Electric contributions to magnetic force microscopy response from graphene and MoS2 nanosheets

Magnetic force microscopy (MFM) signals have recently been detected from whole pieces of mechanically exfoliated graphene and molybdenum disulfide (MoS2) nanosheets, and magnetism of the two nanomaterials was claimed based on these observations. However, non-magnetic interactions or artefacts are commonly associated with MFM signals, which make the interpretation of MFM signals not straightforward. A systematic investigation has been done to examine possible sources of the MFM signals from graphene and MoS2 nanosheets and whether the MFM signals can be correlated with magnetism. It is found that the MFM signals have significant non-magnetic contributions due to capacitive and electrostatic interactions between the nanosheets and conductive cantilever tip, as demonstrated by electric force microscopy and scanning Kevin probe microscopy analyses. In addition, the MFM signals of graphene and MoS2 nanosheets are not responsive to reversed magnetic field of the magnetic cantilever tip. Therefore, the observed MFM response is mainly from electric artefacts and not compelling enough to correlate with magnetism of graphene and MoS2 nanosheets.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

High N-content holey few-layered graphene electrocatalysts: Scalable solvent-less production

Few layered nitrogen doped graphene (NG) attracts great interest in energy storage and conversion applications due to its electronic and catalytic properties. However, its bulk production cannot be envisioned by the current synthetic methods. Here we report a facile, solvent-less, low cost and high yield process for the synthesis of NG. Mechanochemical solid-state exfoliation allows scalable synthesis of holey and crumple nitrogen-doped few-layered graphene from graphite with controlled high concentration N doping and a high surface area through ball-milling. By adjusting the ratio of starting materials, the nitrogen content can be modulated from 4.87 to 17.83 at.%. Furthermore, the types of nitrogen-containing species in few-layered graphene can also be controlled. The resultant NG exhibits superior oxygen reduction reaction performance and more reliable stability than commercial Pt/C catalysts. This journal is

Synergistic effect of multi walled carbon nanotubes and reduced graphene oxides in natural rubber for sensing application

Utilizing the electrical properties of polymer nanocomposites is an important strategy to develop high performance solvent sensors. Here we report the synergistic effect of multi walled carbon nanotubes (MWCNTs) and reduced graphene oxide (RGO) in regulating the sensitivity of the naturally occurring elastomer, natural rubber (NR). Composites were fabricated by dispersing CNTs alone and together with exfoliated RGO sheets (thermally reduced at temperatures of 200 and 600 °C) in NR by a solution blending method. RGO exfoliation and the uniform distribution of fillers in the composites were studied by atomic force microscopy, Fourier transformation infrared spectroscopy, X-ray diffraction, transmission electron microscopy and Raman spectroscopy. The solvent sensitivity of the composite samples was noted from the sudden variation in electrical conductivity which was due to the breakdown of the filler networks during swelling in different solvents. It was found that the synergy between CNTs and RGO exfoliated at 200 °C imparts maximum sensitivity to NR in recognizing the usually used aromatic laboratory solvents. Mechanical and dynamic mechanical studies reveal efficient filler reinforcement, depending strongly on the nature of filler-elastomer interactions and supports the sensing mechanism. Such interactions were quantitatively determined using the Maier and Göritz model from Payne effect experiments. It is concluded that the polarity induced by RGO addition reduces the interactions between CNTs and ultimately results in the solvent sensitivity. © 2013 The Royal Society of Chemistry.

Graphene oxide decorated diatom silica particles as new nano-hybrids: Towards smart natural drug microcarriers

Herein, we demonstrate the fabrication of a novel nano-hybrid material based on diatom silica microparticles from diatomaceous earth (DE) and graphene oxide (GO). Two different approaches for the fabrication of nano-hybrids were used, including covalent coupling of GO sheets onto the diatom surface and electrostatic attachment. Covalent attachment was carried out through a facile amine coupling strategy via activation of carboxyl groups on GO, followed by covalent attachment to amine terminal groups of 3-aminopropyl-triethoxysilane (APTES) functionalized DE particles. Electrostatic attachment of GO (i.e. negatively charged) was carried out on positively charged APTES functionalized DE particles. The GO decorated DE nano-hybrids prepared with both the fabrication processes were extensively characterized by SEM, TEM, FTIR, and Raman spectroscopy to confirm the new chemical composition and structure. The application of the GO-DE nano-hybrid as a smart pH sensitive micro-drug carrier at pH 7.4 and pH 3.5 was demonstrated using a model drug, indomethacin (IMC). Finally, the drug release data were fitted to zero-order and Korsmeyer-Peppas models to understand the mechanism of drug release. This journal is © The Royal Society of Chemistry.

RAFT controlled synthesis of graphene/polymer hydrogel with enhanced mechanical property for pH-controlled drug release

A pH-sensitive, mechanically strong and thermally stable graphene/poly (acrylic acid) (graphene/PAA) hydrogel was prepared via reversible addition fragmentation transfer (RAFT) polymerizations in the presence of a cross-linking agent. The RAFT agent was covalently coupled onto graphene basal planes via an esterification reaction, with benzoic acid functionalities pre-attached on graphene with its aryl diazonium salt precursor. AFM and SEM analysis revealed the successful preparation of single layered graphene sheets and graphene/polymer hydrogels with pH controlled porous structures. Attenuated total reflection infrared (ATR-IR) and thermogravimetric analyzer (TGA) verified the successful stepwise preparation of graphene/PAA hydrogel. This graphene/PAA hydrogel was pH-sensitive and more mechanically elastic than the PAA hydrogel prepared without graphene. The pH sensitivity of the hydrogel was further utilized for controlled drug release. Doxorubicin was chosen as a model drug and loaded into the hydrogels. The drug loading and release experiment indicated that this hydrogel can be used to efficiently control drug release in the intestine environment (pH = 7.4), better than release in a more acidic environment.© 2013 Elsevier Ltd. All rights reserved.

Molecular-level dispersion of graphene into epoxidized natural rubber: Morphology, interfacial interaction and mechanical reinforcement

The interfacial interaction of composites dominates the properties of polymeric/inorganic nanocomposites. Herein, epoxy and hydroxyl groups are introduced into the natural rubber (NR) molecular chains to anchor oxygenous functional groups on the surface of graphene oxide (GO) sheets and therefore enhance the interfacial interaction between GO and rubber. From the morphological observation and interaction analysis, it is found that epoxidized natural rubber (ENR) latex particles are assembled onto the surfaces of GO sheets by employing hydrogen bonding interaction as driving force. This self-assembly depresses restacking and agglomeration of GO sheets and leads to homogenous dispersion of GO within ENR matrix. The formation of hydrogen bonding interface between ENR and GO demonstrates a significant reinforcement for the ENR host. Compared with those of pure ENR, the composite with 0.7 wt% GO loading receives 87% increase in tensile strength and 8.7 fold increase in modulus at 200% elongation after static in-situ vulcanization.

Tuning the grade of graphene: Gamma ray irradiation of free-standing graphene oxide films in gaseous phase

A direct approach to functionalize and reduce pre-shaped graphene oxide 3D architectures is demonstrated by gamma ray irradiation in gaseous phase under analytical grade air, N2 or H2. The formation of radicals upon gamma ray irradiation is shown to lead to surface functionalization of the graphene oxide sheets. The reduction degree of graphene oxide, which can be controlled through varying the γ-ray total dose irradiation, leads to the synthesis of highly crystalline and near defect-free graphene based materials. The crystalline structure of the graphene oxide and γ-ray reduced graphene oxide was investigated by x-ray diffraction and Raman spectroscopy. The results reveal no noticeable changes in the size of sp2 graphitic structures for the range of tested gases and total exposure doses suggesting that the irradiation in gaseous phase does not damage the graphene crystalline domains. As confirmed by X-ray photoemission spectroscopy, the C/O ratio of γ-ray reduced graphene oxide is increasing from 2.37 for graphene oxide to 6.25 upon irradiation in hydrogen gas. The removal of oxygen atoms with this reduction process in hydrogen results in a sharp 400 times increase of the electrical conductivity of γ-ray reduced graphene oxide from 0.05 S cm-1 to as high as 23 S cm-1. A significant increase of the contact angle of the γ-ray reduced graphene oxide bucky-papers and weakened oxygen rich groups characteristic peaks across the Fourier transform infrared spectra further illustrate the efficacy of the γ-ray reduction process. A mechanism correlating the interaction between hydrogen radicals formed upon γ-ray irradiation of hydrogen gas and the oxygen rich groups on the surface of the graphene oxide bucky-papers is proposed, in order to contribute to the synthesis of reduced graphene materials through solution-free chemistry routes.

Achieving outstanding mechanical performance in reinforced elastomeric composite fibers using large sheets of graphene oxide

A simple fiber spinning method used to fabricate elastomeric composite fibers with outstanding mechanical performance is demonstrated. By taking advantage of the large size of as-prepared graphene oxide sheets (in the order of tens of micrometers) and their liquid crystalline behavior, elastomeric composite fibers with outstanding low strain properties have been fabricated without compromising their high strain properties. For example, the modulus and yield stress of the parent elastomer improved by 80- and 40-fold, respectively, while maintaining the high extensibility of ∼400% strain inherent to the parent elastomer. This outstanding mechanical performance was shown to be dependent upon the GO sheet size. Insights into how both the GO sheet size dimension and dispersion parameters influence the mechanical behavior at various applied strains are discussed.

Scalable production of wrinkled and few-layered graphene sheets and their use for oil and organic solvent absorption

High-quality wrinkled and few-layered graphene sheets have been produced via a mechano-thermal exfoliation process for a simple, effective and low-cost mass production. Graphene sheets were produced by first ball milling of graphite with ammonium chloride followed by thermal annealing at 800 °C in nitrogen gas. The few layered graphene sheets show highly efficient selectivity and capacity for the absorption of petroleum products as well as organic solvents such as ethanol, cyclohexane and chloroform (up to 82, 42 and 98 times of their own weight, respectively). The saturated few-layered graphene sheets can be cleaned for reuse by simply burning in air. The low-cost strategy for mass production and easy recycling routes demonstrate the great potential of few-layered graphene sheets for oil removal.

Promoted water transport across graphene oxide-poly(amide) thin film composite membranes and their antibacterial activity

Hybrid composite membranes have great potential for desalination applications since water transport can be favorably promoted by selective diffusion at the interface between matrix and reinforcement materials. In this paper, graphene oxide nano-sheets were successfully incorporated across 200nm thick poly(amide) films by interfacial polymerization to form novel thin-film composite membranes. The impact of the graphene oxide on the morphology, chemistry, and surface charge of the ultra-thin poly(amide) layer, and the ability to desalinate seawater was investigated. The graphene oxide nano-sheets were found to be well dispersed across the composite membranes, leading to a lower membrane surface energy and an enhanced hydrophilicity. The iso-electric point of the samples, key to surface charge repulsion during desalination, was found to be consistently shifted to higher pH values with an increasing graphene oxide content. Compared to a pristine poly(amide) membrane, the pure water flux across the composite membranes with 0.12wt.% of graphene oxide was also found to increase by up to 80% from 0.122 to 0.219L·μm·m-2·h-1·bar-1 without significantly affecting salt selectivity. Furthermore, the inhibitory effects of the composite membrane on microbial growth were evaluated and the novel composite membranes exhibited superior anti-microbial activity and may act as a potential anti-fouling membrane material.

Fabrication of conductive elastic nanocomposites via framing intact interconnected graphene networks

Electrically conductive elastic nanocomposites with well-organized graphene architectures offer significant improvement in various properties. However, achieving desirable graphene architectures in cross-linked rubber is challenging due to high viscosity and cross-linked nature of rubber matrices. Here, three dimensional (3D) interconnected graphene networks in natural rubber (NR) matrix are framed with self-assembly integrating latex compounding technology by employing electrostatic adsorption between poly(diallyldimethylammonium chloride) modified graphene (positively charged) and NR latex particles (negatively charged) as the driving force. The 3D graphene structure endows the resulted nanocomposites with excellent electrical conductivity of 7.31. S/m with a graphene content of 4.16. vol.%, extremely low percolation threshold of 0.21. vol.% and also analogous reinforcement in mechanical properties. The developed strategy will provide a practical approach for developing elastic nanocomposites with multi-functional properties. © 2014 Elsevier Ltd.

Electrically conductive graphene-filled polymer composites with well organized three-dimensional microstructure

Electrically conductive graphene-filled polystyrene nanocomposites with well-organized three dimensional (3D) microstructures were simply prepared by electrostatic assembly integrated latex technology. First, positively charged polystyrene was synthesized via disperse polymerization in ethanol/water medium by using a cationic co-monomer, and then directly co-assembled with graphene oxide. Eventually, a honeycomb-like graphene 3D framework was embedded in polystyrene matrix after in situ chemical reduction and hot compression molding. Due to the 3D conductive pathway derived from graphene based network evidenced by morphology studies, the fabricated nanocomposites show excellent electrical properties, i.e. extremely low percolation threshold of 0.09 vol% and high saturated conductivity of 25.2 S/m at GNs content of 1.22 vol%. © 2014 Elsevier B.V.

Single step preparation of meso-porous and reduced graphene oxide by gamma-ray irradiation in gaseous phase

A facile and highly efficient route to produce simultaneously porous and reduced graphene oxide by gamma ray irradiation in hydrogen is here demonstrated. Narrowly distributed nano-scale pores (average size of ∼3 nm and surface density >44,900 pore μm-2) were generated across 10 μm thick graphene oxide bucky-papers at a total irradiation dose of 500 kGy. The graphene oxide sheet reduction was confirmed to occur homogeneously across the structures by Fourier transform infrared spectroscopy and Raman analysis. This one-step, catalyst-free, high penetration and through-put technique, offers great promises potential for the mass production of reduced graphene oxide from cheap graphene oxide. © 2013 Elsevier Ltd. All rights reserved.