Synthesis and characterization of electrically conductive polyethylene-supported graphene films

We describe a simple mechanical approach for low-density polyethylene film coating by multilayer graphene. The technique is based on the exfoliation of nanocrystalline graphite (few-layer graphene) by application of shear stress and allows to obtain thin graphene layers on the plastic substrate. We report on the temperature dependence of electrical resistance behaviors in films of different thickness. The experimental results suggest that the semiconducting behavior observed at low temperature can be described in the framework of the Efros-Shklovskii variable-range-hopping model. The obtained films exhibit good electrical conductivity and transparency in the visible spectral region.

PACS

72.80.Vp; 78.67.Wj; 78.66.Qn; 85.40.Hp     

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

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

Synthesis of electrochemically-reduced graphene oxide film with controllable size and thickness and its use in supercapacitor

An electrochemical synthesis method of reducing graphene oxide (GO) under constant potential is reported. Electrochemical technique offers control over reaction parameters such as the applied voltage, electrical current and reduction time; whereas the desired size and thickness of the film can be pre-determined by controlling the amount of precursor GO deposited on the electrode with defined shape and surface area. This synthesis technique produces high quality electrochemically reduced GO (ERGO) film with controllable size and thickness. Electrochemical symmetrical supercapacitors based on ERGO films achieved a specific capacitance of 128 F/g with an energy density of 17.8 Wh/kg operating within a potential window of 1.0 V in 1.0 M NaNO₃. The supercapacitor was shown to be stable, retaining ca. 86% of the original specific capacitance after 3500 charge–discharge cycles. The results indicate that this simple synthesis technique for providing graphene-like materials has great potential in various applications such as energy storage.     

Effects of graphene oxide and chemically reduced graphene oxide on the curing kinetics of epoxy amine composites

The curing kinetics of epoxy nanocomposites prepared by incorporating graphene oxide (GO) and chemically reduced graphene oxide (rGO) have been studied using isothermal and nonisothermal differential scanning calorimetry. The kinetic parameters of the curing processes in these systems have been determined by a Kamal and Sourour phenomenological model expanded by a diffusion factor. The predicted curves determined using the kinetic parameters fit well with the isothermal DSC thermograms revealing the proposed kinetic equation clearly explains the curing kinetics of the prepared epoxy amine nanocomposites. Experimental and modeling results demonstrate the presence of an accelerating effect of the GO on the cure of the resin matrix. The use of rGO instead of GO resulted in a slight acceleration reaction rate due to the reduced presence of oxidation groups in rGO. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44803.     

Synthesis of hydrophobic carbon nanotubes/reduced graphene oxide composite films by flash light irradiation

Carbon nanotubes/graphene composites have superior mechanical, electrical and electrochemistry properties with carbon nanotubes as a hydrophobicity boosting agent. Their extraordinary hydrophobic performance is highly suitable for electrode applications in lithium ion batteries and supercapacitors which often employ organic electrolytes. Also the hydrophobic features enable the oil enrichment for the crude oil separation from seawater. The ever reported synthesis routes towards such a composite either involve complicated multi-step reactions, e.g., chemical vapor depositions, or lead to insufficient extrusion of carbon nanotubes in the chemical reductions of graphene oxide, e.g., fully embedding between the compact graphene oxide sheets. As a consequence, the formation of standalone carbon nanotubes over graphene sheets remains of high interests. Herein we use the facile flash light irradiation method to induce the reduction of graphene oxides in the presence of carbon nanotubes. Photographs, micrographs, X-ray diffraction, infrared spectroscopy and thermogravimetric analysis all indicate that graphene oxides has been reduced. And the contact angle tests confirm the excellent hydrophobic performances of the synthesized carbon nanotube/reduced graphene oxide composite films. This one-step treatment represents a straightforward and high efficiency way for the reduction of carbon nanotubes/graphene oxides composites.

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水热法制备还原氧化石墨烯及其导电性调控

导电性可调控的还原氧化石墨烯（rGO）在结构功能材料和化工新材料等领域具有重要的应用前景。本文利用水热还原法实现了rGO的绿色制备,并通过调控反应温度和时间,获得了电导率可控的rGO产品,其电导率范围为10^-4～1 S·cm^-1。采用UV-vis、FT-IR、XPS、SEM、XRD和Raman等表征方法系统研究了rGO还原过程中结构与组成的变化。发现GO还原过程中,其含氧官能团于120℃时开始明显分解,高于140℃后含量显著降低,GO片层sp2区域逐渐恢复,电导率逐渐增大到1 S·cm^-1,同时层间距从8.2 Å减少到3.6 Å（1 Å=0.1 nm）。对比热还原法,水热法有效避免了rGO片层的堆叠,产物分散性较好,有望规模化制备导电性可控的rGO产品。本研究成果对rGO生产和应用具有重要意义。     

Synthesis of fluorinated graphene with tunable degree of fluorination

An easy, low-cost and effective synthesis of fluorinated graphene with tunable C/F atomic ratio (R_C/F) has been realized by the reaction between dispersed graphene oxide and hydrofluoric acid. The results show that fluorine is grafted onto the basal plane of graphene, and the R_C/F can be easily adjusted by controlling the reaction conditions. The as-synthesized fluorinated graphene exhibits a sheet-like morphology with 1–2 layered thickness and tunable bandgap energy from 1.82 to 2.99 eV, which has potential applications in optoelectronic and photonic devices.     

原位聚合法制备GO/PAN复合膜及其性能的研究（英文）

通过原位聚合法制备了氧化石墨烯/聚丙烯腈(GO/PAN)聚合物,采用水相成膜法制得GO/PAN复合膜,探讨了聚合过程中GO用量对PAN的单体转化率(Y)和增比黏度(ηsp)的影响,研究了GO/PAN复合膜的结构和性能。结果表明:GO的加入使PAN的ηsp和Y都有所提高;当加入GO质量分数为2%时,相对于PAN,其Y提高了13.4%,ηsp提高了77.3%;GO片层均匀地分布在GO/PAN复合膜基体当中,并且GO与PAN之间存在一定的作用力;与纯PAN相比,GO/PAN复合膜的结晶度、热稳定性和力学性能都得到一定程度提高,当GO质量分数为2%时,所制得的GO/PAN复合膜的结晶度为47.9%,最大分解温度304℃,600℃时质量保持率为49.8%,强度为6.0 MPa。     

Low temperature elastic properties of chemically reduced and CVD-grown graphene thin films

We have measured internal friction and shear modulus of both reduced graphene oxide and chemical-vapor deposited graphene films measuring as thin as 5 nm. Graphene oxide films were deposited from solutions by spin-coating, and graphene films were synthesized by chemical-vapor deposition (CVD) on Ni thin films. In both cases, these films were transferred from their host substrate into a water bath, then re-deposited onto to a high-Q single crystal silicon mechanical double-paddle oscillator. A minimal thickness dependence of both internal friction and shear modulus was found within the experimental uncertainty for reduced graphene oxide films varying thickness from 5 to 90 nm. The internal friction of all films exhibits a temperature independent plateau below 10 K. The values of the plateaus are similar for both the reduced graphene oxide films and CVD graphene films, and they are as high as the universal “glassy range” where the tunneling states dominated internal friction of amorphous solids lies. This result shows that from a mechanical loss point of view, both graphene oxide and CVD graphene films have high and similar level of disorder. Raman measurements performed on the same samples show higher structure order in CVD graphene films than in graphene oxide films. Our results suggest that internal friction probes different sources of disorder from those by Raman, and the disorder is not directly related to the existence of C–O binding in the graphene oxide films. The shear modulus averages 53 GPa after subtracting Young's modulus component from the vibration mode used in experiments.     

化学还原氧化石墨制备石墨烯实验条件探索研究

通过选取水合肼和硼氢化钠作为氧化石墨制备石墨烯的还原剂,进行还原效果的比较,筛选出硼氢化钠作为较适合还原剂来制备石墨烯,并对实验条件进行探索性研究。结果表明,随着还原剂用量的增大以及反应时间的延长,氧化石墨的特征峰逐渐消失,其含氧基团会被逐渐脱除,还原效果较好。     

化学还原氧化石墨制备石墨烯实验条件探索研究

通过选取水合肼和硼氢化钠作为氧化石墨制备石墨烯的还原剂,进行还原效果的比较,筛选出硼氢化钠作为较适合还原剂来制备石墨烯,并对实验条件进行探索性研究。结果表明,随着还原剂用量的增大以及反应时间的延长,氧化石墨的特征峰逐渐消失,其含氧基团会被逐渐脱除,还原效果较好。     

Synthesis of transfer-free graphene films on dielectric substrates with controllable thickness via an in-situ co-deposition method for electrochromic devices

The solutions and polymer supported materials in graphene transfer process would introduce lots of containments, defects and wrinkles, which weakens the performance of graphene. Herein, an in-situ co-deposition method is carried out to obtain transfer-free graphene films with controllable thickness on several dielectric substrates. The amorphous carbon (carbon source) and copper (catalyst) are co-deposited on dielectric substrates. Followed by an in-situ annealing process, the amorphous carbon is transformed to few-layer graphene. High co-deposition temperature could promote the decomposition of Cu(acac)₂ precursors, leading to the controllable thickness of amorphous carbon layer in Cu@C films. Finally, 3-, 5-, 8- and 10- layers graphene films with transmittance of up to 93.5% and square resistance of 0.8 kΩ·sq^?1 are obtained and a high-performance electrochromic device is fabricated using 3 layers graphene films as electrodes. The “color” and “bleach” time of the electrochromic device is 16.6 s and 6.8 s with the transmittance of 26.8% and 79.7% separately. This method paves an alternative way for the batch production of transfer-free graphene film as electrode materials.     

Enhanced sound absorption properties of porous ceramics modified by graphene oxide films

Under the condition of constant thickness, improving the low-frequency sound absorption performance of conventional sound-absorbing materials is a challenging research topic. To address this issue, a new reduced graphene oxide/polyvinyl alcohol (RGO/PVA) porous composite ceramic was fabricated using freeze-drying and optimized by redesigning the internal connecting pores of porous ceramic matrixes with a reticular microstructure using RGO and PVA. The as-prepared porous structure showed significant enhancement in the low-frequency sound absorption band compared with pristine porous ceramics. In addition, the hybrid porous ceramics exhibited low thermal conductivity. These favorable properties indicate that the hybrid sound-absorbing ceramics have potential application prospects for noise reduction in the fields of construction and electrical and mechanical devices.     

Evolution of the band-gap and optical properties of graphene oxide with controllable reduction level

The dependence of the absorbance of few-layer graphene oxide on reduction level is shown to originate from different inter- and intra-band transitions using infrared–visible spectroscopy. In addition, the band-gap of reduced graphene oxide is tunable from 2 to 0.02 eV depending on its reduction level. These results indicate that reduced graphene oxide possesses great potential as a candidate for photodetection in the mid-infrared range by controlling its band-gap. This study not only gives further insight into the absorption mechanism of graphene oxide reduced to different levels, but also reveals a way to tune and measure the band-gap of graphene-based materials using a simple, economical, and nondestructive approach. This approach should be readily adapted for use in photodetection applications.     

Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets

A number of functionalized graphite oxides were prepared by treatment of graphite oxide (GO) with organic isocyanates. These isocyanate-treated GOs (iGOs) can then be exfoliated into functionalized graphene oxide nanoplatelets that can form a stable dispersion in polar aprotic solvents. Characterization of iGOs by FT-IR spectroscopy and elemental analysis suggested that the isocyanate treatment results in the functionalization of the carboxyl and hydroxyl groups in GO via formation of amides and carbamate esters, respectively. The degree of GO functionalization can be controlled via either the reactivity of the isocyanate or the reaction time. When used with functionalized isocyanates, the described methodology allows for the elaboration of graphene oxide nanoplatelets with different surface functional groups.     

Green preparation of reduced graphene oxide using a natural reducing agent

A simple and efficient method was introduced for the high-conversion preparation of graphene oxide (GO) from large graphite flakes (average flake size=100 μm) using a simplified Hummer׳s method. Natural reducing agents such as lemon juice and vinegar were compared with hydrazine (N₂H₄) as potential reducing agents. Graphene was prepared by chemical reduction of GO because this method was low cost and could be used for large-scale graphene production. This one-pot graphene preparation was performed at room temperature. Different degrees of oxidation of graphite flakes were obtained by stirring graphite in a mixture of sulfuric acid and potassium permanganate at different oxidation times, and highly exfoliated GO sheets were produced. GO was subsequently reduced effectively by lemon juice, a new, green, and potential reducing agent with pH 2.3. This reduced GO exhibited a high electrical conductance of 24.6 μS attributed to its higher C/O ratio (≈8:2) compared with other samples.     

In situ chemical reduction and functionalization of graphene oxide for electrically conductive phenol formaldehyde composites

We report an efficient one-step approach to reduce and functionalize graphene oxide (GO) during the in situ polymerization of phenol and formaldehyde. The hydrophilic and electrically insulating GO is converted to hydrophobic and electrically conductive graphene with phenol as the main reducing agent. Simultaneously, functionalization of GO is realized by the nucleophilic substitution reaction of the epoxide groups of GO with the hydroxyl groups of phenol in an alkali condition. Different from the insulating GO and phenol formaldehyde resin (PF) components, PF composites are electrically conductive due to the incidental reduction of GO during the in situ polymerization. The electrical conductivity of PF composite with 0.85 vol.% of GO is 0.20 S/m, nearly nine orders of magnitude higher than that of neat PF. Moreover, the efficient reduction and functionalization of GO endows the PF composites with high thermal stability and flexural properties. A striking increase in decomposition temperature is achieved with 2.3 vol.% of GO. The flexural strength and modulus of the PF composite with 1.7 vol.% GO are increased by 316.8% and 56.7%, respectively.     

Simultaneous surface functionalization and reduction of graphene oxide with octadecylamine for electrically conductive polystyrene composites

Simultaneous surface functionalization and reduction of graphene oxide (GO) was realized by simple refluxing of GO with octadecylamine (ODA) without the use of any reducing agents. The presence of the long octadecyl chain made the hydrophilic GO hydrophobic, evidenced by the selective dispersion of the ODA-functionalized GO (GO–ODA) in chloroform solvent rather than in water. Interestingly, different from the insulating GO, GO–ODA became electrically conductive due to the reduction in the presence of ODA. The electrical conductivity of GO–ODA was further increased by incidental thermal reduction during the compression-molding of its polystyrene (PS) composites at 210 °C, which exhibited a sharp transition from electrically insulating to conducting with a low percolation threshold. The high conductivity of the PS/GO–ODA composites is attributed to the improved dispersion and the reduction of GO–ODA in comparison with GO.     

Synthesis and antifungal activity of reduced graphene oxide nanosheets

Reduced graphene oxide (rGO) nanosheets were produced using a modified Hummers method. Antifungal activity of rGO nanosheets was tested against three fungi i.e., Aspergillus niger (A. niger), Aspergillus oryzae (A. oryzae) and Fusarium oxysporum (F. oxysporum). The rGO inhibits the mycelial growth of the fungi and it is believed that this is due to its sharp edges. The half maximal inhibitory concentration (IC₅₀), a measure of the effectiveness of the rGO in inhibiting the fungi, was investigated. IC₅₀ values of the rGO against F. oxysporum, A. niger, and A. oryzae are 50, 100, and 100 μg ml^?1, respectively.     

Synthesis of enhanced hydrophilic and hydrophobic graphene oxide nanosheets by a solvothermal method

We report that the hydrophilic affinity of graphene oxide nanosheets can be significantly increased by reacting with allylamine. High resolution transmission electron microscopy and electron diffraction analysis confirmed that the graphene oxide nanosheets were amorphous in structure. Hydrophobic graphene oxide nanosheets were also prepared via functionalising with phenylisocynate (C₆H₅NCO) through a solvothermal synthesis process. Hydrophobic graphene oxide nanosheets can be used as additives in polymer-based composites and other functional applications.