An efficientfficient,controllable and facile two-step synthesis strategy: Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@RGO composites with various Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles and their supercapacitance properties

An efficient,controllable,and facile two-step synthetic strategy to prepare graphene-based nanocomposites is proposed.A series of Fe3O4-decorated reduced graphene oxide (Fe3O4@RGO) nanocomposites incorporating Fe3O4 nanocrystals of various sizes were prepared by an ethanothermal method using graphene oxide (GO) and monodisperse Fe3O4 nanocrystals with diameters ranging from 4 to 10 nm.The morphologies and microstructures of the as-prepared composites were characterized by X-ray diffraction,Raman spectroscopy,nitrogen adsorption measurements,and transmission electron microscopy.The results show that GO can be reduced to graphene during the ethanothermal process,and that the Fe3O4 nanocrystals are well dispersed on the graphene sheets generated in the process.The analysis of the electrochemical properties of the Fe3O4@RGO materials shows that nanocomposites prepared with Fe3O4 nanocrystals of different sizes exhibit different electrochemical performances.Among all samples,Fe3O4@RGO prepared with Fe3O4 nanocrystals of 6 nm diameter possessed the highest specific capacitance of 481 F/g at 1 A/g,highlighting the excellent capability of this material.This work illustrates a promising route to develop graphene-based nanocomposite materials with a wide range of potential applications.     

Research on the Relationship between Density of States and Conducting Properties of Single-walled Carbon Nanotubes

The analytical expression of the electronic density of states (DOS) for single-walled carbon nanotubes (SWNTs) has been derived on the basis of graphene approximation of the energy E(k) near the Fermi level EF. The distinctive properties of the DOS, the normalized differential conductivity and the current vs bias for SWNTs are deduced and analyzed theoretically. The singularities in the DOS (or in the normalized differential conductivity) predict that the jump structure of current (or conductance)--bias of SWNTs exists. All conclusions from the theoretical analysis are in well agreement with the experimental results of SWNT‘s electronic structure and electronic transport. In other words, the simple theoretical model in this paper can be applied to understand a range of spectroscopic and other measurement data related to the DOS of SWNTs.     

Preparation of Nano-structured LiFe_xMn_(1-x)PO_4(x=0,0.2,0.4) by Reflux Method and Research on the Influences of Fe(Ⅱ) Substitution

Nano structured LiFexMn1-xPO4(x=0,0.2,0.4) materials were successfully prepared by one-step reflux method in a water/PEG400 mixed solvent, and were coated by carbon using glucose as the precursor. The materials were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The electrochemical properties of the materials were investigated by galvanostatic cycling, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It was found that the materials consisted of nanorods with a diameter of 50 nm and a length of 500 nm. Galvanostatic cycling showed that the capacity of LiMnPO 4 could be largely increased by Fe2+ substitution. At a current rate of C/20, the capacity of the three samples (x=0,0.2,0.4) were 47, 107 and 150 mA·h·g-1 , respectively. CV result showed that the Fe2+ substitution could decrease the polarization during charging/discharging, accelerating the electrochemical process. EIS result showed that the Fe2+ substitution could decrease the charge transfer resistance between the electrode and electrolyte,     

Nano-TiO_2 Decorated Radial-Like Mesoporous Silica: Preparation,Characterization, and Adsorption-Photodegradation Behavior

Supported nanocrystalline Ti_O2 with a diameter of 15–30 nm was prepared from previously synthesized radial mesoporous silica(RMS) by a post-synthesis method. In addition, their adsorption-photocatalytic activity toward the degradation of methylene blue(MB) was determined. RMS was tailor-made with the main template of CTAB and the Si_O2 precursor of TEOS through a facile self-assembly process. The structural, morphological and textural properties of the well-designed Ti_O2/RMS samples were characterized.The RMS structure was retained after loading Ti_O2, but its surface area and pore diameter decreased as a result of partial pore blocking. The removal activity of MB for Ti_O2/RMS was significantly higher than that of commercial Ti_O2 nanoparticles. The optimal Ti_O2 loading(20 wt%) on the support could achieve the complete removal of MB within 70 min. The prepared Ti_O2/RMS particles can be easily separated and display good durability after six reaction cycles.     

Growth of Variable Aspect Ratio ZnO Nanorods by Solochemical Processing

In this work,variable aspect ratio(length divided by diameter) zinc oxide nanorods were synthesized through a simple solochemical method by reacting a Zn~(2+) precursor with sodium hydroxide at low reaction temperatures.The analysis of the X-ray diffraction data indicated that the samples had hexagonal wurtzite structure and nanometric size crystallites.The transmission electron microscopy(TEM) images of the products prepared at60 and 80 ℃ exhibited rod-like architecture,showing that the reaction temperature did not affect the ZnO morphology.The average aspect ratio of the ZnO nanorods decreased from 3.4 to 2.4 when the reaction temperature was raised from 60 to 80 ℃.The samples presented a blue shift in the excitonic absorption compared to ZnO bulk that increased alongside with reaction temperature.In addition,this research investigated the results obtained by varying the concentration of zinc chloride solution.At the same temperature,it could be verified that when the zinc concentration was increased,the diameter of the ZnO nanorods also slightly increased,and much shorter nanorods were achieved,especially in the reactions performed at 50 and 70 ℃.Finally,the growth mechanism of the ZnO nanostructures was proposed based on the results obtained by changing the zinc precursor concentration and reaction temperature.     

Hydrogen Storage Alloy and Carbon Nanotubes Mixed Catalyst in a Direct Borohydride Fuel Cell

In this study, carbon nanotubes (CNTs) were mixed with AB5-type hydrogen storage alloy (HSA), as catalyst for an anode in a direct borohydride fuel cell (DBFC). As comparision, a series of traditional carbon materials, such as acetylene black, Vulcan XC-72R, and super activated carbon (SAC) were also employed. Electrochemical measurements showed that the electrocatalytic activity of HSA was improved greatly by CNTs. The current density of the DBFC employing the HSA/CNTs catalytic anode could reach 1550 mA·cm-2 (at -0.6 V vs the Hg/HgO electrode) and the maximum power density of 65 mW·cm-2 for this cell could be achieved at room temperature. Furthermore, the life time test lasting for 60 h showed that the cell displayed a good stability.     

Study on Fine Structure of Gas Atomized LaNis-based Alloys

The fine structure of hydrogen storage alloy powders MlNi4.3-xCoxMn0.4Al0.3(x=0.75, 0.45, 0.10; Ml: La-rich misch metal) prepared by rapidly solidifying gas atomization was investigated using a Rietveld analysis method. Two sets of CaCus-type crystal constants were observed in the studied alloys and one set was larger than the other. With decreasing powder radius the solidification rate of powder increased, and so did the percentage of a particle part with larger crystal constants. The reason why there were two sets of crystal constants might be the difference of solidification rate between the outside and inside of a particle.     

Effect of Substrate Pretreatment on Controllable Growthof TiO2 Nanorod Arrays

Well-aligned TiO2 nanorod arrays(TNAs) were prepared on the pretreated quartz substrates.The effect of the pretreatment conditions on the growth of TNAs was systematically investigated by X-ray diffraction(XRD),field-emission scanning electron microscopy(FE-SEM) and high-resolution transmission electron microscopy(HRTEM).It is demonstrated that the pre-coating TiO2 crystal seeds on the substrates can greatly improve the growth orientation of TNAs.Rutile TiO2 crystal seeds induce the nucleation and growth of TNAs more preferably than the anatase TiO2 seeds.The growth density and diameter distribution of TNAs strongly depend on the TiO2 crystal seeds density.It is proved that TNAs with different morphologies can be controllably synthesized by using hydrothermal approach by pretreating substrates.The photocatalytic activity of TNAs was investigated by measuring the photodegradation rate of methyl blue aqueous solution under UV irradiation(254 nm).And the results show that TNAs with large growth density and small diameter size exhibit relatively higher photocatalytic activity.     

Giant Rheological Effect of Shear Thickening Suspension Comprising Silica Nanoparticles with No Aggregation

The spherical silica particles in narrow size distribution with different diameters of 90 nm, 200 nm, 320 nm and 400 nm were prepared by the modified St?ber method and characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and dynamic light scattering(DLS). The phase composition of particles was characterized by X-ray diffraction. The results indicated that each of the silica particle samples was in amorphous state. The shear thickening fluids(STFs) comprising 53 vol.%of silica particles and 47 vol.% of polyethylene glycol with molecular weight of 200 g mol~(-1)(PEG200) were prepared and evaluated. The influence of size and size distribution on the critical shear rate and the intensity of shear thickening were analyzed. The STFs prepared by silica nanoparticles with a diameter of90 nm showed the giant rheological effect with the critical shear rate of 2.51 s~(-1), the largest viscosity of45,500 Pa·s and the yield stress of 181 kPa. The experiments and the analysis results demonstrated that the suspensions prepared by nanoparticles have high intensity of shear thickening.     

Transport Properties of Bi_2S_3 Single Crystals

Bi2S3 single crystals were grown by using a modification of Bridgman method. Measurements of the electrical conductivity, Hall effect and thermoelectric power （TEP） were preformed in two crystallographic directions （parallel and perpendicular to the c-axis）. The measurements showed that the electrical conductivity, Hall mobility, and Seebeck coefficient have anisotropic nature. From these measurements some physical parameters were estimated and the crystals showed n-type of conduction mechanism. Also, values of the energy gap were found to be different in the two directions.     

Electrochemical hydrogen storage in single-walled carbon nanotube paper

Single-walled carbon nanotube (SWNT) papers were successfully prepared by dispersing SWNTs in Triton X-100 solution, then filtered by PVDF membrane (0.22 microm pore size). The electrochemical behavior and the reversible hydrogen storage capacity of single-walled carbon nanotube (SWNT) papers have been investigated in alkaline electrolytic solutions (6 N KOH) by cyclic voltammetry, linear micropolarization, and constant current charge/discharge measurements. The effect of thickness and the addition of carbon black on hydrogen adsorption/desorption were also investigated. It was found that the electrochemical charge-discharge mechanism occurring in SWNT paper electrodes is somewhere between that of carbon nanotubes (physical process) and that of metal hydride electrodes (chemical process), and consists of a charge-transfer reaction (Reduction/Oxidation) and a diffusion step (Diffusion).     

Selective etching of metallic single-wall carbon nanotubes with hydrogen plasma

We present Raman scattering and scanning tunnelling microscopy (STM) measurements on hydrogen plasma etched single-wall carbon nanotubes (SWNTs). Interestingly, both the STM and Raman spectroscopy show that the metallic SWNTs are dramatically altered and highly defected by the plasma treatment. In addition, structural characterizations show that metal catalysts are detached from the ends of the SWNT bundles. For semiconducting SWNTs we observe no feature of defects or etching along the nanotubes. Raman spectra in the radial breathing mode region of plasma-treated SWNT material show that most of the tubes are semiconducting. These results show that hydrogen plasma treatment favours etching of metallic nanotubes over semiconducting ones and therefore could be used to tailor the electronic properties of SWNT raw materials.     

Cadmium-catalyzed surface growth of single-walled carbon nanotubes with high efficiency

We demonstrate that cadmium (Cd) can catalyze the growth of single-walled carbon nanotubes (SWNTs) with high efficiency. The Cd nanocatalysts, prepared using a diblock copolymer templating method, were uniformly spaced over a large deposition area with an average diameter of 1.9 nm and narrow size distribution. By using the normal-heating and fast-heating method, random and horizontally aligned arrays of SWNTs can be generated. The density of the SWNTs can be altered by the chemical vapor deposition conditions. The morphology and microstructure of the SWNTs characterized by scanning electron microscopy, Raman spectroscopy, atomic force microscopy, and high-resolution transmission electron microscopy revealed that the grown nanotubes do not have carbonaceous particles and have good crystallinity. In addition, after careful check with superlong nanotubes 735 out of 790 nanotubes were found to be deposited with Ag (93%) and only 7% SWNTs without Ag deposition. While for superlong SWNT arrays from Fe, 32% long SWNTs without Ag deposition was found, the high percentage of SWNTs with Ag deposition from Cd indicates that the SWNTs have better conductivity and better structural uniformity with less defects.     

Single-walled carbon nanotubes used as stationary phase in GC

Single-walled carbon nanotubes (SWNTs) have high surface area, high adsorption ability, and nanoscale interactions. In this study, capillary columns including SWNTs, ionic liquid (IL), and IL + SWNTs for GC were prepared. The separation results showed that SWNTs possessed a wide selectivity toward alkanes, alcohols, aromatic compounds, and ketones, and a SWNT capillary column was a very useful GC column for the separation of gas samples. Coating the IL stationary phase on the SWNT capillary column, the SWNTs were able to improve chromatographic characteristic of ionic liquid. Comparing the IL coated on three graphite carbon black capillary columns, which were prepared by dynamic coating, static coating, and chemical bonding the Carbopack C with on SWNTs capillary column, the capacity factors were much higher on the SWNT column. The SEM showed that SWNTs could be bonded to the inner surface of capillary tubing, and most of them were linked end-to-end to form a layer of network structure of skeletons resulting in a high surface area, which increased the interactions between stationary phase and analytes. This is the first single-wall carbon nanotubes bonded to the fused-silica capillary tubing. In the first approach, SWNTs assist ionic liquid with enhanced chromatographic characteristic in GC. This work indicates that SWNTs make it possible to extend the application range on the newly prepared chromatographic stationary phases for GC.     

Temperature-mediated growth of single-walled carbon-nanotube intramolecular junctions

Single-walled carbon nanotubes (SWNTs) possess superior electronic and physical properties that make them ideal candidates for making next-generation electronic circuits that break the size limitation of current silicon-based technology. The first critical step in making a full SWNT electronic circuit is to make SWNT intramolecular junctions in a controlled manner. Although SWNT intramolecular junctions have been grown by several methods, they only grew inadvertently in most cases. Here, we report well-controlled temperature-mediated growth of intramolecular junctions in SWNTs. Specifically, by changing the temperature during growth, we found that SWNTs systematically form intramolecular junctions. This was achieved by a consistent variation in the SWNT diameter and chirality with changing growth temperature even though the catalyst particles remained the same. These findings provide a potential approach for growing SWNT intramolecular junctions at desired locations, sizes and orientations, which are important for making SWNT electronic circuits.     

Fractionation of SWNT/nucleic acid complexes by agarose gel electrophoresis

We show that aqueous dispersions of single-walled carbon nanotubes (SWNTs), prepared with the aid of nucleic acids (NAs) such as RNA or DNA, can be separated into fractions using agarose gel electrophoresis. In a DC electric field, SWNT/NA complexes migrate in the gel in the direction of positive potential to form well-defined bands. Raman spectroscopy as a function of band position shows that nanotubes having different spectroscopic properties possess different electrophoretic mobilities. The migration patterns for SWNT/RNA and SWNT/DNA complexes differ. Parallel elution of the SWNT/NA complexes from the gel during electrophoresis and subsequent characterization by AFM reveals differences in nanotube diameter, length and curvature. The results suggest that fractionation of nanotubes can be achieved by this procedure. We discuss factors affecting the mobility of the nanotube complexes and propose analytical applications of this technique.     

Mechanical properties of epoxy nanocomposites reinforced with very low content of amino-functionalized single-walled carbon nanotubes

Functionalized single-walled carbon nanotubes (SWNTs) with amino groups were prepared by oxidation, acylation, and amidation of SWNT surfaces. Epoxy/SWNT composite membranes were fabricated using a very low content of amino-grafted SWNTs (< or = 0.08 wt%) as fillers. SWNTs with amino groups acted as a curing agent, covalently bonding to the epoxy matrix. The influence of SWNT content on the mechanical properties of epoxy/amino-functionalized SWNT composite membrane was investigated. It is found that the tensile strength of composites is enhanced with the increase of SWNTs. Only 0.01 wt% of SWNT-R-NH, leads to improvement of the epoxy tensile strength by 9.5%, and 0.08 wt% of SWNT-R-NH2 increased tensile strength by 13.6%. For comparison purposes, epoxy/pristine-SWNT films were also prepared. The improvement of the tensile strength of the amino-functionalized SWNTs system is more remarkable than that of pristine SWNT system at very low weight-percentage loading. The amino groups on the surface of SWNTs can be covalently attached to the epoxy matrix, which effectively improves the dispersion and adhesion of SWNTs in epoxy. This leads to the enhancement in mechanical properties of the epoxy composite. Mechanical results between functionalized and pristine nanotubes are discussed in detail.     

Size separation of single-wall carbon nanotubes by flow-field flow fractionation

Flow-field flow fractionation (flow-FFF) is used to separate single wall carbon nanotubes (SWNTs) dispersed in aqueous medium by the use of DNA. Online measurements are made of SWNT concentration, molar mass, and size by using UV-vis absorption and multiangle light scattering (MALS). Separations are made of both unfractionated SWNTs and SWNT fractions made by use of size exclusion chromatography (SEC). The SEC fractions are well resolved by flow-FFF. SWNT hydrodynamic volume from calibrations with polymer latex particles in flow-FFF are compared to calibrations of hydrodynamic volume from the SEC fractions derived from dissolved polymers. Rod lengths of the SWNTs are calculated from online measurements of MALS and those are compared to rod lengths from hydrodynamic models based on latex sphere calibrations. Samples with varied sizes were prepared by fracturing SWNTs through extended sonication. Flow-FFF of these fractured samples shows very broad size distributions compared to the original SEC and flow-FFF fractions.     

Chirality‐Selective Photoluminescence Enhancement of ssDNA‐Wrapped Single‐Walled Carbon Nanotubes Modified with Gold Nanoparticles

In this work, a convenient method to enhance the photoluminescence (PL) of single‐walled carbon nanotubes (SWNTs) in aqueous solutions is provided. Dispersing by single‐stranded DNA (ssDNA) and modifying with gold nanoparticles (AuNPs), about tenfold PL enhancement of the SWNTs is observed. More importantly, the selective PL enhancement is achieved for some particular chiralities of interest over all other chiralities, by using certain specific ssDNA sequences that are reported to recognize these particular chiralities. By forming AuNP–DNA–SWNT nanohybrids, ssDNA serves as superior molecular spacers that on one hand protect SWNT from direct contacting with AuNP and causing PL quench, and on the other hand attract the AuNP in close proximity to the SWNT to enhance its PL. This PL enhancement method can be utilized for the PL analysis of SWNTs in aqueous solutions, for biomedical imaging, and may serve as a prescreening method for the recognition and separation of single chirality SWNTs by ssDNA.     

Assessment of the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes

Scanning electrochemical microscopy (SECM) has been employed in the feedback mode to assess the electrochemical behavior of two-dimensional networks of single-walled carbon nanotubes (SWNTs). It is shown that, even though the network comprises both metallic and semiconducting SWNTs, at high density (well above the percolation threshold for metallic SWNTs) and with approximately millimolar concentrations of redox species the network behaves as a thin metallic film, irrespective of the formal potential of the redox couple. This result is particularly striking since the fractional surface coverage of SWNTs is only approximately 1% and SECM delivers high mass transport rates to the network. Finite element simulations demonstrate that under these conditions diffusional overlap between neighboring SWNTs is significant so that planar diffusion prevails in the gap between the SECM tip and the underlying SWNT substrate. The SECM feedback response diminishes at higher concentrations of the redox species. However, wet gate measurements show that at the solution potentials of interest the conductivity is sufficiently high that lateral conductivity is not expected to be limiting. This suggests that reaction kinetics may be a limiting factor, especially since the low surface coverage of the SWNT network results in large fluxes to the SWNTs, which are characterized by a low density of electronic states. For electroanalytical purposes, significantly, two-dimensional SWNT networks can be considered as metallic films for typical millimolar concentrations employed in amperometry and voltammetry. Moreover, SWNT networks can be inexpensively and easily formed over large scales, opening up the possibility of further electroanalytical applications.