Chemically modified graphene oxide/polybenzimidazobenzophenanthroline nanocomposites with improved electrical conductivity

Graphene/polybenzimidazobenzophenanthroline nanocomposites were prepared through the liquid-phase exfoliation of graphene oxide (GO) and reduced graphene oxide (rGO) in methanesulfonic acid with subsequent solution mixing. Various chemical and combined chemical-thermal methods were examined to be effective for producing rGO with highly graphitic structure and excellent electrical conductivity. Raman and X-ray photoelectron spectroscopy showed higher degree of reduction of the GO with the combined chemical-thermal method compared to other chemical reduction processes. Structural characterization of the nanocomposites by X-ray diffraction, scanning electron microscopy and transmission electron microscopy showed good exfoliation and dispersion of both GO and rGO fillers in the polymer matrix. The thermogravimetric analysis found that the nanocomposites with rGO have higher onset and maximum weight loss temperatures than those with GO. Compared with the pure polymer, the electrical conductivity of the nanocomposites containing 10 wt% GO and GO reduced by the combined chemical-thermal treatment showed a remarkable increase by four and seven orders of magnitude, respectively. Long-term in-situ thermal reduction was performed to further improve the conductivities of the nanocomposites.     

Highly soluble polyetheramine-functionalized graphene oxide and reduced graphene oxide both in aqueous and non-aqueous solvents

Among many methods to synthesize graphene, solution-based processing provides many advantages owing to its low cost, high productivity, chemical versatility, and scalability. In particular, graphene oxide (GO) is one of the most promising nanocarbons that enable the incorporation of graphene and related materials into bulk materials and nanocomposites. GO has hydrophilic nature that enables straightforward dispersion in aqueous solution by sonication, but GO show poor dispersibility in common organic solvents, which prevent much wider applications such as solution-mixing polymer nanocomposites. Here we prepared highly soluble, functionalized GO in both aqueous and non-aqueous solvents. This was achieved by reacting polyetheramine consisting of amphiphilic components, e.g., polypropylene oxide and polyethylene oxide, with carboxylic acid groups at GO edges. Moreover, the reduced GO (rGO) was also highly dispersible in aqueous solution as well as non-aqueous solutions. These functionalized GO and rGO can be used for many solution-processed graphene composites.     

Hydrazine-reduction of graphite- and graphene oxide

We prepared hydrazine-reduced materials from both graphite oxide (GO) particles, which were not exfoliated, and completely exfoliated individual graphene oxide platelets, and then analyzed their chemical and structural properties by elemental analysis, XPS, TGA, XRD, and SEM. Both reduced materials showed distinctly different chemical and structural properties from one another. While hydrazine reduction of graphene oxide platelets produced agglomerates of exfoliated platelets, the reduction of GO particles produced particles that were not exfoliated. The degree of chemical reduction of reduced GO particles was lower than that of reduced graphene oxide and the BET surface area of reduced GO was much lower than that of reduced graphene oxide.     

Easy preparation of ultrathin reduced graphene oxide sheets at a high stirring speed

This work explored the synthesis of rGO sheets from graphene oxide (GO) using hydrazine solvent as reducing agent through chemical reduction. Meanwhile, GO films with a 2D structure were prepared from graphite flakes (starting material with an average flake size of 150 nm) by an Improved Hummer׳s method. Results showed that the chemical oxidation of graphite flakes carried out at room temperature could be used to prepare GO sheets in the initial stage. The conversion of GO into large-area rGO sheets with ~85% of carbon content could then be achieved by chemical reduction. RGO sheets with a lateral dimension of up to ~45 nm were obtained, which indicated the formation of an extremely thin layer of rGO sheets. A high degree of GO reduction was also realized using a high stirring speed (1200 rpm) for 72 h in a mixture of acids and potassium permanganate, resulting in a high carbon content of rGO with a large lateral dimension and area. Overall, our Improved Hummer׳s method with a high stirring speed (1200 rpm) for 72 h provided an easy approach to the preparation of large-area and ultrathin rGO sheets.     

The role of microwave absorption on formation of graphene from graphite oxide

By means of manipulating the oxygen content in graphite oxides (GO) and/or graphene-based materials, we demonstrate that the microwave absorption capacity of carbon materials is highly dependent on their chemical composition and structure. The increase of oxygen in GO remarkably decreases its microwave absorption capacity due to the size decrease of the π–π conjugated structure in these materials, and vice versa. It was revealed that graphene is an excellent microwave absorbent while GO with poor microwave absorption capacity, the unoxidized graphitic region “impurities” in GO act as the microwave absorbents to initiate the microwave-induced deoxygenation. The addition of a small amount graphene to GO leads to avalanche-like deoxygenation reaction of GO under microwave irradiation (MWI) and graphene formation, which was used for electrode materials in supercapacitors. The interaction between microwaves and graphene or graphene-based materials may be used for the fabrication of a variety of graphene-based nanocomposites with exceptional properties and a wealth of practical applications.     

Conversion of pencil graphite to graphene/polypyrrole nanofiber composite electrodes and its doping effect on the supercapacitive properties

Graphene platelets were synthesized from pencil flake graphite and commercial graphite by chemical method. The chemical method involved modified Hummer's method to synthesize graphene oxide (GO) and the use of hydrazine monohydrate to reduce GO to reduced graphene oxide (rGO). rGO were further reduced using rapid microwave treatment in presence of little amount of hydrazine monohydrate to graphene platelets. Chemically modified graphene/polypyrrole (PPy) nanofiber composites were prepared by in situ anodic electropolymerization of pyrrole monomer in the presence of graphene on stainless steel substrate. The morphology, composition, and electronic structure of the composites together with PPy fibers, graphene oxide (GO), rGO, and graphene were characterized using X‐ray diffraction (XRD), laser‐Raman, and scanning electron microscopic (SEM) methods. From SEM, it was observed that chemically modified graphene formed as a uniform nanocomposite with the PPy fibers absorbed on the graphene surface and/or filled between the graphene sheets. Such uniform structure together with the observed high conductivities afforded high specific capacitance and good cycling stability during the charge–discharge process when used as supercapacitor electrodes. A specific capacitance of supercapacitor was as high as 304 F g^?1 at a current density of 2 mA cm^?1 was achieved over a PPy‐doped graphene composite. POLYM. ENG. SCI., 55:2118–2126, 2015. © 2014 Society of Plastics Engineers     

Preparation and properties of acrylonitrile–butadiene rubber–graphene nanocomposites

The graphene oxide (GO) was prepared by sonication‐induced exfoliation from graphite oxide, which was produced by oxidation from graphite flakes with a modified Hummer's method. The GO was then treated by hydrazine to obtain reduced graphene oxide (rGO). On the basis of the characterization results, the GO was successfully reduced to rGO. Acrylonitrile–butadiene rubber (NBR)–GO and NBR–rGO composites were prepared via a solution‐mixing method, and their various physical properties were investigated. The NBR–rGO nanocomposite demonstrated a higher curing efficiency and a change in torque compared to the gum and NBR–GO compounds. This agreed well with the crosslinking density measured by swelling. The results manifested in the high hardness (Shore A) and high tensile modulus of the NBR–rGO compounds. For instance, the tensile modulus at a 0.1‐phr rGO loading greatly increased above 83, 114, and 116% at strain levels of 50, 100, and 200%, respectively, compared to the 0.1‐phr GO loaded sample. The observed enhancement was highly attributed to a homogeneous dispersion of rGO within the NBR matrix; this was confirmed by scanning electron microscopy and transmission electron microscopy analysis. However, in view of the high ultimate tensile strength, the NBR–GO compounds exhibited an advantage; this was presumably due to strong hydrogen bonding or polar–polar interactions between the NBR and GO sheets. This interfacial interaction between GO and NBR was supported by the marginal increase in the glass‐transition temperatures of the NBR compounds containing fillers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42457.     

Graphene and graphene oxide and their uses in barrier polymers

Currently, there is great interest in graphene‐based devices and applications because graphene has unique electronic and material properties, which can lead to enhanced material performance. Graphene may be used in a wide variety of potential applications from next‐generation transistors to lightweight and high‐strength polymeric composite materials. Graphene, which has atomic thickness and two‐dimensional sizes in the tens of micrometer range or larger, has also been considered a promising nanomaterial in gas‐ or liquid‐barrier applications because perfect graphene sheets do not allow diffusion of small gases or liquids through its plane. Recent molecular simulations and experiments have demonstrated that graphene and its derivatives can be used for barrier applications. In general, graphene and its derivatives can be applied via two major routes for barrier polymer applications. One is the transfer or coating of few‐layered, ultrathin graphene and its derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), on polymeric substrates. The other is the incorporation of fully exfoliated GO or rGO nanosheets into the polymeric matrix. In this article, we review the state‐of‐the‐art research on the use of graphene, GO, and rGO for barrier applications, including few‐layered graphene or its derivatives in coated polymeric films and polymer nanocomposites consisting of chemically exfoliated GO and rGO nanosheets, and their gas‐barrier properties. As compared to other nanomaterials being used for barrier applications, the advantages and current limitations are discussed to highlight challenging issues for future research and the potential applications of graphene/polymer, GO/polymer, and rGO/polymer composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39628.     

Green Carbon Nanostructures for Functional Composite Materials

Carbon nanostructures are widely used as fillers to tailor the mechanical, thermal, barrier, and electrical properties of polymeric matrices employed for a wide range of applications. Reduced graphene oxide (rGO), a carbon nanostructure from the graphene derivatives family, has been incorporated in composite materials due to its remarkable electrical conductivity, mechanical strength capacity, and low cost. Graphene oxide (GO) is typically synthesized by the improved Hummers’ method and then chemically reduced to obtain rGO. However, the chemical reduction commonly uses toxic reducing agents, such as hydrazine, being environmentally unfriendly and limiting the final application of composites. Therefore, green chemical reducing agents and synthesis methods of carbon nanostructures should be employed. This paper reviews the state of the art regarding the green chemical reduction of graphene oxide reported in the last 3 years. Moreover, alternative graphitic nanostructures, such as carbons derived from biomass and carbon nanostructures supported on clays, are pointed as eco-friendly and sustainable carbonaceous additives to engineering polymer properties in composites. Finally, the application of these carbon nanostructures in polymer composites is briefly overviewed.     

Fabrication of tough,self-recoverable,and electrically conductive hydrogels by in situ reduction of poly(acrylic acid) grafted graphene oxide in polyacrylamide hydrogel matrix

Developing electrically conductive hydrogels with good electronic properties and excellent mechanical performance is significant to their potential applications. In this article, we present a strategy to fabricate tough, self-recoverable and electrically conductive hydrogels containing reduced graphene oxide (rGO). Poly(acrylic acid) grafted graphene oxide (GO-g-PAA) was synthesized and incorporated into chemically crosslinked polyacrylamide (PAM) networks to obtain GO-g-PAA/PAM hydrogels, which were further treated with ascorbic acid solution at ambient temperature to give rGO-g-PAA/PAM hydrogels. The interfacial interaction between GO/rGO and hydrogel matrix was improved by reversible hydrogen bonds between the grafted PAA chains and PAM matrix. Consequently, both GO-g-PAA/PAM and rGO-g-PAA/PAM hydrogels exhibited improved tensile properties, excellent energy dissipation, and rapid self-recovery. The in situ chemical reduction of GO-g-PAA in hydrogel matrix endowed rGO-g-PAA/PAM hydrogels with satisfactory electrical conductivity and obvious resistance change upon stretching. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48781.     

Vacuum-assisted microwave reduction/exfoliation of graphite oxide and the influence of precursor graphite oxide

One-step synthesis of high quality graphene at gram-scale quantities is important for industrial applications, e.g. in electrochemistry for sensing and energy storage. Currently, thermal reduction/exfoliation of graphite oxide (GO) is a typical method of choice. However, it has the drawback of requiring specialized equipment for rapid thermal shock. A recent alternative method, microwave-assisted exfoliation, usually suffers from poor reduction of graphite oxide and thus low C/O ratios. Herein we show that vacuum-assisted microwave reduction/exfoliation of graphite oxide in a closed system leads to high C/O ratios and partial hydrogenation of graphene (2.6 at.% of H). Microwave irradiation of graphite oxide in vacuum leads to outgassing from GO and the creation of plasma which aids temperature distribution and hydrogenation. This plasma is quickly extinguished by further dramatic evolution of gases from GO and consequent pressure increase. We assess the influence of precursor graphite oxide, prepared by Hummers, Staudenmaier, and Hofmann methods, upon the materials properties of microwave exfoliated graphene. We show that microwave-exfoliated graphenes prepared from different graphite oxides show very fast heterogeneous electron transfer rates, with similar electrochemical behaviour to thermally reduced graphene oxide.     

The synthesis of rGO/RuO2, rGO/PANI,RuO2/PANI and rGO/RuO2/PANI nanocomposites and their supercapacitors

Polymer Bulletin - In this work, reduced graphene oxide (rGO) was obtained by chemical reduction of graphene oxide (GO) using sodium borohydride (NaBH4). Four different nanocomposites rGO/ruthenium...     

Non-covalent modification of graphene sheets in PEDOT composite materials by ionic liquids

An ionic liquid (IL) supported composite of poly(3,4-ethylene dioxythiophene) (PEDOT) and graphene oxide (GO) is presented. GO was dispersed in ILs and electropolymerization carried out after loading of EDOT to the dried dispersion. The content of GO was optimized to obtain high electrical conductivity of the composite material. The IL acts as the dispersant for GO and as dopant in the synthesis of PEDOT leading to films with a highly porous structure indicated from the scanning electron microscopy (SEM) images. Subsequently, GO was reduced electrochemically by cyclic voltammetry to obtain PEDOT/rGO composite films. The successful formation of composite materials was confirmed using Raman and X-ray photoelectron spectroscopy (XPS) techniques. XPS was also used to verify removal of oxygen-containing functional groups upon electrochemical reduction of the composite films. The electrochemical properties of PEDOT, PEDOT/GO and PEDOT/rGO were studied using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The results show that electrochemical reduction clearly increases the capacitance of the composite and furthermore the cycling stability. Such an increase could be obtained if >20 cycles, extending to highly negative potentials (−2.0 V), was used during the electroreduction of incorporated GO. Owing to the high porosity, favorable electrochemical properties and cycling stability these hybrid materials shows great potential towards supercapacitor applications.     

氧化石墨烯的制备及形成机理研究

氧化石墨烯(GO)作为一种石墨烯衍生物,结构中含有大量羟基、环氧基、羧基和羰基等含氧官能团,使其易与其他物质通过相互作用复合,从而提高和拓宽传统材料的性能及应用。GO的结构和尺寸等性质会受石墨氧化过程中制备方法、石墨来源、氧化剂种类、反应条件等因素的影响。针对GO的制备、形成机理、结构控制等方面的研究逐渐引起科研工作者的重视。该文综述近几年有关GO的制备、方法改进、制备过程中涉及到的化学反应和形成机理以及GO结构影响其宏观性能和应用的研究进展,指出确定GO的形成机理和精确控制GO的结构是制约其应用的关键,从工业化生产和可持续性发展的角度对要拓宽和实现GO的应用存在的问题及研究方向进行了总结和展望。     

掺杂石墨烯的ZnO复合材料研究进展

ZnO是一种低成本且应用广泛的材料,石墨烯具有较大的比表面积以及优良的吸附、光电等特性,易于与ZnO结合,可提高ZnO的性能。掺杂石墨烯的ZnO基材料在气体检测、抗菌表面涂层、发光二极管、透明导电电极和光催化等方面都有着应用性。本文概述了近几年来石墨烯掺杂ZnO材料作为导电薄膜、传感器、光催化剂等在光电子、生物医疗、环保等不同领域内的研究与发展,提出了目前该复合材料在制备工艺复杂与可控性差,实际应用与理论有较大差距等问题,并对未来的研究趋势进行了预测和展望。     

Enhanced properties of graphene/fly ash geopolymeric composite cement

This paper reports for the first time the incorporation of in-situ reduced graphene oxide (rGO) into geopolymers. The resulting rGO–geopolymeric composites are easy to manufacture and exhibit excellent mechanical properties. Geopolymers with graphene oxide (GO) concentrations of 0.00, 0.10, 0.35 and 0.50% by weight were fabricated. The functional groups, morphology, void filling mechanisms and mechanical properties of the composites were determined. The Fourier transform infrared (FTIR) spectra revealed that the alkaline solution reduced the hydroxyl/carbonyl groups of GO by deoxygenation and/or dehydration. Concomitantly, the spectral absorbance related to silica type cross-linking increased in the spectra. The scanning electron microscope (SEM) micrographs indicated that rGO altered the morphology of geopolymers from a porous nature to a substantially pore filled morphology with increased mechanical properties. The flexural tests showed that 0.35-wt.% rGO produced the highest flexural strength, Young's modulus and flexural toughness and they were increased by 134%, 376% and 56%, respectively.     

Reduced graphene oxide for Li–air batteries: The effect of oxidation time and reduction conditions for graphene oxide

Reduced graphene oxide (rGO) has shown great promise as an air-cathode for Li–air batteries with high capacity. In this article we demonstrate how the oxidation time of graphene oxide (GO) affects the ratio of different functional groups and how trends of these in GO are extended to chemically and thermally reduced GO. We investigate how differences in functional groups and synthesis may affect the performance of Li–O₂ batteries. The oxidation timescale of the GO was varied between 30 min and 3 days before reduction. Powder X-ray diffraction, micro-Raman, FE-SEM, BET analysis, and XPS were used to characterize the GO’s and rGO’s. Selected samples of GO and rGO were analyzed by solid state ¹³C MAS NMR. These methods highlighted the difference between the two types of rGO’s, and XPS indicated how the chemical trends in GO are extended to rGO. A comparison between XPS and ¹³C MAS NMR showed that both techniques can enhance the structural understanding of rGO. Different rGO cathodes were tested in Li–O₂ batteries which revealed a difference in overpotentials and discharge capacities for the different rGO’s. We report the highest Li–O₂ battery discharge capacity recorded of approximately 60,000 mAh/g_carbon achieved with a thermally reduced GO cathode.     

Mechanical,thermal conductive,and dielectric properties of fluoroelastomer/reduced graphene oxide composites in situ prepared by solvent thermal reduction

Fluoroelastomer (FKM)/reduced graphene oxide (rGO) composites are in situ prepared by solvent thermal reduction method in N,N‐dimethylformamide (DMF) solution. The reduction of graphene oxide (GO) is characterized by X‐Ray photoelectron (XPS), ultraviolet–visible (UV–vis), and Fourier transform infrared (FTIR) spectra. GO and rGO are both efficient fillers to improve the mechanical properties of FKM. The dispersibility of rGO is improved after solvent thermal reduction which is confirmed by scanning electron micrograph (SEM) and X‐ray diffraction (XRD). The homogenous suspension of FKM/rGO composites in DMF can stay stable for more than a month. The dielectric permittivity of FKM/rGO (5 phr) is 26.4 at the frequency of 10⁻¹ Hz, higher than the pure FKM (8.1). The thermal conductivity of rGO/FKM composites increases. POLYM. COMPOS., 35:1779–1785, 2014. © 2013 Society of Plastics Engineers     

Fabrication of ZrO2/rGO nanocomposites by flash sintering under AC electric fields

Ceramic matrix nanocomposites containing graphene possess superior mechanical properties. However, these nanocomposites are very difficult to be prepared using the conventional methods due to severe grain growth and simultaneous degradation of the graphene at high sintering temperatures and long dwell time. Herein, the dense ZrO₂/rGO (reduced graphene oxide) nanocomposites are successfully fabricated by flash sintering of the green compacts consisting of ZrO₂ nanoparticles and graphene oxide (GO) at 893–951℃ in merely 5 seconds under the alternating current (AC) electric fields of 130–150 V cm⁻¹. The GO can be in situ thermal reduced during the flash sintering. The as-prepared ZrO₂/rGO nanocomposites exhibit excellent mechanical properties. This study presents a green and simple approach to fabricate the dense ceramic matrix nanocomposites reinforced with graphene at low temperatures in a short time.     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.