A comparative analysis of graphene oxide films as proton conductors

The electrical conductivity of graphene oxide (GO) films in vapors of water and acid solutions is found to be close to the conductivity of a film formed after drying the solution of phenol-2,4-disulfonic acid in polyvinyl alcohol, which is known to be a proton conductor. We found that the conductivity of a GO film in vapors of the H₂O–H₂SO₄ electrolyte possesses a sharp maximum at ~1 % by weight of sulfuric acid. The highest conductivity of GO films can be expected when placing the films over acid vapors where the acid concentration is essentially lower than in the acid solutions at their maximum conductivity. Since the conductivity of the H₂O–H₂SO₄ electrolyte itself has a maximum at ~30 % by weight of sulfuric acid, the use of intermediate concentrations of H₂SO₄ is recommended in practical applications. The GO films permeated with water or acid solution in water are expected to possess the proton-exchange properties similar to those of other proton-exchanging membranes.     

Tuning of electronic properties and dynamical stability of graphene oxide with different functional groups

The structural, electronic and vibrational properties of graphene oxide (GO) with varying proportion of epoxy and hydroxyl functional groups have been studied using density functional theory. The functional groups and oxygen density have an obvious influence on the electronic and vibrational properties. The dependence of band gap on associated functional groups and oxygen density shows a possibility of tuning the band gap of graphene by varying the functional groups as well as oxidation level. The absorption of high oxygen content in graphene leads to the gap opening and resulting in a transition from semimetal to semiconductor. Phonon dispersion curves show no imaginary frequency or no softening of any phonon mode throughout the Brillouin zone which confirms the dynamical stability of all considered GO models. Different groups and different oxygen density result into the varying characteristics of phonon modes. The computed results show good agreement with the experimental observations. Our results present interesting possibilities for engineering the electronic properties of graphene and GO and impact the fabrication of new electronics.     

Microwave-reduced graphene oxide for efficient and stable hole extraction layers of polymer solar cells

Microwave-assisted reduced graphene oxide (MR-GO) layer was applied to hole extraction layer (HEL) of polymer solar cells (PSCs) and was compared with the widely used poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) in bulk hetero-junction (BHJ) solar cells. The power conversion efficiency (PCE) of 3.57% was achieved with the MR-GO layer, which is 21% higher than that of PSCs with the conventional PEDOT:PSS HEL material. This enhancement of PCE is mainly attributed to the increase of short-circuit current density originated from the hydrophobic surface of the MR-GO layer. The hydrophobic graphene oxide surface is believed to improve wetting property and physical contact of active blends. In addition, the MR-GO interfacial layer is found to show the excellent device stability in atmospheric condition. The PCE of conventional PEDOT:PSS based PSCs showed total degradation when the device was exposed to atmospheric condition for 1000 h without any encapsulation, while that of MR-GO based PSC showed over 85% of PCE.     

Hydrothermal method for the production of reduced graphene oxide

Reduced graphene oxide, RGO (also called chemically modified graphene, CMG) was synthesized by a simple hydrothermal method, with graphite oxide (GO), prepared by the modified Hummers method, served as the raw material. Structural and morphological studies indicate the degree of reduction is dependent on the temperature, which is also verified by Raman analysis. The variation in interlayer distance and the intensity ratio of the D to G Raman modes (I_D/I_G) indicates higher reaction temperature can accelerate the reduction of GO. The conductivity also varies with the degree of reduction, as verified by electrochemical analyzer. Moreover, the reaction process affects organic functional groups, the mechanism during the reaction process is discussed.     

Ecofriendly Route for the Synthesis of Highly Conductive Graphene Using Extremophiles for Green Electronics and Bioscience

Highly conductive biocompatible graphene is synthesized using ecofriendly reduction of graphene oxide (GO). Two strains of non‐pathogenic extremophilic bacteria are used for reducing GO under both aerobic and anaerobic conditions. Degree of reduction and quality of bacterially reduced graphene oxide (BRGO) are monitored using UV–vis spectroscopy, X‐ray photoelectron spectroscopy, and Raman spectroscopy. Structural morphology and variation in thickness are characterized using electron microscopy and atomic force microscopy, respectively. Electrical measurements by three‐probe method reveal that the conductivity has increased by 10⁴–10⁵ fold from GO to BRGO. Biocompatibility assay using mouse fibroblast cell line shows that BRGO is non‐cytotoxic and has a tendency to support as well as enhance the cell growth under laboratory conditions. Hereby, a cost effective, non‐toxic bulk reduction of GO to biocompatible graphene for green electronics and bioscience application is achieved using halophilic extremophiles for the first time.     

Localized insulator-conductor transformation of graphene oxide thin films via focused laser beam irradiation

By scanning a focused laser beam over graphene oxide (GO) film deposited on SiO₂/Si substrates, conductive strips as small as 1 μm can be patterned directly either as a channel in the insulating matrix, or as a stand-alone micro belt. The conductivity was increased by at least two orders of magnitude with the mobility estimated in the range of 1–10 cm²/V s. Raman mapping and X-ray photoelectron spectroscopy studies demonstrated the reduction of GO in the laser-irradiated area. The conductance of the patterned channel was independent of the change in oxide-electrode contact resistance of the graphene, and increased linearly with increasing channel width. Increasing irradiation power by repeated scanning initially increased the conductivity of the irradiated area and saturated at a conductivity of ∼36 S/cm. Partial oxidative burning combined with photothermal reduction was identified as the underlying mechanism for the enhancement of the conductivity after laser irradiation on the GO film. Oxidative burning can be controlled by varying the film thickness and laser power.     

Reduced graphene oxide foils for ion stripping applications

ABSTRACT

Reduced graphene oxide (rGO) films can be employed as ion strippers in an accelerator. They show some advantages with respect to the graphite foils, due to their high thermal and electrical conductivity, low density, high mechanical resistance and high stability. Thin graphene oxide (GO) films with a sub-micron thickness have been synthesized and transformed into reduced GO (rGO) by ion beam irradiations. Physical characterizations of the pristine and ion irradiated GO films have been performed. Measurements of stripping efficiency have been carried out by using helium, lithium, carbon and oxygen ion beams. The rGO stripper films demonstrate a significantly high charge production, comparable to that of the graphite films but with the advantage of a longer lifetime.     

Solution processable reduced graphene oxide decorated ATO electrode for organic solar cells

A novel concept based on the use of solutions containing already qualified crystalline antimony-doped tin oxide SnO₂:Sb (ATO) nanoparticles has been developed. ATO nanoparticles are decorated by reduced graphene oxide (rGO) through a hydrothermal synthesis method. The electrical and optical properties of the graphene oxide films are investigated systematically. The sheet resistance (R _□) of the ATO–rGO films decreases with the increase in the rGO content in the precursor solution. The R _□ can be decreased after the ATO–rGO films annealing in the air for 1 h and can be further decreased by depositing Au on the surface of the films. The optimum property of the ATO–rGO film shows that the R _□ is 80 Ω/□ and the transmittance is about 70 %. The ATO–rGO films are used as the anode of the organic solar cells. The anode film impact on the performance of the devices is studied. Finally, the power conversion efficiency (PCE) of the device based on the poly-(3-hexylthiophene): [6, 6]-phenyl C61-butyric acid methyl ester (PCBM) blended is 1.85 %, and the PCE of the device based on the poly-benzo[1,2-b:4,5-b′] dithio-phene thieno[3,4-b] thiophene:PCBM blended is 3.4 %.     

Laser and ion beams graphene oxide reduction for microelectronic devices

Reduced graphene oxide (rGO) is a two-dimensional material, which is attracting increasing attention due to its special properties. It can be obtained by laser or ion beam irradiations of pristine graphene oxide (GO). It shows high mechanical resistance, considerable electric and thermal conductivity. All these rGO characteristics together with the high number of molecular species that can be embedded between its layers, make graphene oxide a potential material for electronic sensors or efficient support on which conductive strips, condensers, and micrometric electronic devices can be designed. In particular, as it is described in this paper, it is possible to carry out high spatial resolution lithography in GO by using a focused laser or micro ion beam in order to design macro, micro, and submicron geometrical structures. The use of the reduced graphene oxide for the laser and ion beam fabrication of electrical resistances and capacitances is presented.     

DFT study of graphene oxide reduction by a dopamine species

Recently a large interest has arisen for using less active reducers of graphene oxide, GO, that are friendly with the environment. In the present work, a DFT theoretical study on the reduction process of GO model surfaces is performed taking into account zwitterionic dopamine, ZDA, as reducing agent. Several periodic models representing epoxy and hydroxyl patches on GO basal plane are proposed. As the number of oxide groups in a patch of epoxies or hydroxyls on the surface of graphene increases from 1 to 5, these systems become more stable. Whereas the adsorption of ZDA on patches of GO with 5 epoxy groups is non-dissociative, that of ZDA on patches of GO with 5 hydroxyl groups is fundamentally dissociative, reducing the surface of graphene oxide. The H₂O molecule produced in the GO reduction becomes trapped to ZDA through a hydrogen bond. The ZDA binding to GO was analysed by considering electrostatic effects and attractive non-covalent contributions due to vdW interactions.     

Transition of hexagonal to square sheets of Co3O4 in a triple heterostructure of Co3O4/MnO2/GO for high performance supercapacitor electrode

Cobalt oxide and manganese oxides are promising electrode materials amongst the transition metal oxides (TMOs) for pseudocapacitors. The lack of reversibility and deterioration of capacitance at higher current densities is major flaw in Co₃O₄ as an electrode for supercapacitor while MnO₂ suffers from low electrical conductivity and poor cycling stability. It is inevitable to bridge the performance gap between these two TMOs to obtain a high performance supercapacitor based on environmental benign and earth abundant materials. Herein, we fabricated a hybrid triple heterostructure high-performing supercapacitor based on hexagonal sheets of Co₃O₄, MnO₂ nanowires and graphene oxide (GO) to form a composite structure of Co₃O₄/MnO₂/GO by all hydrothermal synthesis route. The Co₃O₄ square sheets serves as an excellent backbone with good mechanical adhesion with the current collector providing a rapid electronic transfer channel while the integrated nanostructure of MnO₂ NW/GO permits more electrolyte ions to penetrate capably into the hybrid structure and allows effective utilization of more active surface areas. A triple heterostructured device exhibits a high areal capacitance of 3087 mF cm⁻² at 10 mV s⁻¹ scan rate along with the exceptional rate capability and cycling stability having capacitance retention of ∼170% after 5000 charge/discharge cycles. The TMOs based pseudocapacitor with the conducting scaffolds anchoring based on graphene derivatives like this will pave an encouraging alternatives for next generation energy storage devices.     

Improvement of water softening efficiency in capacitive deionization by ultra purification process of reduced graphene oxide

Capacitive deionization (CDI) is the next generation of water desalination and softening technology by using relatively low capacitive current of electrochemical double layer. Among various carbon-based materials used for making electrode, reduced graphene oxide (rGO) has been intensively studied due to its excellent electrical conductivity and high surface area. Although Hummer method for making graphene oxide (GO) and rGO is a simple process, it remains some impurities in inherent GO and rGO which affect negatively to the CDI performance. In this work, we successfully prepared ultra purified GO and rGO by modifying Hummer method in order to remove entirely excess elements degrading the CDI performance. The electrosorption capacity of ultra purified rGO is considerably better than that of previous rGO, and maximum removal achieves 3.54 mg g⁻¹ at applied voltage of 2.0 V. Thus, this result could be comparable to other researches in CDI process.     

Graphene Modified Lipophilically by Stearic Acid and its Composite With Low Density Polyethylene

Graphene, prepared by the thermal reduction of graphite oxide (GO), was modified with stearic acid to enhance its lipophilicity. A novel method, using the intrinsic epoxy groups on the graphene, was utilized for reaction with stearic acid to minimize the negative impact of the normal functionalization method on the π-electronic system of graphene. Gravimetric analysis, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) showed that the stearic acid was effectively attached to the graphene. In addition, Raman spectroscopy and electric conductivity of the graphene showed that this novel modification method, utilizing intrinsic defects, did not damage the π-electronic system of the sp² bonded carbons. The dispersion of graphene in a low density polyethylene (LDPE) matrix was enhanced; consequently, the reinforcing effect in tensile testing was improved by the lipophilic modification. The crystallization behavior observed by differential scanning calorimetry (DSC) showed that the crystallization of LDPE was hindered by dispersed graphene, more evidently when dispersed uniformly.     

Core–Shell Composite Synthesized through In Situ Polymerization in Emulsion with High Electrical Conductivity Sensitive to Humidity

A core–shell composite has been synthesized through in situ polymerization in emulsion with an average of 205 nm of diameter. Each composite consists of a graphene oxide (GO) core and a poly(methyl methacrylate/butyl acrylate) shell. The latex is homogeneous without any aggregation after stability testing in normal temperature for 100 d and can be applied as an ideal conductive adhesive whose glass transition temperature (T _g) is under ?30 °C and lucid conductive film whose T _g is above 17 °C. There exists half core–shell structure in the composite with part of GO exposed which contributes to the electrical conductivity of film formed by composite. The electrical conductivity of the composite is sensitive to humidity, increasing from 0.233 to 0.357 S m^?1, while the related humidity ranges from 0% to 60%. The flexible aliphatic shell established by polyacrylate chains with nanolevel of interspaces makes it easy for hydrone to move in and interact with the oxygen groups on the chains, and then the interaction enhances the difficulty for hydrone to move out, on account of which film formed by core–shell composite can hold hydrone and exhibit advanced electrical conductivity in high humidity atmosphere.     

Graphene oxide doped poly(vinylidene fluoride-co-hexafluoropropylene) gel electrolyte for lithium ion battery

Gel poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer electrolytes doped with graphene oxide (GO) (GO/PVDF-HFP) were designed and fabricated through a phrase inversion method and followed by LiPF₆ solution uptake. It was demonstrated that the as-prepared GO/PVDF-HFP polymer electrolytes have uniform porous morphologies, and their crystalline state, thermal stability, interfacial resistance, and electrolyte uptake and retention capabilities can be tuned by varying the GO contents. Further, it was found that the GO can prominently enhance the ionic conductivity of the GO/PVDF-HFP polymer electrolyte. The electrochemical property measurements show that the lithium ion batteries using as-prepared GO/PVDF-HFP polymer electrolytes afford admirable charge/discharge rate and cycle stability.     

Electro‐optic switching with liquid crystal graphene

Graphene oxide (GO) particles in aqueous dispersions can form liquid crystal (LC) phases at extremely low concentrations due to the extremely high aspect ratio of the flakes and noticeably, they possess an extremely large Kerr coefficient attractive for low power consumption electro‐optic devices. Reduced graphene does not easily form LC phases in water due to its hydrophobic nature but here we show that stable dispersions of reduced graphene oxide can be realized with surfactants and that they exhibit birefringence upon shearing as well as under application of electric fields. The performance of the system is largely superior to GO LC possessing longer time stability and drastically improved electro‐optic properties with an induced birefringence twice as large at the same field strength thanks to the almost recovery of graphene properties upon reduction. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Co$lt;sub$gt;2$lt;/sub$gt;SnO$lt;sub$gt;4$lt;/sub$gt;/Graphene复合材料的制备与电化学性能研究

实验首先采用改进的Hummers法制备氧化石墨,然后以氧化石墨烯为前驱体,通过水热法将锡酸钴纳米颗粒均匀镶嵌在石墨烯薄膜基片上,最终获得Co₂SnO₄/Graphene镶嵌复合材料. 采用X射线衍射（XRD）、扫描电子显微镜（SEM）对材料的结构和形貌进行表征,通过恒电流充放电（CC）、循环伏安法（CV）与交流阻抗法（EIS）测试了材料的电化学性能. 实验结果表明,石墨烯良好的分散性及较高的电子导电率,可以提高锡酸钴材料的电化学性能,材料首次可逆容量达到1415.2 mA·h/g,50次循环后仍能保持469.7 mA·h/g的放电比容量. 关键词： 2SnO₄')" href="#">Co₂SnO₄ 石墨烯 电化学性能 锂离子电池     

Synthesis of graphene oxide sheets decorated by silver nanoparticles in organic phase and their catalytic activity

The graphene oxide(GO) sheets decorated by Ag nanoparticles were prepared using a liquid–liquid two-phase method at the room temperature. The synthesized samples existed in the organic phase and were characterized by X-ray diffraction, transmission electron microscopy, UV–vis spectroscopy and Raman spectra. The results demonstrate that these silver-nanoparticles with diameter of about 10 nm assembled on graphene oxide sheets are flexible and can form stable suspensions in organic phase. Raman signals of graphene oxide sheets are increased by the attached silver nanoparticles, displaying higher surface-enhanced Raman scattering activity. Furthermore, Ag/GO are found to serve as effective catalysts to activate the reduction of 4-nitrophenol (4NP) in the presence of NaBH₄.     

Structural,electrical and optical properties of MgO-reduced graphene oxide nanocomposite for optoelectronic applications

MgO-reduced graphene oxide nanocomposites (NCs) were synthesized by a simple two-step chemical method. The microstructure, surface morphology, and composition of the prepared samples have been studied. X-ray diffractometer (XRD) analysis confirmed the crystalline cubic MgO nanoparticle and rGO sheets. Scanning electron microscope (SEM) showed the spherical MgO nanoparticles well dispersed over the graphene sheets. UV–visible spectroscopy analysis demonstrated that a red shift in the wavelength dependent absorbance curve. The band gap of the samples was found to be decreased with the increase of rGO content. The dielectric studies have been examined in the frequency range 500 Hz−5 MHz and found significant improvement in the dielectric constant, dielectric loss, and electric properties due to rGO addition.This is mainly attributed to the strong interfacial polarization (Maxwell–Wagner polarization) between MgO and rGO sheets. Further, the modulation of charge carrier density with rGO additions help to enhance the electrical conductivity of NCs and thus, encouraging to have wider application in electronic and energy technologies.     

Thermoelectric power of mixed electronic-ionic conductors II. Case of titanium dioxide

The purpose of the present work is the determination of the thermopower components corresponding to different charge carriers (electrons, electron holes and ions) for TiO₂ and the use of these data for evaluation of the effect of symmetry between these two properties. The procedure of the determination of these components was based on the following two approximations:

The first approximation is based on a symmetrical model assuming a consistency between thermopower and electrical conductivity within the n-p transition (minimum of electronic component of the electrical conductivity corresponds to zero value of the electronic component of thermopower).

The second approximation is based on the apparent asymmetry between thermopower and electrical conductivity within the n-p transition as determined from the first approximation.

The analysis, based on the data of the electronic components of thermopower and electrical conductivity for TiO₂ single crystal, results in the band gap (using the Jonker formalism). The determined band gap is equal to 2.77 eV and 2.57 eV at the first and the second approximations, respectively, while the band gap determined from the experimentally measured data is equal 3.35 eV. These values are consistent with the band gap determined from the data of electrical conductivity corresponding to the n-p transition point (E_g=3.16 eV) and for the data measured experimentally and those free of the ionic conductivity component (E_g=2.79 eV). The obtained results indicate that thermopower and electrical conductivity most likely exhibit the effect of symmetry.