Poly(N,N-dimethylaminoethyl methacrylate)/graphene oxide hybrid hydrogels: pH and temperature sensitivities and Cr(VI) adsorption

Different amounts of graphene oxide (GO) were incorporated to N,N-dimethylaminoethyl methacrylate (DMAEMA), fabricating a series of pH and temperature dual sensitive PDMAEMA/GO hybrid hydrogels by in situ polymerization. Their microscopic network structures as well as swelling properties and Cr(VI) adsorption were characterized. The equilibrium swelling ratios (ESR) of hydrogels increased significantly with 0.5 wt% GO feeding of DMAEMA amount, and then decreased with further GO loading increasing. All hydrogels showed obvious deswelling when pH value of swelling mediums increased from 5 to 10 gradually. At pH 7, hydrogels revealed slight ESR increment with temperature up to 50 °C, above which obvious deswelling occurred. In pH 8 buffer, 0.5 wt% of GO loading triggered lower critical solution temperature (LCST) to decrease by 3 °C, and 2–7 °C increment was observed when 1–6 wt% of GO was loaded, as compared with that of GO-free PDMAEMA hydrogel. Cr(VI) adsorption of hydrogels was also improved by the introduction of GO to some extent, and the maximum Cr(VI) adsorption of 180 mg/g was realized, indicating that the obtained PDMAEMA/GO hybrid hydrogels possess excellent adsorption performance.     

Gelation of graphene oxides induced by different types of amino acids

We have investigated gelation of graphene oxide (GO) sheets induced by amino acids. For gelation of single layer GO sheets, six different types of amino acids were added to GO suspension as gelators. To understand gelation mechanism, we varied the concentration and type of amino acids as well as the pH of suspension, and monitored the morphology and rheological properties of reaction mixtures. Gelation was observed in acidic pH only with three types of amino acids (arginine, tryptophan, and cysteine) whereas no gel was formed at other pH values (neutral and basic). As the type of amino acid was varied, both the binding strength between amino acid and GO and the moduli (G′ and G′′) of reaction mixtures followed the same order, arginine > cysteine > tryptophan > asparagine > aspartic acid > glycine. To rationalize these results, we considered interactions between amino acid side chains and GO sheets (i.e., electrostatic interaction, π–π stacking, and hydrogen bonding), and found that the hydrogel formed by electrostatic attraction with arginine exhibited shorter gel time and larger moduli than the other samples. Finally, synthesis of GO hydrogel at physiological pH was demonstrated by increasing the concentration of GO sheets.     

High-efficiency loading of hypocrellin B on graphene oxide for photodynamic therapy

A novel hybrid of graphene oxide (GO) and hypocrellin B (HB) was prepared using a simple noncovalent method. An efficient loading of HB on GO as high as 2 mg/mg was obtained. Mechanism analysis indicated that the π–π stacking interaction is the dominant driving force in the noncovalent interaction between HB and GO. Irradiation of HB and GO hybrid (HB–GO) results in efficient generation of singlet oxygen (¹O₂). In vitro studies have demonstrated the active uptake of HB–GO into the cytosol of tumor cells. Significant damage to such impregnated tumor cells was observed upon irradiation.     

Reduction of graphite oxide to graphene with laser irradiation

Reduction of graphite oxide (GO) to graphene induced by picosecond pulsed laser irradiation has been studied by Raman spectroscopy, scanning electron microscopy together with modeling of temperature dynamics in the materials. Dependence of the D, G, and 2D Raman band parameters on the laser pulse energy and the irradiation dose was evaluated. The exponential decline of the full width at half maximum of the Raman lines with increasing product of the pulse energy and irradiation dose was observed indicating ordering in the film and reduction in the number of graphene layers during the laser treatment. The minimum concentration of structural defects and the largest relative intensity of the 2D peak were found for the 50 mW mean laser power and the 30 mm/s scanning speed. Modeling of temperature dynamics revealed that the temperature of the GO film irradiated with a single laser pulse at a fluence of 0.04 J/cm² (50 mW) increased up to 1400 °C for a few nanoseconds, which was sufficient for the effective reduction of GO to graphene with successive laser pulses.     

Tuning the catalytic property of non-noble metallic impurities in graphene

The stable configuration, electronic structure, magnetic property and catalytic activity of single-atom non-noble-metal (NNM) catalysts on graphene are investigated using the first-principles method. In contrast to the pristine graphene, a vacancy defect in graphene strongly stabilises the NNM adatom and makes it more positively charged. The charging leads to the CO adsorption unfavourable, while facilitate the O₂ adsorption, thus alleviating the CO poisoning and improving the reaction possibility for CO oxidation. Besides, there are more electrons transferred between NNM doped-graphene and O₂ molecule, which enhance their interaction and induce changes in the electronic structures and magnetic properties of the systems. Moreover, the sequential processes of CO oxidation on the Co–, Al– and Zn–graphene systems have lower enough energy barriers (<0.4 eV) by the Langmuir–Hinshelwood (LH) reaction (CO + O₂ → OOCO → CO₂ + O_ads) than that on the Ni–graphene substrate. Among the reaction processes, the rate-controlling step is the breaking of the O–O bond of the OOCO complex to form the CO₂ molecule and the atomic O_ads. The results validate the reactivity of NNM catalysts at the atomic scale and initiate a clue for fabricating graphene-based catalysts with low cost and high activity.     

An efficient method of producing stable graphene suspensions with less toxicity using dimethyl ketoxime

A highly stable graphene suspension has been prepared using dimethyl ketoxime (DMKO) as reductant. Nitrogen was doped into the graphene plane at the same time as the graphene oxide (GO) sheets were reduced. X-ray photoelectron spectroscopy indicated that the C/O ratio of graphene was significantly increased after GO was treated with DMKO and the quantity of nitrogen incorporated into the graphene lattice was 3.67 at.%. The electrical conductivity of the graphene paper was found to be ～10² S m^?1, which was 5 orders of magnitude better than that of GO, and this demonstrated the effective chemical reduction of GO. The mechanism of the chemical reaction of GO with DMKO was also discussed. The as-produced graphene material showed good capacitive behavior and long cycle life with a specific capacitance of ～140 F g^?1.     

Enhancing polymer/graphene oxide gas barrier film properties by introducing new crystals

A transparent, gas barrier film comprised of poly(vinyl alcohol) (PVA) and graphene oxide (GO) is synthesized through combined methods of solution blending and isothermal recrystallization. The recrystallized PVA/GO film with only 0.07 vol% GO gives an O₂ transmission rate <0.005 cc m⁻² day⁻¹ and an O₂ permeability <5.0 × 10⁻²⁰ cm³ cm cm⁻² Pa⁻¹ s⁻¹; hence, it is far superior to other blend polymer/inorganic composites. The excellent O₂ barrier properties are attributed to a unique hybrid of PVA crystals and GO sheets. PVA crystals form around the GO during isothermal recrystallization, indicating that a GO sheet can act as a nucleating agent. The newly formed PVA crystals fill in the spaces between the GO sheets, and together they become ultra-large impermeable regions, which can prevent the passage of O₂. The hybrid film has potential applications in flexible electronics, pharmaceuticals, and food packaging.     

Hydrous-ferric oxide nanorods grown on PEGylated graphene oxide with superior capacity for selective adsorption of albumin

A ferrate functionalized graphene-based composite is prepared by growth of hydrous ferric oxide (FeOOH) on the polyethylene glycol (PEG) modified graphene oxide (GO) sheets. The obtained GO–PEG–FeOOH composite is characterized by ATR-FTIR, TEM, AFM, XPS and ICP-MS. The PEGylation significantly changes the surface property of the bare graphene oxide, which not only generates a nano-bio-interface for protein interaction but also reduces the non-specific adsorption of proteins. The PEGylation and growth of FeOOH nanorods on GO sheets obviously enhanced the selectivity toward the adsorption of albumin through strong hydrogen bonding interaction, exhibiting an ultra-high adsorption capacity of 1377.4 mg g⁻¹ for bovine serum albumin (BSA). It is obviously higher than those achieved by any hitherto reported graphene based materials and other carbon nanomaterials. Albumin retained by the composite could be effectively recovered with a 4.0 mM B–R buffer through the affinity of boronic acid toward protein, giving rise to a recovery of 70%. Circular dichroism (CD) spectra indicate no conformational change for BSA during the process of adsorption/desorption. The practical applicability of the GO nanocomposite is further demonstrated by the selective adsorption/isolation of albumin from complex biological samples matrixes, e.g., human whole blood.     

Spillover enhanced hydrogen storage in Pt-doped MOF/graphene oxide composite produced via an impregnation method

Pt-doped MOF/graphene oxide (GO) composites were synthesized via a colloidal Pt nanoparticle (NP) incipient-wetness impregnation method for the first time. The composites Pt@HKUST-1/GO and Pt@ZIF-8/GO were characterized by X-ray diffraction, electron microscopy and gas adsorption. The hydrogen uptakes of both composites at 298 K and 860 mm Hg were enhanced by a factor of 3.6 or 4.1 compared to MOFs, although Pt NPs were obviously aggregated throughout MOF/GO networks. This significant enhancement is mainly attributed to the combination of high porosities of MOF/GO supports and hydrogen spillover mechanism, in which Pt NPs and MOF/GO act as dissociation source and receptor, respectively.     

Three-dimensional hybrid materials of fish scale-like polyaniline nanosheet arrays on graphene oxide and carbon nanotube for high-performance ultracapacitors

Three-dimensional (3D) hybrid materials composed of 2D fish scale-like polyaniline (PANI) nanosheet arrays on graphene oxide sheets and carbon nanotubes were synthesized by a one-step process using a simplified template-free polymerization method. PANI nanosheet growth is proposed to be accomplished through electrostatic interaction, hydrogen bonding, and π–π stacking interaction. Such a material exhibits specific capacitances of 589 and 413 F g⁻¹ at 0.2 and 5 A g⁻¹, respectively, compared to pristine PANI of 397 and 180 F g⁻¹. After 1000 cycles, the composite still retains 81% of its initial capacitance, while PANI retains only 48%.     

Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids

We report a simple but highly-effective hydrohalic acid reducing method to reduce graphene oxide (GO) films into highly conductive graphene films without destroying their integrity and flexibility at low temperature based on the nucleophilic substitution reaction. GO films reduced for 1 h at 100 °C in 55% hydroiodic (HI) acid have an electrical conductivity as high as 298 S/cm and a C/O ratio above 12, both of which are much higher than films reduced by other chemical methods. The reduction maintains good integrity and flexibility, and even improves the strength and ductility, of the original GO films. Based on this reducing method, a flexible graphene-based transparent conductive film with a sheet resistance of 1.6 kΩ/sq and 85% transparency was obtained, further verifying the advantage of HI acid reduction.     

One-pot synthesized multi-functional graphene oxide as a water-tolerant and efficient metal-free heterogeneous catalyst for cycloaddition reaction

A series of functional graphene oxide (F-GO) materials were prepared by silylanization of graphene oxide (GO) with chlorine-terminal silanes and subsequent nucleophilic substitution reaction with tertiary amine in a one-pot approach. The quaternary ammonium salt was generated and immobilized simultaneously in situ, and the primary amine is beneficial to improve the number of surface functionalities on GO. This is the first time that a multi-functional GO material was designed, prepared and used for the synthesis of cyclic carbonates through the cycloaddition of carbon dioxide (CO₂) to epoxides. The F-GO catalyst can be easily separated and reused for at least five times without significant loss of activity (TOF = 46.4 h⁻¹). The excellent performance is attributed to the synergetic effect of silanol group and halide anion for ring opening of epoxide as well as the role of amine for CO₂ adsorption and activation. A possible mechanism is proposed for the cycloaddition reaction over F-GO.     

Temperature and face dependent copper–graphene interactions

The interaction between graphene and metals represents an important issue for the large-area preparation of graphene, graphene transfer and the contact quality in graphene devices. We demonstrate a simple method for estimating and manipulating the level of interaction between graphene and copper single crystals through heat treatment, at temperatures from 298 K to 1073 K. We performed in-situ Raman spectroscopy showing Cu face-specific behavior of the overlying graphene during the heat treatment. On Cu(1 1 1) the interaction is consistent with theoretical predictions and remains stable, whereas on Cu(1 0 0) and Cu(1 1 0), the initially very weak interaction and charge transfer can be tuned by heating. Our results also suggest that graphene grown on Cu(1 0 0) and Cu(1 1 0) is detached from the copper substrate, thereby possibly enabling an easier graphene transfer process as compared to Cu(1 1 1).     

Rapid and non-destructive identification of graphene oxide thickness using white light contrast spectroscopy

By white light contrast spectroscopy, we have successfully identified number of graphene oxide (GO) layers (⩽10 layers) and obtained a new refractive index of GO sheets (⩽10 layers) of n_GO = 1.2–0.24i. For few layers (⩽10 layers) GO sheets, both the contrast at ∼580 nm wavelength and the Raman intensity of G band linearly increase with the increase of the layer numbers. However, due to the laser induced heating effects and the requirement of a reference Raman spectrum in Raman spectroscopy measurements, contrast spectroscopy is non-destructive and more efficient. Simulations based on the Fresnel’s equations agree well with evolution of the contrast and G band intensity as a function of number of layers. The precise refractive index of GO obtained in this work can be widely used in further study of GO. Therefore, our experimental contrast values can be directly used as a standard to identify the thickness of GO on Si substrate with 300 nm SiO₂ capping layer, which paves a novelty way towards future fundamental research and applications of graphene-based materials.     

Preparation of porous carbon nanofibers derived from graphene oxide/polyacrylonitrile composites as electrochemical electrode materials

Porous carbon nanofibers (CNFs) derived from graphene oxide (GO) were prepared from the carbonization of electrospun polyacrylonitrile nanofibers with up to 15 wt.% GO at 1200 °C, followed by a low-temperature activation. The activated CNFs with reduced GOs (r-GO) revealed a specific surface area and adsorption capacity of 631 m²/g and 191.2 F/g, respectively, which are significantly higher than those of pure CNFs (16 m²/g and 3.1 F/g). It is believed that rough interfaces between r-GO and CNFs introduce oxygen pathways during activation, help to produce large amounts of all types of pores compared to pure activated CNFs.     

High peroxidase catalytic activity of exfoliated few-layer graphene

Few-layer graphene prepared from graphite exfoliated by chitosan has a preserved structure without oxidation or destruction of the sp² character of the carbon plane and exhibits a higher peroxidase catalytic activity than that of graphene oxide (GO) and its reduced form. The peroxidase catalytic activity of as-obtained few-layer graphene is 45 times higher than that of GO and 4 times higher than that of reduced GO with the same concentration of 30 μg mL⁻¹ and the detection limit of hydrogen peroxide is 10 nM. The excellently catalytic performance can be attributed to the fast electron transfer on the surface of few-layer graphene, which is further confirmed by electrochemical characterization. The as-prepared few-layer graphene has been used to determine hydrogen peroxide in three real water samples with satisfactory results.     

Electrochemically synthesized graphene/polypyrrole composites and their use in supercapacitor

Composite films consisting of polypyrrole (PPy) and graphene oxide (GO) were electrochemically synthesized by electrooxidation of 0.1 M pyrrole in aqueous solution containing appropriate amounts of GO. Simultaneous chronoamperometric growth profiles and frequency changes on a quartz crystal microbalance showed that the anionic GO was incorporated in the growing GO/PPy composite to maintain its electrical neutrality. Subsequently, the GO was reduced electrochemically to form a reduced GO/PPy (RGO/PPy) composite by cyclic voltammetry. Specific capacitances estimated from galvanostatic discharge curves in 1 M H₂SO₄ at a current density of 1 A g^?1 indicated that values for the RGO/PPy composite were larger than those of a pristine PPy film and the GO/PPy composite. In the case of 6 mg mL^?1 GO for the preparation of GO/PPy, a high specific capacitance of 424 F g^?1 obtained at the electrochemically prepared RGO/PPy composite indicated its potential for use as an electrode material for supercapacitors.     

Grand canonical Monte Carlo simulations of nitrogen adsorption on graphene materials with varying layer number

Fabrication of monolayer graphene is a challenge and many processes yield few-layer or multi-layer graphene materials instead. The layer number is an important property of those materials and a quality control variable in graphene manufacture. We demonstrated that N₂ adsorption on graphene materials was used to distinguish its layer number. We performed grand canonical Monte Carlo simulation of N₂ adsorption on graphene materials with 1–10 layers to indicate the possibility of distinction of layer number by evaluating the dependence of N₂ adsorption characteristics on the layer number of graphene materials as well as the adsorption mechanism. The threshold relative pressures of monolayer adsorption of N₂ on monolayer and two-layer graphene were 1 × 10⁻³ and 2 × 10⁻⁴, respectively, while those of the others were 1 × 10⁻⁴. In contrast, the threshold pressures of second layer adsorption of N₂ were similar to each other. The difference of threshold pressures is attributed to stabilized energies induced by interactions with graphene materials. Therefore, the layer number of graphene materials could be evaluated from the threshold pressures of adsorption, providing a guide to aid fabrication of graphene materials.     

The size and dispersion effect of modified graphene oxide sheets on the photocatalytic H2 generation activity of TiO2 nanorods

Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO₃, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO₂ nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO₂, GO–COOH–TiO₂ and NGO–TiO₂ composites are used in a comparative study of photocatalytic H₂ generation activity under UV light irradiation. The H₂ generation rate of TiO₂ nanorods was slightly increased from 15 to 30 mL h⁻¹ g⁻¹ by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h⁻¹ g⁻¹ after combining with GO sheets. The further comparative study shows that GO–COOH–TiO₂ composite has higher H₂ generation rate of 180 mL h⁻¹ g⁻¹ than that of GO–TiO₂ and NGO–TiO₂ composites.     

Effect of graphene addition on the mechanical and electrical properties of Al2O3-SiCw ceramics

This paper presents a study on graphene-reinforced Al₂O₃-SiCw ceramic composites and the relationship between graphene oxide (GO) loading and the resulting mechanical and electrical properties. Well-dispersed ceramic-GO powders were fabricated using a colloidal processing route. Dense composites were obtained via spark plasma sintering, a technique that has the ability to reduce GO to graphene in situ during the sintering process. The mechanical properties of the sintered composites were investigated. The composite with only a small amount of graphene (0.5 vol.%) showed the highest flexural strength (904 ± 56 MPa), fracture toughness (10.6 ± 0.3 MPa·m^1/2) and hardness (22 ± 0.8 GPa) with an extremely good dispersion of graphene within the ceramic matrix. In addition to these exceptional mechanical properties, the sintered composites also showed high electrical conductivity, which allows the compacts to be machined using electrical discharge machining and thus facilitates the fabrication of ceramic components with sophisticated shapes while reducing machining costs.