructure and optical properties of these films have been investigated by X-ray diffractometer (XRD), field-emission scanning electron microscope (SEM), UV-visible (vis) spectrophotometer, and fluorescence spectrophotometer. The morphology of these films varies obviously at different applied potentials. Analyses from these characterizations have confirmed that these films are composed of regular, well-faceted, polyhedral crystallites. UV–vis absorption spectra measurements have shown apparent shift in optical band gap from 1.69 to 2.03 eV as the applied potential becomes more cathodic. The emission of FL spectra at 603 nm may be assigned as the near band-edge emission.     

Biomolecule and surfactant-assisted hydrothermal synthesis of PbS crystals

PbS crystals were hydrothermally synthesized using Pb(NO₃)₂, l-cysteine, and N-cetyl pyridinium chloride in solutions with different pH values at 140 °C. Flower-like, granular and truncated cubic PbS crystals composing of Pb and S were detected using an X-ray diffractometer (XRD), a scanning electron microscope (SEM), a transmission electron microscope (TEM), a selected area electron diffraction (SAED) technique and an energy dispersive X-ray (EDX) analyzer. In addition, a Raman spectrometer revealed the presence of the first and second overtone modes at 436 and 602 cm⁻¹, respectively. Emission spectra of the products were detected at 412 nm using a photoluminescence (PL) spectrometer.     

Microwave-assisted synthesis of layered basic zinc acetate nanosheets and their thermal decomposition into nanocrystalline ZnO

We have developed a low-cost technique using a conventional microwave oven to grow layered basic zinc acetate (LBZA) nanosheets (NSs) from a zinc acetate, zinc nitrate and HMTA solution in only 2 min. The as-grown crystals and their pyrolytic decomposition into ZnO nanocrystalline NSs are characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), X-ray diffraction (XRD) and photoluminescence (PL). SEM and AFM measurements show that the LBZA NSs have typical lateral dimensions of 1 to 5 μm and thickness of 20 to 100 nm. Annealing in air from 200°C to 1,000°C results in the formation of ZnO nanocrystalline NSs, with a nanocrystallite size ranging from 16 nm at 200°C to 104 nm at 1,000°C, as determined by SEM. SEM shows evidence of sintering at 600°C. PL shows that the shape of the visible band is greatly affected by the annealing temperature and that the exciton band to defect band intensity ratio is maximum at 400°C and decreases by a factor of 15 after annealing at 600°C. The shape and thickness of the ZnO nanocrystalline NSs are the same as LBZA NSs. This structure provides a high surface-to-volume ratio of interconnected nanoparticles that is favorable for applications requiring high specific area and low resistivity such as gas sensing and dye-sensitized solar cells (DSCs). We show that resistive gas sensors fabricated with the ZnO NSs showed a response of 1.12 and 1.65 to 12.5 ppm and 200 ppm of CO at 350°C in dry air, respectively, and that DSCs also fabricated from the material had an overall efficiency of 1.3%.

PACS

81.07.-b; 62.23.Kn; 61.82.Fk     

TiO_2纳米管电极金属离子掺杂的表征

采用浸渍法对TiO2纳米管电极进行Zn2+、Fe3+、Cu2+离子的掺杂改性,并进行了各种性能表征.扫描电镜(SEM)及X射线衍射光谱(XRD)结果表明,金属离子掺杂后的TiO2纳米管电极依然保持了良好的表面形态及锐钛矿晶型,纳米管的直径为60—100 nm,其晶面主要为101面;可见紫外漫反射光谱(DRS)分析表明,进行掺杂的TiO2纳米管电极的光学性质有不同程度的改变,Zn2+、Fe3+和Cu2+掺杂的TiO2纳米管电极的禁带宽度分别为3.37 eV3、.14 eV、2.86 eV.这表明掺Cu2+的TiO2纳米管电极的吸收边带发生了明显的红移.     

Impregnating ionic Pt species on vanadium oxide nanotubes

Vanadium oxide nanotubes (VNT) have drawn increasing attention as vanadium compounds may be used in a wide range of applications. In this contribution, VNT was synthesized by a hydrothermal treatment from V₂O₅ using hexadecylamine as template. XRD, FTIR, SEM, TEM/HRTEM and TG analyses were used to investigate their chemical stability and suitability to adsorb platinum ionic species without damaging the nanostructure. It was shown that the nanostructures are open-ended multiwalled nanotubes, formed by 13–16 layered walls, with inner diameter of 30–50 nm and outer diameter of 150–200 nm. The impregnation of Pt was found to be feasible but their structure and morphology are sensitive to the pH of the impregnation media.     

Growth of multiwalled carbon nanotubes during the initial stages of aerosol-assisted CCVD

We report a study of the initial stages of growth of aligned multiwalled carbon nanotubes (MWNT) synthesised by catalytic chemical vapour deposition (CCVD) of liquid aerosol obtained from toluene/ferrocene solution. A special experimental procedure has been developed to stop the process after short durations (30 s to 2 min). Two different pyrolysis temperatures are considered: 800 and 850 °C. Both scanning and transmission electron microscopy (SEM, TEM) coupled to energy-dispersive X-ray (EDX) analyses are used in order to determine the location of catalyst particles and to examine their chemical nature, morphology and size distribution when nanotubes start to grow. During the early stages (30 s), we observe the formation of a layer of catalyst particles on silicon substrates before the growth of nanotubes. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements indicate the occurrence of iron oxide (γ-Fe₂O₃ or Fe₃O₄). In addition, XPS analysis reveals the formation of graphite-like carbon, demonstrating that iron oxide particles catalyse the decomposition of toluene vapour. SEM and TEM observations show that these particles are most often located at the nanotube root, suggesting a base growth mechanism responsible for the formation of aligned nanotube when prolonging growth time (2 min).     

Size-controllable synthesis and bandgap modulation of single-layered RF-sputtered bismuth nanoparticles

We here report a simple and efficient method to grow single-layer bismuth nanoparticles (BiNPs) with various sizes on glass substrates. Optimal conditions were found to be 200°C and 0.12 W/cm² at a growth rate of 6 Å/s, with the deposition time around 40 s. Scanning electron microscope (SEM) images were used to calculate the particle size distribution statistics, and high-resolution X-ray diffraction (XRD) patterns were used to examine the chemical interactions between BiNPs and the substrates. By measuring the transmission spectra within the range of 300 to 1,000 nm, we found that the optical bandgap can be modulated from 0.45 to 2.63 eV by controlling the size of these BiNPs. These interesting discoveries offer an insight to explore the dynamic nature of nanoparticles.     

Ferromagnetism and optical properties of La1???x Al x FeO3 nanopowders

La_{1 − x} Al _x FeO₃ (x = 0.0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) nanopowders were prepared by polymerization complex method. All prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and UV-vis spectrophotometry (UV-vis). The magnetic properties were investigated using a vibrating sample magnetometer (VSM). The X-ray results of all samples show the formation of an orthorhombic phase with the second phase of α-Fe₂O₃ in doped samples. The crystallite sizes of nanoparticles decreased with increasing Al content, and they are found to be in the range of 58.45 ± 5.90 to 15.58 ± 4.64 nm. SEM and TEM images show the agglomeration of nanoparticles with average particle size in the range of 60 to 75 nm. The FT-IR spectra confirm the presence of metal oxygen bonds of O-Fe-O and Fe-O in the FeO₆ octahedra. The UV-vis spectra show strong absorption peaks at approximately 285 nm, and the calculated optical band gaps are found to be in the range of 2.05 to 2.09 eV with increasing Al content. The M-H loop of the pure sample is antiferromagnetic, whereas those of the doped samples tend to be ferromagnetic with increasing Al content. The magnetization, remanent magnetization, and coercive field of the Al-doped sample with x = 0.5 are enhanced to 1.665 emu/g, 0.623 emu/g, and 4,087.0 Oe, respectively.     

Converting Layered Zinc Acetate Nanobelts to One-dimensional Structured ZnO Nanoparticle Aggregates and their Photocatalytic Activity

We were successful in synthesizing periodic layered zinc acetate nanobelts through a hydrothermal solution process. One-dimensional structured ZnO nanoparticle aggregate was obtained by simple thermal annealing of the above-mentioned layered ZnO acetate nanobelts at 300 °C. The morphology, microstructure, and composition of the synthesized ZnO and its precursors were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and infrared spectroscopy, respectively. Low angle X-ray diffraction spectra reveal that as-synthesized zinc acetate has a layered structure with two interlayer d-spacings (one is 1.32 nm and the other is 1.91 nm). SEM and TEM indicate that nanobelt precursors were 100–200 nm in width and possesses length up to 30 μm. Calcination of precursor in air results in the formation of one-dimensional structured ZnO nanoparticle aggregates. In addition, the as-prepared ZnO nanoparticle aggregates exhibit high photocatalytic activity for the photocatalytic degradation of methyl orange (MO).     

H2 uptake and synthesis of the fluorinated Li-dispersed nickel oxide nanotubes

Aligned Li-dispersed nickel oxide nanotubes were prepared using LiNO₃, Ni(NO₃)₂·6H₂O and an anodic aluminum oxide (AAO) template for potential applications in H₂ storage. The nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The nickel(II) oxide nanotubes obtained had a trigonal structure with a uniform length, 40–50 nm in wall thickness and 200 ± 10 nm in the outer diameter. The external surface of the nanotubes was modified by fluorination. The level of H₂ adsorption was determined using the gravimetric method. The fluorinated Li-dispersed nickel oxide nanotubes showed a 0.06 wt% and 1.65 wt% increase in weight due to H₂ adsorption under an equilibrium pressure of 47 atm at 298 K and 77 K, respectively.     

Synthesis of PtRu/carbon nanotube composites in supercritical fluid and their application as an electrocatalyst for direct methanol fuel cells

PtRu nanoparticles were decorated on multi-walled carbon nanotubes (MWCNTs) using H₂PtCl₆ and RuCl₃ as precursors with the aid of supercritical CO₂, and the resulting composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy. TEM observation showed that nanoparticles of size about 5 nm were distributed evenly on the MWCNTs, and XRD analysis showed that the particles had a face-centered cubic crystal structure. The loading content of the nanoparticles on the MWCNTs could be adjusted by manipulating the relative ratio of the precursor to MWCNTs. The as-prepared PtRu/MWCNT composites exhibited high activity for methanol electro-oxidation.     

Synthesis and electrochemical performance of lithium vanadium oxide nanotubes as cathodes for rechargeable lithium-ion batteries

A new kind of cathode materials for rechargeable lithium-ion batteries, lithium vanadium oxide nanotubes synthesized by a combined sol-gel reaction and hydrothermal treatment procedure is reported in this paper. SEM, TEM, XRD and XPS techniques were performed to investigate the morphology and structure of the resulting materials. The results confirmed that the synthetic materials are composed of uniformly open-ended multiwalled nanotubes with a length from 1 to 3 μm. The inner and the outer diameters of the obtained nanotubes vary from 30 to 50 nm and 50 to 120 nm, respectively. The electrochemical performance as a cathode material was examined and evaluated by cyclic voltammetry, galvanostatic charge-discharge cycling and AC impedance spectroscopy techniques. The results indicated that the resultant lithium vanadium oxide nanotubes have a high initial discharge capacity of 457 mAh g⁻¹ in the potential range of 1.0-4.0 V (vs. Li/Li⁺) and good cycling performance. The improved electrochemical performance of the products should be due to its special one-dimensional multiwalled tubular structure and the contribution of lithium-ions.     

化学气相沉积法合成纳米碳管阵列研究

研究以环己烷为前驱体采用化学气相沉积法制备纳米碳管阵列。将催化剂二茂铁定量溶解在环己烷中，通过载气夹带进入反应器中，采用化学气相沉积方法定向生长出炭纳米管阵列，此法有效地控制反应体系中的催化剂含量，使生产稳定性及重现性较好。并通过透射电子显微镜、扫描电子显微镜、拉曼光谱及X射线衍射对产品形态和结构进行分析和表征，所制备出的纳米碳管阵列形态比较规整，纯度较高，具有较好的石墨微晶结构；并对纳米碳管的生长机理进行了详细讨论。