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.

Molecularly engineered graphene surfaces for sensing applications: A review.

Graphene is scientifically and commercially important because of its unique molecular structure which is monoatomic in thickness, rigorously two-dimensional and highly conjugated. Consequently, graphene exhibits exceptional electrical, optical, thermal and mechanical properties. Herein, we critically discuss the surface modification of graphene, the specific advantages that graphene-based materials can provide over other materials in sensor research and their related chemical and electrochemical properties. Furthermore, we describe the latest developments in the use of these materials for sensing technology, including chemical sensors and biosensors and their applications in security, environmental safety and diseases detection and diagnosis.

Reflectance response of tapered optical fiber coated with graphene oxide nanostructured thin film for aqueous ethanol sensing

In this work, optical sensing performance of tapered multimode fiber tip coated with graphene oxide (GO) nanostructured thin film towards aqueous ethanol with different concentrations is investigated. The tapering process of the optical fiber is done by a glass processing machine. The multimode optical fiber tip is dip-coated with GO and annealed at 70 °C to enhance the binding of the nanomaterials to the silica fiber. FESEM, Raman microscopy and XRD analyses are performed to micro-characterize the GO thin films. The morphology of the GO is observed to be in sheets forms. The reflectance response of the GO coated fiber tip is compared with the uncoated tip. The measurements are taken using a spectrophotometer in the optical wavelength range of 550-720 nm. The reflectance response of the GO coated fiber tip reduced proportionally, upon exposure to ethanol with concentration range of 5-80%. The dynamic response of the developed sensor showed strong reversibility and repeatability when it is exposed to ethanol with concentrations of 5%, 20% and 40% in distilled water. At room temperature, the sensor shows fast response and recovery as low as 19 and 25 s, respectively. © 2014 Elsevier B.V.

Graphene quantum dots induce apoptosis, autophagy, and inflammatory response via p38 mitogen-activated protein kinase and nuclear factor-κB mediated signaling pathways in activated THP-1 macrophages.

The biomedical application of graphene quantum dots (GQDs) is a new emerging area. However, their safety data are still in scarcity to date. Particularly, the effect of GQDs on the immune system remains unknown. This study aimed to elucidate the interaction of GQDs with macrophages and the underlying mechanisms. Our results showed that GQDs slightly affected the cell viability and membrane integrity of macrophages, whereas GQDs significantly increased reactive oxygen species (ROS) generation and apoptotic and autophagic cell death with an increase in the expression level of Bax, Bad, caspase 3, caspase 9, beclin 1, and LC3-I/II and a decrease in that of Bcl-2. Furthermore, low concentrations of GQDs significantly increased the expression of tumor necrosis factor-α (TNF-α), interleukin-1β (IL-1β), IL-8, whereas high concentrations of GQDs elicited opposite effects on the cytokines production. SB202190, a selective inhibitor of p38 mitogen-activated protein kinase (MAPK), abolished the cytokine-inducing effect of GQDs in macrophages. Moreover, GQDs significantly increased the phosphorylation of p38 MAPK and p65, and promoted the nuclear translocation of nuclear factor-κB (NF-κB). Taken together, these results show that GQDs induce ROS generation, apoptosis, autophagy, and inflammatory response via p38MAPK and NF-κB mediated signaling pathways in THP-1 activated macrophages.

Numerical investigation of a grating and graphene-based multilayer surface plasmon resonance biosensor

A multilayer surface plasmon resonance biosensor (SPRB) incorporating a grating-graphene configuration is investigated for enhanced sensitivity. The numerical analysis of the impact of integrating a periodic array of subwavelength grating on top of a layer of graphene sheet for improving sensitivity is presented. The result of monitoring the biomolecular interactions of DNA hybridization is compared against the outcome of the conventional SPRB, a graphene-based multilayer SPRB, and a multilayer layer grating SPRB, and is mathematically validated. It is demonstrated that the inclusion of a grating and graphene layer on top of the gold thin film is an excellent candidate for a highly sensitive SPRB. To achieve further enhancement of sensitivity, the subwavelength grating is numerically optimized against its geometry including grating configurations (rectangular, sinusoidal, and triangular), grating depth, volume factor, and grating period. © 2014 Taylor & Francis.

Tunable dual-stimuli response of a microgel composite consisting of reduced graphene oxide nanoparticles and poly(N-isopropylacrylamide) hydrogel microspheres

A type of photo- and thermo-responsive composite microsphere composed of reduced graphene oxide nanoparticles and poly(N-isopropylacrylamide) (rGO@pNIPAM) is successfully fabricated by a facile solution mixing method. Due to the high optical absorbance and thermal conduction of rGO, the composite microspheres are endowed with the new property of photo-response, in addition to the intrinsic thermally sensitive property of pNIPAM. This new ability undoubtedly enlarges the scope of applications of the microgel spheres. Furthermore, through controlling the rGO content in the composite, the photo- and thermo-sensitivity of the composite can be effectively modulated. That is, with a lower rGO content (≤32% by weight), the composite microspheres perform only thermally induced changes, such as volume contraction (by ∼45% in diameter) and drug release, when crossing the lower critical solution temperature of pNIPAM. With a higher rGO content (∼47.5%), both temperature and light irradiation can trigger changes in the composite. However, when the rGO content is increased to around 64.5%, the thermo-responsivity of the composite disappears, and the spheres exhibit only photo-induced drug release. With a further increase in rGO content, the environmentally responsive ability of the microspheres vanishes. This journal is © the Partner Organisations 2014.

High-performance multifunctional graphene yarns: toward wearable all-carbon energy storage textiles

The successful commercialization of smart wearable garments is hindered by the lack of fully integrated carbon-based energy storage devices into smart wearables. Since electrodes are the active components that determine the performance of energy storage systems, it is important to rationally design and engineer hierarchical architectures atboth the nano- and macroscale that can enjoy all of the necessary requirements for a perfect electrode. Here we demonstrate a large-scale flexible fabrication of highly porous high-performance multifunctional graphene oxide (GO) and rGO fibers and yarns by taking advantage of the intrinsic soft self-assembly behavior of ultralarge graphene oxide liquid crystalline dispersions. The produced yarns, which are the only practical form of these architectures for real-life device applications, were found to be mechanically robust (Young's modulus in excess of 29 GPa) and exhibited high native electrical conductivity (2508 ± 632 S m(-1)) and exceptionally high specific surface area (2605 m(2) g(-1) before reduction and 2210 m(2) g(-1) after reduction). Furthermore, the highly porous nature of these architectures enabled us to translate the superior electrochemical properties of individual graphene sheets into practical everyday use devices with complex geometrical architectures. The as-prepared final architectures exhibited an open network structure with a continuous ion transport network, resulting in unrivaled charge storage capacity (409 F g(-1) at 1 A g(-1)) and rate capability (56 F g(-1) at 100 A g(-1)) while maintaining their strong flexible nature.

Performance enhancement of single-walled nanotube-microwave exfoliated graphene oxide composite electrodes using a stacked electrode configuration

We report the development of a stacked electrode supercapacitor cell using stainless steel meshes as the current collectors and optimised single walled nanotubes (SWNT)-microwave exfoliated graphene oxide (mw rGO) composites as the electrode material. The introduction of mw rGO into a SWNT matrix creates an intertwined porous structure that enhances the electroactive surface area and capacitive performance due to the 3-D hierarchical structure that is formed. The composite structure was optimised by varying the weight ratio of the SWNTs and mw rGO. The best performing ratio was the 90% SWNT-10% mw rGO electrode which achieved a specific capacitance of 306 F g-1 (3 electrode measurement calculated at 20 mV s-1). The 90% SWNT-10% mw rGO was then fabricated into a stacked electrode configuration (SEC) which significantly enhanced the electrode performance per volume (1.43 mW h cm-3, & 6.25 W cm-3). Device testing showed excellent switching capability up to 10 A g-1, and very good stability over 10000 cycles at 1.0 A g-1 with 93% capacity retention. © the Partner Organisations 2014.

Computational chemistry for graphene-based energy applications: progress and challenges.

Research in graphene-based energy materials is a rapidly growing area. Many graphene-based energy applications involve interfacial processes. To enable advances in the design of these energy materials, such that their operation, economy, efficiency and durability is at least comparable with fossil-fuel based alternatives, connections between the molecular-scale structure and function of these interfaces are needed. While it is experimentally challenging to resolve this interfacial structure, molecular simulation and computational chemistry can help bridge these gaps. In this Review, we summarise recent progress in the application of computational chemistry to graphene-based materials for fuel cells, batteries, photovoltaics and supercapacitors. We also outline both the bright prospects and emerging challenges these techniques face for application to graphene-based energy materials in future.