30 August 2015, Volume 46 Issue 16-石墨烯
    

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    综述 进展
  • Bing-Hui GE
    . 2015, 46(16-石墨烯): 1-0.
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    Graphene has a unique two-dimensional structure and excellent thermal conductivity and electrical conductivity. Synthesis of composite material with polyurethane is a kind of new functional polymer material and the composite material has wide application prospect. This paper reviews the preparation methods of graphene and polyurethane composite materials, as well as the application of the self-healing, UV curing, Shape memory, conductive, electromagnetic shielding, anti-uv and biocompatibility.
  • ;;
    . 2015, 46(16-石墨烯): 2-0.
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    Graphene is a new two-dimensional material, with excellent electrical conductivity, thermal conductivity, light transmittance and mechanical strength. It is known as the 21st century strategic new material for its wide applications, such as electronics, aerospace, optoelectronics, green energy and biological medicine. At present, the large areahigh quality preparation and application of graphene is still in early stage. For this reason, this paper reviewed the research progress of mass production technology of graphene film in China and abroad, as well as, its application situation in the field of intelligent terminal, energy, etc. At last, research focus on graphene industry in the future was put forward.
  • Yu SHANG;zhang dong ;
    . 2015, 46(16-石墨烯): 3-0.
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    Recently, the basic and applied studies of graphene have become research hotspot. The mass production of high quality graphene is the cornerstone of its application. The electrochemical method provides a facile, fast, scalable, economic and environmentally benign pathway to the production of desirable quality graphene materials. This paper first reviews two different routes to electrochemically reduce graphene oxide (GO). This is followed by a discussion on the mechanism of electrochemical reduction. This paper also provides reviews on the characterization of the electrochemically reduced graphene by three aspects: morphology, the reduction degree, the crystal structure. Finally, the future research and development are analyzed and prospected.
  • . 2015, 46(16-石墨烯): 4-0.
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    ABSTRACT: As a two-dimensional (2D) sp2-bonded carbon allotrope, graphene has attracted enormous interest over the past decade due to its unique properties. In the initial research, graphene was isolated from natural graphite, and limited to small sizes and low yields. Recently developed chemical vapor deposition (CVD) techniques have emerged as an important method for the scalable production of large-size and high-quality graphene for various applications. However, CVD-derived graphene is polycrystalline and demonstrates degraded properties induced by grain boundaries. Thus, the next critical step of graphene growth relies on the synthesis of large graphene single crystals. We review four representative pathways of pretreating Cu substrates to make millimeter-sized monolayer graphene grains: electrochemical polishing and high-pressure annealing of Cu substrate, adding of additional Cu enclosures, melting and resolidfying Cu substrates, and oxygen-rich Cu substrates. Then we further discuss recently developed methods of making graphene grains with special spatial structures, including snowflakes, six-lobed flowers, pyramids and hexagonal graphene onion rings. Recent research in synthesizing millimeter-sized monolayer graphene grains with different pretreatments. Although great advancements have been achieved in CVD synthesis of graphene single crystals, potential challenges still exist, such as the growth of wafer-sized graphene single crystals to further facilitate the fabrication of graphene-based devices, as well as a deeper understanding of graphene growth mechanisms and growth dynamics in order to make graphene grains with precisely controlled thicknesses and spatial structures.
  • Cai wen jing; wei xu ling;gong guang bi;;
    . 2015, 46(16-石墨烯): 5-0.
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    Graphene has been considered to be an important filler for the preparation of rubber nanocomposites for its superior mechanical and electronic performances. In this review, the structures, properties and characterizations of graphene and graphene oxide are introduced. And the principles and methods of graphene and graphene oxide reinforcing ESBR and NBR, as well as the performances of rubber nanocomposites are discussed in detail. ESBR and NBR are mainly reinforced by functional and unfunctional graphene and graphene hybrid fillers. The ways to reinforce rubber include Situ polymerization methods, Solution mixing methods, Latex heterocoagulation methods, and then significantly improve mechanical properties, electrical conductivity, thermal conductivity, gas barrier properties, and so on. In addition, the developments of graphene as a reinforcing agent in rubber are prospected.
  • 研究 开发
  • ;;;YAN QIAO
    . 2015, 46(16-石墨烯): 6-0.
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    Reduced graphene oxide (rGO) aerogel with three dimensional porous structure and highly biocompatibility is a kind promising electrode materials for fuel cells and super capacitors. The most often used method for rGO aerogel preparation are hydrothermal reduction but the raw product always possess hydrophobic surface that cannot accessed by electrolyte as well as the bacteria cells in microbial fuel cells (MFCs). In this work, an iron decorated rGO with hierarchical porous structure is developed via freeze-drying assisted hydrothermal method. The ferrous and nitrogen doped rGO aerogel (FNGA) with optimized ratio is developed for MFC anode with ferrous ammonium sulfate as the Fe/N source. The FNGA possesses three dimensional hierarchical porous structure with mesopores, high specific surface area and hydrophilic surface, which deliver high redox peak current and lowest interfacial charge transfer resistance. When it is used in Shewanella putrefaciens MFC anode, the MFC achieves maximum power density of 10.94 W m-2, which is 1.8 fold higher than GA anode. This work will provide a new strategy for developing high performance MFC anode materials.
  • . 2015, 46(16-石墨烯): 7-0.
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    In this article graphene oxide (GO) is used for calcium phosphate cement (CPC) solidification liquid. The setting times, compressive strengths and exothermal behavior of CPC cements with the different GO concentration were investigated by the Vicat needle, mechanical testing machine and isothermal conduction calorimetry. The phase composition and fracture morphologies of the CPC pastes were examined by X-ray diffraction and scanning electron microscopy. The results indicate that GO could influence the fracture appearance and the hydration products of CPC.moreover the setting time of CPC cements increases from (36±4)min to (67±2)min and its compressive strength increases from (20.1±1.7)MPa to (25.6±2.7)MPa.
  • ;Xin-Li GUO
    . 2015, 46(16-石墨烯): 8-0.
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    We studied the in-situ synthesis of Au nanoparticles (Au NPs) on NaBH4-reduced reduction graphene oxide (RGO) film. And this as-prepared Au NPs /RGO hybrid material was used to catalyze the reduction of 4-nitrophenol(4-NP). Au NPs were reduced by RGO and had an uniform and dense coverage on RGO film. It greatly weakened the hydrophobic of RGO and turned it into a hydrophilic material. In addition,there were no surfactants capped on the surface of Au NPs, which ensured the fully-contact between active sites and reactants, thus improving the catalytic rate considerably. The results showed that the Au NPs/RGO hybrids (nAu/n4-NP=3mol%, 4.5mol%, 6mol%) could all end the reduction reaction of 4-NP rapidly with kinetic constants as high as 0.717min-1, 1.21 min-1, 2.511min-1 respectively, higher than adding the same molar weight(nAu/n4-NP=4.5mol%) of Au NPs. This hybrid(nAu/n4-NP=4.5mol%) could still end the reaction within 240s after holding at ~4 oC for 40 days, exhibiting an excellent and stable catalytic activity.
  • guo jian MA;
    . 2015, 46(16-石墨烯): 9-0.
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    A new three-dimensional structure of graphene materials (PA-GO) was prepared via the reaction of phytic acid with graphene oxide via hydrothermal synthesis method. The morphology and structure of PA-GO was then characterized by SEM, FT-IR and XRD,and it demonstrates that the material has a sponge-alike structure.Then the material was used as the adsorbent for methylene blue (MB). and the effects of adsorption time,initial concentration and temperature were investigated, respectively. The results indicated that the adsorption process was completed within 4.5 hours, the maximum sorption capacity of PA - GO for MB was evaluated to be 92.7 mg/g , and the sorption efficiency of MB on the PA-GO increases with the rise of temperature. the adsorption isotherms are according with the Langmuir model.
  • Yuliang An
    . 2015, 46(16-石墨烯): 10-0.
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    The graphene and Fe2O3-graphene nanocomposite were prepared to improve the reversible specific capacities of anode materials for lithium-ion batteries. The XRD and SEM were adopted to characterize the microstructure and morphology of the as-prepared materials. The electrochemical performance of as-prepared composites was investigated by galvanostatic discharged and charged test in detail. Fe2O3-graphene nanocomposite was prepared by hydrothermal method to improve the lithium storage capacity. The results show that Fe2O3 nanoparticles were successfully deposited onto the surfaces of graphene sheets, and Fe2O3 nanoparticles which had a uniformly cubical or spherical morphology. Electrochemical tests show that Fe2O3-graphene nanocomposite possesses higher reversible capacity than graphene or Fe2O3 nanoparticles due to formation of a microporous structure between graphene and Fe2O3 nanoparticles for lithium storage. The reversible capacity of Fe2O3-graphene nanocomposite still was 1252mAhg-1 after 30 cycles. The more increase of grephene, the higher reversible capacity of Fe2O3-graphene nanocomposite was obtained. In addition, Fe2O3-graphene nanocomposite has an excellent cycle performance and rate performance under high current density.
  • ;;Hong-Juan SUN
    . 2015, 46(16-石墨烯): 11-0.
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    Abstract: Graphene oxide (GOS) was prepared by Graphite oxide (GO) which was prepared by the Hummers method, then roasted the GOS under different temperatures to get different reduction degrees of graphene oxide (RGOS). Structure, functional groups, and surface topography of the samples were carried out by AFM,XRD, XPS, and SEM. The GOS and RGOS gas sensors were then fabricated by coating method. Results show that the basal spacing was increasing from 3.36? to7.78? after Graphite was oxidated. The Graphene oxide thickness is 1.08~1.72nm, for single or double GOS. When graphene oxide was reduced from 100℃ to 250℃, the basal spacing of the samples were decreasing from 8.87? to3.68?; With the increasing of the reduction degrees, the O/C atomic ratio was decreasing from 0.43 to 0.32, showed that the oxygen-containing functional groups were gradually reduced, the content of the C-OH functional group was decreased obviously and the C-O-C functional group was changed unconspicuously. Graphene oxide and its lower reduced products show a good sensitivity to CH4 and H2 gas. The GOS sensor had a best sensitivity to CH4 and H2 gas which can reach 81% and 77.2%, respectively. The higher the reduction degrees, the less the oxygen-containing functional groups, the lower the gas sensitivity.
  • ;Yi Liu;;;;;;
    . 2015, 46(16-石墨烯): 12-0.
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    In this work, we built graphene-drug systems by loading a varied size of graphene sheets with four types of anticancer drug molecules, respectively, including CE6, DOX, MTX, and SN38. Then we carried out molecular dynamics calculations to investigate the binding strength and drug diffusion behaviors of the complex systems with focuses on the effects of the sizes of graphene sheets and the number and types of drug molecules as well as the loading modes. Our calculations show that the deformation of graphene is critical to determining the drug-graphene binding energy. The boundary of graphene sheets constrains the diffusion of drug molecules. The double-side loading leads to slower diffusion of drug molecules relative to the single-side loading.
  • Chun-Bao ZHAO ;;;
    . 2015, 46(16-石墨烯): 13-0.
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    A series of thermally conductive cyanate ester resin (CE) composites filled with tetrapod-shaped zinc oxide whiskers (ZnOw) and graphene nanoplatelets (GNP) were prepared. Effects of the varieties and amounts of the fillers on thermal conductivity, electrical insulation and thermal stability properties of the composites were investigated. By adding 50% ZnOw or 10% GNP to cyanate ester resin, the thermal conductivity of the composites reached 0.77 and 0.97 W.m-1.K-1,which were respectively 185% and 259% higher than that of pure CE matrix. Incorporating the mixture of ZnOw and GNP into cyanate ester resin could facilitate to improve the thermal conductivity of the composites. The thermal conductivity of the CE composite is as high as 1.54 W.m-1.K-1 with 40% ZnOw and 10% GNP, which is 470% higher than that of pure CE matrix, while its better electrical insulation is maintained. TGA results showed that the addition of graphene nanoplatelets and zinc oxide whiskers can improve the thermal stability of CE composites significantly.
  • 综述 进展
  • ;;;
    . 2015, 46(16-石墨烯): 14-0.
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    Schottky junction solar cell has attracted more and more attention,because of its simple structure, easinessof preparation and low cost. Graphene, with the property of excellent physical performance,abundant natural resources and low preparation cost, has become a candidate to replace the traditional ITO for the schottky junction solar cell. In this paper, we reviewed the progress of Schottky junction solar cells based on graphene, and discuss the problems in the practical applications. It provides a powerful tool to research potential applications of graphene in schottky junction solar cells in future.
  • Jia-Hua ZHANG;shuisheng wu
    . 2015, 46(16-石墨烯): 15-0.
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    Abstact: Graphene is a kind of unique two-dimensional carbon material. For its high surface area, easily dispersed, easy functionalization and excellent chemical stability, it has been widespread concerned in the catalytic field. Catalytic applications of graphene-based composite materials are important research direction. Currently, the graphene-based catalyst material not only used in photocatalysis, electrocatalysis, but also has made great progress in terms of Suzuki, hydrogenation and oxidation. In this paper, we make the relevant discussion on the synthetic route graphene-based materials. The development, application and catalytic properties of graphene-based catalyst present were reviewed.
  • 工艺 技术
  • Chunming Chen
    . 2015, 46(16-石墨烯): 16-0.
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    Graphene oxide (GO) was prepared using a modified Hummers method with flake graphite as raw materials, then the graphene oxide / titanium dioxide (GO/TiO2) was synthesized through a in situ Sol-Sel method using tetrabutyl titanium as Ti source, and themally reduced graphene oxide/TiO2 composite photocatalyst was prepared by annealing under inert atmosphere.The photocatalyst was characterized by FT-IR、XRD、Raman、SEM、TEM and Uv-vis spectrophotometry. The photocatalytic degradation of methyl orange using the photocatalyst was studied.The results showed that the main phase of products is antase TiO2, the TiO2 nanoparticles with the diameter about 15 nm attached on the surface of reduced graphene oxide matrix and formed a layer of dense TiO2. The composite photocatalyst exhibited a excellent photocatalytic property under visible light region.
  • ; ;
    . 2015, 46(16-石墨烯): 17-0.
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    The graphene oxide (GO) / chitosan (CS) microcapsules were prepared by using the layer by layer (LbL) self-assembly method using SiO2 template. CS concentration, layers and crosslinking agent were studied in this paper. Ibuprofen was used as model drug to study the drug loading and drug release properties of CS/GO microcapsules. The results show that the GO/CS microcapsules have spherical structure, and the microcapsules are monodispersed with the diameter of 760nm. The thickness of microcapsule wall increases with bilayers and CS concentration increased. Crosslinking process can not only improve the morphology of microcapsules, but also can slightly improve the drug loading ratio from 19% to 72% and length the drug release time from 10h to 60h.
  • Yan-Juan ZHANG;Xin-Li GUO
    . 2015, 46(16-石墨烯): 18-0.
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    Three dimensional (3D) graphene foam has been synthesized by chemical vapor deposition (CVD) method, and well-aligned ZnO nanorod arrays were prepared on the surface of graphene foam by seed-mediated hydrothermal growth in aqueous solution. The size distribution is uniform, the ZnO nanorods are about 100 nm in diameters and 2.80μm in length, and the results showed that the ZnO/graphene foam composite has high crystallinity. The products were characterized with XRD、SEM , and its electrochemical performances of detection for hydrogen peroxide (H2O2) were studied by cyclic voltammetry, and amperometric measurements. It is found that the graphene/ZnO exhibits high sensitivity for detection of hydrogen peroxide with the extrapolated lower detection limits of 1.0uM, linear detection range from 10μM to 120μM(R 2=0.99501).
  • Fei-Long ZHANG ;
    . 2015, 46(16-石墨烯): 20-0.
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    Graphene oxide was successfully synthesized in the laboratory by the strong oxidation method using graphite as raw materials, and that was proved by XRD、TEM and IR. The tests show that graphene oxide is a hydrophilic material, and the contact angle of 31.6 °. SEM show that the dispersion of graphene oxide in ethylene glycol is good. graphene oxide / ethylene glycol nanofluids was synthesized without chemical dispersants at room temperature, and it was determined that the optimum mass fraction of graphene oxide which dispersed in ethylene glycol was 0.1%. and stability time of nanofluids is up to half a month. The enhancement of thermal conductivity for graphene oxide nanofluids at 25℃ for a mass fraction of 0.1% are up to 27.2%, 54.2%, and 55.6%, when the base fluids are distilled water, ethylene glycol and propyl glycol, respectively.
  • ;
    . 2015, 46(16-石墨烯): 21-0.
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    In order to improve the photocatalytic performance of TiO2 for splitting water to get hydrogen, S doped TiO2/graphene composites (S-TiO2/RGO) were prepared with a one-step hydrothermal method in the paper. The prepared photocatalysts were characterized by XRD, XPS,FT-IR, TEM, UV-Vis testing techniques. In addition, the photocatalytic activity for splitting water of the prepared photocatalysts was investigated. The results showed that TiO2 particles with size of 14 nm were dispersed on the surface of graphene sheets uniformly in the S-TiO2 /RGO composite. Compared with TiO2 prepared under the same condition,the absorption of S-TiO2/RGO composite in the visible region was significantly enhanced. When S:RGO:TiO2 of mass ratio is 1:0.1:25, the rate of hydrogen production is up to 141.7 μmol?h-1 with composite photocatalysts.
  • ;
    . 2015, 46(16-石墨烯): 22-0.
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    Graphene has been considered as promising material for next generation transparent electrodes due to its excellent optical, electrical, and mechanical properties, but unfortunately the practical use of graphene in end-product devices has not been demonstrated since the yield, size and uniformity problems are yet to be solved to satisfy industrial standards. Here we show large-area monolayer graphene films by precursor-gas preheating thermal chemical vapor deposition (PT-CVD), which enabled mass-produced and larger production of graphene film over 300×300mm2 PET substrate area with an optical transmittance of over 95% and a sheet resistance of 146±15Ω/sq. The uniformity, transmittance and sheet resistance properties of graphene have been characterized by using Scanning electron microscope (SEM), Raman spectroscopy, UV-vis spectrophotometer and four point probe resistivity tester. Finally, we successfully patterned graphene micro/nano-structure and solved vacuum lamination problems for graphene-based truly multi-touch capacitive touch panels in mobile phones.
  • deng ling-feng ;;YU Kai-ming
    . 2015, 46(16-石墨烯): 23-0.
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    We Prepared a "core-shell" structure of graphene/natural graphite composite from Natural graphite and graphene oxide by Carbothermal Reduction. The synthesized material was characterized by means of X-ray diffraction (XRD), scanning electron microscope(SEM) and a variety of testing techniques. Graphene coating were favorable for the formation of SEI film on the surface of natural graphite, at the same time, three solid conductive network has been successfully fabricated by the graphene shell and conductive agent in the electrode to accelerate the electronic exchange rate of between natural graphite particles and current collector, greatly increase the conductivity of composite materials, and improve its electrochemical properties. The electrochemical performance testing results showed that graphene/natural graphene composite exhibited high specific capacity, superior rate performance and excellent cycle stability. Such as its initial charge capacity is 407.7mAh/g with the coulombic efficiency of 99.88% at the rate of 0.1C and capacity retention ratio after 100 cycles is 99.18% at the rate of 1C.
  • Jun-Qing WU;
    . 2015, 46(16-石墨烯): 24-0.
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    The MWCNTs/GnPs-OH hybrid materials with stable structure were prepared by linking MWCNTs and GnPs-OH closely via the bridge poly(acryloyl chloride). The proportion of MWCNTs and GnPs-OH was adjusted from 1:1 to 1:2 and 2:1 respectively to react with poly(acryloyl chloride). The FT-IR, TEM and Raman were used to characterize the successful preparation of hybrid materials. The epoxy resin composites were made by adding different hybrid materials into epoxy resin to study the strengthening and toughening effect of hybrid materials. The tensile tested showed that the 1:2 hybrid material(MWCNTs:GnPs-OH=1:2) owned the best strengthening and toughening effect on epoxy resin. The reason may be attributed to the less MWCNTs-OH can disperse homogeneously into the more GnPs-OH sheets to form stable three-dimensional structure. So the strengthening and toughening effect would be achieved by avoiding local strain when undertake external load.
  • 研究 开发
  • ;
    . 2015, 46(16-石墨烯): 25-0.
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    In this paper, effects of small amount (0%-0.15 vol.%)of graphene nanoplatelets (GnPs) on the mechanical properties, electrical properties and piezoresistivity of cementitious composites is investigated. Results show that the early (7d) compression strength of cement-based composites increases greatly with increase in the GnPs content, while little variation in the 28d strength is observed. The resistivity of cement-based composites changes little with the GnPs content increasing. This may be due to the large surface of GnPs can block the course for ionic transport. Cement-based composites with GnPs can sense strain and stress. The addition of GnPs can improve the sensitivity and repetability
  • Yuan ZHANG;Peng-Gang Ren
    . 2015, 46(16-石墨烯): 26-0.
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    The dodecyl amine (DA) functionalized graphene oxide (DA-GO) /high-density polyethylene (HDPE) membranes were prepared by injection molding method. X-ray diffraction (XRD) showed that the DA could be successfully grafted onto the graphene oxide surface with uncleophilic substitution and amidation reaction. Morphological analysis of nanocomposites showed that DA-GO was homogeneously dispersed and fully exfoliated in the HDPE matrix, which significantly improved the gas barring performance of HDPE. With 0.5wt% RGO loading, the permeability coefficient of O2 of DA-GO/HDPE nanocomposite membranes decreased by 60% from 4.555×10-14cm3cm/(cm2?s?Pa) to 1.830×10-14cm3cm/(cm2?s?Pa). Meanwhile, the thermal stability of HDPE was also dramatically improved?as a result of DA-GO sheets.
  • ;JIA Ying
    . 2015, 46(16-石墨烯): 27-0.
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    The adsorption and diffusion behavior of Li particle on pristine graphene, BC3 and C3N surface have been calculated through the first principle method. Compared with pristine graphene, boron-doping concentration for 25% (atom fraction) significantly enhances the adsorbing energy of Li, whereas the adsorbing energy of Li is slightly weakened when nitrogen-doping concentration for 25% (atom fraction), which should be attributed to the different electronic structures that doping has. The diffusion of Li on graphene, BC3, C3N surface was also computed through nudged elastic band method, and the results revealed that compared to pristine graphene, boron-doping concentration for 25% (atom fraction) weakened the diffusion of Li, nitrogen-doping concentration for 25% (atom fraction) promote the diffusion of Li.
  • ; ;;
    . 2015, 46(16-石墨烯): 28-0.
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    Carbon nanotubes (CNT) and graphene (GNS) have been mixed as a new support, PtRu/CNT-GNS catalysts is prepared by reduction method. PtRu nanoparticles were loaded to the mixed support surface by microwave. The structure and morphology of the samples were characterized by transmission electron microscopy (TEM), PtRu nanoparticles dispersed on the surface of the mixed support uniformly, it has a narrow particle size distribution, the average particle size is about 2.17 nm. The activity and stability of PtRu/CNT-GNS catalysts for methanol electro oxidation were tested by electrochemical method. The results indicated that the PtRu/CNT-GNS catalysts showed higher methanol oxidation activity and better ability of anti poisoning than PtRu/CNT, PtRu/GNS catalysts supported by single carbon.