Hydrothermal synthesis of nanocrystalline VO2 from poly(diallyldimethylammonium) chloride and V2O5

Novel vanadium dioxide nanorods were fabricated from V₂O₅ in the presence of a reducing agent, the poly(diallyldimethylammonium chloride) (PDDA) via a hydrothermal method at 180 °C for 48 h. The samples produced were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (FTIR), nitrogen adsorption (BET) and thermogravimetry (TG/DTG). The nanorods obtained are approximately 50 nm wide and from 300 to 500 nm long and presents high surface area (42 m² g⁻¹). The nanocrystalline B phase VO₂ is not produced by hydrothermal treatment in the absence of the PDDA polyelectrolyte.     

Nanocrystallized steel surface by micro-shot peening for catalyst-free carbon nanotube growth

Nanocrystallized steel surface by micro-shot peening (MSP) were applied to carbon nanotube growth in this study. Micro-shot peening treatment severely deformed steel surface and nanocrystallized surface layer was formed by the plastic deformation. The grain sizes of the nanocrystallized layer were 10-30 nm after 300 s of MSP treatment. On the nanocrystallized surface, carbon nanotubes were formed with thermal chemical vapour deposition without catalysts. Before carbon nanotube growth, the nanocrystallized steel surface was reduced with H₂/N₂ gas at 600 °C. The carbon nanotube growth was performed at 600 °C with C₂H₂ gas carried by H₂/N₂ gas. The carbon nanotubes formed on the nano-structured surface was multi-walled carbon nanotube and the diameter was 10-20 nm. The reduction process before carbon nanotube growth was essential to form carbon nanotubes on the nanocrystallized surface with MSP.     

Pore size control and electrochemical capacitor behavior of chemically activated polyacrylonitrile – Carbon nanotube composite films

Activated polyacrylonitrile (PAN)/carbon nanotube (CNT) composite film based electrodes have been prepared by chemical activation with potassium hydroxide for electrochemical capacitors. This paper analyses the following aspects of specific capacitance, pore size distribution and surface area: influence of activation temperature, molarity of activating agent, composition of PAN/carbon nanotube precursor films and electrolytes. A maximum value of specific capacitance of ∼302 Fg⁻¹ was achieved for the samples activated at 800 °C. Energy density for PAN/CNT 80/20 sample when tested with ionic liquid/organic electrolyte system was as high as ∼22 W h kg⁻¹. Pore size control predominantly below 5 nm was observed in these activated PAN samples. Data analysis showed that micropores make a significant contribution to the capacitance performance of these materials in both 6 M KOH as well as in BMIMBF₄/acetonitrile electrolytes.     

Synthesis and electrochemical performance of LiV3O8/carbon nanosheet composite as cathode material for lithium-ion batteries

To improve the rate capability and cyclability of LiV₃O₈ cathode for Li-ion batteries, LiV₃O₈ was modified by forming LiV₃O₈/carbon nanosheet composite. The LiV₃O₈/carbon nanosheet composite was successfully achieved via a hydrothermal route followed by a carbon coating process. The morphology and structural properties of the samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). TEM observations demonstrated that LiV₃O₈/carbon composite has a very flat sheet-like morphology, with each nanosheet having a smooth surface and a typical length of 400-700 nm, width of 200-350 nm, and thickness of 10-50 nm. Each sheet was surrounded by a thick layer of amorphous carbon. Electrochemical tests showed that the LiV₃O₈/carbon composite cathode features long-term cycling stability (194 mAh g⁻¹ at 0.2 C after 100 cycles) and excellent rate capability (110 mAh g⁻¹ at 5 C, 104 mAh g⁻¹ at 10 C, and 82 mAh g⁻¹ at 20 C after 250 cycles). Electrochemical impedance spectra (EIS) indicated that the LiV₃O₈/carbon composite electrode has very low charge-transfer resistance compared with pristine LiV₃O₈, indicating the enhanced ionic conductivity of the LiV₃O₈/carbon composite. The enhanced cycling stability is attributed to the fact that the LiV₃O₈/carbon composite can prevent the aggregation of active materials, accommodate the large volume variation, and maintain good electronic contact.     

Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy

SiO₂/Al₂O₃ composite microspheres with SiO₂ core/Al₂O₃ shell structure and high surface area were prepared by depositing Al₂O₃ colloid particles on the surface of monodispersed microporous silica microspheres using a simple electrostatic attraction and heterogeneous nucleation strategy, and then calcined at 600 °C for 4 h. The prepared products were characterized with differential thermal analysis and thermogravimetric analysis (DTA/TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It was found that uniform alumina coating could be deposited on the surface of silica microspheres by adjusting the pH values of the reaction solution to an optimal pH value of about 6.0. The specific surface area and pore volume of the SiO₂/Al₂O₃ composite microspheres calcined at 600 °C were 653 m² g⁻¹ and 0.34 ml g⁻¹, respectively.     

Hydrothermal synthesis, characterization, photocatalytic activity and dye-sensitized solar cell performance of mesoporous anatase TiO2 nanopowders

Mesoporous anatase TiO₂ nanopowder was synthesized by hydrothermal method at 130 °C for 12 h. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), HRTEM, and Brunauer-Emmett-Teller (BET) surface area. The as-synthesized sample with narrow pore size distribution had average pore diameter about 3-4 nm. The specific BET surface area of the as-synthesized sample was about 193 m²/g. Mesoporous anatase TiO₂ nanopowders (prepared by this study) showed higher photocatalytic activity than the nanorods TiO₂, nanofibers TiO₂ mesoporous TiO₂, and commercial TiO₂ nanoparticles (P-25, JRC-01, and JRC-03). The solar energy conversion efficiency (η) of the cell using the mesoporous anatase TiO₂ was about 6.30% with the short-circuit current density (Jsc) of 13.28 mA/cm², the open-circuit voltage (Voc) of 0.702 V and the fill factor (ff) of 0.676; while η of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm², Voc of 0.704 V and ff of 0.649.     

Morphology of hydroxyapatite coated nanotube surface of Ti-35Nb-xHf alloys for implant materials

The purpose of this research is to study the morphology of hydroxyapatite coated nanotube surface of Ti-35Nb-xHf for implant materials using various experiments. For this study, Ti-35Nb-xHf (x = 0, 3, 7 and 15 wt.%) alloys were prepared by arc melting and heat treated for 12 h at 1000 °C in an argon atmosphere and then water quenching. Nanotube formation on the Ti-35Nb-xHf alloys was achieved by anodizing in H₃PO₄ electrolytes containing 0.8 wt.% NaF at room temperature. Anodization was carried out using an electrochemical method and all experiments were conducted at room temperature. Hydroxyapatite (HA) was deposited on the nanotubular Ti-35Nb-xHf alloys surface for the biomaterials by radio-frequency (RF) magnetron sputtering method. The morphologies of nanotubular and HA coated surface were characterized by X-ray diffractometer (XRD), optical microscopy (OM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The wettability of HA coated surface was measured by contact angle goniometer.The microstructure of Ti-35Nb-xHf alloys was transformed needle-like to equiaxed structure with Hf content and α″ phase decreased, whereas β phase increased as Hf content increased. HA coating surface was affected by microstructure of bulk and morphology of nanotube formation. In case of low Hf content, tip of nanotube formed at β phase was coated with HA film, whereas α″ phase was not coated with HA film. In case of high Hf content, nanotube surface was coated uniformly with HA film. The wettability of HA coated nanotubular surface was higher than that of non coated samples.     

Influence of morphology and surface characteristics on the photocatalytic activity of rutile titania nanocrystals

This article presents the synthesis of phase-pure rutile titania with different morphologies via hydrothermal method at significantly low temperatures (40-150 °C) without any additives and their application as efficient photocatalyst for environmental remediation. Phase and morphology has been determined with X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ultra violet diffuse reflectance spectroscopy (UV-DRS) shows the optical band-gap in the range of ∼2.8-3.1 eV and Brunauer-Emmett-Teller specific surface area is found to be between 70 and 140 m²/g depending on the synthesis conditions. Raman spectroscopic analyses of the samples provide valuable insights into the structural and stoichiometric details. Photodegradation of the pollutant azo-dye, methyl orange (MO) in presence and absence of oxygen was performed to study the photocatalytic efficiency of the synthesized materials. Complete photodegradation of the dye is confirmed with high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS) study. Dependence of dye photodegradation rate on morphology, specific surface area, surface nonstoichiometry and acidity were investigated in detail. Catalyst performance was compared from the rate constants obtained for each reaction using non-linear least square fitting (NLSF) to the experimental data in a concentration ratio (C₀/C_t) versus time (t) plot which shows extraordinarily high activity for all samples compared to commercial reference. Among them the catalyst synthesized at 40 °C for 16 h showed best activity. Kinetic study of the reaction matches well with simulated fit to experimental data and confirms to be pseudo-first order reaction.     

Agglomerates of amorphous carbon nanoparticles synthesized by a solution-phase method

A novel solution-phase method is developed for preparation of agglomerates of amorphous carbon nanoparticles under ambient atmosphere by the reaction of ferrocene and ammonium chloride in diglycol at 200 °C. Samples are characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and N₂ adsorption-desorption isotherms. It is found that the nanoparticles are complete amorphous and agglomerate together due to the strong surface tension. The agglomerates of amorphous carbon nanoparticles with a diameter of 20-50 nm have a wide size distribution of mesopores with a Brunauer-Emmett-Teller surface area of 75.2 m² g^− 1. It is proposed that the dissolved reactants uniformly dispersing in the solutions could react at a molecular level to form uniform carbon nanoparticles.     

Effect of sodium-ion implantation on the properties of the surface layers formed on CoCrMo alloy (Endocast SL)

This paper is concerned with the surface modification of a cobalt alloy (Endocast) by sodium-ion implantation and with the effect of this modification on its corrosion resistance. The Na ions were implanted at doses of 1×10¹⁷ and 2×10¹⁷ ions/cm² at energy of 25 keV. The chemical composition of the surface layers formed during the implantation was examined by secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS), and their microstructure by transmission electron microscopy (TEM). The corrosion resistance was determined by electrochemical methods in a simulated body fluid (SBF) at a temperature of 37 °C. Prior to the measurements, the samples were exposed to the test conditions for 13 h to allow the corrosion potential E_corr to stabilize, and for 181, 733 and 2200 h to investigate how the long-time exposures affect the corrosion resistance. The surfaces of the samples were examined by optical microscopy and by SEM-EDS. The TEM results indicate that the surface layers formed during the Na-implantation are amorphous. The results of the electrochemical examinations obtained for the Na-implanted Endocast samples indicate that the corrosion resistance of the alloy is reduced.     

Synthesis of flower-like Boehmite (AlOOH) via a simple solvothermal process without surfactant

Boehmite (AlOOH) with hierarchical flower-like structures was synthesized by the solvothermal reaction of AlCl₃·6H₂O in the presence of ethanol and toluene at 200 °C for 24 h. The product was characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that boehmite with flower-like nanostructures, which aggregated together by the weak hydrogen bonds, was formed through dissolution-deposition process of boehmite microcrystals and the toluene has a great effect on the morphology of product in the reaction system. Meanwhile, the γ-Al₂O₃ was also obtained by calcination of above product at 500 °C for 2 h, and the flower-like morphology kept no change. The surface area of γ-Al₂O₃ powder was determined to be 166.8 m²/g by N₂ adsorption measurement. The possible formation mechanism of flower-like boehmite nanostructures was proposed and discussed.     

Fabrication of carbon nanotubes by electrical breakdown of carbon-coated Au nanowires

A carbon nanotube has been generated by the electrically-induced breakdown of a carbon-coated Au nanowire. Under high current density the Au in the nanowire migrates towards both the anode and cathode resulting in a free-standing carbon nanotube and a 73% reduction in resistance. The resistivity of the carbon nanotube was < 8 × 10^− 5 Ω m and it could cope with a current density > 1.8 × 10¹¹ A/m², indicating a structural change from amorphous to graphitic carbon. The dimensions of carbon nanotubes produced in this way have an internal diameter controlled by the parent metal nanowire template.     

Honeycomb-like graphitic ordered macroporous carbon prepared by pyrolysis of ammonium bicarbonate

Honeycomb-like graphitic macroporous carbon (HGMC) was synthesized by means of pyrolysis of NH₄HCO₃ using Mg powder as reductant in an autoclave at 550 °C. The characterization of structure and morphology was carried out by X-ray diffraction (XRD), Raman spectrum, field-emission scanning electron microscopy (FESEM), and (High-resolution) transmission electron microscope [(HR)TEM]. The results of nitrogen adsorption-desorption indicate that the products are macropore materials with the pore size of 1-3 μm, and the Brunauer-Emett-Teller (BET) surface area was 14 m²/g. As a typical morphology, the possible growth process of HGMC was also investigated and discussed. The experimental results show that the in situ formed MgO microparticles play a template role during the HGMC formation.     

Luminescence response and CL degradation of combustion synthesized spherical SiO2:Ce nanophosphor

This study was aimed to systematically investigate the luminescence response of SiO₂:Ce³⁺ nanophosphors with different excitation sources. The powders were synthesized by using an urea assisted combustion method. SiO₂:Ce_1m% samples were also annealed at 1000 °C for 1 h in a charcoal environment to reduce incidental Ce⁴⁺ to partial Ce³⁺ ions. High resolution transmission electron microscopy (HRTEM) images of the as synthesized and annealed powder samples confirmed that the particles were spherical and in the size range of 3-8 nm in diameter. X-ray diffraction (XRD) and electron dispersion spectroscopy (EDS) results showed that the SiO₂ was crystalline and pure. Diffused reflectance, photoluminescence (PL) and cathodoluminescence (CL) results of the SiO₂:Ce³⁺ samples were obtained and compared with each other. The CL degradation and the surface reactions on the surface of the SiO₂:Ce³⁺ were studied with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). A clear improvement in the chemical stability of the SiO₂:Ce³⁺ annealed at 1000 °C were obtained.     

Carbon rich surface of LiFePO4 grain enhancing its rate capability

LiFePO₄/C composite with carbon content of 5 wt.% was synthesized by solid state reaction. Core-shell structure was confirmed by scanning electron microscope (SEM) and transmission electron microscopy (TEM). Rechargeable Lithium ion battery based on this compound has reached a high rate capacity of 121.5 mAhg^− 1 under 5 C. The rate capability retention between 0.1 C and 5 C is 86.9%, which is the highest as far as we know. We found the carbon content was 12.7% on the surface of LiFePO₄ grain, although the whole carbon content was about 5 wt.%. We attribute the improvement of rate capability retention to the existence of the carbon rich surface.     

Synthesis and performance of LiMn0.7Fe0.3PO4 cathode material for lithium ion batteries

Pure and carbon-containing olivine LiMn_0.7Fe_0.3O₄ were synthesized at 600 °C by the method of solid-state reaction. Structure, surface morphology and charge/discharge performance of LiMn_0.7Fe_0.3O₄ were characterized by X-ray diffraction, scanning electron microscopy, and electrochemical measurement, respectively. The prepared materials with and without carbon both show the single olivine structure. The morphologies of primary particles are greatly affected by the addition of carbon. Large particles (500-1000 nm) and densely sintered blocks were observed in pure LiMn_0.7Fe_0.3PO₄, which made the insertion and extraction of lithium ions difficult. Battery made from this sample can not charge and discharge effectively. The carbon-containing LiMn_0.7Fe_0.3PO₄ has a small particle size (100-200 nm) and a regular appearance. This material demonstrates high reversible capacity of about 120 mAh g⁻¹, perfect cycling performance, and excellent rate capability. It is obvious that the addition of carbon plays an important role in restricting the particle size of the material, which helps to prepare LiMn_0.7Fe_0.3PO₄ with excellent electrochemical performance. The electrochemical reaction resistance is much lower in the partly discharged state than in the fully charged or fully discharged state by the measurement of ac impedance for carbon-containing LiMn_0.7Fe_0.3PO₄. It is indicated that the mixed-valence of Fe³⁺/Fe²⁺ or Mn³⁺/Mn²⁺ is beneficial to the transfer of electron which happens between the interface.     

PEG-300 assisted hydrothermal synthesis of 4ZnO·B2O3·H2O nanorods

4ZnO·B₂O₃·H₂O is commonly used as a flame-retardant filler in composite materials. The microstructure of the powder is of importance in its applications. In our study, for the first time, one-dimensional (1D) nanostructure of 4ZnO·B₂O₃·H₂O with rectangle rod-like shape has been synthesized by a hydrothermal route in the presence of surfactant polyethylene glycol-300 (PEG-300). The nanorods have been characterized by X-ray powder diffraction (XRD), inductively coupled plasma with atomic emission spectroscopy (ICP-AES), thermogravimetry (TG) and differential thermal analysis (DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) equipped with selected area electron diffraction (SAED) as well as high-resolution transmission electron microscopy (HRTEM). These nanorods are about 70 nm in thickness, 150-800 nm in width and have lengths up to a few microns. 4ZnO·B₂O₃·H₂O nanorods crystallize in the monoclinic space group P2₁/m, a = 6.8871(19) Å, b = 4.9318(10) Å, c = 5.7137(16) Å, β = 98.81(21)° and V = 191.779(71) Å³.     

High capacity and good cycling stability of multi-walled carbon nanotube/SnO2 core-shell structures as anode materials of lithium-ion batteries

The multi-walled carbon nanotube/SnO₂ core-shell structures were fabricated by a wet chemical route. The electrochemical performance of the core-shell structures as anode materials of lithium-ion batteries was investigated. The initial discharge capacity and reversible capacity are up to 1472.7 and 1020.5 mAh g⁻¹, respectively. Moreover, the reversible capacity still remains above 720 mAh g⁻¹ over 35 cycles, and the capacity fading is only 0.8% per cycle. Such high capacities and good cyclability are attributed to SnO₂ network structures, excellent mechanical property and good electrical conductivity of the multi-walled carbon nanotubes.     

Porous zirconium complex—layered titanate nanohybrids with gas adsorption and photocatalytic activity

Porous zirconium complex-layered titanate nanohybrids were synthesized by reassembling reaction between negative-charged layered titanate nanosheets and positive-charged zirconium complex. According to powder X-ray diffraction and electron microscopy, titanate monolayers were interstratified with zirconium species with the repeating unit of ~ 1.2 nm. X-ray absorption spectroscopy at Zr K-edge and Ti K-edge clearly demonstrated that mononuclear zirconium complex was intercalated into lepidocrocite-structured titanate layers. From N₂ adsorption-desorption isotherm measurement, the hybridization reaction produced highly porous material with the expanded surface area of ~ 176 m²g^− 1. The zirconium complex-layered titanate nanohybrids showed functionalities not only for adsorption of CO₂ gas but also for photodegradation of organic molecules. This finding underscored that the reassembling of layered metal oxide with zirconium ions provides powerful ways to synthesize highly porous materials applicable for gas adsorbents and photocatalysts.     

Ultra-thin zinc oxide film on Mo(100)

Zinc oxide films on a single crystal Mo(100) substrate were fabricated by annealing the pre-deposited metal Zn films in 10^− 5-10^− 4 Pa O₂ ambience at 300-525 K, and were characterized by in situ Auger electron spectroscopy, electron energy loss spectroscopy, low energy electron diffraction and high-resolution electron energy loss spectroscopy. The results show that the atomic ratio of oxygen to zinc in zinc oxide film is significantly dependent on sample annealing temperature and O₂ pressure. A stoichiometric zinc oxide film has been obtained under ∼10^− 4 Pa O₂ at about 400 K. A redshift of Fuchs-Kliewer phonon energy correlated with surface oxygen deficiency is observed.