Fe~(3+)对石墨烯氧化物荧光淬灭机理的研究

采用改进的Humer法合成了石墨烯氧化物,利用搭建的时间分辨光谱探测系统详细探究了Fe~(3+)(浓度为0.5、1、2 mmol/L)对石墨烯氧化物荧光淬灭物理机制。稳态荧光发射光谱中,随着Fe~(3+)浓度的增加,石墨烯氧化物的荧光强度急剧减弱。时间分辨荧光光谱和飞秒瞬态吸收光谱研究证实,加入不同浓度Fe~(3+)的GO其动力学衰减曲线基本没有任何变化。结果表明,Fe~(3+)对石墨烯氧化物的荧光淬灭主要是静态的荧光淬灭过程。     

Synthesis of Blue‐, Green‐, Yellow‐, and Red‐Emitting Graphene‐Quantum‐Dot‐Based Nanomaterials with Excitation‐Independent Emission

A one‐pot method is described for the preparation of graphene quantum dots/graphene oxide (GQDs/GO) hybrid composites with emission in the visible region, through heteroatom doping and hydroxyl‐radical‐induced decomposition of GO. The NH₄OH‐ and thiourea‐mediated dissociation of H₂O₂ produces hydroxyl radicals. Treatment of GO with hydroxyl radicals results in the production of small‐sized GO sheets and GQDs, which self‐assemble to form GQDs/GO through strong π–π interactions. For example, the reaction of GO with a mixture of NH₄OH and H₂O₂ for 40, 120, and 270 min generates yellow‐emitting GQDs/GO (Y‐GQDs/GO), green‐emitting GQDs/GO, and blue‐emitting GQDs, while red‐emitting GQDs/GO (R‐GQDs/GO) are prepared by incubating GO with a mixture of thiourea and H₂O₂. From the analysis of these four GQD‐based nanomaterials by transmission electron microscopy, atomic force microscopy, and fluorescence lifetime spectroscopy, it is found that this tunable fluorescence wavelength results from the differences in particle size. All four GQD‐based nanomaterials exhibit moderate quantum yields (1–10%), nanosecond fluorescence lifetimes, and excitation‐independent emissions. Except for R‐GQDs/GO, the other three GQD‐based nanomaterials are stable in a high‐concentration salt solution (e.g., 1.6 m NaCl) and under high‐power irradiation, enabling the sensitive (high‐temperature resolution and large activation energy) and reversible detection of temperature change. It is further demonstrated that Y‐GQD/GO can be used to image HeLa cells.     

Ultrasound assisted synthesis of Sn nanoparticles-stabilized reduced graphene oxide nanodiscs

Sn nanoparticles-stabilized reduced graphene oxide (RGO) nanodiscs were synthesized by a sonochemical method using SnCl₂ and graphene oxide (GO) nanosheets as precursors in a polyol medium. TEM and XPS were used to characterize the Sn-stabilized RGO nanodiscs.     

Molecular responses of cells to 2-mercapto-1-methylimidazole gold nanoparticles (AuNPs)-mmi: investigations of histone methylation changes

Reduced graphene oxide (RGO) sheet was functionalized with nanocrystalline cellulose (NCC) via click coupling between azide-functionalized graphene oxide (GO-N₃) and terminal propargyl-functionalized nanocrystalline cellulose (PG-NCC). First, the reactive azide groups were introduced on the surface of GO with azidation of 2-chloroethyl isocyanate-treated graphene oxide (GO-Cl). Then, the resulted compounds were reacted with PG-NCC utilizing copper-catalyzed azide-alkyne cycloaddition. During the click reaction, GO was simultaneously reduced to graphene. The coupling was confirmed by Fourier transform infrared, Raman, DEPT135, and ¹³C NMR spectroscopy, and the complete exfoliation of graphene in the NCC matrix was confirmed with X-ray diffraction measurement. The degree of functionalization from the gradual mass loss of RGO-NCC suggests that around 23 mass % has been functionalized covalently. The size of both NCC and GO was found to be in nanometric range, which decreased after click reaction.     

Investigation on fluorescence quenching of dyes by graphite oxide and graphene

Rhodamine B (Rh B), eosin (E) and methylene blue (MB) were used as a probe to investigate the molecular structure and charge of the dyes on the sensitized efficiency of graphite oxide (GO) and graphene (G). The structure of the prepared GO and G were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. To study the electron transfer between dyes and GO or G, UV-vis absorption spectra (UV-vis), steady state fluorescence spectra (FL) and time resolved fluorescence spectra have been determined. It has been found that the electron transfer from the excited dyes to G was more efficient than to GO, and the transfer from excited MB to G was easier than to Rh B and E, because of the different electrostatic attraction between the dye and G.     

pH‐dependent surface‐enhanced Raman scattering of aromatic molecules on graphene oxide

Graphene has become an ideal substrate for surface‐enhanced Raman scattering (SERS) to study the chemical enhancement mechanism. In comparison with mechanically exfoliated graphene, graphene oxide (GO) has been found to be a better substrate due to its highly negatively charged oxygen functional groups. In this work, the pH‐dependent SERS effect of aromatic molecules on GO are investigated. The results demonstrate that the Raman enhancement of dyes deposited on GO performs differently over a wide range of pH values (2 to 10). Adsorption experiments show that the pH‐dependent SERS effect is closely related to the adsorption of aromatic molecules on GO, which is dominated by the electrostatic interaction. Thus, the influence of pH in GO‐mediated SERS should be carefully considered, especially in its biomedical application. Copyright © 2012 John Wiley & Sons, Ltd.     

A Significant Fluorescent Aptamer Sensor Based on Carbon Dots and Graphene Oxide for Highly Selective Detection of Progesterone

In this paper, a fluorescent aptamer sensor was constructed based on the carbon dots (CDs) and graphene oxide (GO). This sensor combines the excellent fluorescence performance of CDs with the high specificity of aptamer, which can detect progesterone (P₄) with high sensitivity and selectivity. In the absence of P₄, the CDs-aptamer system and GO form a fluorescence resonance energy transfer process (FRET), which quenches the fluorescence of the CDs. When P₄ is added, the aptamer specifically binds to it, resulting the fluorescence of the CDs is recovered. At optimal conditions, the fluorescence intensity recovered by the CDs has a linear relationship with the concentration of P₄ in the range of 0.1–120 nM and the detection limit is 3.3?×?10^–11 M. Besides, the sensor has satisfactory detection results of P₄ in milk, indicating that constructed method has enormous potential for application in food safety.

     

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.     

氧化石墨烯猝灭罗丹明6G荧光的机理研究

The fluorescence quenching of Rhodamine 6G (R6G) by graphene oxide (GO) was interrogated by R6G fluorescence measurements using a set of controlled GO samples with varied C/O ratios as the quencher.The carbonyl groups on the GO nanosheet turned to play a dominant role in quenching the R6G fluorescence.The quenching in the static regime can be described by the "sphere of action" model.The significant absorption of the R6G fluorescence by the ground-state complex formed between R6G and GO was identified to be responsible for the static quenching.This work offers helpful insights into the fluorescence quenching mechanisms in the R6G/GO system.     

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.     

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.     

Self-assembly of metal–organic frameworks and graphene oxide as precursors for lithium-ion battery applications

We fabricated composites of Fe₂O₃/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal–organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe₂O₃ nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.     

Electrocatalytic oxidation of methanol on Pt catalyst supported on nitrogen-doped graphene induced by hydrazine reduction

Hydrazine is often used to reduce graphene oxide (GO) to produce graphene. Recent observations suggested that when hydrazine is used to reduce GO, the resulting reduced graphene actually contains certain amounts of nitrogen dopants, which may influence the properties of the obtained material, and in some cases may be deployed for beneficial advantage. In this work, we prepared graphene oxide by the chemical oxidation method, then used either hydrazine or sodium borohydride (as a control) to reduce the graphene oxide to graphene and to explore the nature of the nitrogen functionalities introduced by hydrazine reduction. Pt nanoparticles were then deposited on the nitrogen doped (hydrazine-reduced) and undoped (control) graphene substrates, and the morphology, structure, and electrocatalytic methanol oxidation activity were characterized and evaluated. The results show that the nitrogen functional groups introduced into the graphene by hydrazine reduction greatly improve the electrocatalytic activity of the underlying Pt nanoparticles towards the methanol oxidation reaction.     

An easy and novel approach for the decoration of graphene oxide by Fe3O4 nanoparticles

A new and relatively general route was developed to fabricate graphene oxide (GO)-Fe₃O₄ hybrid. X-ray diffraction, transmission electron morphology, X-ray photoelectron spectroscopy (XPS) and energy-dispersive spectrum were used to demonstrate the successful attachment of iron oxide nanoparticles to GO sheets. Transmission electron microscopy observation indicates that the size of the Fe₃O₄ nanoparticles was about 2.7 nm with narrow size distribution. Moreover, this hybrid shows superparamagnetic property and allows the rapid separation under an external-magnetic field. In addition, the method could be extended to further development of graphene-based nanoelectronics.     

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.     

Nanocarbon hybrids of graphene‐based materials and ultradispersed diamond: investigating structure and hierarchical defects evolution with electron‐beam irradiation

We report the influence of electron‐beam (E‐beam) irradiation on the structural and physical properties modification of monolayer graphene (Gr), reduced graphene oxide (rGO) and graphene oxide (GO) with ultradispersed diamond (UDD) forming novel hybrid composite ensembles. The films were subjected to a constant energy of 200 keV (40 nA over 100 nm region or electron flux of 3.9 × 10¹⁹ cm⁻²s⁻¹) from a transmission electron microscope gun for 0 (pristine) to 20 min with an interval of 2.5 min continuously – such conditions resemble increased temperature and/or pressure regime, enabling a degree of structural fluidity. To assess the modifications induced by E‐beam, the films were analyzed prior to and post‐irradiation. We focus on the characterization of hierarchical defects evolution using in situ transmission electron microscopy combined with selected area electron diffraction, Raman spectroscopy (RS) and Raman mapping techniques. The experiments showed that the E‐beam irradiation generates microscopic defects (most likely, interstitials and vacancies) in a hierarchical manner much below the amorphization threshold and hybrids stabilized with UDD becomes radiation resilient, elucidated through the intensity, bandwidth, and position variation in prominent RS signatures and mapping, revealing the defects density distribution. The graphene sheet edges start bending, shrinking, and generating gaps (holes) at ~10–12.5 min owing to E‐beam surface sputtering and primary knock‐on damage mechanisms that suffer catastrophic destruction at ~20 min. The microscopic point defects are stabilized by UDD for hybrids in the order of GO > rGO ≥ Gr besides geometric influence, i.e. the int erplay of curvature‐induced (planar vs curved) energy dispersion/absorption effects. Furthermore, an attempt was made to identify the nature of defects (charged vs residual) through inter‐defect distance (i.e. L_D). The trends of L_D for graphene‐based hybrids with E‐beam irradiation implies charged defects described in terms of dangling bonds in contrast to passivated residual or neutral defects. More importantly, they provided a contrasting comparison among variants of graphene and their hybrids with UDD. Copyright © 2015 John Wiley & Sons, Ltd.     

氧化石墨烯如何猝灭罗丹明6G的荧光

考察了水相溶液中氧化石墨烯对罗丹明6G的高效荧光猝灭．借助稳态及时间分辨荧光光谱测量,结合对该二元体系线性吸收谱变化的细致分析,澄清了相关荧光猝灭机理,即动态猝灭与静态猝灭的联合猝灭机制．提出在静态猝灭过程中罗丹明6G与氧化石墨烯所形成的可能的基态复合物,并进一步讨论了二者之间的光致电子转移过程．     

Preparation and electrochemical properties of LiFePO<Subscript>4</Subscript>/graphene composites from tailoring graphene oxides

LiFePO₄/graphene composites have been prepared by using tailoring graphene oxide (GO) nanosheets as precursors. The structure and electrochemical properties of the composites were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), Raman microscopy, and a variety of electrochemical testing techniques. The decrease in graphene size reduces the contact resistance between activated materials, and enhances the lithium-ion transport in LiFePO₄/graphene composites. With low weight fractions of small-size graphene sheets, the composites show better electrochemical performance than those with large size graphene sheets.     

Physical properties and device applications of graphene oxide

Graphene oxide (GO), the functionalized graphene with oxygenated groups (mainly epoxy and hydroxyl), has attracted resurgent interests in the past decade owing to its large surface area, superior physical and chemical properties, and easy composition with other materials via surface functional groups. Usually, GO is used as an important raw material for mass production of graphene via reduction. However, under different conditions, the coverage, types, and arrangements of oxygen-containing groups in GO can be varied, which give rise to excellent and controllable physical properties, such as tunable electronic and mechanical properties depending closely on oxidation degree, suppressed thermal conductivity, optical transparency and fluorescence, and nonlinear optical properties. Based on these outstanding properties, many electronic, optical, optoelectronic, and thermoelectric devices with high performance can be achieved on the basis of GO. Here we present a comprehensive review on recent progress of GO, focusing on the atomic structures, fundamental physical properties, and related device applications, including transparent and flexible conductors, field-effect transistors, electrical and optical sensors, fluorescence quenchers, optical limiters and absorbers, surface enhanced Raman scattering detectors, solar cells, light-emitting diodes, and thermal rectifiers.     

P–n junction characteristics of graphene oxide and reduced graphene oxide on n-type Si(111)

The semiconductor behavior of graphene oxide (GO) and reduced graphene oxide (RGO) synthesized by the Hummers method on n-type Si(111) were investigated. Graphene oxide is a product of the oxidation of graphite, during which numerous oxygen functional groups bond to the carbon plane during oxidation. RGO was prepared by adding excess hydrazine to the GO showing p-type semiconductor material behavior. In the C–O bond, the O atom tends to pull electrons from the C atom, leaving a hole in the carbon network. This results in p-type semiconductor behavior of GO, with the carrier concentration dependent upon the degree of oxidation. The RGO was obtained by removing most of the oxygen-containing functionalities from the GO using hydrazine. However, oxygen remaining on the carbon plane caused the RGO to exhibit p-type behavior. The I–V characteristics of GO and RGO deposited on n-type Si(111) forming p–n junctions exhibited different turn-on voltages and slope values.