Online citations, reference lists, and bibliographies.
← Back to Search

Hydrothermal Route For Cutting Graphene Sheets Into Blue-luminescent Graphene Quantum Dots.

Dengyu Pan, Jingchun Zhang, Zhen Li, M. Wu
Published 2010 · Materials Science, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy Visualize in Litmaps
Share
Reduce the time it takes to create your bibliography by a factor of 10 by using the world’s favourite reference manager
Time to take this seriously.
Get Citationsy
2010 WILEY-VCH Verlag Gm Graphene-based materials are promising building blocks for future nanodevices owing to their superior electronic, thermal, and mechanical properties as well as their chemical stability. However, currently available graphene-based materials produced by typical physical and chemical routes, including micromechanical cleavage, reduction of exfoliated graphene oxide (GO), and solvothermal synthesis, are generally micrometer-sized graphene sheets (GSs), which limits their direct application in nanodevices. In this context, it has become urgent to develop effective routes for cutting large GSs into nanometer-sized pieces with a well-confined shape, such as graphene nanoribbons (GNRs) and graphene quantum dots (GQDs). Theoretical and experimental studies have shown that narrow GNRs (width less than ca. 10 nm) exhibit substantial quantum confinement and edge effects that render GNRs semiconducting. By comparison, GQDs possess strong quantum confinement and edge effects when their sizes are down to 100 nm. If their sizes are reduced to ca. 10 nm, comparable with the widths of semiconducting GNRs, the two effects will become more pronounced and, hence, induce new physical properties. Up to now, nearly all experimental work on GNRs and GQDs has focused on their electron transportation properties. Little work has been done on the optical properties that are directly associated with the quantum confinement and/or edge effects. Most GNRand GQD-based electronic devices have been fabricated by lithography techniques, which can realize widths and diameters down to ca. 20 nm. This physical approach, however, is limited by the need for expensive equipment and especially by difficulties in obtaining smooth edges. Alternative chemical routes can overcome these drawbacks. Moreover, surface functionalization can be realized easily. Li et al. first reported a chemical route to functionalized and ultrasmooth GNRs with widths ranging from 50 nm to sub-10 nm. Very recently, Kosynkin et al. reported a simple solution-based oxidative process for producing GNRs by lengthwise cutting and unraveling of multiwalled carbon nanotube (CNT) side walls. Yet, no chemical routes have been reported so far for preparing functionalized GQDs with sub-10 nm sizes. Here, we report on a novel and simple hydrothermal approach for the cutting of GSs into surface-functionalized GQDs (ca. 9.6-nm average diameter). The functionalized GQDs were found to exhibit bright blue photoluminescence (PL), which has never been observed in GSs and GNRs owing to their large lateral sizes. The blue luminescence and new UV–vis absorption bands are directly induced by the large edge effect shown in the ultrafine GQDs. The starting material was micrometer-sized rippled GSs obtained by thermal reduction of GO sheets. Figure 1a shows a typical transmission electron microscopy (TEM) image of the pristine GSs. Their (002) interlayer spacing is 3.64 A (Fig. 1c), larger than that of bulk graphite (3.34 A). Before the hydrothermal treatment, the GSs were oxidized in concentrated H2SO4 and HNO3. After the oxidization treatment the GSs became slightly smaller (50 nm–2mm) and the (002) spacing slightly increased to 3.85 A (Fig. 1c). During the oxidation, oxygen-containing functional groups, including C1⁄4O/COOH, OH, and C O C, were introduced at the edge and on the basal plane, as shown in the Fourier transform infrared (FTIR) spectrum (Fig. 1d). The presence of these groups makes the GSs soluble in water. A series of more marked changes took place after the hydrothermal treatment of the oxidized GSs at 200 8C. First, the (002) spacing was reduced to 3.43 A (Fig. 1c), very close to that of bulk graphite, indicating that deoxidization occurs during the hydrothermal process. The deoxidization is further confirmed by the changes in the FTIR and C 1s X-ray photoelectron spectroscopy (XPS) spectra. After the hydrothermal treatment, the strongest vibrational absorption band of C1⁄4O/COOH at 1720 cm 1 became very weak and the vibration band of epoxy groups at 1052 cm 1 disappeared (Fig. 1d). In the XPS C 1s spectra of the oxidized and hydrothermally reduced GSs (Fig. 2a), the signal at 289 eV assigned to carboxyl groups became weak after the hydrothermal treatment, whereas the sp carbon peak at 284.4 eV was almost unchanged. Figure 2b shows the Raman spectrum of the reduced GSs. A G band at 1590 cm 1 and a D band at 1325 cm 1 were observed with a large intensity ratio ID/IG of 1.26. Second, the size of the GSs decreased dramatically and ultrafine GQDswere isolated by a dialysis process. Figure 3 shows typical TEM and atomic force microscopy (AFM) images of the GQDs. Their diameters are mainly distributed in the range of 5–13 nm (9.6 nm average diameter). Their topographic heights are mostly between 1 and 2 nm, similar to those observed in functionalized GNRs with 1–3 layers. More than 85% of the GQDs consist of 1–3 layers.
This paper references
Chem
R. Hoffmann (1475)
10.1021/JA00978A010
The Absorption, Emission, and Excitation Spectra of Diarylmethylenes
A. M. Trozzolo (1967)
10.1021/JA01008A016
Trimethylene and the addition of methylene to ethylene
R. Hoffmann (1968)
10.1021/CR9603744
The Cationminus signpi Interaction.
J. C. Ma (1997)
10.1021/JP972656T
Contribution of the Basal Planes to Carbon Basicity: An Ab Initio Study of the H3O+−π Interaction in Cluster Models
M. A. Montes-Morán (1998)
10.1021/JA9942282
Strong Luminescence of Solubilized Carbon Nanotubes
Jason E. Riggs (2000)
10.1126/SCIENCE.1102896
Electric Field Effect in Atomically Thin Carbon Films
(2004)
10.1021/JA050124H
On the chemical nature of graphene edges: origin of stability and potential for magnetism in carbon materials.
L. Radovic (2005)
10.1021/JA062677D
Quantum-sized carbon dots for bright and colorful photoluminescence.
Y. Sun (2006)
10.1103/PhysRevLett.97.216803
Energy gaps in graphene nanoribbons.
Y. Son (2006)
10.1103/PHYSREVLETT.96.176101
Oxygen-driven unzipping of graphitic materials.
Je-Luen Li (2006)
10.1021/JA0669070
An electrochemical avenue to blue luminescent nanocrystals from multiwalled carbon nanotubes (MWCNTs).
J. Zhou (2007)
10.1038/NMAT1849
The rise of graphene.
Andre K. Geim (2007)
10.1103/PhysRevLett.98.206805
Energy band-gap engineering of graphene nanoribbons.
Melinda Y. Han (2007)
10.1038/nnano.2007.290
Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers.
Adrian Nish (2007)
10.1063/1.2827188
Tunable Coulomb blockade in nanostructured graphene
C. Stampfer (2007)
10.1126/science.1154663
Chaotic Dirac Billiard in Graphene Quantum Dots
L. Ponomarenko (2007)
10.1002/smll.200700578
Surface functionalized carbogenic quantum dots.
A. Bourlinos (2008)
10.1126/science.1150878
Chemically Derived, Ultrasmooth Graphene Nanoribbon Semiconductors
Xiaolin Li (2008)
10.1021/ja800745y
Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets.
Y. Xu (2008)
10.1038/nnano.2007.451
Processable aqueous dispersions of graphene nanosheets.
Dan Li (2008)
10.1103/PhysRevLett.100.206803
Room-temperature all-semiconducting sub-10-nm graphene nanoribbon field-effect transistors.
X. Wang (2008)
10.1021/ja9004514
Wet chemistry route to hydrophobic blue fluorescent nanodiamond.
V. Mochalin (2009)
10.1126/science.1166265
Brightly Fluorescent Single-Walled Carbon Nanotubes via an Oxygen-Excluding Surfactant Organization
Sang-Yong Ju (2009)
10.1038/nnano.2008.365
Gram-scale production of graphene based on solvothermal synthesis and sonication.
M. Choucair (2009)
10.1038/nature07872
Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons
D. V. Kosynkin (2009)
10.1021/ja8094729
How graphene is cut upon oxidation?
Z. Li (2009)
10.1002/ADMA.200801602
The Interaction of Bromide Ions with Graphitic Materials
A. Mehta (2009)



This paper is referenced by
10.1016/j.talanta.2021.122874
One-pot alkali cutting-assisted synthesis of fluorescence tunable amino-functionalized graphene quantum dots as a multifunctional nanosensor for sensing of pH and tannic acid.
Xueying Zhu (2022)
10.1016/j.mtchem.2021.100617
Recent advances on bioprinting of hydrogels containing carbon materials
(2022)
10.1016/j.carbon.2021.10.002
The synthetic strategies, photoluminescence mechanisms and promising applications of carbon dots: Current state and future perspective
Chuang He (2022)
10.1016/b978-0-323-90937-2.00010-1
Graphene: Structure, properties, preparation, modification, and applications
(2022)
10.1016/j.carbon.2021.09.071
Universal dry synthesis and patterning of high-quality and -purity graphene quantum dots by ion-beam assisted chemical vapor deposition
(2022)
10.1016/b978-0-323-90937-2.00013-7
Graphene quantum dots, graphene nanoplatelets, and graphene nanoribbons with polymers
(2022)
10.1016/J.JECE.2021.106154
Role of precursor microstructure in the development of graphene quantum dots from biomass
Aumber Abbas (2021)
10.1016/J.FLATC.2021.100246
Applications of novel quantum dots derived from layered materials in cancer cell imaging
Salar Khaledian (2021)
10.1016/B978-0-12-822548-6.00014-5
Functionalized Advanced Carbon-Based Nanomaterials for Sensing
Anerise de Barros (2021)
10.1002/CEY2.134
A review of carbon dots and their composite materials for electrochemical energy technologies
Yiming Liu (2021)
10.1021/acsomega.0c05993
Glycothermally Synthesized Carbon Dots with Narrow-Bandwidth and Color-Tunable Solvatochromic Fluorescence for Wide-Color-Gamut Displays
Taishu Yoshinaga (2021)
10.3390/ma14206153
Shedding Light on Graphene Quantum Dots: Key Synthetic Strategies, Characterization Tools, and Cutting-Edge Applications
S. Dorontić (2021)
10.1016/J.MSSP.2021.105729
Electrospun polyacrylonitrile nanofibers as graphene oxide quantum dot precursors with improved photoluminescent properties
O. Zaca-Morán (2021)
10.1007/978-981-16-1052-3_2
Synthesis of Carbon Allotropes in Nanoscale Regime
Abhyavartin Selvam (2021)
10.1002/ppsc.202100170
Doping and Surface Modification of Carbon Quantum Dots for Enhanced Functionalities and Related Applications
Varsha Lisa John (2021)
10.1016/J.ENSM.2021.01.020
Functionalized carbon dots for advanced batteries
Ruiting Guo (2021)
10.3390/APP11020614
A Review on Recent Advancements of Graphene and Graphene-Related Materials in Biological Applications
Federica Catania (2021)
10.1016/j.mattod.2021.07.028
The development of carbon dots: From the perspective of materials chemistry
Shuo Li (2021)
10.3390/molecules26051246
Synthesis of Fluorescent Carbon Dots and Their Application in Ascorbic Acid Detection
Tengfei Wang (2021)
10.3390/nano11082089
Towards Red Emissive Systems Based on Carbon Dots
Spyridon Gavalas (2021)
10.1016/j.saa.2021.119468
Chitosan-derived N-doped carbon dots for fluorescent determination of nitrite and bacteria imaging.
Lili Sun (2021)
10.1007/s11356-020-11880-z
Facile synthesis of N-doped carbon dots for direct/indirect detection of heavy metal ions and cell imaging
Zijun Xu (2021)
10.1149/1945-7111/ABF4B3
Graphene Quantum Dots from Partially Unzipped Multi-Walled Carbon Nanotubes: Promising Materials for Oxygen Electrodes
M. O. Danilov (2021)
10.1039/d1ra04248c
Recent advances in heteroatom-doped graphene quantum dots for sensing applications
Neeraj Sohal (2021)
10.1016/J.FLATC.2021.100271
Recent advances in the rational synthesis of red-emissive carbon dots for nanomedicine applications: A review
Zahra Hallaji (2021)
10.3390/nano11113094
Frictional Pressure Drop and Cost Savings for Graphene Nanoplatelets Nanofluids in Turbulent Flow Environments
(2021)
10.1007/s42823-021-00278-7
Recent advances on the preparation and application of graphene quantum dots for mercury detection: a systematic review
W. Danial (2021)
10.1016/J.JICS.2021.100069
Recent advances in synthesis and biological applications of graphene quantum dots
Sudip Karmakar (2021)
10.1007/978-3-030-10614-0_32-1
Applications of Graphene-Based Nanomaterials
Rüstem Keçili (2021)
10.3390/molecules26164994
Chlorine Modulation Fluorescent Performance of Seaweed-Derived Graphene Quantum Dots for Long-Wavelength Excitation Cell-Imaging Application
Weitao Li (2021)
10.1039/d0se01630f
Carbon dots for photocatalytic H2 production in aqueous media with molecular Co catalysts
K. Ladomenou (2021)
10.1039/D0RA10310A
Enhancing room-temperature NO2 gas sensing performance based on a metal phthalocyanine/graphene quantum dot hybrid material
Wenkai Jiang (2021)
See more
Semantic Scholar Logo Some data provided by SemanticScholar