Pristine Graphene Quantum Dots Research Articles

Tuning Enhancement Efficiency of Multiple Emissive Centers in Graphene Quantum Dots by Core-Shell Plasmonic Nanoparticles.

Graphene quantum dots (GQDs) are emerging luminescent nanomaterials for energy, bioimaging, and optoelectronic applications. However, unlike conventional fluorophores, GQDs contain multiple emissive centers that result in a complex interaction with external electromagnetic fields. Here we utilize core-shell plasmonic nanoparticles to simultaneously enhance and modulate the photoluminescence (PL) intensities and spectral profiles of GQDs. By analyzing the spectral profiles, we show that the emissive centers are highly influenced by the proximity to the metal particles. Under optimal spacer thickness of 25 nm, the overall PL displays a four-fold enhancement compared with a pristine GQD. However, detailed lifetime measurements indicate the presence of midgap states that act as the bottleneck for further enhancement. Our results offer new perspectives for fundamental understanding and new design of functional luminescent materials (e.g., GQDs, graphene oxide, carbon dots) for imaging, sensing, and light harvesting.

Production of graphene quantum dots by ultrasound-assisted exfoliation in supercritical CO2/H2O medium

In this research, three kinds of graphene quantum dots (GQDs)—pristine graphene quantum dots (PGQDs), expanded graphene quantum dots (EGQDs) and graphene oxide quantum dots (GOQDs)—were produced from natural graphite, expanded graphite, and oxide graphite respectively in an ultrasound-assisted supercritical CO2 (scCO2)/H2O system. The effects of aqueous solution content ratio, system pressure, and ultrasonic power on the yields of different kinds of GQDs were investigated. According to these experiment results, the combination of the intense knocking force generated from high-pressure acoustic cavitation in a scCO2/H2O system and the superior penetration ability of scCO2 was considered to be the key to the successful exfoliation of such tiny pieces from bulk graphite. An interesting result was found that, contrary to common experience, the yield of PGQDs from natural graphite was much higher than that of GOQDs from graphite oxide. Based on the experimental analysis, the larger interlayer resistance of natural graphite, which hindered the insertion of scCO2 molecules, and the hydrophobic property of natural graphite surface, which made the planar more susceptible to the attack of ultrasonic collapsing bubbles, were deduced to be the two main reasons for this result. The differences in characteristics among the three kinds of GQDs were also studied and compared in this research. In our opinion, this low-cost and time-saving method may provide an alternative green route for the production of various kinds of GQDs, especially PGQDs.

Graphene Quantum Dots Functionalized with 4-Amino-2, 2, 6, 6-Tetramethylpiperidine-N-Oxide as Fluorescence "Turn-ON" Nanosensors.

In this study, we report on the fabrication of simple and rapid graphene quantum dots (GQDs)-based fluorescence "turn-ON" nanoprobes for sensitive and selective detection of ascorbic acid (AA). Pristine GQDs and S and N co-doped-GQDs (SN-GQDs) were functionalized with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4-amino-TEMPO, a nitroxide free radical). The nitroxide free radicals efficiently quenched the fluorescence of the GQDs and upon interaction of the nanoconjugates with ascorbic acid, the quenched fluorescence was restored. The linear ranges recorded were 0.5-5.7μM and 0.1-5.5μM for GQDs-4-amino-TEMPO and SN-GQDs-4amino-TEMPO nanoprobes, respectively. Limits of detection were found to be 60nM and 84nM for SN-GQDS-4-amino-TEMPO and GQDs-4-amino-TEMPO for AA detection, respectively. This novel fluorescence "turn-ON" technique showed to be highly rapid and selective towards AA detection.

Surface plasmon enhancement of photoluminescence in photo-chemically synthesized graphene quantum dot and Au nanosphere

Graphene quantum dots (GQDs) are promising candidates for potential applications such as novel optoelectronic devices and bio-imaging. However, insufficient light absorption to exhibit their intriguing characteristics. The strong confinement of light caused by the Au nanoparticles as an antenna can considerably boost the light absorption. With the assistance of ultraviolet irradiation, we prepared bluish-green luminescent nanospheres by the hybridization of GQD and Au nanoparticles (GQD/Au). These nanospheres showed a photoluminescence quantum yield of up to 26.9%. The GQD/Au nanospheres were synthesized using a solution of GQDs and HAuCl4 by a photochemical method with the reduction of GQDs and the formation of metallic Au. The GQDs and Au nanoparticles self-assembled and aggregated into nanospheres via aurophilicity and hydrogen bonding interactions. The average size of the GQD/Au nanospheres was found to be in the range of 150–170 nm, which is much larger than that of the pristine GQDs (4–7 nm). The GQD/Au nanospheres exhibited an absorption band at 541 nm, which indicates the presence of Au in the nanospheres. The typical absorbance features of GQDs were observed near 236 and 303 nm. The photoluminescence characteristics were investigated using the excitation and emission spectra. The GQD/Au nanospheres exhibited two emission peaks at 468 and 529 nm in the visible range. The green fluorescent peak located at 529 nm was newly generated by the hybridization. The GQD/Au nanospheres showed an emission efficiency which was two times more than that of the intrinsic GQDs. The reason for this increase was the surface plasmon resonance from the Au particles, which improved the fluorescence property of the resulting nanospheres. These nanospheres can be perceived as outstanding candidates for applications such as displays, optoelectronic devices, and imaging of the biological samples with high emission intensity.

Exploring pentagon-heptagon pair defects in the triangular graphene quantum dots: A computational study

We have applied density functional calculations to investigate Stone Wales (SW) and carbon ad-dimer (CD) defect formation in triangular graphene quantum dots (GQDs). According to our results, defect formation energies depend on the positions of SW defects, such that the rotation of the CC bond located near the vertex of triangular GQD is easier than the rotation of other CC bonds. Therefore, the multiply defective GQDs with isolated SW defect sites are the most favorable while the formation of pentalene like structures in the connected SW defect sites costs larger formation energies. Introducing of carbon dimer defects on a triangular GQD induces a curvature at the defective sites, which leads to a more complex defect configuration with cone-like structure in the CD defective GQD with three defective sites. Then, formation energies for CD defective GQDs are higher than those for SW defective ones. The electrophilicity values calculated for SW and CD defective GQDs are greater than those for pristine GQDs. Moreover, perturbation of strong sp2 bonding network of graphitic carbons on the GQD, leading to the formation of more localized CC bonds, results in further electron deficiency of multiply SW and CD defective GQDs with increasing of electrophilicity values.

Advantages of nitrogen-doped graphene quantum dots as a green sensitizer with ZnO nanorod based photoanodes for solar energy conversion

Graphene quantum dots (GQDs) and nitrogen-doped graphene quantum dots (N-GQDs) have been synthesized by a hydrothermal process. Optical absorption study revealed strong ultraviolet photoabsorption for both GQDs. An additional broad absorption band in the visible region has been observed for N doped GQDs. GQDs and N-GQDs both are highly luminescent and exhibit excitation dependent emission behaviors. Photoelectrochemical properties of GQD and N-GQD sensitized ZnO nanorods have been investigated in details. GQD modified nanorod photoanodes demonstrated superior photoconversion efficiency and incident photon to current conversion efficiency (IPCE) than pristine ZnO nanorods. N-GQD sensitized nanorods exhibited better photoelectrochemical properties than pristine GQD due to higher visible photoabsorption and lower interfacial resistance.

A fluorometric assay for tyrosinase activity and its inhibitor screening based on graphene quantum dots

Pristine graphene quantum dots (GQDs) without any functionalization were used as probes to develop a sensitive and selective fluorescence sensing platform for the detection of tyrosinase (TYR) activity and its inhibitor screening for the first time.

The Synthesis of Amphiphilic Luminescent Graphene Quantum Dot and Its Application in Miniemulsion Polymerization

Although emulsion applications of microscale graphene sheets have attracted much attention recently, nanoscale graphene platelets, namely, graphene quantum dots (GQDs), have been rarely explored in interface science. In this work, we study the interfacial behaviors and emulsion phase diagrams of hydrophobic-functionalized graphene quantum dots (C18-GQDs). Distinctive from pristine graphene quantum dots (p-GQDs), C18-GQDs show several interesting surface-active properties including high emulsification efficiency in stabilizing dodecane-in-water emulsions. We then utilize the C18-GQDs as surfactants in miniemulsion polymerization of styrene, achieving uniform and relatively small polystyrene nanospheres. The high emulsification efficiency, low production cost, uniform morphology, intriguing photoluminescence, and extraordinary stability render C18-GQDs an attractive alternative in surfactant applications.

Surface engineering of graphene quantum dots and their applications as efficient surfactants.

The surface properties of graphene quantum dots (GQDs) control their dispersion and location within the matrices of organic molecules and polymers, thereby determining various properties of the hybrid materials. Herein, we developed a facile, one-step method for achieving systematic control of the surface properties of highly fluorescent GQDs. The surfaces of the as-synthesized hydrophilic GQDs were modified precisely depending on the number of grafted hydrophobic hexylamine. The geometry of the modified GQDs was envisioned by conducting simulations using density functional theory. In stark contrast to the pristine GQDs, the surface-modified GQDs can effectively stabilize oil-in-water Pickering emulsions and submicron-sized colloidal particles in mini-emulsion polymerization. These versatile GQD surfactants were also employed in liquid-solid systems; we demonstrated their use for tailoring the dispersion of graphite in methanol. Finally, the particles produced by the GQD surfactants were fluorescent due to luminescence of the GQDs, which offers great potential for various applications, including fluorescent sensors and imaging.

Pristine graphene quantum dots for detection of copper ions

Abstract

Luminescence properties of boron and nitrogen doped graphene quantum dots prepared from arc-discharge-generated doped graphene samples

Substitution of heteroatoms in graphene is known to tailor its band gap. Another approach to alter the band gap of graphene is to create zero-dimensional graphene quantum dots (GQDs). Here we present the synthesis and photoluminescence properties of B-doped graphene quantum dots (B-GQDs) for the first time, having prepared the B-GQDs by chemical scissoring of B-doped graphene generated by arc-discharge in gas phase. We compare the photoluminescence properties of B-GQDs with nitrogen-doped GQDs and pristine GQDs. Besides, excitation wavelength independent PL emission, excellent upconversion of PL emission is observed in GQDs as well as B- and N-doped GQDs.

Enhancement in the fluorescence of graphene quantum dots by hydrazine hydrate reduction

A simple and effective chemical method was reported to enhance the fluorescence of graphene quantum dots (GQDs). Specifically, water-soluble GQDs, prepared by solvothermal synthesis from graphene oxide, are chemically reduced by hydrazine hydrate to produce reduced GQDs (rGQDs). The results show that the hydrazine hydrate reduction not only decreases the O/C atomic ratio of GQDs, also changes the bonding type of N atoms. Such surface/edge chemical bond change of GQDs results in that as-made rGQDs exhibit more than two times fluorescence intensity as strong as that of the pristine GQDs.

Graphene Quantum Dots: Facile Synthetic Method for Pristine Graphene Quantum Dots and Graphene Oxide Quantum Dots: Origin of Blue and Green Luminescence (Adv. Mater. 27/2013)

Pristine graphene quantum dots and graphene oxide quantum dots are synthesized by chemical exfoliation from graphite nanoparticles with high uniformity in terms of shape (circle), size (less than 4 nm), and thickness (monolayer). The origin of the blue and green photoluminescence of GQDs and GOQDs is attributed to intrinsic and extrinsic energy states, respectively. Further details can be found in the article by Tae Seok Seo, Yong-Hoon Cho, and co-workers on page 3657.

Facile Synthetic Method for Pristine Graphene Quantum Dots and Graphene Oxide Quantum Dots: Origin of Blue and Green Luminescence

Pristine graphene quantum dots and graphene oxide quantum dots are synthesized by chemical exfoliation from the graphite nanoparticles with high uniformity in terms of shape (circle), size (less than 4 nm), and thickness (monolayer). The origin of the blue and green photoluminescence of GQDs and GOQDs is attributed to intrinsic and extrinsic energy states, respectively.

Surface functionalization of graphene quantum dots with small organic molecules from photoluminescence modulation to bioimaging applications: an experimental and theoretical investigation

Surface chemistry provides an alternative approach to modulate the emission colour and efficiency of graphene quantum dots. We systematically investigated the surface chemistry of graphene quantum dots functionalized with a series of small organic molecules combining experimental and theoretical approaches. Experimental results indicated that surface functionalization with functional groups such as alcohol, amine and thiol can effectively tune the fluorescence of graphene quantum dots, and proved that amino groups can highly elevate the quantum yields of modified graphene quantum dots. The emission efficiency of 1,2-ethylenediamine functionalized graphene quantum dots reached up to 17.6% due to specific proton transfer to the conjugated fluorophore-like structure from ammonium formed by protonation. The polyaromatic structure within the graphene quantum dots was proposed to explain the fluorescence enhancement mechanism of graphene quantum dots functionalized by diamines. The computational results suggested that not only the size of the polyaromatic structures within graphene quantum dots can change their emissions, but surface functionalization can also tune their photoluminescence through modulating their band gaps. Toxicity experiments indicated that diamine-functionalized graphene quantum dots showed low cell toxicity similar to that of pristine graphene quantum dots. Moreover, the bioimaging experiments suggested that functionalized graphene quantum dots had identical abilities to label cells at a lower concentration than pristine graphene quantum dots owing to their higher quantum yields.