Morphology,thermal, mechanical,and barrier properties of graphene oxide/poly(lactic acid) nanocomposite films

To improve the physical and gas barrier properties of biodegradable poly(lactic acid) (PLA) film, two graphene nanosheets of highly functionalized graphene oxide (0.3 wt% to 0.7 wt%) and low-functionalized graphene oxide (0.5 wt%) were incorporated into PLA resin via solution blending method. Subsequently, we investigated the effects of material parameters such as loading level and degree of functionalization for the graphene nanosheets on the morphology and properties of the resultant nanocomposites. The highly functionalized graphene oxide (GO) caused more exfoliation and homogeneous dispersion in PLA matrix as well as more sustainable suspensions in THF, compared to low-functionalized graphene oxide (LFGO). When loaded with GO from 0.3 wt% to 0.7 wt%, the glass transition temperature, degree of crystallinity, tensile strength and modulus increased steadily. The GO gave rise to more pronounced effect in the thermal and mechanical reinforcement, relative to LFGO. In addition, the preparation of fairly transparent PLA-based nanocomposite film with noticeably improved barrier performance achieved only when incorporated with GO up to 0.7wt%. As a result, GO may be more compatible with hydrophilic PLA resin, compared to LFGO, resulting in more prominent enhancement of nanocomposites properties.     

Graphene oxide-anchored reactive sulfonated copolymer via simple one pot condensation polymerization: proton-conducting solid electrolytes

A rapid and efficient post-polymerization functionalization of poly(urea-co-urethane) (PUU) onto the graphene oxide (GO) nanosheets has been developed to produce super-acidic polymer/GO hybrid nanosheets. Thus, the surface of GO nanosheets were functionalized with 3-(triethoxysilyl)propyl isocyanate (TESPIC) from hydroxyl groups to yield isocyanate functionalized graphene oxide nanosheets. Then, sulfonated polymer/GO hybrid nanosheets were prepared by condensation polymerization of isocyanate-terminated pre-polyurea onto isocyanate functionalized graphene oxide nanosheets through the formation of carbamate bonds. FTIR and TGA results indicated that TESPIC modifier agent and poly(urea-co-urethane) were successfully grafted onto the GO nanosheets. The grafting efficiency of poly(urea-co-urethane) polymer onto the GO nanosheets was estimated from TGA thermograms to be 205.9%. Also, sulfonated polymer/GO hybrid nanosheets showed a proton conductivity as high as 3.7 mS cm^?1. Modification and morphology of GO nanosheets before and after modification processes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD).     

One pot preparation of reduced graphene oxide (RGO) or Au (Ag) nanoparticle-RGO hybrids using chitosan as a reducing and stabilizing agent and their use in methanol electrooxidation

An environment-friendly approach to synthesizing reduced graphene oxide (RGO) was developed by using chitosan (CS) as both a reducing and a stabilizing agent. Factors that affect the reduction of graphene oxide (GO), such as the ratio of CS/GO, pH and temperature, were explored to obtain optimum reaction conditions. The RGO was characterized with UV visible absorption spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction spectroscopy, thermo-gravimetric analysis, and X-ray photoelectron spectroscopy and transmission electron microscopy. Analysis shows that CS macromolecules can efficiently reduce GO at a comparatively low temperature and their adsorption onto the RGO nanosheets allows a stable RGO aqueous dispersion to be formed. Since CS is a natural, nontoxic and biodegradable macromolecule, this approach provides a new green method for GO reduction that would facilitate the large scale production of RGO, which has great value for graphene applications. Moreover, CS can reduce GO and AgNO₃ (or HAuCl₄) in one pot to obtain Ag nanoparticle-RGO hybrids or Au nanoparticle-RGO hybrids that exhibit good electrochemical activity.     

Process intensification of uniform loading of SnO2 nanoparticles on graphene oxide nanosheets using a novel ultrasound assisted in situ chemical precipitation method

In this paper, a novel ultrasound assisted, solution-based chemical synthesis method for the preparation of SnO₂–graphene nanocomposite is presented. Graphene oxide (GO) was prepared by the modified Hummers–Offeman method in presence of ultrasonic irradiation. Further loading of SnO₂ on GO was carried out with an ultrasound assisted solution-based synthesis route. The prepared GO and SnO₂–graphene nanocomposite were characterized by XRD, TEM, FTIR spectra, TGA and DTA analysis in order to confirm the formation of graphene–SnO₂ nanocomposite. TEM analysis of ultrasonically prepared graphene–SnO₂ composite shows the uniform and fine loading of SnO₂ particles (3–5 nm) on graphene nanosheets. However agglomerated morphology was observed in case of conventionally prepared graphene–SnO₂ composite. The cavitational effects generated due to the ultrasonic irradiations during the synthesis of graphene–SnO₂ composite improve the fine and uniform loading of SnO₂ on graphene nanosheets by oxidation–reduction reaction between GO and SnCl₂·2H₂O compared to conventional synthesis methods. The formed material was used for the preparation of anode in lithium ion batteries and its electrochemical performance was characterized by cyclic voltammetry and charge/discharge cycles. It is found that the capacity of SnO₂–graphene nanocomposite based Li-battery is stable for around 120 cycles, and the battery could repeat stable charge–discharge reaction.     

Ionic-liquid-assisted facile synthesis of silver nanoparticle-reduced graphene oxide hybrids by gamma irradiation

A simple and environmentally friendly approach for the preparation of graphene nanosheets decorated with silver nanoparticles (Ag NPs) has been developed by gamma irradiation at room temperature. Graphene oxide (GO) and silver ions are simultaneously reduced by the electrons generated from the radiolysis of solvent. The addition of ionic liquid plays an important role in GO reduction by scavenging oxidative radicals generated during irradiation. Besides, the ionic liquid also benefits the dispersion and size distribution of Ag NPs. Raman signals of the obtained Ag-reduced graphene oxide are significantly enhanced, exhibiting obvious surface-enhanced Raman scattering activity.     

Graphene nanosheets based on controlled exfoliation process for enhanced lithium storage in lithium-ion battery

A facile and rapid approach was used for the fabrication of chemically derived graphene nanosheets based on the reduction of graphite oxide (GO) in tube furnace assembly at different temperatures. The morphologies, microstructures, specific surface areas and other features of GO and graphene nanosheets were characterized. Structure characterization indicates that the platelet thickness of graphene nanosheets obtained at 300 °C was 1.62 nm, which corresponds to an approximately 5 layers stacking of the monoatomic graphene nanosheets. Electrochemical performances of the as-prepared graphene nanosheets were performed, the result of which could prove the above observation that graphene nanosheets (5 layers) obtained at 300 °C actually displayed the most remarkable electrochemical performances: the first discharge and charge capacities of graphene nanosheets were as high as 2137 mAh/g and 994 mAh/g, respectively, and after 100 cycles graphene nanosheets still possessed a high capacity of 478 mAh/g.     

Silicon nanowire arrays-induced graphene oxide reduction under UV irradiation

This paper reports on efficient UV irradiation-induced reduction of exfoliated graphene oxide. Direct illumination of an aqueous solution of graphene oxide at λ = 312 nm for 6 h resulted in the formation of graphene nanosheets dispersible in water. X-Ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, atomic force microscopy (AFM) and electrochemical measurements (cyclic voltammetry and electrochemical impedance spectroscopy) suggest a restoration of the sp(2) carbon network. The results were compared with graphene nanosheets prepared by photochemical irradiation of a GO aqueous solution in the presence of hydrogenated silicon nanowire (SiNW) arrays or silicon nanowire arrays decorated with silver (SiNW/Ag NPs) or copper nanoparticles (SiNW/Cu NPs). Graphene nanosheets obtained by illumination of the GO aqueous solution at 312 nm for 6 h in the presence of SiNW/Cu NPs exhibited superior electrochemical charge transfer characteristics. This is mainly due to the higher amount of sp(2)-hybridized carbon in these graphene sheets found by XPS analysis. The high level of extended conjugated carbon network was also evident by the water insoluble nature of the resulting graphene nanosheets, which precipitated upon photochemical reduction.     

Enhanced thermal stability in graphene oxide covalently functionalized with 2-amino-4,6-didodecylamino-1,3,5-triazine

In this study 2-amino-4,6-didodecylamino-1,3,5-triazine (ADDT) was synthesized from cyanuric chloride and covalently functionalized onto graphene oxide nanosheets. The chemical structure of the alkylated melamine and the functionalized graphene oxide (GO) nanosheets were characterized with ¹H NMR, FT-IR, XPS, TGA and TEM. The results indicate that two chlorine atoms on the triazine ring of cyanuric chloride were substituted by two long alkyl chains. Covalent functionalization of ADDT onto the graphene oxide nanosheets was confirmed with both FT-IR and XPS results. The reduced mass loss rate along with enhanced residue formation (TGA results) indicates significant improvement in thermal stability for GO-ADDT compared to GO. Moreover good solubility of GO-ADDT in organic solvents suggests the potential of GO-ADDT as a nanoadditive for polymeric systems.     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

石墨烯/玻璃块体复合材料的制备及性能

本文报道了还原氧化石墨烯/钠钙硅(rGO/SLS)玻璃块体复合材料的热压制备和力学性能。首先以3-氨基丙基三乙氧基硅烷为表面活性剂修饰玻璃粉微粒;然后在水溶液中带负电的氧化石墨烯(GO)纳米片通过静电自组装与被氨基修饰过带正电的玻璃颗粒相结合生成复合颗粒。通过高温真空热压烧结,GO被还原成rGO,从而原位生成rGO/SLS玻璃块状复合材料。结果表明,rGO均匀分布在玻璃基质中,并明显增强了复合材料的机械性能。rGO/SLS玻璃块体复合材料中rGO的含量为0.5%(质量分数)时,复合材料的弯曲强度比纯的SLS玻璃提高了约一倍。     

A novel monolithic Pd catalyst supported on cordierite with graphene coating

Immobilization on a structured substrate is a prerequisite for exploiting practical applications for graphene as a catalytic support. Here we report that graphene oxide (GO) nanosheets can readily form a stable coating on a cordierite honeycomb substrate without any need of stabilizers. FT-IR and ¹H NMR characterization revealed that GO nanosheets were probably immobilized on the cordierite surface by hydrogen bonding. TEM analysis indicated that palladium particles loaded on the graphene/cordierite exhibited a uniform size of less than 5 nm, which led to 4 times higher activity for styrene hydrogenation than that loaded on the cordierite.     

Antibacterial activity of dithiothreitol reduced graphene oxide

A green and simple approach is described for the large scale synthesis of reduced graphene oxide (rGO). The transition of graphene oxide (GO) into graphene was confirmed using various analytical techniques. Raman spectroscopy data indicate the partial removal of oxygen-containing functional groups from the surface of GO and formation of graphene. X-ray diffraction (XRD) was used to investigate the crystallinity of graphene nanosheets. The antibacterial activity of GO and rGO was evaluated using cell viability, reactive oxygen species (ROS) production and DNA fragmentation assays. The results suggest that GO and rGO possessed an excellent antimicrobial activity against Escherichia coli.     

Sub-20 nm anatase particles uniformly anchored on graphene oxide and reduced graphene oxide nanosheets and their photocatalytic oxidation and Li-ion storage capabilities

Nanosized anatase TiO₂ particles anchored on nanocarbon substrates have great potential for practical applications in high-performance lithium ion batteries and efficient photocatalysts. The synthesis of this material usually utilizes calcination to crystallize amorphous titania, which normally causes the formation of aggregates and some side effects. In this work, we demonstrated that sub-20 nm anatase particles uniformly anchored on graphene oxide and reduced graphene oxide nanosheets in aqueous solution at a temperature of 90 °C and atmospheric pressure, without further calcination. The photocatalytic oxidation activity and electrochemical properties of graphene oxide/anatase TiO₂ (GO/A) and reduced graphene oxide/anatase TiO₂ (RGO/A) were comparatively investigated. We found that GO/A showed higher photocatalytic oxidation activity than RGO/A under UV light irradiation. Graphene oxide accepted electrons and suffered reduction, which finally decreased GO/A’s photocatalytic oxidation activity to an extent similar to RGO/A. We also found that, as anode material for Li-ion battery, the specific capacity of RGO/A was nearly three times that of GO/A at the same current rate. This study will inspire better design of metal oxide/nanocarbon nanocomposites for high performance lithium ion battery and photocatalysis applications.     

Facile solid-state synthesis of Ag/graphene oxide nanocomposites as highly active and stable catalyst for the reduction of 4-nitrophenol

A facile solid-state synthetic route was used to fabricate graphene oxide (GO) decorated with Ag nanoparticles. Ag/GO nanocomposites were prepared by reducing silver acetate with ascorbic acid in the presence of GO at ambient conditions. The characterization results showed that Ag nanoparticles with an average diameter of ~ 50 nm were well dispersed on the surface of GO nanosheets. Moreover, an application of the obtained Ag/GO nanocomposites as a catalyst in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol by NaBH₄ was demonstrated. The Ag/GO nanocomposites exhibited high activity and stability for the catalytic reduction of 4-NP.     

Chitosan–graphene oxide nanocomposites: Effect of graphene oxide nanosheets and glycerol plasticizer on thermal and mechanical properties

In this study, graphite oxide (GO) is synthesized from natural graphite flakes by the modified Hummers method. Characterization by Fourier transform infrared, X‐ray photoelectron, Raman and ultraviolet‐visible spectroscopies, X‐ray diffraction, and thermogravimetric analysis is conducted on GO to confirm the oxidation of graphite. Unplasticized and glycerol plasticized chitosan/graphene oxide (CS/GO) nanosheets nanocomposites with different GO loadings are prepared by solution casting. The combined effect of GO and glycerol on structure, thermal and mechanical properties of nanocomposite films is studied. GO nanosheets are well dispersed throughout the CS matrix due to the hydrogen bonding and electrostatic interactions between CS and GO nanosheets. The incorporation of GO within the CS matrix results in a decrease of the crystallinity, an improvement of thermal stability, and a significant enhancement of the stiffness and tensile strength that is emphasized by the glycerol. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45092.     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Graphene nanosheets prepared by low-temperature exfoliation and reduction technique toward fabrication of high-performance poly(1-butene)/graphene films

Thermal exfoliation and reduction of graphene oxide (GO) were performed to prepare graphene nanosheets at 300 °C under the ambient atmosphere without any supplementary conditions. The microstructure and morphology of the resulting graphene nanosheets were characterized with scanning electron microscopy, transmission electric microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The composite films based on poly(1-butene) (PB) and graphene nanosheets were prepared successfully through solution blending and compression molding. The morphological investigation suggested that the graphene nanosheets with nanoscale thickness achieved a homogeneous dispersion in the PB matrix. The composite films exhibited a sharp transition from insulating state to the conducting one with a low percolation threshold, followed by a high electrical conductivity at graphene content higher than 1.6 vol %. The composite films also achieved high dielectric constant with low dielectric loss due to the effective electrical conductive path established by graphene nanosheets in a local range. Moreover, the mechanical evaluation demonstrated that a considerable reinforcement was achieved for the composite films due to the strong interfaces between the graphene nanosheets and PB matrix. The introduction of graphene nanosheets not only enhanced the nucleation capability and crystallinity of PB domain but also improved the thermal stability of the composite films. In addition, the composite films showed an increase in storage modulus and a decrease in loss factors due to the incorporation of graphene nanosheets.     

Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid

An easy bottom–up method for the preparation of photoluminescent (PL) graphene quantum dots (GQDs) and graphene oxide (GO) has been developed by tuning the carbonization degree of citric acid and dispersing the carbonized products into alkaline solutions. The GQDs are nanosheets ～15 nm in width, and 0.5–2.0 nm in thickness. They show a relatively strong (9.0%) PL quantum yield and an excitation-independent PL emission activity. In contrast, the GO nanostructures consist of sheets that are hundreds of nanometers in width and ～1 nm in height. They exhibit a relatively weak (2.2%) PL quantum yield and an excitation-dependent PL emission activity.     

Facile synthesis of two-dimensional graphene/SnO₂ /Pt ternary hybrid nanomaterials and their catalytic properties

In this paper, we reported a simple, aqueous-phase route to the synthesis of two-dimensional graphene/SnO(2) composite nanosheets (GSCN) hybrid nanostructures consisting of 5 nm Pt nanoparticles supported on the both sides of GSCN. Functional two-dimensional GSCN were obtained through the reduction of graphene oxide (GO) using SnCl(2) in the presence of polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA). The main advantages of this preparation are that the reduction of GO, the formation of SnO(2) and the functionalization of GSCN were achieved simultaneously through one-pot reaction. GSCN/Pt ternary hybrid nanomaterials were generated by in situ reduction of negatively charged PtCl(6)(2-) precursors adsorbed on the positively charged surface of GSCN through electrostatic attraction. The as-synthesized GSCN/Pt ternary hybrid nanomaterials exhibited high cycle stabilization during the catalytic reduction of p-nitrophenol into p-aminophenol by NaBH(4). Additionally, our approach is expected to extend to other hybrid nanomaterials. We believe that the obtained GSCN/Pt ternary hybrid nanomaterials have great potential for applications in other field, such as electrochemical energy storage, sensors, and so on.     

Preparation and tribological properties of novel boehmite/graphene oxide nano-hybrid

Novel boehmite/graphene oxide nano-hybrid (GO–GPTS–AlOOH) was prepared through a simple covalent bond method, which was subsequently explored as lubricant additive. For this purpose, the 3-glycidoxypropyl-trimethoxysilane (GPTS) was first chemically grafted on nano-boehmite (AlOOH) to fabricate the modified boehmite (GPTS–AlOOH). Then the GPTS–AlOOH was anchored on graphene oxide (GO) nanosheets to prepare GO–GPTS–AlOOH nano-hybrid through a coupled reaction. The structure, composition and morphology of GO–GPTS–AlOOH was characterized by FT-IR, XRD, TG/DTG, SEM and TEM, revealing that nano-boehmite was uniformly coated on GO surface. More importantly, tribological properties of GO–GPTS–AlOOH as lubricating oil additive were investigated using a ball-on-disc testing machine and a four-ball machine. It was found that the friction reduction and anti-wear ability of lubricant oil containing GO–GPTS–AlOOH hybrid was highly improved compared to bare base oil (VHVI8). Specifically, friction coefficient (COF), wear scar diameter (WSD) and wear rate were reduced by 14%, 28% and 73%, respectively. The enhancement can be attributed to the synergistic effect of the nanobearing mechanism and ultimate strengthen of graphene sheets between the frictional interfaces.