Microwave-assisted one-pot synthesis of metal/metal oxide nanoparticles on graphene and their electrochemical applications

An effective synthesis strategy of hybrid metal (PtRu)/metal oxide (SnO₂) nanoparticles on graphene nanocomposites is developed using a microwave-assisted one-pot reaction process. The mixture of ethylene glycol (EG) and water is used as both solvent and reactant. In the reaction system for the synthesis of SnO₂/graphene nanocomposite, EG not only reduces graphene oxide (GO) to graphene, but also results in the formation of SnO₂ facilitated by the presence of a small amount of water. On the other hand, in the reaction system for preparation of PtRu/graphene nanocomposites, EG acts as solvent and reducing agent for reduction of PtRu nanoparticles from their precursors and reduction of graphene from graphene oxide. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) characterizations confirm the feasibility of the microwave-assisted reaction system to simultaneously reduce graphene oxide and to form SnO₂ or PtRu nanoparticles. The as-synthesized SnO₂/graphene hybrid composites show a much higher supercapacitance than the pure graphene, and the as-prepared PtRu/graphene show much better electrocatalytic activity for methanol oxidation compared to the commercial E-TEK PtRu/C electrocatalysts.     

Morphology,crystallization, and mechanical properties of poly(ethylene terephthalate)/multiwalled carbon nanotubes composites

Poly(ethylene terephthalate)/multiwalled carbon nanotubes (PET/MWCNTs) with different MWCNTs loadings have been prepared by in situ polymerization of ethylene glycol (EG) containing dispersed MWCNTs and terephthalic acid (TPA). From scanning electronic microscopy images of nanocomposites, it can be clearly seen that the PET/MWCNTs composites with low‐MWCNTs contents (0.2 and 0.4 wt %) get better MWCNTs dispersion than analogous with high‐tube loadings (0.6 and 0.8 wt %). The nonisothermal crystallization kinetics was analyzed by differential scanning calorimetry using Mo kinetics equation, and the results showed that the incorporation of MWCNTs accelerates the crystallization process obviously. Mechanical testing shows that, in comparison with neat PET, the Young's modulus and the yield strength of the PET nanocomposites with incorporating 0.4 wt % MWCNTs are effectively improved by about 25% and 15%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface modification of carbon nanotubes with ethylene glycol plasma

Multi-walled carbon nanotubes (MWCNTs) were modified using plasma polymerization with ethylene glycol (EG) as monomer. Conditions of the EG plasma process in a specially designed reactor and the plasma-polymerized ethylene glycol (PPEG) coating were studied. The study involved varying the plasma powers of 10 and 20 W at a constant process time of 60 min, and EG flow rate of 0.15 cm³/min. Dispersion of the modified MWCNTs was evaluated in several solvents, showing hydrophilic behavior. Morphology of the PPEG coating and the functional groups (hydroxyl) on its surface were characterized by both transmission electron microscope and FTIR spectroscopy. Characterization by thermogravimetric analysis and FTIR suggested that the hydroxyl groups of the PPEG coating residing inside the nanotubes possessed higher thermal stability than the ones outside.     

On the electrocatalysis of ethylene glycol oxidation

In the present paper, PtRu electrodes are used to study the electrooxidation of ethylene glycol (EG) in acid medium. The voltammetric results show that current-potential curves are shifted by about 0.2 V towards more negative potentials through the promoting effect of Ru on Pt. As in the case of pure platinum, FTIR spectra on PtRu surfaces prove that CO₂, glycolic acid and, possibly, oxalic acid are formed in parallel reactions. The catalytic activity, measured as the current density at constant potential, increases with the Ru content. But the complete oxidation of EG to CO₂ is favored by a high Pt content. In order to compare the catalytic activity of different PtRu compositions, currents measured at electrodeposited electrodes are normalized using the data for the oxidation of a CO monolayer.Results of a test using a laboratory PEM EG/O₂ cell with Pt:Ru (50:50) are presented.     

Preparation and characterization of novel polyethylene/carbon nanotubes nanocomposites with core–shell structure

Preparation of novel polyethylene/carbon nanotubes (CNTs) nanocomposites with core–shell structure was presented. The method involved in situ ethylene polymerization in which nanotube surface was treated with Grignard Agent, followed by reacting with active transition metal compound, TiCl₄. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerize ethylene to form polymer nanocomposite. MWCNTs were homogeneously dispersed within polymer matrix, and as expected, the resultant nanocomposites featured core–shell structure which was confirmed by HRTEM. For the nanocomposite, the microscopic examination of the cryogenically fractured surface not only ensured a good distribution of carbon nano-particles in the PE matrix but also revealed the ductile-like fracture. The Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed for the study of covalent sidewall functionalization and chemical bonding environment of MWCNTs, also indicated effective immobilization of titanium catalyst on the MWCNTs surface. The crystalline properties, dielectric property and thermal stability of the nanocomposites were determined by WAXD, impedance analyzer and TGA. The dielectric result showed a slight decline of the dielectric constant of the nanocomposites with increase of the polymerization time, and lower dielectric loss was also observed.     

Solution-cast Nafion ionomer membranes: preparation and characterization

Perfluorosulfonate ionomer dispersions in three different solvents (ethylene glycol (EG), dimethyl sulfoxide (DMSO) and dimethylformamide (DMF)) were used to prepare solution-cast membranes. The dispersions were obtained by dissolution of Nafion^® 112 membranes in a reactor using a water-ethanol solution. Measurements of water uptake and solubility of the cast membranes were conducted. Conductivities were measured directly on carbon paper/membrane/carbon paper assemblies fully immersed in deionized water and were registered by means of impedance spectroscopy as a function of temperature. Results show that all cast samples have lower chemical stability than commercial membranes. Moreover, only membranes cast from dimethylformamide-based dispersions gave conductivity performance comparable to those of Nafion^® 112 and 115. Casting process from dispersion obtained using Nafion^® rejects gave better results than the process utilizing commercial dispersion.     

Effect of compatibility between solvent and poly(vinyl chloride) on dechlorination of poly(vinyl chloride)

In this study, the use of diethylene glycol (DEG), triethylene glycol (TEG), n-C₁₀H₂₁OH, and ethylene glycol (EG) as solvents for NaOH in the dechlorination of poly(vinyl chloride) (PVC) was investigated. In the early reaction time, the degrees of dechlorination for DEG, TEG, and n-C₁₀H₂₁OH were notably higher than that for EG. Further, the high compatibility between PVC and the solvents was considered to result in the easy penetration of the solvent and OH⁻ into PVC particles, leading to the acceleration of dechlorination in the early reaction stage. An improvement of the dechlorination was actually observed for DEG and TEG compared with EG. The solvent with the best compatibility to PVC, n-C₁₀H₂₁OH, however, showed little improvement due to the formation of a protective polyene layer on the surface of the PVC particles.     

Electro-oxidation of ethanol and ethylene glycol on carbon-supported nano-Pt and -PtRu catalyst in acid solution

Present paper reports kinetics of electro-oxidation of ethanol (EtOH) and ethylene glycol (EG) onto Pt and PtRu nanocatalysts of different compositions in the temperature range of 298–318 K. These catalysts have been characterized by SEM, EDX, XRD, CV and amperometry. It has been observed that apparent activation energies for oxidation of EtOH and EG pass through a minimum at about 15–20 at.% of Ru in the PtRu alloy catalysts. Anodic peak current vs. composition curve also shows a maximum around this composition.The results have been explained by a geometric model, which proposes requirement of an ensemble of three Pt atoms with an adjacent Ru atom onto PtRu surface for an efficient electro-oxidation of EtOH or EG. This is further supported from statistical data analysis of probability of occurrence of such ensembles onto PtRu alloy surface.Present results also suggest that electro-oxidation of EG onto nano-PtRu catalyst surfaces follows a different path from that of EtOH at alloy composition less than 15 at.% of Ru.     

Catalysed titanium mesh electrodes for ethylene glycol fuel cells

Electrodes comprising thermally deposited Pt, PtRu and PtRuW on titanium mesh were evaluated for the oxidation of ethylene glycol in acidic electrolyte. The electrodes were characterised using cyclic voltammetry, scanning electron microscopy and X-ray diffraction and the effect of reactant concentration and temperature were examined. Single fuel cell tests employing the titanium mesh anode with the PtRuW catalyst showed better performance than that of the PtRu catalyst. A peak power density of 15 mW cm⁻² was obtained at a temperature of 90 °C with 1.0 M ethylene glycol solution. The performance of the catalysed PtRu mesh electrode was comparable to that of a commercial, alcohol oxidation, PtRu carbon supported catalyst.     

Synthesis of well-dispersed PtRuSnOx by ultrasonic-assisted chemical reduction and its property for methanol electrooxidation

PtRuSnO_x supported on multi-wall carbon nanotubes (MWCNTs) was prepared by ultrasonic-assisted chemical reduction method. The as-prepared catalyst was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns indicate that Pt exists as the face-centered cubic structure, Ru is alloyed with platinum, while non-noble metal oxide SnO_x exists as an amorphous state. From TEM observation, PtRuSnO_x is well dispersed on the surface of MWCNTs with the particle size of several nanometers. The electrochemical properties of the as-prepared catalyst for methanol electrooxidation were studied by cyclic voltammetry (CV) and chronoamperometry (CA). The onset potential of methanol oxidation on PtRuSnO_x and PtRu catalysts is much more negative than that on Pt catalyst, shifting negatively by about 0.20 V, while the peak current density of methanol oxidation on PtRuSnO_x is higher than that on PtRu. Electrochemical impedance spectroscopy (EIS) studies also show that the reaction kinetics of methanol oxidation is improved with the presence of SnO_x. The addition of non-noble metal oxide SnO_x to PtRu promotes the catalytic activity for methanol electrooxidation and the possible reaction mechanism is proposed.     

The effects of triethylenetetramine grafting of multi‐walled carbon nanotubes on its dispersion,filler‐matrix interfacial interaction and the thermal properties of epoxy nanocomposites

This study describes the influence of triethylenetetramine (TETA) grafting of multi‐walled carbon nanotubes (MWCNTs) on the dispersion state, interfacial interaction, and thermal properties of epoxy nanocomposites. MWCNTs were first treated by a 3:1 (v/v) mixture of concentrated H₂SO₄/HNO₃, and then TETA grafting was performed. Chemically grafted MWCNT/bisphenol‐A glycidol ether epoxy resin/2‐ethyl‐4‐methylimidazole nanocomposites were prepared. TETA grafting could establish the connection of MWCNTs to the epoxy matrix and transform the smooth and nonreactive MWCNT surface into a hybrid material that possesses the characteristics of both MWCNTs and TETA, which facilitates homogeneous dispersion of MWCNTs and improves nanotube‐epoxy interfacial interaction. Therefore, the impact property, glass transition temperature, thermal stability, and thermal conductivity of epoxy nanocomposites are enhanced. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Electrochemical behavior of aluminum in 1-<Emphasis Type="Italic">n</Emphasis>-butyl-3-methylimidazolium tetrafluoroborate ionic liquid electrolytes for capacitor applications

This study compares two series of solvents for application in aluminum electrolytic capacitors: ethylene glycol (EG) and water mixtures, and ethylene glycol and 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI.BF₄) ionic liquid (IL) mixtures. Electrochemical impedance spectroscopy and cyclic voltammetry were carried out with a previously anodized aluminum disk electrode. Comparative measurements of solution resistance, polarization resistance, AC capacitance, and passive current were made. The results show that EG–IL mixtures with low amounts of IL (10% IL–90% EG v/v) have a low solution resistance. Low values of solution resistance, high values of polarization resistance, small passive current, and uniform capacitance of anodized aluminum in EG–IL mixtures are favorable properties of the BMI.BF₄ IL for use as an electrolyte in the construction of electrolytic aluminum capacitors.     

Synthesis and characterization of (Fe3O4/MWCNTs)/ epoxy nanocomposites

A sonochemical technique is used for in situ coating of iron oxide (Fe₃O₄) nanoparticles on outer surface of MWCNTs. These Fe₃O₄/MWCNTs were characterized using a high‐resolution transmission electron microscope (HRTEM), X‐ray diffraction, and thermogravimetric analysis. The as‐prepared Fe₃O₄/MWCNTs composite nanoparticles were further used as reinforcing fillers in epoxy‐based resin (Epon‐828). The nanocomposites of epoxy were prepared by infusion of (0.5 and 1.0 wt %) pristine MWCNTs and Fe₃O₄/MWCNTs composite nanoparticles. For comparison purposes, the neat epoxy resin was also prepared in the same procedure as the nanocomposites, only without nanoparticles. The thermal, mechanical, and morphological tests were carried out for neat and nanocomposites. The compression test results show that the highest improvements in compressive modulus (38%) and strength (8%) were observed for 0.5 wt % loading of Fe₃O₄/MWCNTs. HRTEM results show the uniform dispersion of Fe₃O₄/MWCNTs nanoparticles in epoxy when compared with the dispersion of MWCNTs. These Fe₃O₄/MWCNTs nanoparticles‐infused epoxy nanocomposite shows an increase in glass transition (T_g) temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrical conductivity behavior of epoxy matrix nanocomposites with simultaneous dispersion of carbon nanotubes and clays

In this work, nanocomposites with simultaneous dispersion of multiwalled carbon nanotubes (MWCNT) and montmorillonite clays in an epoxy matrix were prepared by in situ polymerization. A high energy sonication was employed as the dispersion method, without the aid of solvents in the process. The simultaneous dispersion of clays with carbon nanotubes (CNT) in different polymeric matrices has shown a synergic potential of increasing mechanical properties and electrical conductivity. Two different montmorillonite clays were used: a natural (MMT‐Na⁺) and an organoclay (MMT‐30B). The nanocomposites had their electrical conductivity (σ) and dielectric constant (ε_r) measured by impedance spectroscopy. The sharp increase in electrical conductivity was found between 0.10 and 0.25 wt% of the MWCNTs. Transmission electron microscopy (TEM) of the samples showed a lower tendency of MWCNT segregation on the MMT‐30B clay surface, which is connected to intercalation/exfoliation in the matrix, that generates less free volume available for MWCNTs in the epoxy matrix. Data from electrical measurement showed that simultaneously adding organoclay reduces the electrical conduction in the nanocomposite. Moreover, conductivity and permittivity dispersion in low frequency suggest agglomeration of nanotubes surrounding the natural clay (MMT‐Na⁺) particles, which is confirmed by TEM. POLYM. COMPOS., 37:1603–1611, 2016. © 2014 Society of Plastics Engineers     

Combination of Plasma Functionalization and Phase Inversion Process Techniques for Efficient Dispersion of MWCNTs in Polyamide 6: Assessment through Morphological,Electrical, Rheological and Thermal Properties

Different contents of multiwalled carbon nanotube (MWCNTs) functionalized by He-dielectric barrier discharge (DBD) plasma followed by an exposure to NH₃ were incorporated into PA6 matrix via a phase inversion based solution method. Optical and electron microscopic results were indicative of the excellent dispersion state of the MWCNTs. The differential scanning calorimetry and thermogravimetric analysis measurements revealed that even addition of a slight amount of the MWCNTs significantly increased the thermal stability and crystallization temperature. Moreover, the low electrical percolation threshold of the PA 6/functionalized MWCNTs nanocomposites was another confirmation for achieving a good dispersion state of MWCNTs using this approach.     

Comprehensive study of the role of ethylene glycol when preparing Ag@SBA-15 in supercritical CO2

Well-defined Ag nanowires were obtained in SBA-15 at a short deposition time of 5 min in supercritical CO₂ when adding a small amount of ethylene glycol as the co-solvent. Ethylene glycol played a key role in dictating the nanowire morphology. Through detailed investigation of the whole deposition process, including the dissolution of precursor assisted by the co-solvent, the diffusion properties of the precursor into the nano-scale channels of the substrate, and the interaction between the precursor and the substrate, we found that a small amount of precursors were reduced into Ag⁰ by ethylene glycol at the initial stage of the deposition. The resultant Ag⁰ then acted as nuclei leading to a non-equilibrium sorption of the precursor. The rapid adsorption of the precursor onto the substrate resulted in a high loading of Ag in a short deposition time and the formation of nanowire morphology. Furthermore, this method was successfully extended to other porous substrates such as γ-Al₂O₃, SiO₂ and KIT-6, demonstrating its great potentials in the synthesis of nanocomposites.     

Structure and properties of multi‐walled carbon nanotubes/polyethylene nanocomposites synthesized by in situ polymerization with supported Cp2ZrCl2 catalyst

Multi‐walled carbon nanotubes (MWCNTs)/polyethylene (PE) nanocomposites were prepared via in situ polymerization with MWCNTs supported Bis‐ (cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂) catalyst. X‐ray photoelectron spectroscopy (XPS) and field emission scanning electron microscope (FESEM) results implied that Cp₂ZrCl₂ catalyst was immobilized in the surface of the MWCNTs supports via a bridge of methylaluminoxane (MAO). The efficient dispersion of MWCNTs in PE matrix and the strong compressive forces associated with PE on the MWCNTs were demonstrated by means of transmission electron microscope (TEM), FESEM and Raman spectra. With introducing 0.2 wt% MWCNTs, both the tensile strength and elongation of MWCNTs/PE nanocomposite were improved by factors of 1.6 (from 29 to 45 MPa) and 1.5 (from 909% to 1360%) comparing with the pure PE, respectively. Morphology observation of fractured surface revealed that the PE firmly adhered to the nanotubes, which was responsible for the significant improvement of the mechanical properties of nanocomposites. Thermal stabilities of the nanocomposites were significantly improved. In addition, the MWCNTs/PE nanocomposites showed very high ultraviolet (UV) shielding property, which could increase photooxidative stability of the PE. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Separation of Ethylene Glycol/Water Mixtures using NaA Zeolite Membranes

Inorganic membranes and particularly zeolite membranes are usually used for the dehydration of organic solvents by pervaporation (PV). This work reports an experimental study on the PV dehydration of ethylene glycol (EG)/water mixtures using commercial nanoporous NaA zeolite membranes. The concentration range investigated (C_EG > 70 wt %) was selected according to existing industrial requirements. The recirculation flow rate was kept at a value of 1.5 L/min. The fluxes and separation factors were monitored as the dehydration proceeded. In addition, the activation energy of permeation (E_a) was calculated. The effect of temperature was investigated in the range 50–70 °C. The results obtained demonstrated the successful performance of the membrane for the dehydration of EG/water mixtures. It was observed that at 70 °C and with 70 wt % initial EG concentration, larger fluxes and separation factors could be obtained, i.e., 0.94 kg m^–2h^–1 and 1177, respectively. The Pervaporation Separation Index (PSI) of the membrane was found to be high compared to that of polymeric membranes.     

Fabrication of core-shell structured MWCNT-Ti(TiC) using a one-pot reaction from a mixture of TiCl3, TiH2, and MWCNTs

Multi-walled carbon nanotubes (MWCNTs) coated with metal titanium or carbide layers were prepared by heating a mixture of TiCl₃, TiH₂, and MWCNTs under vacuum. The resulting MWCNT-Ti(TiC) materials had a uniform and conformal core-shell structure. The thickness of the Ti(TiC) layer was determined by the deposition temperature and time. The amount of TiC in the shell depended primarily on the deposition temperature. Whether a metal or carbide coating was obtained was determined by controlling the deposition temperature. Ti(TiC)-coated MWCNTs showed better field emission properties than did pristine MWCNTs. This deposition method should prove to be a versatile route for fabricating other one-dimensional core-shell materials.     

1-辛烯氢甲酰化反应Co/CNTs催化剂的制备与表征

用浸渍法、化学气相沉积法（MOCVD）、乙二醇液相还原法制备碳纳米管负载钴催化剂, 以1-辛烯的氢甲酰化反应为探针反应, 对比研究了所制得的Co/CNTs催化剂的催化性能, 并用XRD和TEM等技术研究了催化剂的粒子大小及粒径分布, 考察了1-辛烯的氢甲酰化反应性能与催化剂粒径大小的关系.发现用MOCVD法制备的Co/CNTs催化剂的平均粒径最小, 其平均粒径为7.5 nm左右且分布均匀; 该催化剂在1-辛烯的氢甲酰化反应中具有最高的催化活性和C₉-醛的选择性.