Influence of the nanofibrous morphology on the catalytic activity of NiO nanostructures: an effective impact toward methanol electrooxidation

In this study, the influence of the morphology on the electrocatalytic activity of nickel oxide nanostructures toward methanol oxidation is investigated. Two nanostructures were utilized: nanoparticles and nanofibers. NiO nanofibers have been synthesized by using the electrospinning technique. Briefly, electrospun nanofiber mats composed of polyvinylpyrolidine and nickel acetate were calcined at 700°C for 1 h. Interestingly, compared to nanoparticles, the nanofibrous morphology strongly enhanced the electrocatalytic performance. The corresponding current densities for the NiO nanofibers and nanoparticles were 25 and 6 mA/cm², respectively. Moreover, the optimum methanol concentration increased to 1 M in case of the nanofibrous morphology while it was 0.1 M for the NiO nanoparticles. Actually, the one-dimensional feature of the nanofibrous morphology facilitates electrons'' motion which enhances the electrocatalytic activity. Overall, this study emphasizes the distinct positive impact of the nanofibrous morphology on the electrocatalytic activity which will open a new avenue for modification of the electrocatalysts.     

Novel electrospun nanofiber mats as effective catalysts for water photosplitting

Two novel photocatalysts based on ceramic materials for hydrogen production from water splitting under the solar radiation are introduced. CdS-doped and CdS–PdS-doped poly(vinyl acetate) electrospun nanofiber mats reveal good activity toward water photosplitting. The efficient ceramic nanoparticles were in situ synthesized in the polymer solution which was subjected to the electrospinning process. CdS–PdS-doped poly(vinyl acetate) nanofibers produce more hydrogen compared to the naked CdS NPs. Immobilization of the CdS and CdS–PdS nanoparticles inside the polymer nanofibers is an effective strategy to overcome the photocorrosion and toxicity problems of the CdS-based materials.     

Tunable microwave absorption properties of nickel-carbon nanofibers prepared by electrospinning

The nickel-carbon nanofibers (Ni-C NFs) were fabricated by the electrospinning of poly(vinyl alcohol) (PVA) and nickel acetate tetrahydrate (NiAc) solution precursor with succedent PVA pyrolyzation and calcination process. The microwave absorption performance and electromagnetic (EM) parameters of the NFs were researched over the frequency range of 2.0–18.0?GHz. Both the impedance matching and EM wave absorption properties of the Ni-C NFs were improved by changing the carbonization temperature. The effect of graphitization degree on reflection loss (RL) and the possible loss mechanisms were directly displayed in the comparative study of each sample. The optimal RL value of ??44.9?dB and an effective frequency bandwidth of 3.0?GHz under a thickness of 3.0?mm can be reached by a sample calcined at 650?°C. These lightweight Ni-C NFs composites can be promising candidates for EM wave absorbers due to the combination of multiple loss mechanisms, nano-size effect and good impedance matching between Ni nanoparticles and CNFs.     

Influence of carbon‐based nanofillers on the electrical and dielectric properties of ethylene vinyl acetate nanocomposites

A comparative study of ethylene vinyl acetate nanocomposites based on expanded graphite, multiwalled carbon nanotubes, and carbon nanofibers has been carried out to investigate the effect of different carbon nanofillers on the electrical properties of the corresponding composites. The composites were prepared by ultrasonic dispersion of fillers in ethylene vinyl acetate solution, followed by casting and compression molding. The dependence of AC conductivity and dielectric constant on the frequency and filler concentration was investigated. Carbon nanofibers provided maximum conductivity as well as lowest percolation threshold (8.2 vol%) compared to expanded graphite and multiwalled carbon nanotubes filled composites. The improvement in both electrical conductivity and dielectric constant was attributed to the high filler aspect ratio and the formation of conducting networks. The relationship of dielectric constant with filler volume fraction for all the composite systems is estimated using a power law. The pressure sensing capability of the composites at respective percolation thresholds was also compared. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis of ordered mesoporous carbon/cobalt oxide nanocomposite for determination of glutathione

In the paper, a novel ordered mesoporous carbon/cobalt oxide nanocomposite (OMC–Co) was easily synthesized. After encapsulating cobalt oxide nanoparticles in the wall of the ordered mesoporous carbon (OMC), the mesostructure of the nanocomposite material remained highly ordered and intact. For the first time, OMC–Co material was used to modify the glassy carbon (GC) electrode, and the obtained OMC–Co/GC modified electrode showed strong electrocatalytic properties towards glutathione (GSH). The use of OMC–Co film to mediate the GSH oxidation exhibited remarkably strong and stable electrocatalytic response compared to that seen at OMC/GC electrode. These results showed that the electrocatalytic properties of OMC could be improved when the cobalt oxide nanoparticles were incorporated into this new material. A sensitive GSH sensor was developed based on the OMC–Co/GC electrode, which showed a high sensitivity and a remarkably low detection limit. Moreover, OMC–Co/GC modified electrode can be used for selective amperometric determination of GSH in the presence of glucose, dopamine (DA) and uric acid (UA).     

The graphitization of carbon nanofibers produced by catalytic decomposition of methane: Synergetic effect of the inherent Ni and Si

The catalytic effect of the inherent Ni and Si on the graphitization of carbon nanofibers produced by catalytic decomposition of methane is reported. The participation of the inherent Ni and Si metals as co-catalysts in the graphitization of the carbon nanofibers through the formation of Ni₂Si and SiC was inferred. Taking advantage of this catalytic effect, graphite materials showing structural characteristics comparable to oil-derived graphites which are employed in several industrial applications have been prepared from the carbon nanofibers. Unlike SiC which is further descomposed to graphite, the role of Ni₂Si remains unclear. At the CNFs heat treatment temperatures employed, Ni₂Si is in a liquid state where the carbon can be dissolved to form a supersaturated solution from which the SiC can be produced by segregation, thus being an intermediate stage in the catalytic graphitization of the carbon nanofibers. Further work are currently in progress to go insight this issue.     

Studies on the characterization of partly hydrolysed derivatives of poly(vinyl acetate) and their red iodine complex

Three samples of poly(vinyl acetate) 36% hydrolysed, respectively, by saponification, transesterification and acid-equilibrium have been characterized through the refractive indices and light-scattering properties of their solutions in 10% aqueous methanol at 25°C. The original poly(vinyl acetate) sample and its iodine/iodide complex have been similarly characterized, respectively, in methanol at 5°C and in 9.1% methanolic water over the range 5–15°C. The apparent weight-average molecular weights of the vinyl polymers show that the three hydrolytic processes degrade the 130 000 average molecular weight of the original poly(vinyl acetate) macromolecules hardly at all. It is suggested that values of the apparent second virial coefficient might be used as criteria for the characterization of hydrolysed poly(vinyl acetate) specimens which have otherwise identical degrees of hydrolysis and blockiness of their residual acetate groups, but contrasting polydisperse characteristics and surface-active properties. The apparent average root-mean-square radius of gyration of the poly(vinyl acetate) macromolecules is reduced to ≈33% or less of its value on formation of the complex. The characteristics and structure of such complexes are discussed.     

Electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions

Chitosan bicomponent fibers were prepared via the electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions with different concentrations. With a 4% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were lower than 80/20, electrospinning nanofibers could be obtained. With a 90% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were less than 95/5, good nanofibers could be electrospun. The average diameter of the nanofibers gradually decreased, and its distribution became narrower as the poly(vinyl alcohol) concentration increased. Chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions could be electrospun at various concentrations by the adjustment of the chitosan and poly(vinyl alcohol) concentrations. The effects of the viscosity and conductivity of the blend solution on the morphologies of the fiber mats were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5692–5697, 2006     

Solvent-free generation of poly(vinyl acetals) directly from poly(vinyl acetate)

The simultaneous methanolysis and butryalization of poly(vinyl acetate) was conducted via the reaction of methanol and butyraldehyde with polyvinyl acetate under batch conditions at temperatures from 70°C to 90°C at the vapor pressure of the reactants. It was found that use of an acid catalyst allowed for the methanolysis to be the rate limiting step of a simultaneous methanolysis-butyralization reaction, minimizing the buildup of alcohol repeat units in the polymer during the reaction. As such, use of an excess of aldehyde was counterproductive in that it served to dilute both the methanol and the acetate groups in the polymer phase, lowering the overall rate of the reaction. With 20% stoichiometric excesses of methanol and butyraldehyde, it was possible to produce poly(vinyl butyral) directly from poly(vinyl acetate) with very low residual acetate and overall conversions equivalent to commerical samples. Further, carbon dioxide was evaluated as a reversible plasticizer for polyvinyl acetate during methanolysis. Results at various pressures were consistent with the expectation that the presence of CO₂ would lower the reaction rate, primarily because of dilution of reactants in the CO₂-swollen polymer phase. Finally, it was shown that the simultaneous reaction procedure can be used to generate polyvinyl acetals from a variety of aldehydes.     

Synthesis of hermetically-sealed graphite-encapsulated metallic cobalt (alloy) core/shell nanostructures

Hermetically-sealed graphite encapsulated cobalt core/shell nanostructures have been prepared by the CO Boudouard reaction using in situ generated cobalt as the catalyst. Only core/shell nanostructures were obtained, rather than a mixture of cobalt nanoparticles with carbon nanotubes or nanofibers. The magnetic cobalt nanoparticles are highly crystallized with a hexagonal-close packed crystal phase (average diameter of ca. 25 nm) and coated with an 8–9 nm thick graphitic shell. The nanostructures have a high saturation magnetization of 85 emu/g and can be easily separated by an external magnet. The creation of the hermetically-sealed graphitic shell not only keeps the magnetic cobalt nanoparticles from reacting with strong mineral acids, but also has biocompatibility and makes further functionalization easy. A pseudo-planar aromatic molecule, xylenol orange, was used as the model molecule because it can be absorbed on the graphitic shell mainly by π–π stacking interaction. This was confirmed by Raman and ultraviolet–visible spectroscopy. Graphite encapsulated Fe₂Co and Fe_0.64Ni_0.36 alloy core/shell nanostructures were also fabricated by this method.     

Effect of ultrafine carbon precursors on the morphology of silicon carbide nanoparticles

A comparative analysis of carbon precursors used for the synthesis of silicon carbide nanoparticles has been carried out. Phenol-formaldehyde resin, colloidal graphite, poly(vinyl alcohol), carbon black obtained as a byproduct of fullerene synthesis, and multiwall carbon nanotubes have been used as carbon sources in the synthesis of the starting ultrafine composition nC + mSiO₂. After carbothermic synthesis, the morphology of silicon carbide nanoparticles was studied by scanning and transmission electron microscopy. The morphologic features and particle-size distribution of the materials were comparatively studied.     

Electrospun CdS–TiO2 doped carbon nanofibers for visible-light-induced photocatalytic hydrolysis of ammonia borane

CdS/TiO₂ NPs-decorated carbon nanofibers were introduced as a novel photocatalyst working under visible light radiation for the effective hydrolytic dehydrogenation of ammonia borane. Calcination of electrospun nanofiber mats composed of titanium tetraisopropoxide, poly (vinyl pyrrolidone) (PVP), and cadmium acetate dihydrate with a few drops of ammonium sulfide in argon atmosphere at 850 °C led to the production of CdS–TiO₂ decorated carbon nanofibers. As-synthesized nanocomposite exhibited a strong photocatalytic activity for catalytic hydrolysis of ammonia–borane. The favorable electrons-transfer properties, better dispersion, high surface area, and adsorption property are the main features of nanocomposites that exhibit high catalytic efficiency.     

Physicochemical characterization of hydrogels based on polyvinyl alcohol–vinyl acetate blends

Hydrogels made of polyvinyl alcohol–vinyl acetate and its blends with water soluble polymer were studied in terms of swelling behavior, microstructure, and dynamic mechanical properties. Hydrogels prepared by blending polyvinyl alcohol–vinyl acetate with either polyacrylic acid or poly(4‐vinyl pyridine) exhibited a strong pH dependency. When poly(vinyl pyrrolidone) was used for blending, an unusual pH dependency was observed. An increase in the equilibrium water content in all systems resulted in an increase in the freezable water as determined by DSC. Critical point drying led to a striated surface on polyacrylic acid–polyvinyl alcohol–vinyl acetate hydrogels, whereas a porous structure was observed on the freeze‐dried poly(vinyl pyrrolidone)–polyvinyl alcohol–vinyl acetate gels. Hydrogels with elevated storage modulus were obtained when either polyvinyl alcohol–vinyl acetate alone or polyacrylic acid–polyvinyl alcohol–vinyl acetate blends were thermally treated at high temperatures (i.e., 150°C). Low storage modulus was observed for both poly(vinyl pyrrolidone) and poly(4‐vinyl pyridine)‐containing hydrogels. Temperature dependency of storage modulus from 20 to 60°C was observed only for poly(4‐vinyl pyridine)–polyvinyl alcohol–vinyl acetate hydrogels. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3578–3590, 2001     

Removal of sodium acetate in poly(vinyl alcohol) and its quantification by 1H NMR spectroscopy

A major impurity in poly (vinyl alcohol) (PVA) is sodium acetate which remains after its preparation by a base catalyzed hydrolysis of poly(vinyl acetate), and the amount of sodium acetate in commercial PVA samples may reach several percentages. To establish an optimal condition for the removal of sodium acetate, several washing parameters such as washing period, solvent polarity, and temperature were investigated in this study. Nuclear magnetic resonance (NMR) spectroscopy was successfully applied to determine the residual amounts of sodium acetate in the purified poly(vinyl alcohol). The relative integral value for the methyl peak of sodium acetate in PVA was converted to a relative mass value and finally to the sodium acetate content contained in PVA. The results showed that over 95% of sodium acetate in PVA was removed by a washing of PVA with distilled water within 2 h. When methanol was used as a washing solvent, a higher temperature than room temperature was required for an effective removal of sodium acetate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of iron (III) acetylacetonate on structure and electrical conductivity of Fe3O4/carbon composite nanofibers

Fe₃O₄/carbon composite nanofibers were prepared by electrospinning polyacrylonitrile (PAN), iron (III) acetylacetonate (AAI) and dimethyl formamide (DMF) compound solutions, followed by stabilization and carbonization processes. Emphasis was put on the influence of AAI on reactions during stabilization and carbonization. The effect of Fe₃O₄ on catalytic graphitization and electrical conductivity was also studied. Experimental results show that AAI has participated in the reactions and structural changes of PAN during stabilization and carbonization, and is evidenced to promote the processes. Fe₃O₄ nanoparticles exhibit catalytic effect on carbonization process that promote graphitization by a catalytic effect at low AAI content and inhibit the formation of graphitized layers when AAI content is excessive. Therefore, there exists an optimum AAI content (C_o) where composite nanofibers show the maximum graphitization degree and electrical conductivity. With proper amount of AAI addition, Fe₃O₄/carbon composite nanofibers showing high graphite degree and electrical conductivity could be achieved.     

Electrocatalytic properties of Pt/carbon composite nanofibers

Pt/carbon composite nanofibers were prepared by electrodepositing Pt nanoparticles directly onto electrospun carbon nanofibers. The morphology and size of Pt nanoparticles were controlled by the electrodeposition time. The resulting Pt/carbon composite nanofibers were characterized by running cyclic voltammograms in 0.20 M H₂SO₄ and 5.0 mM K₄[Fe(CN)₆] + 0.10 M KCl solutions. The electrocatalytic activities of Pt/carbon composite nanofibers were measured by the oxidation of methanol. Results show that Pt/carbon composite nanofibers possess the properties of high active surface area and fast electron transfer rate, which lead to a good performance towards the electrocatalytic oxidation of methanol. It is also found that the Pt/carbon nanofiber electrode with a Pt loading of 0.170 mg cm⁻² has the highest activity.     

Magnetron sputtering of platinum nanoparticles onto vertically aligned carbon nanofibers for electrocatalytic oxidation of methanol

The electrochemical activities of Pt-sputtered electrodes based on vertically aligned carbon nanofibers (Pt/VACNFs) directly grown on the carbon paper are investigated. Different Pt loading (0.01 mg cm⁻², 0.025 mg cm⁻² and 0.05 mg cm⁻²) electrodes are developed. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that the Pt nanoparticles are homogeneously dispersed on the surface of vertically aligned carbon nanofibers. TEM and X-ray diffraction (XRD) results reveal the Pt nanoparticles diameter increase with increasing Pt loading. The Pt/VACNFs electrodes show good electrochemical active surface area, methanol oxidation peak current density and CO tolerance. The electrochemical catalyst activities weaken as the diameter grows larger. Compared to common electrodes prepared by commercial catalyst in a conventional ink-process, the performance improvement suggests that unique structure of Pt/VACNFs electrode ensures the electronic pathway and Pt nanoparticles exposed to three-phase boundary, which leads to a significant improvement of the Pt utilization and a potential application in direct alcohol fuel cells.     

Shape- and Composition-Controlled Pt–Fe–Co Nanoparticles for Electrocatalytic Methanol Oxidation

We report the preparation of several shape and composition-controlled platinum-based nanoparticles: Pt–Fe nanocubes, Pt–Fe–Co nanocubes, Pt–Fe–Co branched nanocubes, Pt–Fe–Co nanoparticles with low cobalt content, and Pt–Fe–Co nanoparticles with high cobalt content. Pt–Fe–Co branched nanocubes, in particular, showed the best activity and durability for electrocatalytic methanol oxidation.     

Spider-net within the N6, PVA and PU electrospun nanofiber mats using salt addition: Novel strategy in the electrospinning process

Electrospun nanofibers are promising candidates in the nanotechnological applications due to the advantages of the nanofibrous morphology. Therefore, many attempts were reported to modify the electrospun mats to gain more beneficial properties. In the present study, we are introducing a strategy to synthesize electrospun polymeric nanofiber mats containing spider-net binding the main nanofibers. Addition with long stirring time of a metallic salt having tendency to ionize rather than formation of sol–gel in the host polymer solution reveals to synthesize a spider-net within the electrospun nanofibers of the utilized polymer. Nylon6, polyurethane and poly(vinyl alcohol) have been utilized; NaCl, KBr, CaCl₂ and H₂PtCl₆ have been added to the polymeric solutions. In the case of nylon6 and poly(vinyl alcohol), addition of the inorganic salts resulted in the formation of multi-layers spider-network within the electrospun nanofibers mats. The synthesized spider-nets were almost independent on the nature of the salt; the optimum salt concentration was 1.5 wt%. The metallic acid led to form trivial spider-nets within both of nylon6 and poly(vinyl alcohol) nanofibers. In a case of polyurethane, few spider-nets were formed after salt addition due to the low polarity of the utilized solvents. According to TEM analysis, the synthesized spider-net consisted of joints; the later issued from the main nanofibers at Taylor's cone zone. The spider-net improved the mechanical properties and the wetability of the nylon6 nanofiber mats, accordingly a mat having amphiphilic feature has been prepared.     

CuO and MWCNTs Nanoparticles Filled PVA–PVP Nanocomposites: Morphological,Optical, Thermal,Dielectric, and Electrical Characteristics

Journal of Inorganic and Organometallic Polymers and Materials - Copper dioxide (CuO) nanoparticles and Multiwall carbon nanotubes (MWCNTs) filled poly(vinyl alcohol) (PVA) and poly(vinyl...