Carbon nanotubes and carbon nanofibers fabricated on tubular porous Al2O3 substrates

Carbon nanotubes and carbon nanofibers were grown at different temperatures on porous ceramic Al₂O₃ substrates with single channel geometry by means of a chemical vapor deposition technique using methane as carbon source and palladium as catalyst. Time-resolved in-situ Fourier transformed infrared spectroscopy was used for the investigation of methane decomposition for characterizing the catalyst’s performance. With increasing synthesis temperature, a structural transition from carbon nanofibers to carbon nanotubes was observed. At a synthesis temperature of 700 °C, solely carbon nanofibers were found, whereas at 800 °C a mixture of two types of bamboo-shaped carbon nanofibers were obtained, suggesting a structural transition. A synthesis temperature to 850 °C results in bamboo-shaped multi-walled carbon nanofibers and multi-walled carbon nanotubes. The carbon products and the observed structural transition were characterized by means of field emission scanning electron microscopy, high-resolution transmission electron microscopy, thermal gravimetric analysis, and Raman spectroscopy.     

Hydrothermal synthesis of dumbbell-shaped ZnO microstructures

Dumbbell-shaped ZnO microstructures have been successfully synthesized by a facile hydrothermal method using only Zn(NO₃)₂·6H₂O and NH₃·H₂O as raw materials at 150 °C for 10 h. The results from X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) show that the prepared ZnO samples exhibit dumbbell-shaped morphology and hexagonal wurtzite structure. The length of ZnO dumbbells is about 5–20 μm, the diameters of the two ends and the middle part are about 1–5 μm and 0.5–3 μm, respectively. The dumbbell-shaped ZnO microstructures may be formed by self-assembly of ZnO nanorods with 1–5 μm in length and 100–200 nm in diameter. The photoluminescence (PL) spectrum of dumbbell-shaped ZnO microstructures at room temperature shows three emission peaks at about 362, 384 and 485 nm.     

Effect of the boron content on the steam activation of boron-doped diamond electrodes

In order to investigate the initial stages of the steam-activation process of boron-doped diamond (BDD) electrodes, polycrystalline BDD electrodes with different levels of boron doping (800, 2500 and 5000 ppm) and crystal orientation were treated with water vapor at 800 °C. A higher degree of etching was observed for BDD electrodes with higher boron content. Based on scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, it is suggested that the {1 1 1} planes are preferentially etched. Thus, high-boron containing BDD electrodes which have a higher abundance of the {1 1 1} planes are heavily etched, while low-boron containing BDD electrodes with a mixed surface of {1 0 0} and {1 1 1} planes are less corroded. The steam activation of BDD electrodes have a higher electrochemically active surface area and wider potential window compared to pristine BDD electrodes.     

Glucose sensing,photocatalytic and antibacterial properties of graphene–ZnO nanoparticle hybrids

A simple and efficient approach was developed to uniformly decorate graphene nanosheets with zinc oxide (ZnO) nanoparticles. A single source precursor, zinc benzoate dihydrazinate complex, has been used for the in situ generation of ZnO nanoparticles onto graphene at a relatively low temperature, 200 °C. Physico chemical analyses such as X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that ZnO nanoparticles were finely dispersed on the surface of graphene. ZnO–graphene hybrids were further characterized by Raman spectroscopy and ultraviolet visible spectroscopy and room-temperature photoluminescence. The materials exhibited excellent photocatalytic activity as evident from the degradation of methylene blue in ethanol under UV irradiation. An electrochemical glucose biosensor was fabricated by immobilization of glucose oxidase on the ZnO–graphene hybrids. This biosensor showed improved sensitivity towards glucose as compared to graphene. Also, the hybrids showed significant antibacterial activity against E. coli, gram negative bacteria. This simple and economical preparation strategy may be extended for the preparation of other graphene-based hybrids.     

ZnO-capped nanorod gas sensors

This paper reports on the synthesis of pristine α-Fe₂O₃ nanorods and Fe₂O₃–ZnO core–shell nanorods using a combination of thermal oxidation and atomic layer deposition (ALD) techniques; the completed nanorods were then used for ethanol sensing studies. The crystal structure and morphology of the synthesized nanostructures were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sensing properties of the pristine and core–shell nanorods for gas-phase ethanol were examined using different concentrations of ethanol (5–200 ppm) at different temperatures (150–250 °C). The XRD and SEM revealed the excellent crystallinity of the Fe₂O₃–ZnO core–shell nanorods, as well as their uniformity in terms of shape and size. The Fe₂O₃–ZnO core–shell nanorod sensor showed a stronger response to ethanol than the pristine Fe₂O₃ nanorod sensor. The response (i.e., the relative change in electrical resistance R_a/R_g) of the core–shell nanorod sensor was 22.75 for 100 ppm ethanol at 200 °C whereas that of the pristine nanorod sensor was only 3.85 under the same conditions. Furthermore, under these conditions, the response time of the Fe₂O₃–ZnO core–shell nanorods was 15.96 s, which was shorter than that of the pristine nanorod sensor (22.73 s). The core–shell nanorod sensor showed excellent selectivity to ethanol over other VOC gases. The improved sensing response characteristics of the Fe₂O₃–ZnO core–shell nanorod sensor were attributed to modulation of the conduction channel width and the potential barrier height at the Fe₂O₃–ZnO interface accompanying the adsorption and desorption of ethanol gas as well as to preferential adsorption and diffusion of oxygen and ethanol molecules at the Fe₂O₃–ZnO interface.     

Synthesis and electrochemical performance of Li4Ti5O12/C composite by a starch sol assisted method

Li₄Ti₅O₁₂/C composite anode materials were synthesized by a simple starch sol assisted method using TiO₂-anatase and Li₂CO₃ as raw materials and soluble starch as carbon source. The influences of calcination temperature and starch amounts on the microstructure and electrochemical performance were systematically investigated. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and constant-current charge/discharge cycling tests. The results showed that the Li₄Ti₅O₁₂/C composite with 10 wt.% starch synthesized at 800 °C for 6 h had homogeneous particle size distribution with an average particle size of 200–300 nm and exhibited the optimal electrochemical performance with specific discharge capacities of 168.5, 160.8, 155.1 and 141.8 mAh g^? 1 at 0.2 °C, 1 °C, 2 °C and 5 °C rates, respectively, and satisfactory cycling stability. It could be attributed to the homogeneous ultrafine particles and in situ carbon coating, which enhanced the electronic conductivity and diffusion of lithium ions in the electrode.     

Effect of strontium and cerium doping on the structural characteristics and catalytic activity for C3H6 combustion of perovskite LaCrO3 prepared by sol–gel

Two series of Sr- or Ce-doped La_1−xM_xCrO₃ (x = 0.0, 0.1, 0.2 and 0.3) catalysts were prepared by thermal decomposition of amorphous citrate precursors followed by annealing at 800 °C in air atmosphere. The effect of Ce and Sr on the morphological/structural properties of LaCrO₃ was investigated by means of thermogravimetric/differential thermal analysis (TG/DTA) of the precursors decomposition under air, X-ray diffraction (XRD), electron paramagnetic resonance (EPR), transmission electron microscopy–X-ray energy dispersive spectroscopy (TEM–XEDS), S_BET determination, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The characterization results are employed to explain catalytic activity results for C₃H₆ combustion. It is shown that the lanthanum chromite perovskite structure is obtained upon thermal treatment of the sol–gel derived precursors at T > ca. 800 °C. The presence of the dopant generally induces the formation of segregated oxide phases in the samples calcined at 800 °C although some introduction of the Sr in the perovskite structure is inferred from EPR measurements. The oxidation activity becomes maximised upon formation of such doped perovskite structure.     

Synthesis and transport properties of La0.67Sr0.33MnO3 conformally-coated on carbon nanotubes

We report for the first time the fabrication of nanostructured ferromagnetic lanthanum strontium manganite La_0.67Sr_0.33MnO₃ (LSMO) conformally coated onto bamboo-like carbon nanotubes (BCNTs) by pulsed laser deposition. Scanning electron microscopy revealed that one-dimensional LSMO/BCNTs with diameters ranging from 100-160 nm and lengths over 10 μm were obtained. Line-scanned energy-dispersive X-ray spectroscopy profiles, selected area electron diffraction rings, and energy-filtered transmission electron microscopy maps provided further insight into the hybrid nanostructures. LSMO/BCNT and BCNT were also investigated via in situ electrical probing in a transmission electron microscope using a piezo-driven scanning tunneling microscopy holder. Modeling of the I–V characteristics of individual hybrid nanotubes yielded the resistivity, bandgap, and electron density of LSMO and BCNT. The results show that the transport properties of LSMO/BCNT are superior to those of BCNT. This research advances the integration of oxide materials and carbon nanotubes, bringing forth new avenues for miniaturization and fabrication of one-dimensional core-multishell materials with multifunctional properties that can be used as building blocks in nanodevices.     

Preparation and characterization of graphene and Ni-decorated graphene using flower petals as the precursor material

A simple method is reported for preparing graphene and nickel-decorated graphene from the petals of lotus and hibiscus flowers by heating the original petals and petals soaked in a nickel(II) chloride solution ranging 800–1600 °C under a flowing argon atmosphere for 0.5 h. The products have been characterized by scanning and transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Graphene prepared at high temperature (>1200 °C) is purer than that obtained at a lower temperature (800 °C). The presence of nickel has been found to have improved the quality of the graphene and electron density near the Fermi energy level.     

Nucleation and growth of ZnO nanorods on the ZnO-coated seed surface by solution chemical method

ZnO nanorods on ZnO-coated seed surfaces were fabricated by solution chemical method using supersaturated (ZnNO₃)₂/NaOH at 70 °C. The seed surfaces were coated on glass substrates by sol–gel processing, and their texture was dominated by heating temperatures, cooling styles and layer thickness per dipping. The effects of the seed surface on the morphology of the resultant nanorods were primarily discussed. The orientation and morphology of both the seed surface and successive nanorods were analyzed by using XRD and SEM. It is proved that when the seed size increases from 15 to 50 nm with temperature increasing, the average diameter of the resultant nanorods increase from 25 to 50 nm, with a length of 800 nm after growing for 1.5 h. The seed surface prepared by heating at 300–400 °C, fast cooling or drawing at lower speed has better orientation and few surface defects, which leads to higher density of nuclei on the seed surface and thus to the optimal preferred crystal growth of ZnO rods standing perpendicular onto substrates.     

Facile synthesis of ZnO nanostructures and enhancement of their sinterability via short-time cryo-milling

Zinc oxide (ZnO), a wide band-gap semiconductor, has received a great interest due to its potential applications in various fields both as nanostructures and as sintered compacts. In this study, we report on the synthesis of the ZnO nanostructures and facilitation of their sintering for the production of fine-grained dense compacts. The facile synthesis of gram scale ZnO nanostructures was achieved by thermal decomposition of zinc acetate dihydrate (Zn(Ac)₂·2H₂O) or Zn(Ac)₂·2H₂O/graphite mixtures at 300 °C for 12 h. Thermal decomposition of Zn(Ac)₂ resulted in the formation of mostly ZnO nanoparticles with wurtzite structure along with ZnO nanorods, while the addition of graphite significantly promoted the growth of ZnO nanowires. Microstructural and phase properties of the obtained ZnO nanostructures were determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution TEM (HRTEM) techniques, all of which revealed the successful synthesis of high quality ZnO nanostructures. In addition to synthesis and characterization of the ZnO nanostructures, we report on the enhancement of their sinterability by a subsequent cryogenic milling for a short duration of 5 min. As a result of the applied cryo-milling, fabrication of highly dense (96.2%) sintered compacts with fine grain sizes (572 nm) could be achieved after pressureless sintering at 1000 °C for 2 h.     

Hierarchical heterostructure of porous NiO nanosheets on flower-like ZnO assembled by hexagonal nanorods for high-performance gas sensor

A novel hierarchical heterostructure consisting of porous NiO nanosheets and flower-like ZnO assembled by hexagonal nanorods was successfully fabricated by a simple two-step hydrothermal approach. Flower-like ZnO was obtained by the first step hydrothermal method. Through the second step hydrothermal method, porous NiO nanosheets grew on the surface of flower-like ZnO to realize integration of ZnO and NiO, so the p-n heterostructure between ZnO and NiO formed. The samples were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX). Gas sensing test results showed that the sensor based on NiO/ZnO composite exhibited superior sensing properties to acetone. The sensor response to 100 ppm acetone was about 205.14 at the optimum working temperature of 240 °C, and the response and recovery times were about 7 and 20 s, respectively. The enhanced response might be attributed to heterojunction and larger specific surface area provided by attached porous NiO nanosheets. The rapid response and recovery characteristics and improved selectivity attributed to the porous structure and good catalytic actions of NiO nanosheets.     

CVD growth and field electron emission of aligned carbon nanotubes on oxidized Inconel plates without addition of catalyst

Direct growth of carbon nanotubes (CNTs) on Inconel 600 sheets was investigated using plasma enhanced hot filament chemical vapor deposition in a gas mixture of methane and hydrogen. The Inconel 600 sheets were oxidized at different temperatures (800 °C, 900 °C, 1000 °C, and 1100 °C) before CNT deposition. The structure and surface morphology of the pre-treated substrate sheets and the deposited CNTs were studied by scanning electron microscopy (SEM) and X-ray diffraction. The field electron emission (FEE) properties of the CNTs were also tested. The SEM results show that well aligned CNTs have been grown on the pre-treated Inconel sheets without addition of any catalysts and the higher treatment temperature resulted in CNTs with better uniformity, indicating that the oxidation pre-treatment of the substrate is effective to enhance the CNT growth. FEE testing shows that CNTs with better height uniformity exhibit better FEE characteristics.     

Fabrication of self-binding noble metal/flexible graphene composite paper

Self-binding noble metal (Pt, Au, and Ag)/graphene composite papers as large as 13 cm in diameter were fabricated using a flow-directed method where in situ reduced graphene served as a “binder”. The papers were characterized by X-ray diffraction, scanning and transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. This approach yielded well dispersed metals with various nanostructures both on and between the graphene layers to form papers with good conductivity and flexiblility. The 300 °C-annealed Ag/graphene papers were evaluated as binder-free anodes for lithium ion batteries, delivering a reversible charge capacity of 689 mAh/g at a current density of 20 mA/g.     

In situ transmission electron microscope tensile testing reveals structure–property relationships in carbon nanofibers

Tensile tests were performed on carbon nanofibers in situ a transmission electron microscope (TEM) using a microelectromechanical system (MEMS) tensile testing device. The carbon nanofibers tested in this study were produced via the electrospinning of polyacrylonitrile (PAN) into fibers, which are subsequently stabilized in an oxygen environment at 270 °C and carbonized in nitrogen at 800 °C. To investigate the relationship between the fiber molecular structure, diameter, and mechanical properties, nanofibers with diameters ranging from ∼100 to 300 nm were mounted onto a MEMS device using nanomanipulation inside the chamber of a Scanning Electron Microscope, and subsequently tested in tension in situ a TEM. The results show the dependence of strength and modulus on diameter, with a maximum modulus of 262 GPa and strength of 7.3 GPa measured for a 108 nm diameter fiber. In particular, through TEM evaluation of the structure of each individual nanofiber immediately prior to testing, we elucidate a dependence of mechanical properties on the molecular orientation of the graphitic structure: the strength and stiffness of the fibers increases with a higher degree of orientation of the 0 0 2 graphitic planes along the fiber axis, which coincides with decreasing fiber diameter.     

Hydrothermal processing and in situ surface modification of metal oxide nanomaterials

In situ surface modification of TiO₂ and ZnO metal oxide particles has been carried out under hydrothermal conditions within a wide range of temperature and pressure (T = 150–400 °C; P = up to 20 MPa). The influence of the surfactant and selective doping with active metal ions on the crystal size, morphology, and photocatalytic activity of TiO₂ and ZnO particles has been carried out. A systematic characterization of the product has been carried out using powder XRD, FTIR, TGA, SEM/TEM, and UV–vis spectroscopy. Similarly the photocatalytic activity in these metal oxides varies with the size, shape and dopant metals.     

Synthesis and electrochemical properties of nickel oxide/carbon nanofiber composites

The electrospinning of polyacrylonitrile (PAN) with a polyaniline and graphene sol–gel mixture produced uniform, smooth fibers with an average diameter of 0.3 μm. These electrospun fibers were stabilized for 2 h at 200 °C and then carbonized at 800 °C for 5 h. Composites were prepared by depositing Ni(OH)₂ on the carbon nanofibers (CNFs) and calcining them at different temperatures. The composites were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The effect of the calcination temperatures on the electrochemical properties was studied using cyclic voltammetry and electrochemical impedance spectroscopy. The specific capacitance (SC) was found to be highest (738 F g⁻¹) at a calcination temperature of 400 °C. The charge transfer resistance (R_p) decreased as the calcination temperature was increased. However, the electrical double layer capacitance (EDLC) increased with an increase in the calcination temperature. The EDLC increased from 0.144 F g⁻¹ at a calcination temperature of 100 °C to 485 F g⁻¹ at a calcination temperature of 500 °C.     

Characterization and gas sensing properties of bead-like ZnO using multi-walled carbon nanotube templates

We report bead-like ZnO nanostructures for gas sensing applications, synthesized using multi-walled carbon nanotube (MWCNT) templates. The ZnO nanostructures are grown following a two-step process: in the first, ZnO nanoparticles are synthesized on MWCNTs by thermal evaporation of a Zn powder; and in the second, the hybrid nanostructures are heat-treated at 800 °C. Scanning and transmission electron microscopy images indicate that the bead-like ZnO nanostructures have surface protuberances with nanoparticle sizes ranging from 20 to 60 nm, and a well-crystallized hexagonal structure. Gas sensors based on multiple-networked bead-like ZnO showed considerably enhanced electrical responses and better stability to both oxidizing (NO₂) and reducing (CO) gases compared with previously reported nanostructured gas sensors, even if the response to CO gas was slow to increase. Both the NO₂ and CO gas sensing properties increased dramatically when the working temperature was increased up to 300 °C. The response sensitivities measured were 2953%, 5079%, 9641%, 3568%, and 3777% to 20 ppm NO₂ at 200, 250, 300, 350 and 400 °C, respectively. For CO gas on the other hand, the response sensitivities were 107%, 110%, 114%, 118%, and 122% at 5, 10, 20, 50, and 100 ppm concentrations, respectively. For concentrations between 5 and 20 ppm, the recovery time of the oxidizing gas was much shorter than the response time. The origin of the NO₂/CO gas sensing mechanism of the bead-like ZnO nanostructures is discussed.     

Fracture toughness,strength and creep of transparent ceramics at high temperature

Fracture toughness, four-point bending strength of transparent spinel, Y₂O₃ and YAG ceramics in function of temperature (from room temperature up to 1500° C) were measured. Creep resistance at 1500–1550° C was studied too. Grain size distribution was determined on polished and etched surfaces of samples. Fracture surfaces after tests were examined by scanning electron microscopy. The obtained results showed that: in the case of spinel ceramics fracture toughness and strength decreased from 20 to 800° C, increased from 800 to 1200° C and decreased at higher temperature; in the case of Y₂O₃ ceramics they increased from 400 to 800° C, and next kept constant up to 1500° C; in the case of YAG ceramics they kept constant from 20 to 1200° C and then decreased. The creep strain rate was measured for spinel and YAG but not for Y₂O₃ ceramics which appeared creep resistant. The hypotheses concerning toughening and creep mechanisms were proposed.     

Synthesis and photocatalytic performance of hollow sphere particles of SiO2-TiO2 composite of mesocellular foam walls

Hollow Microspheres of SiO₂-TiO₂ photocatalysts whose walls are made up of mesoporous cellular foams were synthesized with the aid of hexane as a swelling agent and P123 as a pore template by an emulsion templating method. Pore structure of materials and crystal phase of titanium oxide was tailored by hydrothermal and calcination temperature during synthesis of samples. The samples were characterized with field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N₂ adsorption–desorption experiments, X-ray photoelectron spectroscopy (XPS) and X ray diffraction (XRD) techniques. The effect of pore structure and titania phase on photoactivity were evaluated by methylene blue (MB) degradation test under UV light as well. Results showed that hydrothermal temperature during synthesis process has a significant effect on pore and window sizes of mesostructured cellular foam. Interestingly, for the sample hydrothermally treated at higher temperature (130 °C), anatase to rutile transformation was avoided after calcination treatment as high as 800 °C. The highest photocatalytic activity was detected from the sample hydrothermally treated at 130 °C and calcined at 800 °C for which the highest degree of crystallinity and anatase phase as well as enhanced pore connectivity was obtained.