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
Share
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
10.1002/ADMA.200801602
The Interaction of Bromide Ions with Graphitic Materials
A. Mehta (2009)
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)
10.1038/nnano.2008.365
Gram-scale production of graphene based on solvothermal synthesis and sonication.
M. Choucair (2009)
10.1021/JA062677D
Quantum-sized carbon dots for bright and colorful photoluminescence.
Y. Sun (2006)
10.1021/CR9603744
The Cationminus signpi Interaction.
J. C. Ma (1997)
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/JA01008A016
Trimethylene and the addition of methylene to ethylene
R. Hoffmann (1968)
10.1103/PHYSREVLETT.96.176101
Oxygen-driven unzipping of graphitic materials.
Je-Luen Li (2006)
10.1021/ja8094729
How graphene is cut upon oxidation?
Z. Li (2009)
10.1038/nnano.2007.451
Processable aqueous dispersions of graphene nanosheets.
Dan Li (2008)
10.1038/NMAT1849
The rise of graphene.
Andre K. Geim (2007)
10.1103/PhysRevLett.100.206803
Room-temperature all-semiconducting sub-10-nm graphene nanoribbon field-effect transistors.
X. Wang (2008)
10.1126/science.1154663
Chaotic Dirac Billiard in Graphene Quantum Dots
L. Ponomarenko (2008)
10.1038/nature07872
Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons
D. V. Kosynkin (2009)
10.1126/science.1166265
Brightly Fluorescent Single-Walled Carbon Nanotubes via an Oxygen-Excluding Surfactant Organization
Sang-Yong Ju (2009)
10.1021/ja800745y
Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets.
Y. Xu (2008)
10.1126/SCIENCE.1102896
Electric Field Effect in Atomically Thin Carbon Films
K. Novoselov (2004)
10.1002/smll.200700578
Surface functionalized carbogenic quantum dots.
A. Bourlinos (2008)
10.1021/ja9004514
Wet chemistry route to hydrophobic blue fluorescent nanodiamond.
V. Mochalin (2009)
10.1038/nnano.2007.290
Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers.
Adrian Nish (2007)
10.1103/PhysRevLett.98.206805
Energy band-gap engineering of graphene nanoribbons.
M. Han (2007)
10.1103/PhysRevLett.97.216803
Energy gaps in graphene nanoribbons.
Y. Son (2006)
10.1063/1.2827188
Tunable Coulomb blockade in nanostructured graphene
C. Stampfer (2008)
10.1021/JA0669070
An electrochemical avenue to blue luminescent nanocrystals from multiwalled carbon nanotubes (MWCNTs).
J. Zhou (2007)
10.1126/science.1150878
Chemically Derived, Ultrasmooth Graphene Nanoribbon Semiconductors
Xiaolin Li (2008)
Chem
R. Hoffmann (1475)
10.1021/JA9942282
Strong Luminescence of Solubilized Carbon Nanotubes
Jason E. Riggs (2000)
10.1021/JA00978A010
The Absorption, Emission, and Excitation Spectra of Diarylmethylenes
A. M. Trozzolo (1967)



This paper is referenced by
10.1021/acssuschemeng.7b03566
Green Strategy to Reduced Nanographene Oxide through Microwave Assisted Transformation of Cellulose
N. Erdal (2018)
10.1007/s10853-019-03469-w
Quantum dots-reinforced luminescent silkworm silk with superior mechanical properties and highly stable fluorescence
Lan Cheng (2019)
Growth and Characterization of Graphene on Texture-Controlled Platinum Films
Jae-Kyung Choi (2015)
10.1063/1.4881176
Enhanced visible photoluminescence emission from multiple face-contact-junction ZnO nanorods coated with graphene oxide sheets
J. Ding (2014)
10.1186/1556-276X-9-108
Cellular distribution and cytotoxicity of graphene quantum dots with different functional groups
X. Yuan (2014)
Novel liquid phase routes for the synthesis of metal sulphide nanomaterials and their thin films
R. Clark (2017)
10.1021/ACS.JPCC.5B08516
Unravelling the Multiple Emissive States in Citric-Acid-Derived Carbon Dots
Namasivayam Dhenadhayalan (2016)
10.1021/acsami.5b06057
Luminescent Polymer Composite Films Containing Coal-Derived Graphene Quantum Dots.
A. Kovalchuk (2015)
10.1039/C4RA03542A
A general route to enhance the fluorescence of graphene quantum dots by Ag nanoparticles
C. Ran (2014)
10.1021/nn300760g
Deep ultraviolet photoluminescence of water-soluble self-passivated graphene quantum dots.
L. Tang (2012)
10.1039/C3EE41776J
A carbon quantum dot decorated RuO2 network: outstanding supercapacitances under ultrafast charge and discharge
Yirong Zhu (2013)
10.1115/IMECE2013-64756
Tunable Optical Properties of Graphene Quantum Dots by Centrifugation
Junhua Wei (2013)
10.3389/fchem.2020.00123
Facile and Efficient Fabrication of Bandgap Tunable Carbon Quantum Dots Derived From Anthracite and Their Photoluminescence Properties
Jianbo Jia (2020)
10.1002/9781119468455.ch61
Graphene‐Based Scroll Structures: Optical Characterization and Its Application in Resistive Switching Memory Devices
J. R. Rani (2019)
10.1016/j.msec.2019.02.014
Chemosensing properties and logic gate behaviors of graphene quantum dot-appended terpyridine.
Si-Yuan Kang (2019)
10.1039/C9AY00068B
Carbon quantum dots: synthesis, properties, and sensing applications as a potential clinical analytical method
Huang Saipeng (2019)
10.1016/J.POLY.2018.12.025
A multi-responsive luminescent sensor based on flexible and ultrastable Zn-MOF@SWCNT hybrid nanocomposite film
H. Lin (2019)
10.1039/C8RA08088G
Carbon quantum dots and their biomedical and therapeutic applications: a review
M. J. Molaei (2019)
10.1039/C8RA09577A
A review on graphene-based nanocomposites for electrochemical and fluorescent biosensors
S. Krishnan (2019)
10.1016/J.SNB.2018.04.090
Folic acid encapsulated graphene quantum dots for ratiometric pH sensing and specific multicolor imaging in living cells
Xin Hai (2018)
10.1039/C8EN00346G
High-concentration organic dye removal using Fe2O3·3.9MoO3 nanowires as Fenton-like catalysts
Y. Su (2018)
10.1016/J.PMATSCI.2017.02.005
Nanostructured materials for microwave receptors
Kazem Majdzadeh-Ardakani (2017)
10.1016/J.ICA.2017.07.046
Rheology of a carbon dot gel
Yiwen Ji (2017)
10.1039/C6TC04030F
Optical and electrical effects of thin reduced graphene oxide layers on textured wafer-based c-Si solar cells for enhanced performance
A. Nandi (2017)
10.1039/c7cc04831a
How functional groups influence the ROS generation and cytotoxicity of graphene quantum dots.
Y. Zhou (2017)
10.1038/srep27145
Energy transfer from an individual silica nanoparticle to graphene quantum dots and resulting enhancement of photodetector responsivity
S. Kim (2016)
10.1016/J.JLUMIN.2016.08.021
Influence of chemical states of doped nitrogen on photoluminescence intensity of hydrothermally synthesized carbon dots
Shinichiro Niino (2016)
10.1039/c6an00543h
A fluorometric assay platform for caffeic acid detection based on the G-quadruplex/hemin DNAzyme.
Nan Cai (2016)
10.1002/anie.201713299
A Supramolecular Polymer Network of Graphene Quantum Dots.
Yuichiro Uemura (2018)
10.1039/C7NJ03621C
Carbon dots prepared in different solvents with controllable structures: optical properties, cellular imaging and photocatalysis
L. Chen (2018)
10.1038/ncomms3943
Coal as an abundant source of graphene quantum dots.
Ruquan Ye (2013)
10.1063/1.4867487
Red shift in the photoluminescence of colloidal carbon quantum dots induced by photon reabsorption
Wenxia Zhang (2014)
See more
Semantic Scholar Logo Some data provided by SemanticScholar