Structural,magnetic, and textural properties of iron oxide-reduced graphene oxide hybrids and their use for the electrochemical detection of chromium

Superparamagnetic Fe₃O₄ nanoparticles were anchored on reduced graphene oxide (RGO) nanosheets by co-precipitation of iron salts in the presence of different amounts of graphene oxide (GO). A pH dependent zeta potential and good aqueous dispersions were observed for the three hybrids of Fe₃O₄ and RGO. The structure, morphology and microstructure of the hybrids were examined by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, Raman and X-ray photoelectron spectroscopy. TEM images reveal lattice fringes (d₃₁₁ = 0.26 nm) of Fe₃O₄ nanoparticles with clear stacked layers of RGO nanosheets. The textural properties including the pore size distribution and loading of Fe₃O₄ nanoparticles to form Fe₃O₄–RGO hybrids have been controlled by changing the concentration of GO. An observed maximum (～10 nm) in pore size distribution for the sample with 0.25 mg ml^?1 of GO is different from that prepared using 1.0 mg ml^?1 GO. The superparamagnetic behavior is also lost in the latter and it exhibits a ferrimagnetic nature. The electrochemical behavior of the hybrids towards chromium ion was assessed and a novel electrode system using cyclic voltammetry for the preparation of an electrochemical sensor platform is proposed. The textural properties seem to influence the electrochemical and magnetic behavior of the hybrids.     

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.     

Highly thermal conductive composites with polyamide-6 covalently-grafted graphene by an in situ polymerization and thermal reduction process

The thermal conductive polyamide-6/graphene (PG) composite is synthesized by in situ ring-opening polymerization reaction using ε-caprolactam as the monomer, 6-aminocaproic acid as the initiator and reduced graphene oxide (RGO) as the thermal conductive filler. The generated polyamide-6 (PA6) chains are covalently grafted onto graphene oxide (GO) sheets through the “grafting to” strategy with the simultaneous thermal reduction reaction from GO to RGO. The homogeneous dispersion of RGO sheets in PG composite favors the formation of the consecutive thermal conductive paths or networks at a relatively low GO sheets loading, which improves the thermal conductivity (λ) from 0.196 W m⁻¹ K⁻¹ of neat PA6 to 0.416 W m⁻¹ K⁻¹ of PG composite with only 10 wt% GO sheets loading.     

Low-cost preparation of a conductive and catalytic graphene film from chemical reduction with AlI3

AlI₃ synthesized by I₂ and Al in ethanol was used as reductive agent to directly obtain flexible reductive graphene oxide (RGO) films with high conductivity of 5320 S/m from graphene oxide (GO) films at a low temperature of 80 °C. This reductive method has provided a low-cost and effective route for large-scale production of graphene with high catalytic activity. Structural evolution during the reduction of GO was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The RGO films served as counter electrode exhibited high electrochemical activity.     

Large scale production of highly conductive reduced graphene oxide sheets by a solvent-free low temperature reduction

A novel one-pot process that can produce freestanding reduced graphene oxide (RGO) sheets in large scale through a mechanochemical method is presented, which is based on a 1:1 adduct of hydrazine and carbon dioxide (H₃N⁺NHCO₂⁻, solid hydrazine). We were able to synthesize RGO sheets by grinding solid hydrazine with graphene oxide (GO), followed by storing the mixed powder at 50 °C for 10 min. No solvents, nor large vessels, nor post-annealing at high temperatures are required. The resulting RGO sample was characterized by elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Brunauer–Emmett–Teller measurement, thermo gravimetric analysis, Fourier transform infrared spectroscopy, solid state nuclear magnetic resonance spectroscopy, and conductivity measurement. It exhibits excellent conductivity and possesses a high specific surface area. This reduction method was successfully applied for the fabrication of inkjet-printed RGO devices on a flexible substrate.     

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.     

One-step electrodeposition synthesis of silver-nanoparticle-decorated graphene on indium-tin-oxide for enzymeless hydrogen peroxide detection

Silver-nanoparticles-decorated reduced graphene oxide (rGO) was electrodeposited on indium tin oxide (ITO) by a cyclic voltammetry method. The results of X-ray diffraction, Fourier-transform infrared transmission spectroscopy and Raman spectroscopy confirmed the simultaneous formation of cubic phase silver nanoparticles and reduction of GO through the electrodeposition process. Field emission scanning electron microscope images showed a uniform distribution of nanometer-sized silver nanoparticles with a narrow size distribution on the RGO sheets, which could only be achieved using silver ammonia complex instead of silver nitrate as precursor. The composite deposited on ITO exhibited notable electrocatalytic activity for the reduction of H₂O₂, leading to an enzymeless electrochemical sensor with a fast amperometric response time less than 2 s. The corresponding calibration curve of the current response showed a linear detection range of 0.1–100 mM (R² = 0.9992) while the limit of detection was estimated to be 5 μM.     

Dielectric and electromagnetic wave absorption properties of reduced graphene oxide/barium aluminosilicate glass–ceramic composites

BaAl₂Si₂O₈ (BAS) glass–ceramic powders were prepared by sol–gel method. Graphene oxide (GO)/BAS mixture powders were prepared by a simple mixing process of GO and BAS. Dense and uniform reduced graphene oxide (RGO)/BAS composites were fabricated by the hot-pressing of GO/BAS, which was accompanied by the in-situ thermal reduction of GO. Microstructure, phase composition, dielectric and electromagnetic wave (EM) absorption properties of RGO/BAS were investigated. The results reveal that RGO can promote the hexacelsian-to-celsian phase transformation of BAS. In the frequency range from 8 GHz to 12 GHz, the complex permittivity of RGO/BAS increases with increasing RGO content. The composite with 1.5 wt% of RGO shows good EM absorbing ability. When the sample thickness is 2.1 mm, the minimum reflection coefficient (RC) reaches −33 dB, and the effective absorption bandwidth is more than 3.1 GHz.     

Highly efficient synthesis of graphene/MnO2 hybrids and their application for ultrafast oxidative decomposition of methylene blue

A highly efficient method has been reported to fabricate the reduced graphene oxide/MnO₂ (RGO/MnO₂) hybrid materials, a kind of catalysts for oxidative decomposition of methylene blue (MB). The pristine suspension of graphene oxide/manganese sulfate (GO/MnSO₄) produced by the modified Hummers method is in situ transformed into GO/MnO₂ composites in combination with KMnO₄, and then further into RGO/MnO₂ composites by means of glucose-reduction. It is found that MnO₂ nanoparticles with the size of 20–30 nm are uniformly distributed in the structure of RGO. A series of composites with different mass ratios of RGO to MnO₂ has been proved superior catalytic activities, much higher than that of the bare MnO₂ for decomposition of MB dye in the presence of H₂O₂. Typically, 50 mL of MB (50 mg L⁻¹) can be completely decolorized and nearly 66% mineralized at 50 °C in 5 min with 10 mg of the RGO/MnO₂ hybrid. According to the adsorption–oxidation–desorption mechanism, the high activity of RGO/MnO₂ composites for decomposition of MB is closely related to the positive synergistic effect of RGO and MnO₂ with the assistance of H₂O₂.     

Synthesis and supercapacitor performance studies of N-doped graphene materials using o-phenylenediamine as the double-N precursor

N-doped graphene (NG) materials have been prepared through a one-step solvothermal reaction by using o-phenylenediamine as a double-N precursor. N-doping and reduction of graphene oxide (GO) are both achieved simultaneously during the solvothermal reaction. The results of scanning electron microscopy and high resolution transmission electron microscopy measurements indicate that NG is highly crumpled. And the N-doping is confirmed by elemental analysis, X-ray photoelectron spectroscopy, Raman spectroscopy, Fourier transformed infrared spectroscopy and ultraviolet–visible spectroscopy. The doping level of nitrogen reaches up to 7.7 atom% and the types in NG are benzimidazole-N and phenazine-N. The NG materials exhibit excellent electrochemical performance for symmetric supercapacitors with a high specific capacitance of 301 F g⁻¹ at a current density of 0.1 A g⁻¹ in 6 M KOH electrolyte, which is remarkably higher than the solvothermal products of pristine GO (210 F g⁻¹ at 0.1 A g⁻¹). The NG materials also exhibit superior cycling stability (97.1% retention) and coulombic efficiency (99.2%) after 4000 cycles, due to the high content of nitrogen atoms, unique types of nitrogen and improved electronic conductivity.     

Excellent electrocatalytic performance of Pt nanoparticles on reduced graphene oxide nanosheets prepared by a direct redox reaction between Na2PtCl4 and graphene oxide

A simple and environment-friendly method was used to prepare Pt/reduced graphene oxide (Pt/RGO) hybrids. This approach used a redox reaction between Na₂PtCl₄ and graphene oxide (GO) nanosheets and a subsequent thermal reduction of the material at 200 °C for 24 h in a vacuum oven. In contrast to other methods that use an additional reductant to prepare Pt nanoparticles, the Pt²⁺ was directly reduced to Pt⁰ in the GO solution. GO was used as the reducing agent, the stabilizing agent and the carrier. The resulting Pt/RGO hybrid was characterized by X-ray diffraction, thermo-gravimetric analysis, X-ray photoelectron spectroscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. Electrochemical measurements showed that the Pt/RGO hybrids exhibit good activity as catalysts for the electro-oxidation of methanol and ethanol in acid media. Interestingly, the Pt/RGO hybrids showed better electrocatalytic activity and stability for the oxidation of methanol than Pt/C and Pt/RGO hybrids made from other Pt precursors. This indicates that the Pt/RGO hybrids should have great potential applications in direct methanol and ethanol fuel cells.     

Increasing the antioxidant activity of green tea polyphenols in the presence of iron for the reduction of graphene oxide

An easy method for green and low-temperature (40 °C) reduction of graphene oxide (GO) by increasing the antioxidant activity of green tea polyphenols (GTPs) in the presence of iron was developed. The reduction level (obtained by X-ray photoelectron spectroscopy) and electrical conductivity (obtained by current–voltage measurement) of the GO sheets reduced by GTPs in the presence of iron were comparable to those of hydrazine-reduced GO and much better than those of the GO reduced by only GTPs (in the absence of iron) at reduction temperatures of 40–80 °C. Raman spectroscopy indicated that application of GTPs in the presence of iron, in contrast to hydrazine, resulted in better recovering of the sp²-hybridized structure of the sheets. The lasting water dispersion of the polyphenolic-reduced GO sheets in the presence of iron was assigned to π–π adsorption of Fe²⁺-polyphenol radicals on surface of the reduced sheets. A mechanism describing the role of iron in the reduction of the GO by epicatechin gallate and epigallocatechin gallate of green tea was also proposed.     

Simultaneous reduction,exfoliation, and nitrogen doping of graphene oxide via a hydrothermal reaction for energy storage electrode materials

Nitrogen (N)-doped graphene (NG) sheets were prepared using (NH₄)₂CO₃ and an aqueous dispersion of graphene oxide (GO) by an eco-friendly hydrothermal reaction. The in situ produced ammonia played an important role in the simultaneous nitrogen doping, the reduction and exfoliation of GO. The (NH₄)₂CO₃/GO mass ratio and reaction temperature were varied to investigate the effects on the N doping level. The elemental analysis determined from the X-ray photoelectron spectroscopy showed that the nitrogen content of the NG was about 10.1 at.% and the oxygen content decreased significantly due to the hydrothermal reduction of GO. The electrochemical performances of the NG sheets increased with increasing doped N content. The highest specific capacitance of 295 F g⁻¹ at a current density of 5 A g⁻¹ and the highest specific surface area of 412 m² g⁻¹ were observed with the sample processed at 130 °C. The retention of the specific capacitance was maintained at ∼89.8% after 5000 charge–discharge cycles. These results imply that NG sheets obtained by this simple eco-friendly approach are suitable for use in high performance energy storage electrode materials.     

The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites

The effect of dispersion state of graphene on mechanical properties of graphene/epoxy composites was investigated. The graphene sheets were exfoliated from graphite oxide (GO) via thermal reduction (thermally reduced GO, RGO). Different dispersions of RGO sheets were prepared with and without ball mill mixing. It was found that the composites with highly dispersed RGO showed higher glass transition temperature (T_g) and strength than those with poorly dispersed RGO, although no significant differences in both the tensile and flexural moduli are caused by the different dispersion levels. In particular, the T_g was increased by nearly 11 °C with the addition of 0.2 wt.% well dispersed RGO to epoxy. As expected, the highly dispersed RGO also produced one or two orders of magnitude higher electrical conductivity than the corresponding poorly dispersed RGO. Furthermore, an improved quasi-static fracture toughness (K_IC) was measured in the case of good dispersion. The poorly and highly dispersed RGO at 0.2 wt.% loading resulted in about 24% and 52% improvement in K_IC of cured epoxy thermosets, respectively. RGO sheets were observed to bridge the micro-crack and debond/delaminate during fracture process due to the poor filler/matrix and filler/filler interface, which should be the key elements of the toughening effect.     

Graphene oxide hole injection layer for high-efficiency polymer light-emitting diodes by using electrophoretic deposition and electrical reduction

Graphene oxide (GO) is a fascinating nanomaterial with tremendous potential for electronic devices which show high performance when the properties of GO are properly tuned like reduced graphene oxide (RGO). Here, we report a simple, cost effective and precisely controllable methods to fabricate high-quality RGO films as a hole injection layer (HIL) for high efficiency polymer light-emitting diodes (PLEDs). First, GO is electrophoretically deposited and electrically reduced to produce RGO films. The deposition and reduction of films are electrical methods; hence the thickness and the degree of reduction for GO films can be easily manipulated by controlling electrical parameters and time. The performance of PLEDs with RGO film as HIL is measured and compared with GO and (poly(3,4-ethylenedioxythiophene)polystyrene sulfonate) (AI4083), and shows better results for luminance and current density. The optimized maximum luminance and current efficiency of the PLEDs with RGO as HIL are found to be 12830 cd/m² and 3.35 cd/A, respectively.     

Synthesis and catalytic application of Pd nanoparticles in graphite oxide

Pd nanoparticles of 1–6 nm were synthesized in graphite oxide (GO) via cation exchange. The synthesis procedure involved immobilization of the precursor Pd(NH₃)₄(NO₃)₂ in GO, followed by reduction in flowing H₂. The resulting low-loaded Pd–GO material was characterized by X-ray diffraction (XRD), infrared (IR) spectroscopy and transmission electron microscopy (TEM). Structural characterization revealed that intercalation of the precursor took place in GO and the reduced Pd nanoparticles were situated both on the external surface and in the interlamellar space of the GO lamellae. The catalytic behaviour of Pd–GO was investigated in the liquid-phase hydrogenations of 3-hexyne and 4-octyne under standard conditions. For both reactants, marked turnover frequencies (18–36 s^?1) and pronounced (Z)-alkene stereoselectivities (93–98.4%) were obtained, indicating that Pd–GO was a highly active and stereoselective catalyst. For the stereoselective hydrogenation of 3-hexyne, Pd–GO exhibited an outstanding catalytic performance: at reactant:Pd (S:Pd) ratios ? 5000, complete conversions were achieved in 8–15 min and the (Z)-alkene stereoselectivities exceeded 98%.     

Synthesis of bimetallic PtPd nanocubes on graphene with N,N-dimethylformamide and their direct use for methanol electrocatalytic oxidation

Bimetallic PtPd nanocubes supported on graphene nanosheets (PtPdNCs/GNs) were prepared by a rapid, one-pot and surfactant-free method, in which N,N-dimethylformamide (DMF) was used as a bi-functional solvent for the reduction of both metal precursors and graphene oxide (GO) and for the surface confining growth of PtPdNCs. The morphology, structure and composition of the thus-prepared PtPdNCs/GNs were characterized by transmission electron microscopy (TEM), high resolution TEM, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Because no surfactant or halide ions were involved in the proposed synthesis, the prepared PtPdNCs/GNs were directly modified onto a glassy carbon electrode and showed high electrocatalytic activity for methanol oxidation in cyclic voltammetry without any pretreatments. Moreover, with the synergetic effects of Pt and Pd and the enhanced electron transfer by graphene, the PtPdNCs/GNs composites exhibited higher electrocatalytic activity (j_p = 0.48 A mg⁻¹) and better tolerance to carbon monoxide poisoning (I_f/I_b = 1.27) compared with PtPd nanoparticles supported on carbon black (PtPdNPs/C) (j_p = 0.28 A mg⁻¹; I_f/I_b = 1.01) and PtNPs/GNs (j_p = 0.33 A mg⁻¹; I_f/I_b = 0.95). This approach demonstrates that the use of DMF as a solvent with heating is really useful for reducing GO and metal precursors concurrently for preparing clean metal–graphene composites.     

Hydrogen-assisted pulsed KrF-laser irradiation for the in situ photoreduction of graphene oxide films

We report on the use of pulsed KrF-laser irradiation for the in situ reduction of graphene oxide (GO) films under both vacuum and partial hydrogen pressure. By exposing GO films to 500 pulses of a KrF-laser, at a fluence of 10 mJ/cm², their sheet resistance (R_s) is dramatically reduced from highly insulating (∼10¹⁰ Ω/sq) to conductive values of ∼3 kΩ/sq. By increasing the laser fluence, from 10 to 75 mJ/cm², we were able to identify an optimal fluence around 35 mJ/cm² that leads to highly conductive films with R_s values as low as 250 Ω/sq and 190 Ω/sq, under vacuum (10⁻⁵ Torr) and 50 mTorr of H₂, respectively. Raman spectroscopy analyses confirmed the effective reduction of the KrF-laser irradiated GO films through the progressive recovery of the characteristic 2D band of graphene. Furthermore, systematic Fourier-transform infrared spectroscopy analysis has revealed that KrF-laser induced reduction of GO preferentially occurs through photodissociation and removal of carboxyl (COOH) and alcohol (OH) groups. A direct correlation is established between the electrical resistance of photoreduced GO films and their COOH and OH bond densities. The KrF-laser induced reduction of GO films is found to be more efficient under H₂ background than under vacuum. It is concluded that our KrF-laser reduced GO films mainly consist of turbostratic graphite built from randomly organized few-layers-graphene building blocks, which contains some residual oxygen atoms and defects. Finally, by monitoring the KrF-laser fluence, it is shown that reduced GO films combining optical transmission as high as ∼80% along with sheet resistance as low as ∼500 Ω/sq can be achieved with this room-temperature and on-substrate process. This makes the laser-based reduction process developed here particularly attractive for photovoltaic hybrid devices using silicon substrates.     

Synthesis of highly dispersed titanium dioxide nanoclusters on reduced graphene oxide for increased glucose sensing

Highly dispersed titanium dioxide nanocluster (TDN) was synthesized on reduced graphene oxide (RGO) in a toluene–water system under microwave irradiation. The prepared RGO–TDN hybrids were used to modify glassy carbon electrode for loading glucose oxidase. The fabricated glucose biosensor exhibits excellent performance for glucose sensing including low work potential (−0.7 V), high sensitivity (35.8 μA mM⁻¹ cm⁻²), low detection limit (4.8 μM), wide linear range from 0.032 to 1.67 mM, small Michaelis–Menten constant (K_m) (0.81 mM), and short response time (10 s).     

Hydrogen reduced graphene oxide/metal grid hybrid film: towards high performance transparent conductive electrode for flexible electrochromic devices

The metal grid and reduced graphene oxide (RGO) are both promising transparent conductive materials for replacing the indium tin oxide (ITO) in flexible optoelectronics. However, the large empty area that exists in the grid together with the relatively high sheet resistance of RGO hinder both the materials for practical applications. In this work, we report for the first time a novel strategy for efficient combination of the metal grid and RGO by using a newly developed room-temperature reduction technique. The obtained RGO/metal grid hybrid films not only overcome the shortcomings of individual components but exhibit enhanced optical and electrical performances (R_s = 18 Ω sq⁻¹ and T = 80%) and excellent flexural endurance. With this hybrid film as the window electrode, a highly flexible electrochromic device with excellent stability and ultra-fast response shorter than 60 ms has been successfully fabricated. Considering its high efficiency, high quality, low cost and large area, the strategy would be particularly useful for economically fabricating various metal grid/RGO films which are quite promising high performance transparent and conductive materials for next generation optoelectronic devices.