Noble Metal-Free Surface-Enhanced Raman Scattering Enhancement from Bandgap-Controlled Graphene Quantum Dots

Graphene quantum dot (GQD) represents an emerging noble metal-free surface-enhanced Raman scattering (SERS)-active nanomaterials for applications such as optoelectronics, chemical sensing, and biomedical imaging and therapy. However, it lacks a scalable method to synthesize GQD with selective structures and the fundamental understanding of their SERS enhancement through charge transfer between GQD and probe molecules. Here a bottom–up liquid-phase synthesis of colloidal GQDs with selective bandgaps using atmospheric-pressure microplasmas is reported. Electron microscopic and optical spectroscopic characterizations suggest that highly crystalline GQDs with nanographene structures can be synthesized with ambient conditions using microplasmas. Moreover, the bandgaps of GQDs are tuned from 2.8 to 3.18 eV by controlling the size of organosulfate micelles. Raman spectroscopic study demonstrates that the as-synthesized GQDs exhibit a unique quantum dot bandgap-dependent SERS enhancement property with an improved charge transfer between the GQD and probe molecules. This study provides an insight into the fundamental of semiconductor-enhanced Raman scattering of GQDs and scalable production of structure-controlled GQDs using plasma-activated chemistry.     

Probing the electronic structure and optical response of a graphene quantum disk supported on monolayer graphene

In this paper, we show that a graphene quantum disk (GQD) can be generated on monolayer graphene via structural modification using the electron beam. The electronic structure and local optical responses of the GQD, supported on monolayer graphene, were probed with electron energy-loss spectrum imaging on an aberration-corrected scanning transmission electron microscope. We observe that for small GQD, ~1.3 nm in diameter, the electronic structure and optical response are governed by the dominating edge states, and are distinctly different from either monolayer graphene or double-layer graphene. Highly localized plasmon modes are generated at the GQD due to the confinement from the edge of the GQD in all directions. The highly localized optical response from GQDs could find use in designing nanoscale optoelectronic and plasmonic devices based on monolayer graphene.     

General monogamy property of global quantum discord and the application

We provide a family of general monogamy inequalities for global quantum discord (GQD), which can be considered as an extension of the usual discord monogamy inequality. It can be shown that those inequalities are satisfied under the similar condition for the holding of usual monogamy relation. We find that there is an intrinsic connection among them. Furthermore, we present a different type of monogamy inequality and prove that it holds under the condition that the bipartite GQDs do not increase when tracing out some subsystems. We also study the residual GQD based on the second type of monogamy inequality. As applications of those quantities, we investigate the GQDs and residual GQD in characterizing the quantum phase transition in the transverse field Ising model.     

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.     

溶剂对石墨烯量子点荧光性质的影响

采用柠檬酸热解法制备了石墨烯量子点(GQDs),研究了非极性溶剂戊烷,极性溶剂乙醇、丙酮、乙二醇对GQDs荧光性质的影响。透射电子显微镜(TEM)和原子力显微镜(AFM)图像表明,制备的GQDs尺寸分布在2~12 nm(平均尺寸为4.9 nm),分散均匀,高度分布在0.5~2 nm。吸收光谱表明,GQDs具有明显的紫外吸收特性,吸收峰位于259 nm和274 nm。光致发光谱表明,GQDs的发光具有明显的溶剂依赖性。GQDs在极性溶剂乙醇、丙酮、乙二醇中,发光峰的位置依赖于激发波长,发射波长在可见光区。而在非极性溶剂戊烷中,GQDs表现出对激发波长不依赖的荧光性能,且发射波长在近紫外。     

一步水热法合成的石墨烯量子点及其在锰离子探测中的应用

以还原氧化石墨烯为前驱体,采用一步水热法成功制备出了近似球状、分散性良好、尺寸均一的石墨烯量子点。通过傅立叶红外光谱(FTIR)、紫外-可见吸收光谱、荧光光谱等光学手段对样品的结构和光学性能进行了表征,结果显示制备的石墨烯量子点表面含有丰富的含氧官能团,在紫外区有很强的吸收,发射峰强而窄,表现出激发波长不依赖的荧光性能。研究结果表明石墨烯量子点可应用于Mn2+微量探测,石墨烯量子点的荧光强度会随着所加入的Mn2+浓度的增大而降低,在0~400μmol/L间的校准曲线呈线性相关。     

Shungite - a carbon-mineral filler for polymeric composite materials

Shungite rock material after fine grinding was investigated as a filler for polymeric composites. Shungite carbon structural and physico-chemical peculiarities predetermine shungite filler behaviour in polymeric matrixes. Specific interaction between the network of globules (the main structural units of shungite carbon of nanoscale size) and the network of mineral phase structural units in every shungite filler particle leads to the amphiphylic surface properties of the filler. Influence on rheological properties of different polymeric composite materials was demonstrated as an example of advanced potential possibilities of shungite filler. The metastable structure of shungite carbon and its reactivity seemed to be the key to understanding the observed effect.     

Global quantum discord and quantum phase transition in XY model

We study the relationship between the behavior of global quantum correlations and quantum phase transitions in XY model. We find that the two kinds of phase transitions in the studied model can be characterized by the features of global quantum discord (GQD) and the corresponding quantum correlations. We demonstrate that the maximum of the sum of all the nearest neighbor bipartite GQDs is effective and accurate for signaling the Ising quantum phase transition, in contrast, the sudden change of GQD is very suitable for characterizing another phase transition in the XY model. This may shed lights on the study of properties of quantum correlations in different quantum phases.     

Size‐Dependent Structural and Optical Characteristics of Glucose‐Derived Graphene Quantum Dots

It is of scientific importance to obtain graphene quantum dots (GQDs) with narrow‐size distribution in order to unveil their size‐dependent structural and optical properties, thereby further to explore the energy band diagram of GQDs. Here, a soft‐template microwave‐assisted hydrothermal method to prepare GQDs with diameters less than 5 nm ± 0.55 nm is reported. The size‐dependent photoluminescence (PL) quantum yield (QY) decay lifetime and electron energy loss spectroscopy (EELS) of the GQDs are studied systematically. The QY of the GQDs with an average diameter of 2 nm is the highest (15%) among all the samples investigated and the QY decreases with increasing diameter of the GQDs. The size‐dependence of the PL decay lifetime is also observed. The result suggests that spatial confinement effects related to radiative relaxation play an important role in the size‐dependent decay lifetime. A realistic energy band diagram of the GQDs is deduced from the experimental results.     

Facilitative effect of graphene quantum dots in MoS_2 growth process by chemical vapor deposition

The substrate treatment with seeding promoter can promote the two-dimensional material lateral growth in chemical vapor deposition(CVD) process. Herein, graphene quantum dots(GQDs) as a novel seeding promoter were used to obtain uniform large-area MoS_2 monolayer. The obtained monolayer MoS_2 films were confirmed by optical microscope,scanning electron microscope, Raman and photoluminescence spectra. Raman mapping revealed that the MoS_2 monolayer was largely homogeneous.     

Facile One‐Pot Conversion of Petroleum Asphaltene to High Quality Green Fluorescent Graphene Quantum Dots and Their Application in Cell Imaging

Benefiting from the natural nano‐size graphene‐structure in natural asphaltene material, a facile one‐pot route, mild chemical oxidation of low‐value petroleum asphaltene followed by routine ammonium neutralization, is presented to produce high quality graphene quantum dots (GQDs). The asphaltene‐derived GQDs possess a variety of oxygen‐containing and nitrogen‐containing functional groups such as carboxyl, hydroxyl, amine, and nitro groups. They present such excellent fluorescence properties as stable ability to retain strong green fluorescence within a relative broad excitation range in a bio‐suitable pH range of 4–7, high photoluminescence quantum yield of 18% and good fluorescent stability against photobleaching. And they are much smaller and thinner than most reported GQDs, displaying good biocompatibility with low cytotoxicity, effective cellular uptake, and excellent fluorescent probe performance for cancer cell imaging.     

Matrix-assisted pulsed laser evaporation of polyfluorene thin films

Poly(9,9-dioctylfluorene) (PF8) thin films have been deposited by matrix-assisted pulsed laser evaporation (MAPLE) using a KrF excimer laser. The influence of the laser fluence (50-500 mJ/cm²) and the nature of the solvent (chloroform, toluene, tetrahydrofuran) on the films properties have been studied. The chemical composition of the deposited films was investigated by Fourier transform infrared (FTIR) spectroscopy and compared with the one of spin coated films. To investigate the effect of the deposition parameters on the optical properties of the films, photoluminescence (PL) measurements were performed. Poor structural and optical properties were observed for films deposited starting from chloroform solutions. When using toluene as solvent, the spectra characteristics improved with increasing laser fluence, while wide PL spectra were observed. The characteristic emission bands of the PF8 polymer were nicely detected for films deposited starting from a tetrahydrofuran (THF) solution. Moreover, in this last case, the PF8 structure is preserved at high laser fluences, too.     

ZnO@GQDs核壳结构量子点的制备及性能研究

采用原位聚合法制备了以ZnO量子点为核、石墨烯量子点（GQDs）为壳的ZnO@ GQDs核壳结构量子点。通过TEM和HR-TEM对量子点进行形貌和结构的分析表征。结果表明,合成的ZnO@ GQDs核壳结构量子点为球形,粒径为～7 nm,且尺寸均匀。PL光谱研究表明,新型量子点的发射峰位于369 nm,发光峰窄、强度高;相对于ZnO的本征发射峰,GQDs的引入使得ZnO@GQDs核壳量子点的荧光发射峰出现蓝移、强度变高,从而使复合量子点的荧光具有较纯的色度和较高的强度,说明GQDs的引入具有协同优化效应。该量子点有望应用于LED显示器件。     

Optical properties of 3D photonic crystals filled with CdSe/CdS quantum dots

We study 3D globular photonic crystals based on synthetic opals filled with semiconductor core/shell quantum dots CdSe/CdS by measuring the photoluminescence spectra. The spectra were obtained using 369, 384, and 408 nm LED light excitation and involving a pulse YAG laser operating at 365 and 266 nm. The study shows that the photoluminescence spectra of opal filled with CdSe/CdS changes sufficiently in comparison with spectra taken for pure opal and a reference colloidal solution of CdSe/Cds quantum dots in toluene. Such opals may be used to fabricate a narrow-band light sources.     

Specific structural features and thermal resistance of shungite carbon to graphitization

A Raman scattering study is reported of the structural changes in natural glassy carbon in shungite I induced by a thermal treatment within the 500–2700 °C range in an inert atmosphere. It has been found that thermal treatment results in an insignificant increase of the graphite phase content in the bulk of the samples, whereas in the near-surface regions graphitization of the shungite glassy carbon can be more pronounced. The observed resistance of the shungite to graphitization can be explained within a structural model in which the shungite glassy carbon consists of closely packed nanostructures representing hollow multi-layered globules enveloped in random-network carbon. Fiz. Tverd. Tela (St. Petersburg) 41, 1412–1415 (August 1999)     

Investigation of Raman and photoluminescence studies of reduced graphene oxide sheets

In this paper, we are investigating the Raman and photoluminescence properties of reduced graphene oxide sheets (rGO). Moreover, graphene oxide (GO) sheets are synthesized using Hummer’s method and further reduced into graphene sheets using D-galactose. Both GO and rGO are characterized by UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Thermogravimetric (TGA) analysis. Raman analysis of rGO shows the restoration of graphitic domains in GO after reduction. The photoluminescence of rGO showed emission in the UV region which is blue shifted along with luminescent quenching as compared to GO. This blue shift and quenching in photoluminescence arises due to the newly formed crystalline sp² clusters in rGO which created percolation pathways between the sp² clusters already present.     

Graphene Quantum Dots from Polycyclic Aromatic Hydrocarbon for Bioimaging and Sensing of Fe3+ and Hydrogen Peroxide

An easy approach for large‐scale and low‐cost synthesis of photoluminescent (PL) graphene quantum dots (GQDs) based on the carbonization of commercially available polycyclic aromatic hydrocarbon (PAH) precursors with strong acid and followed by hydrothermal reduction with hydrazine hydrate is reported. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) characterizations indicate that the size and height of GQDs are in the range of 5–10 nm and 0.5–2.5 nm, respectively. PAH, which has more benzene rings, generally forms GQDs with relatively larger size. The GQDs show high water solubility, tunable photoluminescence, low cytotoxicity, and good optical stability, which makes them promising fluorescent probes for cellular imaging. In addition, the fluorescence of GQDs shows a sensitive and selective quenching effect to Fe³⁺ with a detection limit of 5 × 10^?9m . By combination with the Fe²⁺/Fe³⁺ redox couple, the PL GQDs are able to detect oxidant, using H₂O₂ as an example. This study opens up new opportunities to make full use of GQDs because of their facile availability, cost‐effective productivity, and robust functionality.     

Synthesis and characterization of graphene quantum dots and their size reduction using swift heavy ion beam

Graphene quantum dots (GQDs) are nanosized fragments of graphene displaying quantum confinement effect. They have shown to be prepared from various methods which include ion beam etching of graphene. However, recently the modification of the GQDs has garnered tremendous attention owing to its suitability for various applications. Here, we have studied the effect of swift ion beam irradiation on the properties of GQDs. The ion beam treatment on the GQDs exhibited the change in observed photoluminescence of GQDs as they exhibited a blue luminescence on excitation with longwave UV (≈365?nm) due to the reduction in size and removal of the ethoxy (–C–O–C–) groups present on the quantum dots. This was confirmed by transmission electron microscopy, particle size analysis, and Fourier transform infrared spectroscopy.     

Luminescence and scintillation properties of some 1, 2-disubstitution products of benzimidazole

The absorption and photoluminescence spectra of 71 derivatives of benzimidazole have been studied. The relation between the chemical structure and the light yield in solution is discussed. The scintillation efficiency of the compounds in toluene solution has been measured. Several easily soluble derivatives of 2-arylbenzimidazole have the same scintillation efficiency as p-terphenyl (5 g/l).The authors are indebted to Professor I. Ya. Postovskii for attention to the work and discussion of the results.     

Versatile Graphene Quantum Dots with Tunable Nitrogen Doping

This paper reports a facile fabrication of N‐doped graphene quantum dots (N‐GQDs) showing controllable chemical properties through a hydrothermal treatment. The N‐GQDs have a uniform size of 3.06 ± 0.78 nm and prefer the equilibrium shapes of circle and ellipse due to the minimization of edge free energy. The N/C atomic ratio in N‐GQDs can be precisely tailored in a range from 8.3 at% to 15.8 at% by simply controlling the concentration of N source (ammonium hydroxide). One order of magnitude quantum yield of 34.5% is achieved by N‐GQDs, compared with the N‐free GQDs, as the substitutional N has an essential role in more effective radiative emission. Excessive N dopants in N‐GQDs can lead to photoluminescence quenching, through nonradiative transition back to the ground state. The N‐GQDs are further found to be suitable as photocurrent conversion materials due to benign energy matching with anatase nanofibers, the ultrafast electron injection at their interface, and efficient electron transfer. This work provides an efficient and inspiring approach to engineering both chemical components and physical properties of N‐GQDs, and will therefore promote their basic research and applications in energy conversion.