Improved dispersibility of graphene oxide in o-dichlorobenzene by adding a poly(3-alkylthiophene)

The dispersibility of graphene oxide (GO) in o-dichlorobenzene was improved by adding poly(3-hexylthiophene) (P3HT). The resulting GO dispersion was stable for up to one week. Transmission electron microscopy, UV–Vis spectroscopy, Raman spectroscopy and photoluminescence spectroscopy indicated that the crystallization of P3HT molecules on the GO surface prevented GO sheets from strong π–π interactions, and thus greatly increased the dispersibility of GO in organic solvent. The crystallization of P3HT molecules is a physical and reversible process, and it is time and temperature dependent. The crystallization process becomes remarkable with prolonged aging time and decreasing temperature. Other conjugated polymers, including poly(3-butylthiophene) and poly(3-hexylthiophene)-b-poly(ε-caprolactone), were further examined by the same method, and similar phenomena were also observed, indicating that the simple method of using a poly(3-alkylthiophene) to improve GO dispersibility in organic solvent is universal.     

Effect of graphene oxide size and structure on synthesis and optoelectronic properties of hybrid graphene oxide‐poly(3‐hexylthiophene) nanocomposites

Conjugated polymer‐layered filler nanocomposites have received extensive interest as multifunctional materials in various futuristic applications. In this study, the effect of graphene oxide (GO) particle size on the synthesis, optical, and electrochemical properties of in situ prepared graphene oxide (GO)‐poly(3‐hexylthiophene) (P3HT) nanocomposites have been studied. The intercalation of GO with P3HT is inferred from shifting and broadening of the characteristic D‐ and G‐bands of GO in Raman spectra and also the vibrational frequencies in FTIR. This interaction is further confirmed from increase of the optical band gap and the ellipsometry data. The UV–visible absorption maximum (λ _max) of P3HT decreases from 438 to 418 nm in the nanocomposite owing to ionic interactions between GO and the polymer causing a decrease of the polymer conjugation length. Compared to the homopolymer, the emission maximum of the composite is broadened and enhanced in intensity with 10 wt% GO but emission quenching is observed with GO nanoparticles. The evidence of polymer intercalation was also deduced from the determination of the basal spacing and unit cell dimensions of GO, using X‐ray diffraction data. Morphological studies using field emission scanning electron microscopy suggest that the crystalline rod‐like structures observed in the homopolymer have changed to more amorphous, flaky, and porous structures. The cyclic voltammetry studies show an increase in current with increasing GO content in the porous nanocomposites. POLYM. COMPOS., 38:852–862, 2017. © 2015 Society of Plastics Engineers     

Nonisothermal crystallization behaviors of poly(3‐hexylthiophene)/reduced graphene oxide nanocomposites

Poly(3‐hexylthiophene) (P3HT)/reduced graphene oxide (rGO) nanocomposites were prepared through in situ reduction of graphene oxide in the presence of P3HT. The nonisothermal crystallization behaviors of P3HT and P3HT/rGO nanocomposites were investigated by differential scanning calorimetry. The Avrami, Ozawa, and Mo models were used to analyze the nonisothermal kinetics. The addition of rGO remarkably increased the crystallization peak temperature and crystallinity of P3HT, but the crystallization half‐time revealed little variation. The crystallization activation energies were calculated by the Kissinger equation. The results suggested that rGO plays a twofold role in the nonisothermal crystallization of P3HT, that is, rGO promotes the crystallization of P3HT as nucleating agent, and meanwhile, it also restricts the motion of P3HT chains. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The effect of ambient humidity on the electrical properties of graphene oxide films

ABSTRACT: We investigate the effect of water adsorption on the electrical properties of graphene oxide (GO) films using the DC measurement and AC complex impedance spectroscopy. GO suspension synthesized by a modified Hummer's method is deposited on Au interdigitated electrodes. The strong electrical interaction of water molecules with GO films was observed through electrical characterizations. The DC measurement results show that the electrical properties of GO films are humidity- and applied voltage amplitude dependent. The AC complex impedance spectroscopy method is used to analyze the mechanism of electrical interaction between water molecules and GO films in detail. At low humidity, GO films exhibits poor conductivity and can be seen as an insulator. However, at high humidity, the conductivity of GO films increases due to the enhancement of ion conduction. Our systematic research on this effect provides the fundamental supports for the development of graphene devices originated from solution-processed graphene oxide.     

The reduction of graphene oxide

Graphene has attracted great interest for its excellent mechanical, electrical, thermal and optical properties. It can be produced by micro-mechanical exfoliation of highly ordered pyrolytic graphite, epitaxial growth, chemical vapor deposition, and the reduction of graphene oxide (GO). The first three methods can produce graphene with a relatively perfect structure and excellent properties, while in comparison, GO has two important characteristics: (1) it can be produced using inexpensive graphite as raw material by cost-effective chemical methods with a high yield, and (2) it is highly hydrophilic and can form stable aqueous colloids to facilitate the assembly of macroscopic structures by simple and cheap solution processes, both of which are important to the large-scale uses of graphene. A key topic in the research and applications of GO is the reduction, which partly restores the structure and properties of graphene. Different reduction processes result in different properties of reduced GO (rGO), which in turn affect the final performance of materials or devices composed of rGO. In this contribution, we review the state-of-art status of the reduction of GO on both techniques and mechanisms. The development in this field will speed the applications of graphene.     

Effect of the regioregularity of poly(3‐hexylthiophene) on the performances of organic photovoltaic devices

BACKGROUND: The highest efficiencies of bulk‐heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) reported so far are close to 6%. Phenomena occurring during the photovoltaic process, such as the creation, diffusion and separation of excitons, as well as charge carrier transport, are governed by the active layer morphology. The latter phenomenon, which depends on the self‐organization of P3HT, can be influenced by its degree of regioregularity. The aim of this work is to clarify the relationship between the regioregularity of P3HT, the composition of P3HT/PCBM blends and the performances of photovoltaic devices. RESULTS: Two types of P3HTs with different degrees of regioregularity have been synthesized and used as active layers with PCBM in photovoltaic cells. The higher performances in photovoltaic devices are obtained for high‐regioregular P3HT and can be explained considering the self‐organizing properties of high‐regioregular P3HT, leading to higher sunlight absorption and higher hole mobilities. In addition, this report demonstrates the importance of the ratio of P3HT versus PCBM in correlation with the regioregularity of P3HT on the optical properties, charge transport and characteristics of photovoltaic cells. CONCLUSION: We have investigated the dependence of the photovoltaic properties of P3HT/PCBM blend‐based photovoltaic devices on the degree of regioregularity of P3HT. We find that the best performance is exhibited by devices based on highly regioregular P3HT. Also, the best performances are not obtained for the same P3HT:PCBM weight ratios for high‐regioregular P3HT (1:0.8) and low‐regioregular P3HT (1:3). Copyright © 2007 Society of Chemical Industry     

High-order graphene oxide nanoarchitectures

We fabricate unique photoluminescent three dimensional graphene oxide (GO) architectures, so-called GO flowers, by self-assembly onto silicon substrates via solvent-mediated volume-controlled growth. The GO flowers exhibited bright photoluminescence and a photoresponse demonstrating their potential for advanced optical and electronic applications, such as advanced photovoltaic devices and organic light emitting diodes.     

Fabrication of free-standing graphene composite films as electrochemical biosensors

We report a simple fabrication method for large-scale free-standing graphene–gold nanoparticle and graphene-single wall carbon nanotube composite films by using a centrifugal vacuum evaporation followed by a thermal reduction process. The homogeneous mixture of a graphene oxide (GO) suspension with gold nanoparticle (Au NP) or single wall carbon nanotube (SWCNT) is self-assembled at the air/liquid interface, resulting in the multilayered GO–Au NP and GO–SWCNT composite films. The cross-sectional image reveals that the graphene layers are orderly stacked in the reduced GO–Au NP film, while the reduced GO–SWCNT film shows a randomly packed morphology due to the dominant π–π interaction between the side wall of SWCNTs and the GO surfaces. In particular, the reduced GO–Au NP film shows an increased electrode kinetics and cyclic voltammetric response in proportion to the amount of Au NPs, and 3-fold enhancement of anodic peak current was observed compared with that of the reduced GO films. We employed the reduced GO–Au NP film as a matrix to immobilize tyrosinase enzyme for phenol detection, and the phenol-induced electrochemical catalytic reaction can be monitored with 3-fold higher sensitivity than the reduced GO film, demonstrating great potential of graphene composite as an electrochemical enzyme biosensor for environmental pollutant screening.     

High thermal conductivity and increased thickness graphene nanosheet films prepared through metal ion-free route

With the miniaturization and integration of electronic devices heat conduction becomes a serious problem. Graphene films catch research's attention because of its excellent thermal performance and graphene oxide (GO) has been used as the most common precursor to prepare graphene films. But mostly film fabricated from GO is thinner than 30 μm and much thicker films are required to meet certain requirements. Also taking GO as raw material has many disadvantages such as the introduction of massive concentrated sulfuric acid and metal ions, huge weight loss in heat treatment and so on. Herein, we propose a new strategy to prepare graphene nanosheet films (GNFs) with a thickness of 100 μm by vacuum filtration of expand graphite through weak oxidation (WEG). Unlike common strategy, WEG without any metal ions introduced instead of GO is chosen as our raw material. The addition of nonionic surfactant and the employment of microfluidization can stabilize WEG dispersion. After graphitization at 2800 °C WEGF is transferred to GNF. The obtained 100 μm-thick film possesses a decent in-plane thermal conductivity (TC) of 760 W/mk and electrical conductivity (EC) of 5.2×10⁵ S/m. Thick films with high TC can guarantee passing more heat flux and fill in larger gaps inside devices.     

Focusing on energy and optoelectronic applications: a journey for graphene and graphene oxide at large scale

Carbon is the only element that has stable allotropes in the 0th through the 3rd dimension, all of which have many outstanding properties. Graphene is the basic building block of other important carbon allotropes. Studies of graphene became much more active after the Geim group isolated "free" and "perfect" graphene sheets and demonstrated the unprecedented electronic properties of graphene in 2004. So far, no other individual material combines so many important properties, including high mobility, Hall effect, transparency, mechanical strength, and thermal conductivity. In this Account, we briefly review our studies of bulk scale graphene and graphene oxide (GO), including their synthesis and applications focused on energy and optoelectronics. Researchers use many methods to produce graphene materials: bottom-up and top-down methods and scalable methods such as chemical vapor deposition (CVD) and chemical exfoliation. Each fabrication method has both advantages and limitations. CVD could represent the most important production method for electronic applications. The chemical exfoliation method offers the advantages of easy scale up and easy solution processing but also produces graphene oxide (GO), which leads to defects and the introduction of heavy functional groups. However, most of these additional functional groups and defects can be removed by chemical reduction or thermal annealing. Because solution processing is required for many film and device applications, including transparent electrodes for touch screens, light-emitting devices (LED), field-effect transistors (FET), and photovoltaic devices (OPV), flexible electronics, and composite applications, the use of GO is important for the production of graphene. Because graphene has an intrinsic zero band gap, this issue needs to be tackled for its FET applications. The studies for transparent electrode related applications have made great progress, but researchers need to improve sheet resistance while maintaining reasonable transparency. Proposals for solving these issues include doping or controlling the sheet size and defects, and theory indicates that graphene can match the overall performance of indium tin oxide (ITO). We have significantly improved the specific capacitance in graphene supercapacitor devices, though our results do not yet approach theoretical values. For composite applications, the key issue is to prevent the restacking of graphene sheets, which we achieved by adding blocking molecules. The continued success of graphene studies will require further development in two areas: (1) the large scale and controlled synthesis of graphene, producing different structures and quantities that are needed for a variety of applications and (2) on table applications, such as transparent electrodes and energy storage devices. Overall, graphene has demonstrated performance that equals or surpasses that of other new carbon allotropes. These features, combined with its easier access and better processing ability, offer the potential basis for truly revolutionary applications and as a future fundamental technological material beyond the silicon age.     

pH-Mediated fine-tuning of optical properties of graphene oxide membranes

We demonstrate a pH-mediated fine-tuning method for the transmittance and optical properties of graphene oxide membranes (GOMs) which are assembled at liquid/air interface starting from graphene oxide (GO) hydrosols. The transmittance of GOM continuously decreases with the increase of the pH value of the parent hydrosol. The size and surface chemistry of GO nanosheets are discussed to how to influence the transmittance of GO hydrosol and the optical properties of the resulting membrane since a size classification occurs in acidic condition and a deoxygenate reaction is initiated by basic environment. This study indicates an easy strategy for precisely adjusting the optical properties of graphene-based membrane, which is very important for developing novel optical devices.     

染料敏化二氧化钛-石墨烯杂化材料光催化水分解制氢

以曙红、石墨氧化物与二氧化钛(P25)为原料,利用水热法制备曙红敏化的二氧化钛-石墨烯杂化材料。通过X射线光电子能谱(XPS)考察了石墨氧化物(GO)以及染料敏化二氧化钛石墨烯杂化材料(T-G-EY)的C1s信号的变化,水热过程使石墨烯含氧官能团含量大幅度减少,透射电镜照片清晰地显示二氧化钛纳米颗粒均匀分散在石墨烯片层上。紫外-可见漫反射光谱(DRS)分析发现复合材料的带隙变窄,从P25的3.25 eV降低到2.75 eV,吸光范围明显向可见光区拓展,并存在曙红的特征吸收峰。从荧光光谱上明显看出复合材料发生了荧光猝灭现象,确认是石墨烯与二氧化钛之间及曙红与石墨烯之间存在一定的相互作用。T-G-EY在500 W氙灯照射下光解水制氢气的效率比P25提高了10.2倍。     

高电活性石墨烯/聚苯胺纳米复合材料的制备和表征

采用了一种简单有效地方法制备了高电活性的石墨烯/聚苯胺复合材料。首先,将苯胺在氧化石墨烯（GO）的水性分散液中氧化聚合,制备了氧化石墨烯/聚苯胺（GO/PANI）,再将GO/PANI与水合肼反应,制得还原-氧化石墨烯/聚苯胺（R（GO/PANI））。利用透射电子显微镜（TEM）,热失重分析（TGA）和循环伏安法（CV）对GO/PANI和R（GO/PANI的形貌,热稳定性和电化学性能进行了分析研究。结果表明,GO表面存PANI,且R（GO/PANI）的热稳定性和电活性都明显高于GO/PANI。     

Photovoltaic and UV detector applications of ZnS/rGO nanocomposites synthesized by a green method

The effect of graphene concentration on the photovoltaic and UV detector applications of ZnS/graphene nanocomposites was investigated. The nanocomposites were synthesized by a green, cost-effective, and simple co-precipitation method with different graphene concentrations (5, 10, and 15 wt%) using L-cysteine amino acid as a surfactant and graphene oxide (GO) powder as a graphene source. Transmission electron microscopy (TEM) images showed that the ZnS NPs were decorated on GO sheets and the GO caused a significant decrease in ZnS diameter size. The results of X-ray diffraction (XRD) patterns, Raman, and Fourier transform infrared (FTIR) spectroscopy indicated that the GO sheets were changed into reduced graphene oxide (rGO) during synthesis process. Therefore, L-cysteine amino acid played its role as a reducing agent to reduce the GO. Photovoltaic measurements showed that the graphene caused to increase the efficiency of solar-cell application of ZnS/rGO nanocomposites. In addition, our observation showed that the nanocomposites were suitable as ultraviolet (UV) detectors and graphene concentration increased the responsibility of the detectors.     

Low voltage resistive memory devices based on graphene oxide–iron oxide hybrid

Low cost resistive switching memory devices using graphene oxide–iron oxide (GF) hybrid thin films, sandwiched between platinum (Pt) and indium-tin-oxide (ITO) electrodes, were demonstrated. The fabricated devices with Pt/GF/ITO structure exhibited reliable and reproducible bipolar resistive switching performance, with an ON/OFF current ratio of 5 × 10³, excellent retention time longer than 10⁵ s, SET voltage of 0.9 V, and good endurance properties. In all aspects of the device characteristics, the GF based devices outperformed graphene oxide (GO) based devices. Ohmic conduction was found to be dominant current conduction mechanism in all switching regions except for the high voltage regime where space charge limited conduction and trap charge limited conduction were found to be the main current conduction mechanism. X-ray photoelectron spectroscopy and transmission electron microscopy/selected area diffraction analysis revealed γ-Fe₂O₃ and Fe₃O₄ iron oxide phases coexist in the hybrid films. While the desorption/adsorption of oxygen-related functional groups on the GO sheets is the dominant resistive switching mechanism in Pt/GO/ITO devices, the formation/rupture of multiple highly conducting Fe₃O₄ filaments at the iron oxide/GO interface additionally facilitate the switching in the present Pt/GF/ITO devices. Thereby, excellent electrical switching performance was achieved.     

Improved stability in P3HT:PCBM photovoltaics by incorporation of well‐designed polythiophene/graphene compositions

Morphological and photovoltaic stabilities of poly(3‐hexylthiophene) (P3HT):phenyl‐C₆₁‐butyric acid methyl ester (PC₇₁BM) solar cells were investigated in pristine and modified states. To this end, four types of patterned/assembled nanostructures, namely reduced graphene oxide (rGO)‐g‐poly(3‐dodecylthiophene)/P3HT patched‐like pattern, rGO–polythiophene/P3HT/PC₇₁BM nanofiber, rGO‐g‐P3HT/P3HT cake‐like pattern and supra(polyaniline (PANI)‐g‐rGO/P3HT), were designed on the basis of rGO and various conjugated polymers. Intermediately covered rGO nanosheets by P3HT crystals (supra(PANI‐g‐rGO/P3HT)) performed better than sparsely (patched‐like pattern) and fully (cake‐like pattern) covered ones in P3HT:PC₇₁BM solar cell systems. Supra(PANI‐g‐rGO/P3HT) nanohybrids largely phase‐separated in active layers (root mean square = 0.88 nm) and also led to the highest performance (power conversion efficiency of 5.74%). The photovoltaic characteristics demonstrated decreasing trends during air aging for all devices, but with distinct slopes. The steepest decreasing plots were obtained for the unmodified P3HT:PC₇₁BM devices (from 1.77% to 0.28%). The two supramolecules with the most ordered structures, that is, cake‐like pattern (10.12 mA cm^?2, 51%, 0.58 V, 2.2 × 10^?6 cm² V^?1 s^?1, 4.3 × 10^?5 cm² V^?1 s^?1, 0.69 nm and 2.99%) and supra(PANI‐g‐rGO/P3HT) (12.51 mA cm^?2, 57%, 0.63 V, 1.2 × 10^?5 cm² V^?1 s^?1, 3.4 × 10^?4 cm² V^?1 s^?1, 0.82 nm and 4.49%), strongly retained morphological and photovoltaic stabilities in P3HT:PC₇₁BM devices after 1 month of air aging. According to the morphological, optical, photovoltaic and electrochemical results, the supra(PANI‐g‐rGO/P3HT) nanohybrid was the best candidate for stabilizing P3HT:PC₇₁BM solar cells. © 2020 Society of Chemical Industry     

A Novel Method for Preparing Vertically Aligned CdS Nanorod Arrays and Its Application in Photovoltaic Cells with P3HT Fibers

Vertically aligned cadmium sulfide (CdS) nanorod arrays were prepared through a novel thermal annealing route. By embedding the as-prepared CdS nanorod arrays into the poly(3-hexylthiophene) (P3HT) nanofiber (NF) matrix, the photovoltaic devices were fabricated with the structure of ITO/PEDOT:PSS/CdS arrays/P3HT NF/Au. The device performance was highly dependent on the P3HT NF layer thickness in this structure, and a power conversion efficiency (PCE) of 0.23 % was obtained for optimal P3HT NF layer thickness of 150 nm. In addition, much higher PCE of 0.84 % was achieved after post-annealing. The significantly improved photovoltaic performance may be caused by the increased interfacial areas between P3HT NFs and CdS nanorods for efficient charge separation, as well as the decreased inter-nanocrystal distance caused by insulating organic ligands after the annealing treatment. The results demonstrate a promising inorganic–organic hybrid photovoltaic structure with vertically aligned CdS nanorods arrays.     

Graphene oxide-anchored reactive sulfonated copolymer via simple one pot condensation polymerization: proton-conducting solid electrolytes

A rapid and efficient post-polymerization functionalization of poly(urea-co-urethane) (PUU) onto the graphene oxide (GO) nanosheets has been developed to produce super-acidic polymer/GO hybrid nanosheets. Thus, the surface of GO nanosheets were functionalized with 3-(triethoxysilyl)propyl isocyanate (TESPIC) from hydroxyl groups to yield isocyanate functionalized graphene oxide nanosheets. Then, sulfonated polymer/GO hybrid nanosheets were prepared by condensation polymerization of isocyanate-terminated pre-polyurea onto isocyanate functionalized graphene oxide nanosheets through the formation of carbamate bonds. FTIR and TGA results indicated that TESPIC modifier agent and poly(urea-co-urethane) were successfully grafted onto the GO nanosheets. The grafting efficiency of poly(urea-co-urethane) polymer onto the GO nanosheets was estimated from TGA thermograms to be 205.9%. Also, sulfonated polymer/GO hybrid nanosheets showed a proton conductivity as high as 3.7 mS cm^?1. Modification and morphology of GO nanosheets before and after modification processes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD).     

A sensitive and selective pyrosine sensor based on palygorskite–graphene modified electrode

Palygorskite–graphene composite was obtained by the electrochemical reduction of palygorskite–graphene oxide (GO), and the resulted palygorskite–graphene modified glassy carbon electrode (GCE) was used as the amperometric sensor for pyrosine determination. Compared to the graphene modified GCE, the detecting sensitivity of pyrosine was greatly improved at the palygorskite–graphene modified GCE. This was mainly attributed to the high adsorption capability of palygorskite. The effect of the mass ratio of GO to palygorskite was investigated, and the optimum mass ratio of GO to palygorskite was chosen as 2:1. The calibration curve was linear for pyrosine concentration from 21 to 598 μM, and the detection limit was as low as 5.98 nM (signal-to-noise ratio of 3). The palygorskite–graphene modified GCE also had satisfactory fabrication reproducibility, good determination precision and high detecting selectivity for pyrosine.     

Preparation and tribological properties of novel boehmite/graphene oxide nano-hybrid

Novel boehmite/graphene oxide nano-hybrid (GO–GPTS–AlOOH) was prepared through a simple covalent bond method, which was subsequently explored as lubricant additive. For this purpose, the 3-glycidoxypropyl-trimethoxysilane (GPTS) was first chemically grafted on nano-boehmite (AlOOH) to fabricate the modified boehmite (GPTS–AlOOH). Then the GPTS–AlOOH was anchored on graphene oxide (GO) nanosheets to prepare GO–GPTS–AlOOH nano-hybrid through a coupled reaction. The structure, composition and morphology of GO–GPTS–AlOOH was characterized by FT-IR, XRD, TG/DTG, SEM and TEM, revealing that nano-boehmite was uniformly coated on GO surface. More importantly, tribological properties of GO–GPTS–AlOOH as lubricating oil additive were investigated using a ball-on-disc testing machine and a four-ball machine. It was found that the friction reduction and anti-wear ability of lubricant oil containing GO–GPTS–AlOOH hybrid was highly improved compared to bare base oil (VHVI8). Specifically, friction coefficient (COF), wear scar diameter (WSD) and wear rate were reduced by 14%, 28% and 73%, respectively. The enhancement can be attributed to the synergistic effect of the nanobearing mechanism and ultimate strengthen of graphene sheets between the frictional interfaces.