Graphene Oxide: Surface Activity and Two‐Dimensional Assembly

Graphene oxide (GO) is a promising precursor for preparing graphene‐based composites and electronics applications. Like graphene, GO is essentially one‐atom thick but can be as wide as tens of micrometers, resulting in a unique type of material building block, characterized by two very different length scales. Due to this highly anisotropic structure, the collective material properties are highly dependent on how these sheets are assembled. Therefore, understanding and controlling the assembly behavior of GO has become an important subject of research. In this Research News article the surface activity of GO and how it can be employed to create two‐dimensional assemblies over large areas is discussed.     

Highly controllable and green reduction of graphene oxide to flexible graphene film with high strength

Graphene film with high strength was fabricated by the assembly of graphene sheets derived from graphene oxide (GO) in an effective and environmentally friendly approach. Highly controllable reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant, in which the reduction process was monitored by XRD analysis and UV–vis absorption spectra. Self-assembly of the as-made CCG sheets results in a flexible CCG film. This method may open an avenue to the easy and scalable preparation of graphene film with high strength which has promising potentials in many fields where strong, flexible and electrically conductive films are highly demanded.     

Principles Governing Control of Aggregation and Dispersion of Graphene and Graphene Oxide in Polymer Melts

Controlling the structure of graphene and graphene oxide (GO) phases is vitally important for any of its widespread intended applications: highly ordered arrangements of nanoparticles are needed for thin-film or membrane applications of GO, dispersed nanoparticles for composite materials, and 3D porous arrangements for hydrogels. By combining coarse-grained molecular dynamics and newly developed accurate models of GO, the driving forces that lead to the various morphologies are resolved. Two hydrophilic polymers, poly(ethylene glycol) (PEG) and poly(vinyl alcohol) (PVA), are used to illustrate the thermodynamically stable morphologies of GO and relevant dispersion mechanisms. GO self-assembly can be controlled by changing the degree of oxidation, varying from fully aggregated over graphitic domains to intercalated assemblies with polymer bilayers between sheets. The long-term stability of a dispersion is extremely important for many commercial applications of GO composites. For any degree of oxidation, GO does not disperse in PVA as a thermodynamic equilibrium product, whereas in PEG dispersions are only thermodynamically stable for highly oxidized GO. These findings—validated against the extensive literature on GO systems in organic solvents—furnish quantitative explanations for the empirically unpredictable aggregation characteristics of GO and provide computational methods to design directed synthesis routes for diverse self-assemblies and applications.     

Thermally stable and highly conductive free-standing hybrid films based on reduced graphene oxide

Thermally stable and highly conductive films have been prepared based on thermally reduced graphene oxide and exfoliated α-zirconium phosphate nanoplatelet (ZrP) hybrids. Exfoliated ZrP and graphene oxide (GO) were first mixed in aqueous solution to form a stable dispersion and then cast into free-standing films through flow-directed assembly. Upon annealing at 750 °C in Argon atmosphere, significant amounts of oxidized species were removed from the GO and a noticeable recovery of sp² structure of the reduced GO sheets was observed. With the incorporation of the inorganic nanoplatelets, the thermal stability and structural integrity of the hybrid films were greatly improved, while the good electrical conductivity of the reduced GO was maintained. Potential applications for graphene-based hybrid films based on the current approach are discussed.     

Self‐Assembly of Graphene Oxide at Interfaces

Due to its amphiphilic property, graphene oxide (GO) can achieve a variety of nanostructures with different morphologies (for example membranes, hydrogel, crumpled particles, hollow spheres, sack‐cargo particles, Pickering emulsions, and so on) by self‐assembly. The self‐assembly is mostly derived from the self‐concentration of GO sheets at various interfaces, including liquid‐air, liquid‐liquid and liquid‐solid interfaces. This paper gives a comprehensive review of these assembly phenomena of GO at the three types of interfaces, the derived interfacial self‐assembly techniques, and the as‐obtained assembled materials and their properties. The interfacial self‐assembly of GO, enabled by its fantastic features including the amphiphilicity, the negatively charged nature, abundant oxygen‐containing groups and two‐dimensional flexibility, is highlighted as an easy and well‐controlled strategy for the design and preparation of functionalized carbon materials, and the use of self‐assembly for uniform hybridization is addressed for preparing hybrid carbon materials with various functions. A number of new exciting and potential applications are also presented for the assembled GO‐based materials. This contribution concludes with some personal perspectives on future challenges before interfacial self‐assembly may become a major strategy for the application‐targeted design and preparation of functionalized carbon materials.     

Controllable Bipolar Doping of Graphene with 2D Molecular Dopants

The fine control of graphene doping levels over a wide energy range remains a challenging issue for the electronic applications of graphene. Here, the controllable doping of chemical vapor deposited graphene, which provides a wide range of energy levels (shifts up to ± 0.5 eV), is demonstrated through physical contact with chemically versatile graphene oxide (GO) sheets, a 2D dopant that can be solution‐processed. GO sheets are a p‐type dopant due to their abundance of electron‐withdrawing functional groups. To expand the energy window of GO‐doped graphene, the GO surface is chemically modified with electron‐donating ethylene diamine molecules. The amine‐functionalized GO sheets exhibit strong n‐type doping behaviors. In addition, the particular physicochemical characteristics of the GO sheets, namely their sheet sizes, number of layers, and degree of oxidation and amine functionality, are systematically varied to finely tune their energy levels. Finally, the tailor‐made GO sheet dopants are applied into graphene‐based electronic devices, which are found to exhibit improved device performances. These results demonstrate the potential of GO sheet dopants in many graphene‐based electronics applications.     

A Cut‐and‐Paste Approach to 3D Graphene‐Oxide‐Based Architectures

Properly cut sheets can be converted into complex 3D structures by three basic operations including folding, bending, and pasting to render new functions. Folding and bending are extensively employed in crumpling, origami, and pop‐up fabrications for 3D structures. Pasting joins different parts of a material together, and can create new geometries that are fundamentally unattainable by folding and bending. However, it has been much less explored, likely due to limited choice of weldable thin film materials and residue‐free glues. Here it is shown that graphene oxide (GO) paper is one such suitable material. Stacked GO sheets can be readily loosened up and even redispersed in water, which upon drying, restack to form solid structures. Therefore, water can be utilized to heal local damage, glue separated pieces, and release internal stress in bent GO papers to fix their shapes. Complex and dynamic 3D GO architectures can thus be fabricated by a cut‐and‐paste approach, which is also applicable to GO‐based hybrid with carbon nanotubes or clay sheets.     

Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties

The chemically stitched graphene oxide (GO) sheets were obtained using a click chemistry reaction between azide-functionalized GO and alkyne-functionalized GO. The click coupled GO (GO-click-GO) sheets showed the largely increased electrical conductivity and near infrared laser-induced photothermal properties compared to the GO sheets, which result from formation of triazole ring as a bridging linker between the GO sheets. The polyurethane (PU) nanocomposites incorporating the GO-click-GO sheets exhibited enhanced mechanical properties of breaking stress and modulus than the GO/PU nanocomposites. The modulus of GO-click-GO/PU nanocomposites was higher than that of the GO/PU nanocomposites at the same filler loading of 0.1 and 0.5 wt%. The GO-click-GO/PU nanocomposites also showed a significantly improved photothermal properties compared to the GO/PU nanocomposites at the same filler loading. The click coupled stitched GO sheets in this study can be used as the superior reinforcing fillers for mechanically and photothermally high performance polymer nanocomposites.     

Wrapping Graphene Sheets Around Organic Wires for Making Memory Devices

Hybrids of organic semiconductors and graphene can generate a whole new class of materials with enhanced properties. A simple solution‐phase route to synthesize a hybrid material made of organic nanowires and graphene oxide (GO) sheets is demonstrated by sonicating tetracene molecules and GO together in diluted fuming nitric acid. The self‐assembled tetracene‐derived organic wires become encapsulated by GO sheets during the reaction to produce an interconnected, one‐dimensional/two‐dimensional lamellar film. Memory devices fabricated using the hybrid film as the sandwiched layer between aluminum electrodes exhibit excellent electrical bistability. The charge retention properties are attributed to charge transfer and a charge‐trapping/detrapping mechanism operational at the interfaces and isolated matrices of the GO–tetracene hybrid.     

Scaly Graphene Oxide/Graphite Fiber Hybrid Electrodes for DNA Biosensors

The demand for a highly sensitive and stable DNA biosensor that can be used for implantable or on‐time monitoring is constantly increasing. In this work, for the first time graphene oxide (GO) sheets are synthesized in situ at the surface of graphite fibers to yield scaly GO/graphite fiber hybrid electrodes. The partially peeled GO sheets, directly connected with the graphite fibers, not only provide a large number of binding sites for single‐stranded DNA, but also favor high electron transfer rates from GO to the graphite fibers. Cyclic voltammetry (CV) confirms that the scaly GO/graphite fiber hybrid electrode has excellent electrochemical activity. As a working electrode in an electrochemical impedance DNA biosensor, the fiber hybrid electrode exhibits high selectivity, sensitivity, and stability. Due to its simplicity, low cost, high stability, small size, and unique microfiber morphology, the scaly GO/graphite fiber hybrid electrode is an excellent candidate for an implantable biosensor. The method developed here could have a profound impact on the design of GO‐based biosensors for DNA detection.     

One-step synthesis of reduced graphite oxide–silver nanocomposite

Here, a general approach for the preparation of reduced graphite oxide (rGO)–silver nanocomposite has been investigated. Graphite oxide (GO) sheets are used as the nanoscale substrates for the formation of rGO–silver composite. GO sheets and Ag ions can be reduced at the same time, under a mild condition using l-ascorbic acid (l-AA) as reducing agent. This simple approach should find practical applications in the production of rGO–silver nanocomposite. The SEM analysis indicates that the silver particles are dispersed on graphene sheets. Raman signals of rGO in the composite are increased by the attached silver nanoparticles, displaying surface-enhanced Raman scattering activity. The degree of enhancement can be adjusted by varying the quantity of silver nanoparticles in the composite. In addition, antibacterial activity of the composite against Escherichia coli was evaluated using zone of inhibition. Composites with Ag clearly showed antibacterial activity against E. coli. While GO alone has almost no effect against this bacteria.     

In situ thermal preparation of polyimide nanocomposite films containing functionalized graphene sheets

Graphene oxides (GO) were exfoliated in N,N-dimethylformamide by simple sonication treatment of the as-prepared high quality graphite oxides. By high-speed mixing of the pristine poly(amic acid) (PAA) solution with graphene oxide suspension, PAA solutions containing uniformly dispersed GO can be obtained. Polyimide (PI) nanocomposite films with different loadings of functionalized graphene sheets (FGS) can be prepared by in situ partial reduction and imidization of the as-prepared GO/PAA composites. Transmission electron microscopy observations showed that the FGS were well exfoliated and uniformly dispersed in the PI matrix. It is interesting to find that the FGS were highly aligned along the surface direction for the nanocomposite film with 2 wt % FGS. Tensile tests indicated that the mechanical properties of polyimide were significantly enhanced by the incorporation of FGS, due to the fine dispersion of high specific surface area of functionalized graphene nanosheets and the good adhesion and interlocking between the FGS and the matrix.     

Fabrication of ultrahigh hydrogen barrier polyethyleneimine/graphene oxide films by LBL assembly fine-tuned with electric field application

In this study, layer-by-layer self-assembly of polyethyleneimine (PEI)/graphene oxide (GO) was successfully controlled by an applied electric field. The influences of the applied electric field direction, voltage, and dipping time on the hydrogen barrier properties of PEI/GO self-assembled film were investigated. Ultraviolet–visible light absorption spectroscopy, ellipsometry, atomic force microscopy, and scanning electron microscopy were used to analyze the effects of the electric field on the growth, nanostructure, and micromorphology of the self-assembled film. Results indicated that an applied electric field accelerates the adsorption rate of assembly and increases the GO adsorption quantity. Additionally, such electric field modifies the composite structure of the self-assembled film and spreads out the GO sheets uniformly on the substrate, which results in the formation of a more compact and ordered gas barrier layer with significantly improved hydrogen barrier properties. Higher applied voltage results in a more noticeable field effect. Under 25 V, the hydrogen transmission rate of the PEI/GO self-assembled 10-layer film reached 81 cm³/m² 24 h 0.1 MPa, which was 65% lower than that of standard composite films prepared without using an electric field.     

Using Graphene Oxide to Enhance the Barrier Properties of Poly(lactic acid) Film

The ultra‐thin (polyethyleneimine/graphene oxide)_n [(PEI/GO)_n]multilayer films on poly(lactic acid) (PLA) were constructed via the layer‐by‐layer assembly. Here, the electrostatic interactions between PEI and GO were used to obtain the nanoscale composite membrane of (PEI/GO)_n on the surface of PLA film. With the number of assembling layers increased, the oxygen permeability (PO₂) of PLA film decreased substantially. As a 0.06 wt% GO solution was used with only four layers, the PO₂ decreased from 53.8 to 0.377 × 10^?4 cm³/m²/d/Pa, only 0.7% of the original PLA film. At the same time, the coated PLA film also presented a good transparency and better mechanical properties. It is a novel way to use GO on biodegradable packaging materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double‐Emulsion Drops

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer‐graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double‐emulsion drops by osmotic‐pressure‐driven water pumping, PVA‐tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol–gel transition. Therefore, the PVA–GO composite remains undissolved when it is directly exposed to water by oil‐shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel‐forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.     

Design of 3D Graphene‐Oxide Spheres and Their Derived Hierarchical Porous Structures for High Performance Supercapacitors

Graphene‐oxide (GO) based porous structures are highly desirable for supercapacitors, as the charge storage and transfer can be enhanced by advancement in the synthesis. An effective route is presented of, first, synthesis of three‐dimensional (3D) assembly of GO sheets in a spherical architecture (GOS) by flash‐freezing of GO dispersion, and then development of hierarchical porous graphene (HPG) networks by facile thermal‐shock reduction of GOS. This leads to a superior gravimetric specific capacitance of ≈306 F g⁻¹ at 1.0 A g⁻¹, with a capacitance retention of 93% after 10 000 cycles. The values represent a significant capacitance enhancement by 30–50% compared with the GO powder equivalent, and are among the highest reported for GO‐based structures from different chemical reduction routes. Furthermore, a solid‐state flexible supercapacitor is fabricated by constructing the HPG with polymer gel electrolyte, exhibiting an excellent areal specific capacitance of ≈220 mF cm⁻² at 1.0 mA cm⁻² with exceptional cyclic stability. The work reveals a facile but efficient synthesis approach of GO‐based materials to enhance the capacitive energy storage.     

Large-area blown bubble films of aligned nanowires and carbon nanotubes

Many of the applications proposed for nanowires and carbon nanotubes require these components to be organized over large areas with controlled orientation and density. Although progress has been made with directed assembly and Langmuir-Blodgett approaches, it is unclear whether these techniques can be scaled to large wafers and non-rigid substrates. Here, we describe a general and scalable approach for large-area, uniformly aligned and controlled-density nanowire and nanotube films, which involves expanding a bubble from a homogeneous suspension of these materials. The blown-bubble films were transferred to single-crystal wafers of at least 200 mm in diameter, flexible plastics sheets of dimensions of at least 225 x 300 mm(2) and highly curved surfaces, and were also suspended across open frames. In addition, electrical measurements show that large arrays of nanowire field-effect transistors can be efficiently fabricated on the wafer scale. Given the potential of blown film extrusion to produce continuous films with widths exceeding 1 m, we believe that our approach could allow the unique properties of nanowires and nanotubes to be exploited in applications requiring large areas and relatively modest device densities.     

Rapid and effective functionalization of graphene oxide by ionic liquid

Functionalized graphene oxide (DDIB-GO) sheets, which can be homogeneously distributed into ortho-dichlorobenene, were obtained via rapid and effective covalent functionalization with imidazolium ionic liquids (1,3-didodecylimidazolium bromine) through ion exchange. The resulting DDIB-GO sheets were characterized by Fourier transform infrared spectroscopy (FTIR), UV Vis NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), Atomic force microscopy (AFM). Furthermore, FTIR, XPS and TGA show that the 1,3-didodecylimidazolium have been covalently attached to the GO sheets. UV Vis NIR, TEM, and AFM demonstrate that after functionalization, the size and shape of DDIB-GO sheets had little change compared with GO sheets and it was mostly dispersed in single layer. And good electronic conductivity of the film prepared from DDIB-GO in ODCB was obtained after high temperature annealing.     

An electrochemical route to graphene oxide

Large-scale graphene oxide (GO) with adjustable resistivity was synthesized from graphite via an electrochemical method using KCl solution as an effective electrolyte. During the exfoliation process, electrostatic force intercalates chloride ions between the expanded graphite layers on the anode. These chloride ions form small gas bubbles between the graphite layers in the electrochemical reaction. It is believed that the gas bubbles expand the gap between graphite sheets and produce a separating force between adjacent graphene layers. This separating force overcomes the Van der Waals force between adjacent sheets and exfoliates graphene layers from the starting graphite. Because the graphene is electrochemically oxidized by chorine during the exfoliation, the exfoliated GO sheets are hydrophilic and easily dispersed in the electrolyte solution. The GO solution prepared by the electrochemical exfoliation can be simply sprayed or spin-coated onto any substrate for device applications. The measured average thicknesses of a monolayer, bilayer, and trilayer exfoliated GO on SiO2 substrate were 1.9, 2.8, and 3.9 nm, respectively. It was observed that the measured resistance of the exfoliated GO sheets increases due to electrochemical oxidation in the solution. This electrochemical approach offers a low-cost and efficient route to the fabrication of graphene based devices.     

Reconfigurable Chiral Self‐Assembly of Peptides through Control of Terminal Charges

Self‐assembly of chiral nanostructures is of considerable interest, since the ability to control the chirality of these structures has direct ramifications in biology and materials science. A new approach to design chiral nanostructures from self‐assembly of N‐(9‐fluorenylmethoxycarbonyl)‐protected phenylalanine‐tryptophan‐lysine tripeptides is reported. The terminal charges can induce helical twisting of the assembled β‐sheets, enabling the formation of well‐defined chiral nanostructures. The degree and direction of twisting in the β‐sheets can be precisely tailored through in situ pH and temperature modulations. This enables the assembly of reconfigurable chiral nanomaterials with easily adjustable size and handedness. These results offer new insight into the mechanism of helical twist formation, which may enable the precise assembly of highly dynamical materials with potential applications in biomedicine, chiroptics, and chiral sensing.