氧化石墨烯水热还原前后的发光光谱

分别采用改进Hummers方法和水热还原法制备了氧化石墨烯(GO)和还原氧化石墨烯(RGO)。 GO和RGO经透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、红外光谱(IR)、荧光发射和激发光谱(PL、PLE)等技术手段进行了表征。 荧光发射光谱显示,氧化石墨烯(GO)在可见光的激发下可以得到波长在600~800 nm范围内的宽谱近红外荧光。 通过比较氧化石墨烯水热还原前后的光谱变化,发现氧化石墨烯近红外荧光起源于氧化石墨烯的表面含氧基团,如C=O、COOH。 近红外荧光穿透性好、对生物组织损坏小,非常适合于生物成像,预示着氧化石墨烯在生物成像方面的应用潜力。     

Investigation of the Thermal Stability of the Carbon Framework of Graphene Oxide

In this study, we use our recently prepared graphene oxide (GO) with an almost intact σ‐framework of carbon atoms (ai‐GO) to probe the thermal stability of the carbon framework for the first time. Ai‐GO exhibits few defects because CO₂ formation is prevented during synthesis. Ai‐GO was thermally treated before chemical reduction and the resulting defect density in graphene was subsequently determined by statistical Raman microscopy. Surprisingly, the carbon framework of ai‐GO is stable in thin films up to 100 °C. Furthermore, we find evidence for an increase in the quality of ai‐GO upon annealing at 50 °C before reduction. The carbon framework of GO prepared according to the popular Hummers’ method (GO‐c) appears to be less stable and decomposition starts at 50 °C, which is qualitatively indicated by CO₂‐trapping experiments in μm‐thin films. Information about the stability of GO is important for storing, processing, and using GO in many applications.     

Controlled Chemistry Approach to the Oxo‐Functionalization of Graphene

Graphene is the best‐studied 2D material available. However, its production is still challenging and the quality depends on the preparation procedure. Now, more than a decade after the outstanding experiments conducted on graphene, the most successful wet‐chemical approach to graphene and functionalized graphene is based on the oxidation of graphite. Graphene oxide has been known for more than a century; however, the structure bears variable large amounts of lattice defects that render the development of a controlled chemistry impossible. The controlled oxo‐functionalization of graphene avoids the formation of defects within the σ‐framework of carbon atoms, making the synthesis of specific molecular architectures possible. The scope of this review is to introduce the field of oxo‐functionalizing graphene. In particular, the differences between GO and oxo‐functionalized graphene are described in detail. Moreover analytical methods that allow determining lattice defects and functional groups are introduced followed by summarizing the current state of controlled oxo‐functionalization of graphene.     

LDPE/EVA/graphene nanocomposites with enhanced mechanical and gas permeability properties

In the present work, graphene oxide (GO) and reduced graphene oxide (RGO) were incorporated at low‐density polyethylene (LDPE)/ethylene vinyl acetate (EVA) copolymer blend using solution casting method. Monolayer GO with 1‐nm thickness and good transparency was synthesized using the well‐known Hummers's method. Fourier transform infrared and X‐ray photoelectron spectroscopy data exhibited efficient reduction of GO with almost high C/O ratio of RGO. Scanning electron microscopy showed the well distribution of GO and RGO within LDPE/EVA polymer matrix. The integrating effects of GO and RGO on mechanical and gas permeability of prepared films were examined. Young's modulus of nanocomposites are improved 65% and 92% by adding 7 wt% of GO and RGO, respectively. The tensile measurements showed that maximum tensile strength emerged in 3 wt% of loading for RGO and 5 wt% for GO. The measured oxygen and carbon dioxide permeability represented noticeably the attenuation of gas permeability in composite films compared with pristine LDPE/EVA blend. Copyright © 2015 John Wiley & Sons, Ltd.     

An Effective Method for Bulk Obtaining Graphene Oxide Solids

We report an effective method for bulk obtaining exfoliated graphene oxide (GO) solids from their aqueous solutions, which were prepared from nature graphite by an oxidation method. Tyndall effect proved that GO solution has a colloidal nature. Different flocculants were used to coagulate GO colloidal, and it was found that NaOH had the most obvious coagulation effect to GO. Transmission electron microscopy, X‐ray diffraction and atomic force microscopy analysis demonstrated that there were a large number of complete few‐layer GO sheets with thickness of about 0.8 nm, and the surfaces were very smooth, almost free of impurities. Liquid state ¹³C NMR and Fourier transformation infrared spectra showed the presence of abundant benzene carboxylic, hydroxyl and epoxide groups in the basal planes of GO. The graphene materials reduced from GO solids had good electrical conductivity. Our work explored a simple and effective route to extract GO from their solution, which is the most important to GO and graphene researches and applications.     

Low‐Temperature Solid‐State Microwave Reduction of Graphene Oxide for Transparent Electrically Conductive Coatings on Flexible Polydimethylsiloxane (PDMS)

Microwaves (MWs) are applied to initialize deoxygenation of graphene oxide (GO) in the solid state and at low temperatures (～165 °C). The Fourier‐transform infrared (FTIR) spectra of MW‐reduced graphene oxide (rGO) show a significantly reduced concentration of oxygen‐containing functional groups, such as carboxyl, hydroxyl and carbonyl. X‐ray photoelectron spectra confirm that microwaves can promote deoxygenation of GO at relatively low temperatures. Raman spectra and TGA measurements indicate that the defect level of GO significantly decreases during the isothermal solid‐state MW‐reduction process at low temperatures, corresponding to an efficient recovery of the fine graphene lattice structure. Based on both deoxygenation and defect‐level reduction, the resurgence of interconnected graphene‐like domains contributes to a low sheet resistance (～7.9×10⁴ Ω per square) of the MW‐reduced GO on SiO₂‐coated Si substrates with an optical transparency of 92.7 % at ～547 nm after MW reduction, indicating the ultrahigh efficiency of MW in GO reduction. Moreover, the low‐temperature solid‐state MW reduction is also applied in preparing flexible transparent conductive coatings on polydimethylsiloxane (PDMS) substrates. UV/Vis measurements indicate that the transparency of the thus‐prepared MW‐reduced GO coatings on PDMS substrates ranges from 34 to 96 %. Correspondingly, the sheet resistance of the coating ranges from 10⁵ to 10⁹ Ω per square, indicating that MW reduction of GO is promising for the convenient low‐temperature preparation of transparent conductors on flexible polymeric substrates.     

Effect of polycarbonate structure and reduction time on graphene oxide dispersion

Polycarbonate (PC)/graphene oxide (GO) composites with different GO reduction time and PC types were prepared by using a twin screw extruder at 260 °C after solution mixing with chloroform. The chemical reaction degree of PC/GO composites with GO reduction time was confirmed by C–H stretching peak at 3000 cm ^?1, and the chemical reaction degree decreased with GO reduction time. The slope for storage (G′) versus loss (G″) modulus plot decreases with an increase in heterogeneous property of the polymer melts. So we can check the GO dispersion of the PC/GO composites using by the slop for G′–G″ plot. According to the G′–G″ slopes for PC/GO composite with GO reduction time, GO was well dispersed within PC matrix when the reduction time decreased. It was re‐confirmed by atomic force microscope (AFM) results. Based on the degradation temperature by Thermogravimetric analysis, G′–G″ slopes, and surface roughness by AFM, the branched PC was better than linear PC for the GO dispersion within PC matrix. The fact was also confirmed by tensile test results that the Young's modulus increased with the improvement of GO dispersion. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface and Interface Engineering of Graphene Oxide Films by Controllable Photoreduction

We report herein the engineering of the surface/interface properties of graphene oxide (GO) films by controllable photoreduction treatment. In our recent works, typical photoreduction processes, including femtosecond laser direct writing (FsLDW), laser holographic lithography, and controllable UV irradiation, have been employed to make conductive reduced graphene oxide (RGO) microcircuits, hierarchical RGO micro‐nanostructures with both superhydrophobicity and structural color, as well as moisture‐responsive GO/RGO bilayer structures. Compared with other reduction protocols, for instance, chemical reduction and thermal annealing, the photoreduction strategy shows distinct advantages, such as mask‐free patterning, chemical‐free modification, controllable reduction degree, and environmentally friendly processing. These works indicate that the surface and interface engineering of GO through controllable photoreduction of GO holds great promise for the development of various graphene‐based microdevices.     

The Route to Functional Graphene Oxide

We report on an easy‐to‐use, successful, and reproducible route to synthesize functionalized graphite oxide (GO) and its conversion to graphene‐like materials through chemical or thermal reduction of GO. Graphite oxide containing hydroxyl, epoxy, carbonyl, and carboxyl groups loses mainly hydroxyl and epoxy groups during reduction, whereas carboxyl species remain untouched. The interaction of functionalized graphene with fluorescent methylene blue (MB) is investigated and compared to graphite, fully oxidized GO, as well as thermally and chemically reduced GO. Optical absorption and emission spectra of the composites indicate a clear preference for MB interaction with the GO derivatives containing a large number of functional groups (GO and chemically reduced GO), whereas graphite and thermally reduced GO only incorporate a few MB molecules. These findings are consistent with thermogravimetric, X‐ray photoelectron spectroscopic, and Raman data recorded at every stage of preparation. The optical data also indicate concentration‐dependent aggregation of MB on the GO surface leading to stable MB dimers and trimers. The MB dimers are responsible for fluorescence quenching, which can be controlled by varying the pH value.     

Graphene preparation and graphite exfoliation

The synthesis of Graphene is critical to achieving its functions in practical applications. Different methods have been used to synthesis graphene, but graphite exfoliation is considered the simplest way to produce graphene and graphene oxide. In general, controlling the synthesis conditions to achieving the optimum yield, keeping the pristine structure to realize on-demand properties, minimum layers with the smallest lateral size, and minimum oxygen content are the most obstacles experienced by researchers. Each application requires a specific graphene model, graphene oxides GO, or even graphene intercalated compounds (GIC) depending on synthesis conditions and approach. This paper reviewed and summarized the most researches in this field and focusing on exfoliation methods.     

A facile approach to obtaining PVDF/graphene fibers and the effect of nanoadditive on the structure and properties of nanocomposites

The key factors in the design of nanocomposites include obtaining a good adhesion between components and homogeneous dispersion of the nanoadditive in the polymer matrix. Direct mixing of graphene with polymers which are then processed by melt compounding method results in strong tendency of nanoadditive to agglomerate. The article presents a new approach to obtaining poly(vinylidene fluoride)/graphene (PVDF/rGO) nanocomposites in the form of fibers. This method is characterized by the use of graphene oxide (GO) dispersed in the plasticizer instead of graphene. The combination of the fibers forming process with simultaneous reduction of GO to rGO allowed the authors to obtain nanocomposites with graphene homogeneously dispersed in the polymer matrix. Moreover, addition of graphene resulted in formation of β-phase in the nanocomposites, which is characteristic for PVDF and responsible for pyroelectric and piezoelectric properties of this polymer.     

Synthesis of polydopamine‐coated graphene–polymer nanocomposites via RAFT polymerization

Graphene‐polymer nanocomposites have significant potential in many applications such as photovoltaic devices, fuel cells, and sensors. Functionalization of graphene is an essential step in the synthesis of uniformly distributed graphene‐polymer nanocomposites, but often results in structural defects in the graphitic sp² carbon framework. To address this issue, we synthesized graphene oxide (GO) by oxidative exfoliation of graphite and then reduced it into graphene via self‐polymerization of dopamine (DA). The simultaneous reduction of GO into graphene, and polymerization and coating of polydopamine (PDA) on the reduced graphene oxide (RGO) surface were confirmed with XRD, UV–Vis, XPS, Raman, TGA, and FTIR. The degree of reduction of GO increased with increasing DA/GO ratio from 1/4 to 4/1 and/or with increasing temperature from room temperature to 60 °C. A RAFT agent, 2‐(dodecylthiocarbonothioylthio)?2‐methylpropionic acid, was linked onto the surface of the PDA/RGO, with a higher equivalence of RAFT agent in the reaction leading to a higher concentration of RAFT sites on the surface. Graphene‐poly(methyl methacrylate), graphene‐poly(tert‐butyl acrylate), and graphene‐poly(N‐isopropylacrylamide) nanocomposites were synthesized via RAFT polymerization, showing their characteristic solubility in several different solvents. This novel synthetic route was found facile and can be readily used for the rational design of graphene‐polymer nanocomposites, promoting their applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3941–3949     

Metal‐Free,Initiator‐Free Graphene Oxide‐Catalyzed Trifluoromethylation of Arenes

The direct C−H trifluoromethylation of arenes catalyzed by graphene oxide (GO) under safe conditions is described. This strategy is metal‐free, initiator‐free, safe, and scalable. It employs a readily available CF₃ source and the reaction can be easily controlled to obtain a mono‐trifluorinated product. This method opens a new avenue for GO‐catalyzed chemistry.     

Reassessing the Necessity of the Drying Step in Hummer's Method for Graphene Oxide Synthesis

The necessity of drying the graphene oxide suspension (GOsus) using Hummer's Method to produce graphene oxide (GO) powder was studied. The undried GOsus was compared to the dried GO. The GO materials were used as Pt supports via NaBH₄ reduction for O₂ reduction. XRD patterns showed similar d-spacing in both while the half-cell tests of the Pt/rGOsus and Pt/rGO catalysts were similar. GOsus film, deposited onto Toray Carbon Paper and electrochemically reduced in aq. H₂SO₄ was tested as a capacitor. The suspension and dried graphene-based capacitor showed similar XRD and XPS patterns and the erGOsus capacitor displayed increased capacitance.     

Study of Anticancer Properties of Graphene Oxide–Metal Oxide Composite

Graphene and graphene oxide (GO) have garnered significant attention due to their exceptional properties. GO, enriched with various functional groups such as epoxy, hydroxyl, and carboxylic groups, has exhibited remarkable potential in biomedical applications. The combination of GO with metals has proven to be a promising platform for cellular imaging, with this study focusing on the preparation of diverse hybrids of GO with metal oxides (GO/MO) and their potential as anticancer agents. In this research, GO is functionalized with MOs like TiO₂, Fe₃O₄, and Cu₂O using specific chemical methods and investigated for the anticancer activity for the application as cancer therapeutic agent. The resulting GO/MO hybrids exhibits favorable thermal and mechanical properties. Moreover, their cytotoxicity against human lung cancer cells is assessed in vitro, revealing the promising anticancer activity of GO/MO hybrids. Notably, the GO/Cu₂O hybrid demonstrates particularly high cytotoxicity in human lung cancer cells.     

Molecular Bridges Stabilize Graphene Oxide Membranes in Water

Recent innovations highlight the great potential of two‐dimensional graphene oxide (GO) films in water‐related applications. However, undesirable water‐induced effects, such as the redispersion and peeling of stacked GO laminates, greatly limit their performance and impact their practical application. It remains a great challenge to stabilize GO membranes in water. A molecular bridge strategy is reported in which an interlaminar short‐chain molecular bridge generates a robust GO laminate that resists the tendency to swell. Furthermore, an interfacial long‐chain molecular bridge adheres the GO laminate to a porous substrate to increase the mechanical strength of the membrane. By rationally creating and tuning the molecular bridges, the stabilized GO membranes can exhibit outstanding durability in harsh operating conditions, such as cross‐flow, high‐pressure, and long‐term filtration. This general and scalable stabilizing approach for GO membranes provides new opportunities for reliable two‐dimensional laminar films used in aqueous environments.     

Injectable Graphene Oxide/Graphene Composite Supramolecular Hydrogel for Delivery of Anti-Cancer Drugs

Injectable hydrogels have attracted a lot of attention in drug delivery, however, their capacity to deliver water-insoluble or hydrophobic anti-cancer drugs is limited. Here, we developed injectable graphene oxide/graphene composite supramolecular hydrogels to deliver anti-cancer drugs. Pluronic F-127 was used to stabilize graphene oxide (GO) and reduced graphene oxide (RGO) in solution, which was mixed with α-cyclodextrin (α-CD) solution to form hydrogels. Native hydrogel was used as control. GO or RGO slightly shortened gelation time. The storage and loss moduli of the hydrogels were tracked by dynamic force measurement. The storage modulus of GO or RGO composite hydrogels was larger than that of the native hydrogel. Hydrogels were unstable in solution and eroded gradually. GO or RGO in Pluronic F-127 solution could potentially improve the solubility of the water-insoluble anti-cancer drug camptothecin (CPT), especially with large drug-loaded CPT amount. Drug release behaviors from solutions and hydrogels were characterized. The nanocomponents (GO or RGO) were able to bind more drug molecules either for CPT or for doxorubicin hydrochloride (DXR) in solution. Therefore, GO or RGO composite hydrogel could potentially enable better controlled and gentler drug release (for both CPT and DXR) than native hydrogel.     

Free‐Radical‐Promoted Conversion of Graphite Oxide into Chemically Modified Graphene

The preparation of chemically modified graphene (CMG) generally involves the reduction of graphite oxide (GO) by using various reducing reagents. Herein, we report a free‐radical‐promoted synthesis of CMG, which does not require any conventional reductant. We demonstrated that the phenyl free radical can efficiently promote the conversion of GO into CMG under mild conditions and produces phenyl‐functionalized CMG. This pseudo‐“reduction” process is attributed to a free‐radical‐mediated elimination of the surface‐attached oxygen‐containing functionalities. This work illustrates a new strategy for preparing CMG that is alternative to the conventional means of chemical reduction. Furthermore, the phenyl‐functionalized graphene shows an excellent performance as an electrode material for lithium‐battery applications.     

Precise Tuning of Surface Composition and Electron‐Transfer Properties of Graphene Oxide Films through Electroreduction

Graphene materials are generally prepared from the exfoliation of graphite oxide (GO) to graphene oxide, followed by subsequent chemical or thermal reduction. These methods, although efficient in removing most of the oxygen functionalities from the GO material, lack control over the extent of the reduction process. We demonstrate here an electrochemical reduction procedure that not only allows for precise control of the reduction process to obtain a graphene material with a well‐defined C/O ratio in the range of 3 to 10, but also one that is able to tune the electrocatalytic properties of the reduced material. A method that is able to precisely control the amount and density of the oxygen functionalities on the graphene material as well as its electrochemical behaviour is very important for several applications such as electronics, bio‐composites and electrochemical devices.     

Ultrafast room-temperature reduction of graphene oxide by sodium borohydride,sodium molybdate and hydrochloric acid

Since graphene-based materials have shown great potential in many fields,it is important to explore ultrafast and high-efficient methods to synthesize reduced graphene oxide(rGO) using inexpensive reducing agents under mild conditions.Here,we reported a novel method for the ultrafast chemical reduction of graphene oxide(GO) at room temperature using sodium borohydride(NaBH₄),sodium molybdate(Na₂MoO₄) and hydrochloric acid(HCl).The reduction was carried out within 2 min.A series of characterization results revealed that the obtained reduced graphene oxide has higher reduction degree than that synthesized by NaBH₄ alone at high temperature.Moreover,rGO electrode based on the present reducing method exhibited a superior specific capacitance of 139.8 F/g at a current density of1 A/g,indicating that it can be used as electrode materials for supercapacitors.