Influences of graphene oxide support on the electrochemical performances of graphene oxide-MnO2 nanocomposites

MnO₂ supported on graphene oxide (GO) made from different graphite materials has been synthesized and further investigated as electrode materials for supercapacitors. The structure and morphology of MnO₂-GO nanocomposites are characterized by X-ray diffraction, X-ray photoemission spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and Nitrogen adsorption-desorption. As demonstrated, the GO fabricated from commercial expanded graphite (denoted as GO(1)) possesses more functional groups and larger interplane gap compared to the GO from commercial graphite powder (denoted as GO(2)). The surface area and functionalities of GO have significant effects on the morphology and electrochemical activity of MnO₂, which lead to the fact that the loading amount of MnO₂ on GO(1) is much higher than that on GO(2). Elemental analysis performed via inductively coupled plasma optical emission spectroscopy confirmed higher amounts of MnO₂ loading on GO(1). As the electrode of supercapacitor, MnO₂-GO(1) nanocomposites show larger capacitance (307.7 F g^-1) and better electrochemical activity than MnO₂-GO(2) possibly due to the high loading, good uniformity, and homogeneous distribution of MnO₂ on GO(1) support.     

Graphite–graphite oxide composite electrode for vanadium redox flow battery

A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer–Emmett–Teller method. The redox reactions of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.     

Preparation of in situ grown silicon carbide whiskers onto graphite for application in Al2O3-C refractories

C-SiC composite powders were prepared by salt-assisted synthesis from Si powders, graphite, and a molten salt medium (NaCl and NaF) with the molar ratio of Si/C =?1/2 at 1300?°C for 3?h. After the C-SiC composite powders part and complete replacement of the graphite, the mechanical properties, oxidation resistance and slag-corrosion resistance of the Al₂O₃-C materials were studied by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), as well as with dedicated equipment. The results indicated that SiC whiskers, with lengths of 10–50?nm, formed on the surface of the flake graphite, and the activation energy of oxidation of the C-SiC composite powder increased by 45.72?kJ?mol^?1 as compared to that of flake graphite. Furthermore, the decarburization area and slag erosion area of the Al₂O₃-C material decreased after 3?wt% of C-SiC composite powder was substituted for the flake graphite. Meanwhile, the cold modulus of rupture was maintained when 3?wt% of C-SiC composite powder was added. This improved both the oxidation and slag resistance of the Al₂O₃-C materials.     

Graphite oxide/polypyrrole composite electrodes for achieving high energy density supercapacitors

Fabrication and characterization of high energy density supercapacitor based on graphite oxide/polypyrrole (GO/PPy) composites is reported. Improvement in charge storage has been obtained by exfoliation of graphite oxide sheets via intercalation of polypyrrole. The formation of composite has been shown by the analysis of X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and Fourier transfer of infrared spectroscopy data. Scanning electron and transmission electron microscopy clearly show sheet-like layered structure of graphite oxide surrounded by polypyrrole. Supercapacitors fabricated using this composite system result in a reduced equivalent series resistance value ~1.85 Ω. Such low value can be attributed to the intercalation of conducting polypyrrole into the graphite sheets. A specific capacitance of ~181 F g^?1 in 1 M Na₂SO₄ aqueous electrolyte with a corresponding specific energy density of ~56.5 Wh kg^?1 could be achieved. These values make GO-based materials suitable for their use as electrodes in high performance supercapacitors.     

Mechanism of formation of polyaniline flakes with high degree of crystallization using a soft template in the presence of cetyltrimethy‐lammonium bromide

Flake‐like polyaniline with various thicknesses was prepared by cationic emulsion polymerization of aniline monomer in the presence of cetyltrimethylammonium bromide (CTAB). The morphology of polyaniline with uniform and smooth flake‐like structure was observed using field‐emission scanning electron microscopy and transmission electron microscopy. The lamellar complex of (CTA)₂S₂O₈, acting as a reactive soft template for the formation of polyaniline, was investigated using low‐angle X‐ray diffraction. The soft template provides an expanding space for the growth of polyaniline, in which the oxidization of aniline monomers can construct effectively a flake‐like structure. The concentration of CTAB plays an important role in adjusting the d‐spacing of the soft template. Crystallization and composition of polyaniline were characterized using X‐ray diffraction and Fourier transform infrared spectroscopy. The X‐ray diffraction pattern has a sharp peak at 2θ = 6.4° (d‐spacing = 13.7 Å), showing that polyaniline has a solid‐state ordering structure and high degree of crystallization. Doping and dispersive experiments were also included in the study. Copyright © 2012 Society of Chemical Industry     

Synthesis of graphene oxides particle of high oxidation degree using a modified Hummers method

High-oxidation-degree graphene oxide particles were synthesized using a modified Hummers' method. Six different types of particles were synthesized by varying the operating conditions, including the temperature, the reactant ratios, and the oxidation time. The oxidation degree, represented by the oxygen content, and the atomic oxygen/carbon (O/C) ratio were determined using CHNSO elemental analysis, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy-universal attenuated total reflectance sensor (FTIR-UATR) and Raman spectroscopy. The structural morphology of graphene oxide was evaluated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The thermal stability of the particles was studied using thermogravimetric analysis (TGA). The SEM images showed that the prepared GO samples had different graphitic layer structures. The TEM images showed different stacking levels and transparency of GO flakes caused by the difference in oxidation level. The oxygen content and O/C ratios ranged between 34.7 and 50.0 wt% and 0.43 and 0.8, respectively. The highest oxygen content and O/C ratio were found to be 50 wt% and 0.8, respectively, for GO prepared at 95 °C with a 1-hr reaction time (GO2-a). A quantitative analysis on the FTIR-UATR spectra was performed and was in reasonable agreement with the CHNSO analysis results. The Raman spectra showed two characteristic bands (D and G) with different relative intensities, as characterized by the I_D/I_G ratio, suggesting that the prepared samples had different crystallite sizes and defects. The crystallite size (L_a) of the prepared GO particles was estimated using the Tuinstra-Koenig model and were ranging between 9 and 24 nm. The TGA results were correlated with the elemental analysis results and showed a clear dependence of the weight loss on the GO elemental compositions. GO2-a exhibited the lowest thermal stability because of a high oxygen content, whereas GO1-b exhibited the highest thermal stability.     

Excellent electrocatalytic performance of Pt nanoparticles on reduced graphene oxide nanosheets prepared by a direct redox reaction between Na2PtCl4 and graphene oxide

A simple and environment-friendly method was used to prepare Pt/reduced graphene oxide (Pt/RGO) hybrids. This approach used a redox reaction between Na₂PtCl₄ and graphene oxide (GO) nanosheets and a subsequent thermal reduction of the material at 200 °C for 24 h in a vacuum oven. In contrast to other methods that use an additional reductant to prepare Pt nanoparticles, the Pt²⁺ was directly reduced to Pt⁰ in the GO solution. GO was used as the reducing agent, the stabilizing agent and the carrier. The resulting Pt/RGO hybrid was characterized by X-ray diffraction, thermo-gravimetric analysis, X-ray photoelectron spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. Electrochemical measurements showed that the Pt/RGO hybrids exhibit good activity as catalysts for the electro-oxidation of methanol and ethanol in acid media. Interestingly, the Pt/RGO hybrids showed better electrocatalytic activity and stability for the oxidation of methanol than Pt/C and Pt/RGO hybrids made from other Pt precursors. This indicates that the Pt/RGO hybrids should have great potential applications in direct methanol and ethanol fuel cells.     

Fabrication of Pt–Cu/RGO hybrids and their electrochemical performance for the oxidation of methanol and formic acid in acid media

Pt–Cu/reduced graphene oxide (Pt–Cu/RGO) hybrids with different Pt/Cu ratios were prepared by the reduction of H₂PtCl₆ and CuSO₄ by NaBH₄ in the presence of graphene oxide (GO). The Pt–Cu nanoparticles were characterized by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The reduction of GO was verified by ultraviolet–visible absorption spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Compared to Pt/RGO, the Pt–Cu/RGO hybrids have superior electrocatalytic activity and stability for the oxidation of methanol and formic acid. Thus they should have potential applications in direct methanol and formic acid fuel cells.     

Mesoporous copper–cerium–oxygen hybrid nanostructures for low temperature catalytic oxidation of carbon monoxide

Mesoporous copper–cerium–oxygen hybrid nanostructures were prepared by one-pot cetyltrimethylammonium bromide surfactant-assisted method, and were characterized by thermogravimetry, X-ray diffraction, transmission electron microscopy, nitrogen adsorption–desorption, X-ray photoelectron spectroscopy and temperature-programmed reduction techniques. Low temperature carbon monoxide oxidation was used as probe reaction to investigate the application of the prepared mesoporous copper–cerium–oxygen hybrid nanostructures in catalysis. The product calcined at 400 °C, with disordered wormlike mesoporous structure, high specific surface area (SSA) of 117.4 m²/g and small catalyst particle size of 8.3 nm, shows high catalytic activity with the 100 % CO conversion at 110 °C, indicating its potential application in catalysis. Catalytic activity results from the samples calcinied at different temperature suggested that high SSA, small catalyst particle size, finely dispersed CuO species and synergistic effect between CuO and CeO₂ were responsible for the high catalytic activity of the catalysts.     

Ablation behavior of graphite/SiO2 composite irradiated by high-intensity continuous laser

Graphite and SiO₂ composite was prepared by hot-pressing at 1300 °C for 3 h under a uniaxial load of 20 MPa. The ablation behavior of graphite and SiO₂ composite by high-intensity continuous laser was investigated. The X-ray diffraction, scanning electron microscopy, 3D-super-depth-digital microscopy, Raman spectroscopy and reflectivity were used to characterize the sample. The results show that under low laser power (500 W/cm²), and no obvious damage appears, while just the irradiation area changes from grey to white and the reflectivity increases. With the laser power increasing, some heat-absorbing chemical reactions between graphite and SiO₂ occurred on the surface, and SiC was produced, which can increase the energy consumption of the surface and thus reduce the absorbed laser energy of the interior. Moreover, at the center of irradiation area, the formation of columnar structure graphite is beneficial to obstruct laser energy conduction from surface to interior material.     

Jatropha curcas oil based alkyd/epoxy/graphene oxide (GO) bionanocomposites: Effect of GO on curing,mechanical and thermal properties

Jatropha curcas oil based alkyd/epoxy/GO bionanocomposites were prepared by direct solution blending of alkyd/epoxy blend matrix with GO nano filler. Structures and properties of the bionanocomposites were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and tensile testing. X-ray diffraction and transmission electron microscopy study demonstrates the formation of highly exfoliated GO layers and its homogeneous dispersion throughout the polymer matrix with 1 and 3 wt% GO. However, the intercalated structure is predominant with 5 wt% GO. The homogeneous dispersion and the strong interaction of the GO layers and the polymer matrix induced the significant improvement in thermal and mechanical properties of the bionanocomposites. The tensile strength and elastic modulus of the bionanocomposite increased by 133% and 68% respectively with 3 wt% GO loading. The thermal stability of the bionanocomposite improved by 39 °C and T_g is shifted toward higher temperature by 20 °C as compared to the pristine polymer. Incorporation of GO significantly decreases the curing time of the alkyd/epoxy resin blend.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Effect of Cu and Zr Co-doped SiO<Subscript>2</Subscript> Nanoparticles on the Stability of Phases (Quartz-Tridymite-Cristobalite) and Degradation of Methyl Orange at High Temperature

SiO₂ nanoparticles doped by 10 mol% Zr and 10 mol% Cu were prepared via the sol-gel method in a controled process. The effects of doping and calcination temperature on the structural and photo-catalytic properties of SiO₂ nanopowders were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Vis absorption spectroscopy. The phases of cristobalite, quartz and tridymite were found at a calcinations temperature range of 800 to 1000 ^°C and only cristobalite phase was formed at a temperature of 1200 ^°C. The degradation of methyl orange was examined under visible light radiation indicating that the effect of doped elements (Zr, Cu) on SiO₂ reduces the band gap effectively.     

CuCe-Ferrite/TiO2 Nanocomposite as an Efficient Magnetically Separable Photocatalyst for Dye Pollutants Decolorization

In this work, a magnetically separated photocatalyst with great efficiency CuCe-Ferrite/TiO₂ composite was prepared and characterized by X-ray diffraction (XRD), UV–Vis spectrophotometry, Fourier transformer infra-red spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray spectroscopy (EDX) and vibrating sample magnetometer (VSM). Single-phase cubic spinel was formed by calcining the prepared sample at a temperature of 550 °C, according to the results. Different concentrations of reactive red 250 (RR250) dye photodegradation was evaluated using different doses of CuCe-ferrite/ TiO₂ and TiO₂ NPs. Higher efficiency of RR250 photodegradation up to 100% was obtained using CuCe-ferrite/ TiO₂. The photodegradation efficiency was confirmed using chemical oxygen demand (COD) test of both treated and untreated samples. The oxidation process was mostly mediated by photogenerated ^.O^2? according to scavenger test results. The catalyst possess higher photodegradation efficiency even after regeneration for ten times.

Graphical Abstract

     

Preparation of graphene/carbon hybrid nanofibers and their performance for NO oxidation

A series of novel microdomain-graphitized polyacrylonitrile (PAN)-based nanofibers were prepared by adding varied amounts of graphene oxide into the precursor via the electrospinning method. These hybrid electrospun nanofibers with were stabilized in ambient atmosphere, carbonized in nitrogen atmosphere and treated in NH₃ atmosphere for NO oxidation with low concentration (50 ppm) at room temperature. The samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and nitrogen adsorption at 77 K. Oxidation of NO into NO₂ at room temperature was investigated in a fiber fixed-bed. The results demonstrated that the reduced graphene oxide sheets provide catalytic active sites embedded in the PAN-based nanofibers. In addition it was determined that nitrogen-containing functional groups played important roles in the enhancement of the catalytic oxidation of NO to NO₂. The samples with 5 wt.% GO exhibit the most catalytic oxidation of NO into NO₂.     

Investigation of hot pressed ZrB2–SiC–carbon black nanocomposite by scanning and transmission electron microscopy

Hybrid ZrB₂-based composite having 10 vol% nano-sized carbon black and 20 vol% SiC was fabricated by vacuum hot pressing at 1850 °C under 20 MPa for 60 min. The microstructure and sinterability of the as-sintered ceramic was studied by X-ray powder diffraction, scanning electron microscopy, X-ray spectroscopy, scanning transmission electron microscopy and transmission electron microscopy analyses. A fully-dense hybrid composite could be achieved by hot pressing method under the aforementioned conditions. No new in-situ phase formation was detected after sintering process. Although the densification progressed in a non-reactive manner, the addition of carbonaceous material assisted the sinterability acting as the surface oxides cleaner. The precise phase and nanostructural investigations of the prepared ceramic verified the partial graphitization of carbon black and conversion of amorphous nano-additive into crystalline graphite nano-flakes.     

Ultrasonic-assisted preparation of AlON from alumina/carbon core-shell nanoparticle

An aluminium oxynitride (AlON) powder was synthesized by carbothermal reduction nitridation (CRN) method. For this purpose, first Al₂O₃/C core-shell nanoparticles were prepared by the pyrolysis of Al₂O₃/polyacrylonitrile (PAN) nanocomposite precursor at 800?°C for 2?h in an argon atmosphere. Alumina/PAN precursor was prepared by ultrasonic method at room temperature. Then, by two-step thermal treatment of Al₂O₃/C core-shell nanoparticles at 1500–1600?°C for 2?h, followed by subsequent heating at 1750?°C for 1?h in N₂ flow, AlON powder was synthesized. The sample was investigated via Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and CHNS elemental analysis.     

Direct characterization of ion implanted pyrolytic carbon coatings deposited from natural gas

Isotropic pyrolytic carbon (IPyC) prepared at 1300 °C by chemical vapor deposition was implanted with ¹²⁹Xe²⁶⁺ ions to obtain a wide range of information and understanding about the coating materials in nuclear energy field. Microstructure of the pristine and ion-implanted IPyC on nuclear graphite substrate was firstly investigated using polarized light microscopy, scanning and transmission electron microscopy, X-ray diffraction, Raman spectroscopy, nanoindentation, and X-ray photoemission spectroscopy. It was demonstrated that the Xe ion irradiation resulted in concurrent changes in both physical and chemical structures of our standard polycrystalline sample. Influences of the thermal annealing temperature on the properties of the implanted IPyC at 500 and 1000 °C were also studied. Ion-irradiation gave rise to the formation of structural deterioration along a and c axis, accompanying with the appearance of widespread clastic morphology among the irradiated zone of IPyC. There was a dose window that could be used to tune the mechanical properties of IPyC: the nanohardness and Young’s modulus increased after an irradiation, but decreased as the amorphization was reached.     

Synthesis of magnetic citric‐acid‐functionalized graphene oxide and its application in the removal of methylene blue from contaminated water

A magnetic nanocomposite of citric‐acid‐functionalized graphene oxide was prepared by an easy method. First, citric acid (CA) was covalently attached to acyl‐chloride‐functionalized graphene oxide (GO). Then, Fe₃O₄ magnetic nanoparticles (MNPs) were chemically deposited onto the resulting adsorbent. CA, as a good stabilizer for MNPs, was covalently attached to the GO; thus MNPs were adsorbed much more strongly to this framework and subsequent leaching decreased and less agglomeration occurred. The attachment of CA onto GO and the formation of the hybrid were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction spectrometry and transmission electron microscopy. The specific saturation magnetization of the magnetic CA‐grafted GO (GO‐CA‐Fe₃O₄) was 57.8 emu g^?1 and the average size of the nanoparticles was found to be 25 nm by transmission electron microscopy. The magnetic nanocomposite was employed as an adsorbent of methylene blue from contaminated water. The adsorption tests demonstrated that it took only 30 min to attain equilibrium. The adsorption capacity in the concentration range studied was 112 mg g^?1. The GO‐CA‐Fe₃O₄ nanocomposite was easily manipulated in an external magnetic field which eases the separation and leads to the removal of dyes. Thus the prepared nanocomposite has great potential in removing organic dyes. © 2014 Society of Chemical Industry     

Meldola blue immobilized on a new SiO2/TiO2/graphite composite for electrocatalytic oxidation of NADH

Meldola blue immobilized on a new SiO₂/TiO₂/graphite composite was applied in the electrocatalytic oxidation of NADH. The materials were prepared by the sol-gel processing method and characterized by several techniques including scanning electronic microscopy coupled to energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electronic microscopy (HRTEM). Si and Ti mapping profiles on the surface showed a homogeneous distribution of the components. Ti2p binding energy peaks indicate that the formation of Si-O-Ti linkage is presumably the responsible for the high rigidity of the matrices. The good electrical conductivity presented by the composites (5 and 11 S cm⁻¹) can be related to a homogeneous distribution of graphite particles observed by TEM. After the materials characterization, a SiO₂/TiO₂/graphite electrode was prepared and some chemical modifications were performed on its surface to promote the adsorption of meldola blue. The resulting system presented electrocatalytic properties toward the oxidation of NADH, decreasing the oxidation potential to −120 mV. The proposed sensor showed a wide linear response range from 0.018 to 7.29 mmol l⁻¹ and limit of detection of 0.008 mmol l⁻¹. SiO₂/TiO₂/graphite has shown to be a promising material to be used as a suitable support in the construction of new electrochemical sensors.