Reduced Graphene Oxide Films Research Articles

Multifunctional Pristine Chemically Modified Graphene Films as Strong as Stainless Steel

Pristine chemically modified graphene films with light weights and excellent mechanical properties can be prepared by chemically engineering the structure of the graphene oxide sheets and the microstructures of the films. Particularly, these reduced graphene oxide films are as strong as stainless steel, ultra-tough, and have high electrical and thermal conductivities.

Preparation of a Three-Dimensional Reduced Graphene Oxide Film by Using the Langmuir-Blodgett Method.

The Langmuir-Blodgett method has always been traditionally utilized in the deposition of two-dimensional structures. In this work, however, we employed the method to deposit three-dimensional reduced graphene oxide layers using an unconventional protocol for the first time. This was achieved by carrying out the dipping process after the collapse pressure or breaking point, which results in the formation of a highly porous three-dimensional surface topography. By varying the number of deposition layers, the porosity could be optimized from nanometer to micrometer dimensions. Employed as bioelectrodes, these three-dimensional reduced graphene oxide layers may allow improved adhesion and biocompatibility compared to the conventional two-dimensional surfaces. A larger number of pores also improves the mass transport of materials and therefore increases the charge-sustaining capacity and sensitivity. This could ultimately improve the performance of biofuel cells and other electrode-based systems.

Biocomposite based on reduced graphene oxide film modified with phenothiazone and flavin adenine dinucleotide-dependent glucose dehydrogenase for glucose sensing and biofuel cell applications.

A novel composite material for the encapsulation of redox enzymes was prepared. Reduced graphene oxide film with adsorbed phenothiazone was used as a highly efficient composite for electron transfer between flavin adenine dinucleotide (FAD)-dependent glucose dehydrogenase and electrodes. Measured redox potential for glucose oxidation was lower than 0 V vs Ag/AgCl electrode. The fabricated biosensor showed high sensitivity of 42 mA M(-1) cm(-2), a linear range of glucose detection of 0.5-12 mM, and good reproducibility and stability as well as high selectivity for different interfering compounds. In a semibiofuel cell configuration, the hybrid film generated high power output of 345 μW cm(-2). These results demonstrate a promising potential for this composition in various bioelectronic applications.

A simple visible light photo-assisted method for assembling and curing multilayer GO thin films

A simple and efficient method for deposition of reduced graphene oxide (RGO) thin films onto arbitrary substrates is described. The present protocol consists in the application of radial compression to a thin layer of graphene oxide (GO) formed at the air–liquid interface of an ammoniacal dispersion of graphene oxide by continuous irradiation with visible light, that drives both the formation and curing of the film. Both infrared and near infrared luminescence spectroscopies were used for the proposition of a chemical mechanism in which the in situ singlet oxygen Δ1O2, generated by the photosensitization of molecular oxygen to visible light, initiates the formation and curing of the film. The GO and RGO films display Raman spectral signatures typical of graphene – based materials, with thickness of ca. 20 nm as evaluated by atomic force microscopy. The deposited films exhibited good transparency to visible light (max. 85%; 550 ± 2 nm), electrical resistivity equals to 14 ± 0.02 Ω m, sheet resistance equals to 5 kΩ sq−1 with associated charge carrier mobility of 200 cm2/V s.

Improving the ammonia sensing of reduced graphene oxide film by using metal nano-materials

Gas sensing is one of the most promising applications for reduced graphene oxide (rGO). High surface-to-volume ratio in conjunction with remaining reactive oxygen functional groups translates into sensitivity to molecular on the rGO surface. The response of the rGO based devices can be further improved by functionalizing its surface with metal nano-materials. In this paper, we report the ammonia (NH3) sensing behavior of rGO based sensors functionalized with nano-structured metal: silver (Ag) or platinum (Pt) or gold (Au) in air at room temperature and atmospheric pressure. The gas response is detected by the monitoring changes in electrical resistance of the rGO/metal hybrids due to NH3 gas adsorption. Compared to bare rGO, significantly improved NH3 sensitivity is observed with the addition of nano-structured metals. These materials are applied to play the small bridges role connecting many graphene islands together to improve electrical conduction of hybrids while maintaining the inherent advantage of rGO for NH3 gas sensitivity.

Ultraviolet light sensor based on graphene quantum dots/reduced graphene oxide hybrid film

Here, we demonstrate a high performance ultraviolet (UV) light sensor based on graphene quantum dots (GQDs)/reduced graphene oxide (RGO) hybrid film with a simple and inexpensive solution process. To fabricate the GQDs/RGO hybrid film, GQDs synthesized by the carbonization of citric acid are simply sprayed on RGO film prepared by spin-coating on a SiO2/Si substrate. The RGO film is employed as the transport channel of the photogenerated electrons from GQDs due to its superior electron mobility and conductivity. By the integration of GQDs and RGO, the UV sensor device shows a high photo responsibility of 8.7×102A/W and an excellent specific detectivity of 7.7×1013 Jones at a low operating voltage. These results are attributed to the strong absorption of GQDs and the photogenerated charge transfer to RGO. Our novel approach based on the integration of GQDs and RGO can be extended for the design of the other promising optoelectronic applications.

Voltammetric Determination of Folic Acid Using Adsorption of Methylene Blue onto Electrodeposited of Reduced Graphene Oxide Film Modified Glassy Carbon Electrode

AbstractThis work presents a sensitive voltammetric method for determination of folic acid by adsorbing methylene blue onto electrodeposited reduced graphene oxide film modified glassy carbon electrode (MB/ERGO/GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology of the MB/ERGO/GCE modified electrode was characterized using scanning electron microscopy, displays that both MB and ERGO distributed homogeneously on the surface of GCE. The MB/ERGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE, MB/GCE, and ERGO/GCE. The electrochemical behaviors of folic acid at MB/ERGO/GCE were investigated by cyclic voltammetry, suggesting that the modified electrode exhibited excellent electrocatalytic activity towards folic acid compared with other electrodes. Under physiological condition, the MB/ERGO/GCE modified electrode showed a linear voltammetric response from 4.0 μM to 167 μM for folic acid, and with the detection limit of 0.5 μM (S/N=3). The stability, reproducibility and anti‐interference ability of the modified electrode were examined. The developed method has been successfully applied to determination of FA in tablets with a satisfactory recovery from 96 % to 100 %. The work demonstrated that the electroactive MB adsorbing onto graphene modified electrode showed an enhanced electron transfer property and a high resolution capacity to FA.

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 12830cd/m2 and 3.35cd/A, respectively.

Strongly Anisotropic Thermal Conductivity of Free‐Standing Reduced Graphene Oxide Films Annealed at High Temperature

Thermal conductivity of free‐standing reduced graphene oxide films subjected to a high‐temperature treatment of up to 1000 °C is investigated. It is found that the high‐temperature annealing dramatically increases the in‐plane thermal conductivity, K, of the films from ≈3 to ≈61 W m−1 K−1 at room temperature. The cross‐plane thermal conductivity, K⊥, reveals an interesting opposite trend of decreasing to a very small value of ≈0.09 W m−1 K−1 in the reduced graphene oxide films annealed at 1000 °C. The obtained films demonstrate an exceptionally strong anisotropy of the thermal conductivity, K/K⊥ ≈ 675, which is substantially larger even than in the high‐quality graphite. The electrical resistivity of the annealed films reduces to 1–19 Ω □−1. The observed modifications of the in‐plane and cross‐plane thermal conductivity components resulting in an unusual K/K⊥ anisotropy are explained theoretically. The theoretical analysis suggests that K can reach as high as ≈500 W m−1 K−1 with the increase in the sp2 domain size and further reduction of the oxygen content. The strongly anisotropic heat conduction properties of these films can be useful for applications in thermal management.

Simple and Sensitive Voltammetric Determination of Esculetin Using Electrochemically Reduced Graphene Oxide Modified Electrode

AbstractA simple and sensitive voltammetric sensor for esculetin, based on electrochemically reduced graphene oxide film modified glassy carbon electrode, was reported for the quantitative determination of esculetin in the Chinese traditional herbal drug Viola yedoensis Makino. Electrochemical impedance spectroscopy and scanning electron microscopy were employed to study the characteristic of the graphene oxide film. The electrochemical behavior of esculetin on this sensor was investigated in pH 3.0 phosphate buffer solution by cyclic voltammetry. Significant advantages were achieved by the excellent conductivity and the high surface‐to‐volume ratio of electrochemically reduced graphene oxide. A calibration plot of oxidation peak currents versus esculetin concentrations was linear in the range of 4.0 ξ 10‐8 mol L‐1 to 5.0 ξ 10‐6 mol L‐1 with a detection limit of 2.0 ξ 10‐8 mol L‐1. The practical application of the present sensor was demonstrated by determining the concentration of esculetin in real sample with no interference.

Effects of reduction methods on the structure and thermal conductivity of free-standing reduced graphene oxide films

In this work, free-standing graphene oxide (GO) films obtained by vacuum filtration were reduced in HI acid or annealed in a confined space to form self-standing reduced graphene oxide (RGO) films. The effects of reduction methods on the reduction degree, microstructure and thermal conductivity of the RGO films were investigated. The RGO films obtained by thermal annealing have higher reduction degree than those treated with HI acid (55%) or treated with the combination of HI acid and 600°C annealing. The X-ray pole figure measurements show that the orientation degree of GO films after reduction is degraded, and the HI acid reduction results in the worst oriented structure. The in-plane thermal conductivities of the RGO films obtained by thermal reduction are higher than those of films reduced by other methods due to their higher reduction degree and the resulting unfolded structure. However, the differences in the thermal conductivity of the RGO films obtained by thermal annealing at different temperatures are minor, even their reduction degree is enhanced with the increasing of annealing temperature, which is probably due to the generated interspaces between the graphene layers during reduction that greatly limit thermal transport.

A general strategy for the fabrication of high performance microsupercapacitors

We propose a generic strategy for microsupercapacitor fabrication that integrates layers of reduced graphene oxide (rGO) and pseudocapacitive materials to create electrode heterostructures with significantly improved cycling stability and performance. Our approach involves a combination of photolithography and a simple transfer method of free-standing reduced graphene oxide film onto an Au/patterned photoresist bilayer. The resulting stack (rGO/Au/patterned resist/substrate) is then used for the electrochemical deposition of various pseudocapacitive materials before the final step of lift-off. To prove the viability of this method, we have successfully fabricated microsupercapacitors (MSCs) with the following interdigitated electrode heterostructures: MnO2/rGO, Co(OH)2/rGO and PANI/rGO. These MSCs show better performance and cycling stability compared to the single layer, (i.e., rGO-free) counterparts. The interdigitated electrode heterostructures result in MSCs with energy densities in the range of 3–12mWh/cm3 and power densities in the range of 400–1200mW/cm3, which is superior to the Li thin film batteries (E=10mWh/cm3), carbon, and metal oxide based MSCs (E=1–6mWh/cm3) while device energy densities are in the range of 1.3–5.3mWh/cm3, corresponding power densities are in the range of 178–533mW/cm3. These results can be explained by a facilitated nucleation model, where surface topology of the rGO film creates a favorable environment for the nucleation and growth of pseudocapacitive materials with strong interfacial contacts and enhanced surface area. This approach opens up a new avenue in fabricating MSCs involving a variety of heterostructures combining electrical double layer carbon type with Faradaic pseudocapacitive materials for enhanced electrochemical performance.

Reduction of Graphene Oxide and its Effect on Square Resistance of Reduced Graphene Oxide Films

Graphite oxide was prepared via the modified Hummers’ method and graphene via chemical reduction. Deoxygenation efficiency of graphene oxide was compared among single reductants including sodium borohydride, hydrohalic acids, hydrazine hydrate, and vitamin C. Two‐step reduction of graphene oxide was primarily studied. The reduced graphene oxide was characterized by XRD, TG, SEM, XPS, and Raman spectroscopy. Square resistance was measured as well. Results showed that films with single‐step N2H4 reduction have the best transmittance and electrical conductivity with square resistance of ~5746 Ω/sq at 70% transmittance. This provided an experimental basis of using graphene for electronic device applications.

A Rapid, Green and Controllable Strategy to Fabricate Electrodeposition of Reduced Graphene Oxide Film as Sensing Materials for Determination of Taxifolin

The electrodeposition of a film of reduced graphene oxide (ERGO) with well-dispersed on a glassy carbon electrode (GCE) was achieved using cyclic voltammetry (CV) in a graphene oxide (GO) colloidal solution. Using square wave adsorptive stripping voltammetry (SWASV), the ERGO film was applied for the first time, in developing a high-sensitive electrochemical sensor for detection of taxifolin. Compared with bare GCE, the resulting electrodes (ERGO/GCE) exhibited excellent response toward the oxidation of taxifolin by significantly enhancing the oxidation peak currents and the decreased peak-to-peak separation. Under selected conditions, the reduction peak currents had linear relationship with taxifolin concentration in the range of 5.0 × 10-8 – 1.5 × 10-6 mol L-1, with detection limit of 4.0 × 10-9 mol L-1. Besides, the method was successfully applied to the quantitative determination of taxifolin in the Prince's-feather fruit with satisfactory results.

Fabrication of gold nanoparticles-decorated reduced graphene oxide as a high performance electrochemical sensing platform for the detection of toxicant Sudan I

In this paper, we are presenting a facile, green and in situ synthesis strategy for the convenient preparation of well-dispersed gold nanoparticles (AuNPs)-decorated reduced graphene oxide (RGO) without the use of any template molecules and poisonous reductant. The as-synthesized nanocomposite has been detailedly characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis as well as electrochemical technologies. The morphological and structural characterizations illustrate that AuNPs can be efficiently decorated on RGO with the Au content of 20.33wt% in the matrix and the size of the embedded AuNPs vary between 25 and 40nm. The electrochemical investigations confirm that the small-sized AuNPs on the RGO film can remarkably boost the electrocatalytic activity for the oxidation of Sudan I, which can be used as an enhanced electrochemical sensing platform for the sensitively detection of the toxicant Sudan I. Moreover, the kinetic parameter studies demonstrate that the Sudan I electro-oxidation at the AuNPs/RGO electrode is a diffusion-controlled process which involves two-electron and two-proton transfer. Under the optimal conditions, a wide linear range of Sudan I detection from 0.01 to 70μmolL−1 with good linearity (R2=0.9965, 0.9942) and a low detection limit (1.0nmolL−1, S/N=3) were obtained. In comparison with the existing analogues ever reported, the AuNPs/RGO eletrode exhibits overwhelmingly superior comprehensive properties for the sensitive detection of Sudan I. Finally, the newly developed sensor was applied to quantitative determination of Sudan I in food samples such as chilli powder and ketchup sauce with satisfactory sensitivity, selectivity and reversibility.

Transferrable superhydrophobic TiO2 nanorods on reduced graphene oxide films using block copolymer templates

Superhydrophobic surfaces are normally fixed on the chosen materials. Here, we report transferrable superhydrophobicity which was enabled by fabricating TiO2 nanorods on a reduced graphene oxide (rGO) film. Superhydrophobic TiO2 nanorods were first synthesized from a nanoporous template of block copolymers (BCPs). The controllability over the dimension and shape of nanopores of the BCP template allowed for the adjustment of TiO2 nanostructures for superhydrophobicity. Since the rGO film provided effective transferring, TiO2 nanorods were conveyed onto a flexible polymer film and a metal substrate. Thus, the surface of the designated substrate was successfully changed to a superhydrophobic surface without alteration of its inherent characteristics.

Enhanced photovoltaic performance of inverted hybrid bulk-heterojunction solar cells using TiO 2 /reduced graphene oxide films as electron transport layers

In this study, we investigated inverted hybrid bulk-heterojunction solar cells with the following configuration: fluorine-doped tin oxide (FTO) |TiO2/RGO|P3HT:PC61BM|V2O5 or PEDOT:PSS|Ag. The TiO2/GO dispersions were prepared by sol-gel method, employing titanium isopropoxide and graphene oxide (GO) as starting materials. The GO concentration was varied from 0.1 to 4.0 wt%. The corresponding dispersions were spin-coated onto FTO substrates and a thermal treatment was performed to remove organic materials and to reduce GO to reduced graphene oxide (RGO). The TiO2/RGO films were characterized by x-ray diffraction, Raman spectroscopy, and microscopy techniques. Atomic force microscopy (AFM) images showed that the addition of RGO significantly changes the morphology of the TiO2 films, with loss of uniformity and increase in surface roughness. Independent of the use of V2O5 or PEDOT: PSS films as the hole transport layer, the incorporation of 2.0 wt% of RGO into TiO2 films was the optimal concentration for the best organic photovoltaic performance. The solar cells based on TiO2/RGO (2.0 wt%) electrode exhibited a ∼22.3% and ∼28.9% short circuit current density (Jsc) and a power conversion efficiency enhancement, respectively, if compared with the devices based on pure TiO2 films. Kelvin probe force microscopy images suggest that the incorporation of RGO into TiO2 films can promote the appearance of regions with different charge dissipation capacities.

Reduction of graphene oxide film with poly (vinyl alcohol)

Graphene oxide (GO), products with various proportions of polyvinyl alcohol (PVA), was characterized to obtain verified patterns of reduced graphene oxide. FT-IR spectra indicated that PVA could lower the reduction temperature of GO by at around 70°C. New peaks near D band and overlapped G band in the Raman spectra appear to indicate that some parts of PVA interact with GO. The sheet resistance of GO/PVA showed that the GO/PVA ratio was optimal between 1/0.25 and 1/2. Using GO/PVA, we printed a line on PET, and after annealing at 140°C, it achieved a resistance of 23kΩ/cm.

Reduced Graphene Oxide for Room Temperature Hydrogen Storage Application

Graphene oxide (GO) is extracted from graphite oxide synthesized using modified Hummers method. The extracted GO solution is then drop casted onto a p type silicon substrate and dried in hot air oven. The dried solution is annealed at a temperature of about 200 degree Celsius for about one hour to obtain thermally reduced graphene oxide (RGO). Such thermally synthesized RGO usually have a lot of structural defects which can act as a binding site for hydrogen. The binding efficiency of hydrogen to defect centers can be increased by applying electric field to RGO as it changes the carrier concentration (doping) on the surface. This induces more polarization in the hydrogen molecule resulting in strong binding force, thereby increasing its hydrogen storage efficiency. In our experiment we have demonstrated room temperature electric field doping in RGO films by modulating the channel current by changing the back gate voltage which is a precursor for employing RGO in hydrogen storage applications.KeywordsGraphene oxide, Reduced graphene oxide, Field effect, Hydrogen storage, and Defects

A graphene field effect capacitive Immunosensor for sub-femtomolar food toxin detection

In this paper we report the sensing of aflatoxin B1(AFB1) by field effect capacitive method using electrophoretically deposited reduced graphene oxide (RGO) films for the first time. The RGO film has been characterized using SEM, surface profilometer and Raman spectroscopy. It has been observed that both quantum capacitance of RGO (Cq) and effective electrical double layer capacitance (CEDL) contribute significantly towards the overall sensitivity for molar concentration in the range of 20–50mM. As Cq and CEDL changes in opposite direction after AFB1 capture and the nature of frequency dependence of Cq and CEDL are different, the sensitivity shows a minima at a particular frequency. Interestingly, the sensitivity minima is also dependent on AFB1 concentration. Further, the maximum sensitivity obtained is around 30% for 10−4ppt (0.1fg/ml) AFB1 which is greater than 1.5 times that of previous reports. This has been possible through the enhanced biomolecule immobilization capability of RGO. Thus the RGO based field effect capacitive sensor provides a combined advantage of both a high sensitivity and concentration dependent frequency behavior.