匡达, 胡文彬. 石墨烯复合材料的研究进展. 无机材料学报, 2013, 28(3): 235-246 KUANG Da, HU Wen-Bin. Research Progress of Graphene Composites. Journal of Inorganic Materials, 2013, 28(3): 235-246
This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China
Abstract
Graphene has recently attracted much interest in material field due to its unique two-dimensional structure and outstanding properties. Various preparation methods of graphene are briefly compared. The physical and mechanical properties of graphene are then introduced. Graphene-based composite becomes one of the most important research frontiers in the application of graphene. A comprehensive review is presented to introduce the latest progress of the graphene related composites, including graphene-polymer composites and graphene-based inorganic nanocomposites, especially introducing the fabrication methods and outstanding performances of the bulk metal-matrix/graphene composites.
图3 ODA-G/EVA复合材料的制备过程示意图[ 86]Fig. 3 Schematic depiction for the preparation of functionalized graphene and its composite with ethylene vinyl acetate co-polymer[ 86]
表2 石墨烯无机纳米材料的制备方法和应用概况Table 2 Various methods for preparation of graphene-inorganic nanocomposites and their respective applications
Materials
Preparation methods
Applications
Ref.
Au/rGO
Au/GO
Sonolytic reduction Electrodeposition In situ reduction
Electrocatalysis Catalytic applications
[94] [96-97] [98]
Ru/rGO
Microwave assisted reduction
Catalysis
[110]
TiO2/rGO
TiO2/GO
Self-assembly of TiO2 nanorods and rGO at two-phase interface Templated hydrolysis Hydrolysis starting with titanium butoxide Hydrothermal starting with P25 and GO Non-covalent adhesion viasolution mixing
Photocatalysis
Photocatalysis Dye-sensitized solar cells Photocatalysis Dye-sensitized solar cells
[112]
[113] [115] [116] [114]
Ag/rGO
Ag/GO
Solution-based chemical approach Redox reaction Sol-Gel technique
Water purification Glucose detection
[100] [101] [102]
Pd/GO
Plasma reduction
[104]
Pt/rGO
Electrodeposition
Selected determination of Rutin
[105]
Ni/rGO
Electroless Ni/plating method
[107]
Cu/rGO
Electrodeposition
Non-enzymatic glucose sensor
[108-109]
Rh/rGO
Impregnation method
[111]
ZnO/rGO
Electrodeposition
Photovoltaics
[118]
SnO2/FGS
Redox reaction
Li ion battery
[119]
MnO2/GO MnO2/rGO
Chemical route in a water-isopropyl alcohol system Redox reaction
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Graphene-based sheets such as graphene, graphene oxide and reduced graphene oxide have stimulated great interest due to their promising electronic, mechanical and thermal properties. Microscopy imaging is indispensable for characterizing these single atomic layers, and oftentimes is the first measure of sample quality. This review provides an overview of current imaging techniques for graphene-based sheets and highlights a recently developed fluorescence quenching microscopy technique that allows high-throughput, high-contrast imaging of graphene-based sheets on arbitrary substrate and even in solution.
(1. Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China; 2. College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China)
Graphene has no oxygen groups on its surface, resulting in a poor dispersion in water. The synthesis of graphene with high water solubility is popular nowadays. In this study, the oxygen content of graphite oxide was adjusted by a low-temperature and high-vacuum expansion process, the resultant graphene sheets exhibited the smallest thickness of about 1.7 nm and size of 1.0 um. The results indicated that prepared graphene could be stable in neutral aqueous solution without surfactant, and the solubility of the water-soluble graphene was 0.07 mg/mL. In addition, the electrical conductivity of the graphene film of around 1000 S/m was higher than many reported noncovalent graphene films.
(College of Science, Chongqing Jiaotong University, Chongqing 400074, China)
Graphene has attracted much interest in recent years due to its unique and outstanding properties. Different routes to prepare graphene have been developed and achieved. Preparation methods of graphene used in recent years are intensively introduced, including micromechanical cleavage, chemical vapor deposition, liquid/gas- phase-based exfoliation of graphite, epitaxial growth on an insulator, chemical reduction of exfoliated graphene oxide, etc. And their advantages and shortcomings are further discussed in detail. The preparations of graphene are also prospected.
(1. Research Institute of Surface Engineering, Taiyuan University of Technology, Taiyuan 030024, China; 2. Institute of Materials Engineering, Ningbo University of Technology, Ningbo 315016, China)
Due to its outstanding physical and electrical properties, graphene has become one of the hot research topics and frontiers in the fields of physics and semiconductor electronics. The physical and electrical properties of graphene were briefly introduced. A comprehensive review was presented to the current research activities concentrated on the epitaxial growth of graphene which could be the most promising strategy among the reported methods to meet the challenge for mass production of graphene with high quality. A systematical discussion was then presented to the epitaxial growth of graphene by using various substrates of SiC and metals. By the end of this article, an overview was made on the recent applications of graphene in opto/electronic devices, such as field-effect transistors, light emitting diodes, supercapacitors and lithium-ion batteries. It is accepted that not only growth of graphene with sizes from nanometer to centimeter could be achieved, but also the thicknesses with monolayer to a few layers could be successfully tailored via epitaxial growth of graphene on SiC/metal substrates. It is promised that the strategy of epitaxial growth could accomplish the mass production of graphene with high quality, low cost and compatibility to the conventional electronic process, which lays the significant foundations for the applications of graphenes in devices.
The synthesis of few-layered graphene sheets with controlled number of layers (3–4) on a large scale was developed using chemical exfoliation by simply controlling the oxidation and exfoliation procedure. The obtained Few-layered Graphene Oxide (FGO) was characterized by atomic force microscopy, X-ray diffraction, thermal gravimetric analysis and Ultraviolet–visible spectroscopy. It is found that the FGO, which contains less functional groups than single-layered graphene oxide (GO), also has excellent water dispersion. Moreover, after reduction treatments under the same conditions as that used for GO, reduced FGO show a much better electrical conductivity of 108 S/cm, two-orders higher than reduced GO.
Reduction of a colloidal suspension of exfoliated graphene oxide sheets in water with hydrazine hydrate results in their aggregation and subsequent formation of a high-surface-area carbon material which consists of thin graphene-based sheets. The reduced material was characterized by elemental analysis, thermo-gravimetric analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, NMR spectroscopy, Raman spectroscopy, and by electrical conductivity measurements.
Graphene nanosheets were directly deposited onto a glassy carbon electrode through cyclic voltammetric reduction of a graphene oxide colloidal solution. The resulting electrodes were characterized by electrochemical methods and scanning electron microscopy. The application of the graphene modified electrodes in simultaneous determination of hydroquinone and catechol was investigated.
Rapid and mild thermal reduction of graphene oxide (GO) to graphene was achieved with the assistance of microwaves in a mixed solution of N,N-dimethylacetamide and water (DMAc/H2O). The mixed solution works as both a solvent for the produced graphene and a medium to control the temperature of the reactive system up to 165 °C. Fourier transform infrared spectrometry, X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermogravimetric analysis confirmed the formation of graphene under this mild thermal reduction condition. The reduction time is found to be in the scale of minutes. The as-prepared graphene can be well dispersed in DMAc to form an organic suspension, and the suspension is stable for months at room temperature. The conductivity of graphene paper prepared by the microwave reduced product is about 104 times than that of GO paper.
(National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China)
Graphene thin films were epitaxial grown on Si(111) substrates by depositing carbon atoms with solid source molecular beam epitaxy (SSMBE). The structural properties of the samples deposited at different substrate temperature (400, 600, 700 and 800℃) were investigated by reflection high energy electron diffraction (RHEED), Fourier transform infrared spectroscope (FTIR), Raman spectroscope (RAMAN) and near-edge X-ray absorption fine-structure (NEXAFS). RAMAN and NEXAFS results indicated that the thin film deposited at 800℃ exhibited the characteristic of graphene, while the thin films deposited at 400℃, 600℃ and 700℃ were attributed to amorphous or polycrystalline carbon thin films. RHEED and FTIR results indicated that C atoms did not bond with Si atoms at the substrate temperature below 600℃, however, above 700℃, C atoms reacted with Si atoms and formed the SiC buffer layer. Furthermore, the better quality of SiC buffer layer could be obtained at 800℃. Thus, high substrate temperature and high-quality SiC buffer layers are essential to the formation of the graphene layers on the Si substrates.
(1. University of Science and Technology, Beijing 100191, China; 2. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China; 3. Research Institute of Chemical Defense, Beijing 102205, China)
A graphene material was prepared by arc discharge method, and its pore structures and electrochemical capacitive properties were studied. The graphene presents developed and open mesopore structure, and its specific surface area and mesopore ratio are 77.8 m2/g and 74.7%, respectively. The electrochemical capacitor using graphene as electrode materials, has a capacitance of 12.9 F/g. Its cyclic voltammograms show rectangular shape even under a high scan rate of 200 mV/s, and the specific frequency f0 on the electrochemical impedance spectroscopy is as high as 18.5 Hz, exhibiting excellent rate capability.
The mechanical properties of zigzag graphene and armchair graphene nanoribbon under tensile and compressive loading are studied by the use of quantum mechanics as well as quantum molecular dynamics (MD) method based on the Roothaan–Hall equation and the Newton motion laws. The similar failure mechanisms and different mechanical properties are found in zigzag graphene and armchair graphene subjected to mechanical load. Under tensile or compressive loadings, the critical loading of the zigzag graphene is larger than that of the armchair graphene. Both zigzag graphene and armchair graphene begin to break at the outmost carbon atomic layers. Applied mechanical loading indeed changes the electronic properties of graphene.
Graphene nanosheets were prepared by complete oxidation of pristine graphite followed by thermal exfoliation and reduction. Polyethylene terephthalate (PET)/graphene nanocomposites were prepared by melt compounding. Transmission electron microscopy observation indicated that graphene nanosheets exhibited a uniform dispersion in PET matrix. The incorporation of graphene greatly improved the electrical conductivity of PET, resulting in a sharp transition from electrical insulator to semiconductor with a low percolation threshold of 0.47 vol.%. A high electrical conductivity of 2.11 S/m was achieved with only 3.0 vol.% of graphene. The low percolation threshold and superior electrical conductivity are attributed to the high aspect ratio, large specific surface area and uniform dispersion of the graphene nanosheets in PET matrix.
1.Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia<br/>2.Branch of the Institute of Energy Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia<br/>
Dependences of the dielectric permittivity of a graphene-filled polymer composite and the ESR signal intensity in γ-irradiated samples of this composite on the concentration of graphene additive have been studied. Anomalous behavior of the permittivity correlates with the ESR signal intensity variation, which is indicative of the possible structural rearrangement in the epoxy resin-graphene filler system.
We have prepared graphene dispersions, stabilised by polyurethane in tetrahydrofuran and dimethylformamide. These dispersions can be drop-cast to produce free-standing composite films. The graphene mass fraction is determined by the concentration of dispersed graphene and can be controllably varied from 0% to 90%. Raman spectroscopy and helium ion microscopy show the graphene to be well-dispersed and well-exfoliated in the composites, even at mass fractions of 55%. On addition of graphene, the Young’s modulus and stress at 3% strain increase by ×100, saturating at 1 GPa and 25 MPa, respectively, for mass fractions above 50 wt%. While the ultimate tensile strength does not vary significantly with graphene content, the strain at break and toughness degrade heavily on graphene addition. Both these properties fall by ×1000 as the graphene content is increased to 90 wt%. However, the rate of increase of Young’s modulus and stress at 3% strain with mass fraction is greater than the rate of decrease of ductility and toughness. This makes it possible to prepare composites with high modulus, stress at low strain and ultimate tensile strength as well as relatively high toughness and ductility. This could lead to new materials that are stiff, strong and tough.
The fabrication and characterization of ultrathin composite films of surfactant-wrapped graphene nanoflakes and poly(vinyl chloride) is described. Free-standing composite thin films were prepared by a simple solution blending, drop casting and annealing route. A significant enhancement in the mechanical properties of pure poly(vinyl chloride) films was obtained with a 2 wt.% loading of graphene, such as a 58% increase in Young’s modulus and an almost 130% improvement of tensile strength. Thermal analysis of the composite films showed an increase in the glass transition temperature of the polymer, which confirms their enhanced thermal stability. The composite films had very low percolation threshold of 0.6 vol.% and showed a maximum electrical conductivity of 0.058 S/cm at 6.47 vol.% of the graphene loading.
This communication reported the substantial improvement in the mechanical and thermal properties of a polyurethane (PU) resulting from the incorporation of well-dispersed graphene oxide (GO). The stress transfer benefited from the covalent interface formed between the PU and GO. The Young’s modulus of the PU was improved by ∼7 times with the incorporation of 4 wt% GO, and the improvement of ∼50% in toughness was achieved at 1 wt% loading of GO without losing elasticity. Significant improvements were also demonstrated in the hardness and scratch resistance measured by nano-indentation. Thermogravimetric analysis revealed that the decomposition temperature was increased by ∼50 °C with the addition of 4 wt% GO.
Functionalized graphene nanosheets (f-GNSs) produced by chemically grafting organosilane were synthesized by a simple covalent functionalization with 3-aminopropyl triethoxysilane. The f-GNSs showed a larger thickness, but smaller width and than the un-treated graphene. The covalent functionalization of graphene with silane was favorable for their homogeneous dispersion in the polymer matrix even at a high nanofiller loading (1 wt.%). The initial thermal degradation temperature of epoxy composite was increased from 314 °C to 334 °C, at a f-GNS content of 1 wt.%. Meanwhile, the addition of 1 wt.% f-GNSs increased the tensile strength and elongation to failure of epoxy resins by 45% and 133%, respectively. This is believed to be attributed to the strong interfacial interactions between f-GNSs and the epoxy resins by covalent functionalization. The experimentally determined Young’s modulus corresponded well with theoretical simulation under the hypothesis that the graphene sheets randomly dispersed in the polymer matrix.
(School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212003, China)
In past few years, we have witnessed the discovery and synthesis of graphene — a kind of ideal two-dimensional flat carbon nanomaterials. Owing to its novel and unique physical and chemical properties, graphene has been attracting more and more attention from scientific community and nowadays has become a sparkling rising star on the horizon of nanomaterials science. The graphene-based inorganic nanocomposites, derived from the decoration of graphene sheets with inorganic nanoparticles, are emerging as a new class of exciting materials that hold promise for many applications. So far, numerous inorganic nanocomposites based on graphene have been successfully synthesized and show desirable combinations of these properties that are not found in the individual components. Herein, we briefly introduce the structure, properties and preparation methods of graphene, and then highlight the advance in the synthesis of inorganic nanomaterials/graphene composites, especially focusing on the metal/graphene and semiconductor/graphene nanocomposites. The potential applications of these nanocomposites are also discussed. These results underscore the exciting opportunities of developing next-generation graphene-based inorganic nanocomposites.
Contents 1 Introduction 2 Preparation of graphene 3 Metal/graphene nanocomposites 3.1 Composites of graphene sheets and platinum metals 3.2 Composites of graphene sheets and silver 3.3 Composites of graphene sheets and gold 3.4 Composites of graphene sheets and other metal 4 Semiconductor/graphene nanocomposites 4.1 Composites of graphene sheets and titanium dioxide 4.2 Composites of graphene sheets and cobalt oxide 4.3 Composites of graphene sheets and tin oxide 4.4 Composites of graphene sheets and zinc oxide 4.5 Composites of graphene sheets and sulfide semiconductor 4.6 Composites of graphene sheets and other semiconductor 5 Graphene/ceramic nanocomposites 6 Graphene-based magnetic nanocomposites 7 Carbon/graphene nanocomposites 8 Conclusions and outlook
A solution-based chemical approach has been used to prepare silver nanoparticle–graphene (Ag–G) hybrids through sequential reduction of graphene oxidation and silver ions. The products can readily form a stable aqueous solution without polymeric or surfactant stabilizers, and this makes it possible to produce graphene–silver hybrids on a large scale using low-cost solution processing techniques. The paper-like Ag–G film obtained by vacuum filtration is glossy and has a high reflectivity and good flexibility. Raman signals of graphene for the film are increased with the dispersion of silver nanoparticles, exhibiting surface-enhanced Raman scattering activity. The increases from three- to eightfold can be obtained with the increase of silver nanoparticle content in the hybrids, indicating that the increase can be tuned by changing the density of silver nanoparticles. The electrochemical properties of the Ag–G film demonstrate their fast electron-transfer kinetics for the redox system.
In this paper, we report on the first preparation of well-defined SiO2-coated graphene oxide (GO) nanosheets (SiO2/GO) without prior GO functionalization by combining sonication with sol–gel technique. The functional SiO2/GO nanocomposites (F-SiO2/GO) obtained by surface functionalization with NH2 group were subsequently employed as a support for loading Ag nanoparticles (AgNPs) to synthesize AgNP-decorated F-SiO2/GO nanosheets (AgNP/F-SiO2/GO) by two different routes: (1) direct adsorption of preformed, negatively charged AgNPs; (2) in situ chemical reduction of silver salts. The morphologies of these nanocomposites were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). It is found that the resultant AgNP/F-SiO2/GO exhibits remarkable catalytic performance for H2O2 reduction. This H2O2 sensor has a fast amperometric response time of less than 2 s. The linear range is estimated to be from 1 × 10−4 M to 0.26 M (r = 0.998) and the detection limit is estimated to be 4 × 10−6 M at a signal-to-noise ratio of 3, respectively. We also fabricated a glucose biosensor by immobilizing glucose oxidase (GOD) into AgNP/F-SiO2/GO nanocomposite-modified glassy carbon electrode (GCE) for glucose detection. Our study demonstrates that the resultant glucose biosensor can be used for the glucose detection in human blood serum.
Highlights
? Well-defined SiO2-coated graphene oxide nanosheets are prepared. ? F-SiO2/GO nanosheets are obtained by surface functionalization with NH2 group. ? F-SiO2/GO nanosheets decorated with Ag nanoparticles by two different routes. ? They show remarkable catalytic performance toward H2O2 reduction. ? They can be used for glucose detection in human blood serum.
(1. Key Laboratory of Aerospace Materials and Performance, Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191, China; 2. State Intellectual Property Office of the People’s Republic of China, Beijing 100088, China)
Graphene-Ag nanoparticles composites were prepared by one step in situ synthesis method, using nontoxic green glucose as reducer. Graphite oxide and ammoniacal silver ions were reduced at the same time without stabilizing agent under mild reaction conditions of aqueous solution. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscope, scanning electronic microscope (SEM), and transmission electronic electron microscope (TEM) were used to characterize the resulting composites. The results of analysis indicate that graphite oxide and ammoniacal silver ions are reduced by glucose simultaneously. Ag nanoparticles (AgNPs) uniformly distribute in the graphene sheets, and most of AgNPs show twin boundary. The quantity of silver nitrate influences the size and range of sizes of the AgNPs. The range of sizes of AgNPs on the graphene sheets centralizes at 25 nm under a suitable concentration of silver ions. The intensities of the Raman signals of graphene in the composites increase 7 fold by the loaded AgNPs.
<li><span class="position">1.</span><span class="affiliation">Advanced Nano Technology Center, School of Chemical Engineering and Technology, Tianjin University, 300072, Tianjin, China</span></li>
Abstract Pd nanoparticles were fabricated on graphene oxide (GO) using a deposition-precipitation method with a glow discharge plasma reduction at room temperature. Argon was employed as the plasma-generating gas. The novel plasma method selectively reduces the metal ions. The graphene oxide has no change with this plasma reduction according to the Fourier transform infrared analysis. The Pd nanoparticles on the GO were uniformly distributed with an average diameter of 1.6 nm. The functional groups on the GO not only prevent Pd nanoparticles from further aggregation but also provide a strong hydrophilic property to the Pd/GO composite, which can form stable colloidal dispersions in water.
(College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China)
Graphene sheets were prepared by using chemical reduction of a colloidal suspension of graphene oxide sheets in water. After hydrophilic treatment and chemical plating, a layer of nickel particles was uniformly coated on the surfaces of the graphene sheets. The morphologies of the pure graphene (GF) and Ni-coated graphene (NGF), nickel element content on the graphene surface and magnetic properties of the NGF were examined by SEM, EDX and VSM, respectively. The complex relative permittivity and permeability of the NGF absorber were measured by using a microwave network analyzer in the frequency range of 2-18 GHz. The reflection loss curves of the GF and NGF were calculated using computer simulation technique. It is found that in the frequency range of 2-18 GHz, with the increase of the matching thickness, the maximum absorbing peaks of the GF and NGF shift to lower frequency region, so GF and NGF are dielectric loss microwave absorption materials. When the matching thickness is 1 mm, the maximum absorption peak of the GF is -6.5dB at about 7GHz. When the matching thickness is 1.5 mm, the maximum absorption peak of the NGF is -16.5dB at 9.25 GHz and the frequency region in which the maximum reflection loss is more than -10.0 dB is 9.5-14.6 GHz.
<font size="2">1. The State Key Laboratory Breeding Base of Refractories and Ceramic, Wuhan University of Science and Technology, Wuhan 430081, China|<br />2. School of Chemistry and Chemical Engineering, Jiujiang University, Jiujiang 332005, China</font>
Ni/graphene sheets were synthesized from graphene oxide sheets using electroless Ni-plating in a NiSO4 solution, with NaBH4 as a reducing agent. The samples were characterized by X-ray diffraction, scanning and transmission electron microscopy. Ni deposited on the surface of the reduced graphene oxide sheets had a high dispersion without aggregation, although the amount of Ni was as high as 32.9% by mass., The stacking of Ni/graphene sheets resulted in the formation of meso- and macropores. Nitrogen adsorption showed that the meso- and macropores had a slit shape and that the Brunauer-Emmett-Teller specific surface area reached 91m2/g. The average pore size calculated by the Barret-Joyner-Halenda method from desorption studies was 3.83nm, with a pore volume of 0.28cm3/g.
Stable ruthenium or rhodium metal nanoparticles were supported on chemically derived graphene (CDG) surfaces with small and uniform particle sizes (Ru 2.2 ± 0.4 nm and Rh 2.8 ± 0.5 nm) by decomposition of their metal carbonyl precursors by rapid microwave irradiation in a suspension of CDG in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate. The graphene-supported hybrid nanoparticles were shown to be active and could be re-used at least 10 times as catalysts for the hydrogenation of cyclohexene and benzene under organic-solvent-free conditions with constant activities up to 1570 mol cyclohexane × (mol metal)−1 × h−1 at 4 bar and 75 °C.
TiO2-graphene nanocomposite was prepared by hydrolysis of titanium isopropoxide in colloidal suspension of graphene oxide and in situ hydrothermal treatment. It provides an efficient and facile approach to yield nanocomposite with TiO2 nanoparticles uniformly embedded on graphene substrate. The electrochemical behavior of adenine and guanine at the TiO2-graphene nanocomposite modified glassy carbon electrode was investigated. The results show that the incorporation of TiO2 nanoparticles with graphene significantly improved the electrocatalytic activity and voltammetric response towards these species comparing with that at the graphene film. The TiO2-graphene based electrochemical sensor exhibits wide linear range of 0.5–200 μM with detection limit of 0.10 and 0.15 μM for adenine and guanine detection, respectively. The excellent performance of this electrochemical sensor can be attributed to the high adsorptivity and conductivity of TiO2-graphene nanocomposite, which provides an efficient microenvironment for electrochemical reaction of these purine bases.
Highlights
? An efficient preparation method was developed for TiO2-graphene nanocomposite. ? Adenine and guanine exhibits enhanced reactivity on TiO2-graphene composite film. ? TiO2-graphene exhibits excellent electrochemical sensing performance.
We present a quick and easy method to synthesize graphene–MnO2 composites through the self-limiting deposition of nanoscale MnO2 on the surface of graphene under microwave irradiation. These nanostructured graphene–MnO2 hybrid materials are used for investigation of electrochemical behaviors. Graphene–MnO2 composite (78 wt.% MnO2) displays the specific capacitance as high as 310 F g−1 at 2 mV s−1 (even 228 F g−1 at 500 mV s−1), which is almost three times higher than that of pure graphene (104 F g−1) and birnessite-type MnO2 (103 F g−1). Interestingly, the capacitance retention ratio is highly kept over a wide range of scan rates (88% at 100 mV s−1 and 74% at 500 mV s−1). The improved high-rate electrochemical performance may be attributed to the increased electrode conductivity in the presence of graphene network, the increased effective interfacial area between MnO2 and the electrolyte, as well as the contact area between MnO2 and graphene.
1.School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, 212013 People’s Republic of China<br/>2.School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang, 212003 People’s Republic of China<br/>3.Key Laboratory of Fine Petrochemical Engineering of Jiangsu Province, Changzhou University, Changzhou, 213164 People’s Republic of China<br/>
Graphene-based nanocomposites are emerging as a new class of materials that hold promise for many applications. In this article, we present a facile approach for the preparation of graphene/NiO nanocomposites using graphite oxide and nickel chloride as starting materials. The as-synthesized composites were characterized using X-ray diffraction, Fourier transform-Infrared spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, thermogravimetry, and differential scanning calorimetry analyses. It was shown that graphene sheets were decorated by the in situ-formed NiO nanoparticles to form a film-like composite structure and as a result, the restacking of the as-reduced graphene sheets was effectively prevented. The NiO-coated graphene nanocomposites can be expected to remarkably improve the electrochemical properties of NiO and would be the promising candidates for a variety of applications in future nanotechnology.
Graphene–metal oxide composites as anode materials for Li-ion batteries have been investigated extensively, but these attempts are mostly limited to moderate rate charge–discharge applications. Here, graphene–nickel oxide nanostructures have been synthesised using a controlled hydrothermal method, which enabled in situ formation of NiO with a coralloid nanostructure on graphene. Graphene/NiO (20%), graphene/NiO (50%) and pure NiO show stable discharge capacities of 185 mAh/g at 20 C (1 C = 300 mA/g), 450 mAh/g at 1 C, and 400 mAh/g at 1 C, respectively. High rate capability and good stability in prolonged charge–discharge cycling permit the application of the material in fast charging batteries for upcoming electric vehicles. To the best of our knowledge such fast rate performance of graphene/metal oxide composite as anode and such stability for pure NiO as anode have not been reported previously.
Highlights
? Graphene/metal oxide anode for fast charge/discharge application was studied. ? Higher NiO% in graphene showed higher capacity at low current rates. ? Lower NiO% in graphene showed faster and good charge/discharge performance. ? Coralloid nanostructure of NiO showed high stability in cycling as an anode at moderate currents. ? Such stability for pure NiO and such fast rates for NiO/graphene have not been reported previously.
(1. School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China; 2. Zhejiang Zanyu Technology Co., LTD., Hangzhou 310009, China)
Graphene/CdS quantum dot composites were prepared via in situ synthesis and its electrochemical performances as anode material for lithium-ion batteries were investigated. Ac impendence spectra reveal that electrolytes form a fine solid electrolyte interphase film (SEI) on the surface of the graphene/CdS quantum dot composites. The initial discharge capacity of the lithium-ion battery using graphene/CdS quantum dot as anode is about to 1264.7mAh/g and reversible capacity is 888.9mAh/g after 20 cycles. The results indicate that the CdS quantum dot improve the stability of the graphene structure and the conductivity between graphene sheets, so the electrochemical performance of graphene/CdS quantum dot composites as anode materials is obviously better than that of graphene materials.
(1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. School of Material Science and Technology, University of Shanghai for Science and Technology, Shanghai 200093, China)
Graphite oxide was synthesized with Staudenmaier method using natural flake graphite as carbon source. After graphite oxide was impregnated into ammonium carbonate saturated solution, NH4+ intercalated graphite oxide was given. Rapid thermal exfoliation and reduction of NH4+ intercalated graphite oxide to graphene was achieved as well as the nitrogen-doping of graphene under the condition of microwave irradiation. SEM, TEM, EDS, XRD, XPS and Raman were performed to characterize the synthesized nitrogen-doping of graphene. The synthesized nitrogen-doped graphene was transparent and wrinkled with 2-5 graphite layers. The nitrogen content of as-prepared nitrogen-doped graphene was 1.56wt%, corresponding to pyridinc N, pyrrolic N and graphitic N incorporated into the graphitic network.
This work demonstrates a novel and facile route for preparing graphene-based composites comprising of metal oxide nanoparticles and graphene. A graphene nanosheet–bismuth oxide composite as electrode materials of supercapacitors was firstly synthesized by thermally treating the graphene–bismuth composite, which was obtained through simultaneous solvothermal reduction of the colloidal dispersions of negatively charged graphene oxide sheets in N,N-dimethyl formamide (DMF) solution of bismuth cations at 180 °C. The morphology, composition, and microstructure of the composites together with pure graphite oxide, and graphene were characterized using powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetry and differential thermogravimetry (TG–DTG). The electrochemical behaviors were measured by cyclic voltammogram (CV), galvanostatic charge–discharge and electrochemical impedance spectroscopy (EIS). The specific capacitance of 255 F g−1 (based on composite) is obtained at a specific current of 1 A g−1 as compared with 71 F g−1 for pure graphene. The loaded-bismuth oxide achieves a specific capacitance as high as 757 F g−1 even at 10 A g−1. In addition, the graphene nanosheet–bismuth oxide composite electrode exhibits the excellent rate capability and well reversibility.
(1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China; 2. School of the Environment, Nanjing University, Nanjing 210046, China)
A novel hybrid material based on graphene oxide was synthesized by utilizing organic synthesis and supramolecular self-assembly techniques. And the structures of graphene derivatives and product were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscopy (SEM). Thermogravimetric analysis (TG) shows that introduction of organic groups would significantly enhance the thermal stability of derivatives based on graphene oxide in the range of 50-400℃. The nanomaterial obtained has great potential practical significance and theoretical value to develop organic-inorganic hybrid materials based on graphene with novel features.
(1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China; 2. College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510640, China)
Graphite oxide/ZnO was prepared at low temperature (80℃) with graphite oxide (GO) and zinc sulfate heptahydrate (ZnSO4·7H2O) as initial reactants. The graphene/ZnO (GNS/ZnO) was then prepared by a low-temperature chemical exfoliation method. The as-prepared GNS/ZnO was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FT-IR), thermo-gravimetric analysis (TG), X-ray photoelectron spectroscopy (XPS), Raman spectra (RS), scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. The results indicate that graphite oxide is completely reduced to graphene and the well-dispersed ZnO nanoparticles are successfully deposited on graphene sheets as spacers to keep the neighboring sheets separate. Photoluminescence spectra of ZnO and GNS/ZnO nanocomposites display the ?uorescence quenching property of GNS/ZnO, implying that the GNS/ZnO nanocomposites are expected for practical use in the field of photoelectronics.
Fully dense graphene nanosheet(GNS)/Al2O3 composites with homogeneously distributed GNSs of thicknesses ranging from 2.5 to 20 nm have been fabricated from ball milled expanded graphite and Al2O3 by spark plasma sintering. The percolation threshold of electrical conductivity of the as-prepared GNS/Al2O3 composites is around 3 vol.%, and this new composite outperforms most of carbon nanotube/Al2O3 composites in electrical conductivity. The temperature dependence of electrical conductivity indicated that the as-prepared composites behaved as a semimetal in a temperature range from 2 to 300 K.