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Cite this: Chem. Commun., 2012, 48, 3686–3699

www.rsc.org/chemcomm FEATURE ARTICLE

Graphene quantum dots: emergent nanolights for bioimaging, sensors,
catalysis and photovoltaic devices
Jianhua Shen, Yihua Zhu,* Xiaoling Yang and Chunzhong Li*
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

Received 6th January 2012, Accepted 17th February 2012

DOI: 10.1039/c2cc00110a

Similar to the popular older cousins, luminescent carbon dots (C-dots), graphene quantum dots
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or graphene quantum discs (GQDs) have generated enormous excitement because of their
superiority in chemical inertness, biocompatibility and low toxicity. Besides, GQDs, consisting of
a single atomic layer of nano-sized graphite, have the excellent performances of graphene, such as
high surface area, large diameter and better surface grafting using p–p conjugation and surface
groups. Because of the structure of graphene, GQDs have some other special physical properties.
Therefore, studies on GQDs in aspects of chemistry, physical, materials, biology and
interdisciplinary science have been in full flow in the past decade. In this Feature Article,
recent developments in preparation of GQDs are discussed, focusing on the main two approaches
(top-down and bottom-down). Emphasis is given to their future and potential development in
bioimaging, electrochemical biosensors and catalysis, and specifically in photovoltaic devices that
can solve increasingly serious energy problems.

1. Introduction become a hallmark of quantum dots and related nanostructures.2

Recent advances have led to the development of dendrimer-
Fluorescent materials produce visible or invisible light as a encapsulated quantum dots,3,4 synthesis of quantum dots in
result of incident light of a different wavelength. The effect ceases mesopores,5,6 core–shell colloidal nanostructured quantum
as soon as the source of excitement is removed. Semiconductor dots,7,8 and mixed semiconductor dots,9,10 and so on.11 However,
based quantum dots (QDs) have proven themselves as powerful compared to conventional semiconductor quantum dots, carbon
inorganic fluorescent probes, especially for long term resistance dots (C-dots) are superior in terms of chemical inertness, low
to photobleaching.1 However, size-tunable properties have cytotoxicity and excellent biocompatibility.12,13 C-dots constitute
a fascinating class of recently discovered nanocarbons that
Key Laboratory for Ultrafine Materials of Ministry of Education, comprise discrete, quasi-spherical nanoparticles with sizes below
School of Materials Science and Engineering, East China University 10 nm.13–28 They possess several favorable attributes, such as
of Science and Technology, Shanghai 200237, China.
E-mail: [email protected], [email protected]; resistance to photobleaching, size- and wavelength-dependent
Fax: +86 21 6425 0624; Tel: +86 21 6425 2022 luminescence emission, ease of production and bioconjugation,

Jianhua Shen obtained his BS Yihua Zhu received his BS

degree from School of Materials degree from Nanjing University
Science and Engineering, and MS and PhD degrees from
East China University of Science East China University of Science
and Technology (ECUST) in and Technology (ECUST).
2009. He is currently a PhD Currently he is a full professor
student in Key Laboratory for in Key Laboratory for Ultrafine
Ultrafine Materials of Ministry Materials of Ministry of
of Education, ECUST, with Education, ECUST. His
Professor Yihua Zhu, focusing research interests include
on graphene quantum dots porous materials and nano-
and multifunctional magnetic structured materials and
nanocomposites. related functional applications,
especially for biosensors, drug
Jianhua Shen Yihua Zhu delivery, catalysis and clean
energy.

3686 Chem. Commun., 2012, 48, 3686–3699 This journal is c The Royal Society of Chemistry 2012
 View Article Online

derivatives have received more attention, as their diameters are

mainly distributed in a larger range (3–20 nm).13,40
Typically, GQDs contain carboxylic acid moieties at the
edge, which is similar to graphene, thus imparting them
with excellent water solubility and suitability for subsequent
Fig. 1 Schematic diagram of confined reaction in nanoreactors to functionalization with various organic, polymeric, inorganic
prepare quantum dots. or biological species (Fig. 2). In addition, GQDs have some
excellent characteristics, such as high surface area, larger
use of cheap and abundant raw materials.13 Advances in this diameter, better surface grafting using the p–p conjugated
area are appearing frequently, with a number of significant network or surface groups and other special physical properties
breakthroughs taking place within the last couple of years. due to the structure of graphene. As a consequence of their
A variety of methods have been developed to prepare C-dots. simple structure, as well as health concerns and biological
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

They can be prepared by laser ablation of graphite,14,15 hazards of QDs, GQDs are at the center of significant research
electrochemical oxidation of graphite,16 supported routes,17 efforts to develop low-toxicity, eco-friendly alternatives that
electrochemical soaking of carbon nanotubes,18 thermal oxidation have the desirable performance characteristics of QDs. It is
of suitable molecular precursors,19,20 from the combustion our aim that the development of this knowledge will offer
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soot of candles21 or natural gas,22 proton-beam irradiation valuable insights; moreover, we hope to inspire research
of nanodiamonds,23 microwave synthesis,24 and so on.25–27 into the origins of the unique properties of emerging novel
Very recently, Zhu et al. have reported a simple bottom-up fluorescent materials such as BN quantum dots, Si quantum
synthesis method for C-dots by using a mesoporous silica dots, nanodiamonds, etc., and to encourage their exploration
microspheres template.28 They proposed the concept of confined in electrochemical biosensors, bioimaging, drug delivery and
reaction in nanoreactors to prepare nanoparticles (Fig. 1). energy conversion.
In addition to the above properties, graphene quantum dots
or graphene quantum discs (GQDs), as a kind of C-dots, have
the excellent performance of graphene. Over the past few 2. Synthetic methods
decades, graphene, a single layer of carbon atoms in a
Approaches for synthesizing GQDs with tunable size can be
honeycomb structure, has generated enormous excitement due
generally classified into two main groups: top-down and
to its large surface area,29,30 high carrier transport mobility,31,32
bottom-up methods (Fig. 3). Top-down approaches refer to
superior mechanical flexibility33 and excellent thermal/chemical
the cutting of graphene sheets into GQDs, the method consists
stability.34–37 With bulk graphene having a zero bandgap, in
of chemical ablation, electrochemical oxidation, and oxygen
principle the bandgap of graphenes can be tuned from 0 eV to
plasma treatment, where GQDs are formed or ‘‘broken off’’
that of benzene by varying their sizes.38–40 To facilitate the
from larger graphene sheets. Bottom-up methods involve the
application of graphene in nanodevices and effectively tune the
synthesis of graphene moieties containing a certain number of
bandgap of graphenes, a promising approach is to convert
conjugated carbon atoms, the approaches consist, for example,
the 2D graphene sheets into 0D GQDs. These GQDs exhibit
of the cage-opening of fullerene, or solution chemistry methods
new phenomena due to quantum confinement and edge effects,
during which the GQDs are formed from molecular precursors.
which are similar to C-dots. However, the disadvantage is that
Typically, these GQDs have surfaces rich in carboxylic acid
C-dots possess size effects, and quasi-spherical nanoparticles
functionalities which can be used to bind surface-passivation
with sizes below 10 nm.13 Therefore, GQDs and their chemical
reagents.

Xiaoling Yang received her Chunzhong Li received his BS,

BS, MS and PhD degrees MS and PhD degrees from East
from East China University China University of Science and
of Science and Technology Technology in 1989, 1992, and
(ECUST). Currently she is 1997, respectively. He became a
an associate professor in Key full professor of school of
Laboratory for Ultrafine materials science and engineering
Materials of Ministry of in 1998, and now he is the
Education, ECUST. Her director of Key Laboratory
current research interests for Ultrafine Materials of the
include materials science and Ministry of Education at East
nano-technology with a China University of Science
particular focus on nano- and Technology. In 2009, he
composites for catalysis and became the winner of the
Xiaoling Yang medical application. Chunzhong Li National Science Fund for
Distinguished Young Scholars.
His research interests include functionalization and fabrication of
nanomaterials and for applications in catalysis, clean energy and
biomedical areas.

This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 3686–3699 3687
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Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

Fig. 2 (a) Depiction of GQDs and (b) structural models after func-
tionalization with surface-passivation reagents.
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Fig. 4 TEM images of (a) blue-luminescent GQDs produced by

hydrothermally cutting graphene sheets, (b) GQDs-PEG obtained by
one-pot hydrothermal reaction and (c) green-luminescent GQDs
obtained by one-step solvothermal method. Reprinted with permission
from refs. 42, 40 and 43. Copyright 2010 and 2011.

from which it was concluded that most of the GQDs were

single or bi-layered (Fig. 4c).
In addition to hydrothermal or solvothermal methods,
GQDs were also prepared by traditional hydrazine hydrate
reduction of oxidized small graphene sheets. Zhu and co-
workers reported GQDs prepared by hydrazine hydrate
reduction of GO with their surface passivated by PEG.44 First,
Fig. 3 Schematic diagram of the top-down and bottom-up methods
GO was further oxidised by HNO3, and cut into small GO
for synthesizing GQDs.
sheets. Then, the GQD precursor was treated with an oligo-
meric PEG diamine (PEG1500N) as a surface passivation agent
2.1. Top-down approaches (Fig. 5). The precursor was finally reduced by hydrazine
2.1.1. Chemical ablation from graphene. In 2008, Dai hydration to fabricate GQDs. Strong blue PL was clearly
and co-workers reported intrinsic luminescence from pre- shown under 365 nm radiation and green fluorescence was
dominantly single-layer nanographene oxide sheets in both observed under a 980 nm laser. The PL quantum yield
the visible and NIR regions.41 Pan et al. developed a hydro- measured using rhodamine B as a reference is 7.4%. Prior to
thermal route to cutting graphene sheets into GQDs, exhibiting this work, Chhowalla and co-workers had reported the PL
blue luminescence.42 Briefly, the large graphene oxide sheets intensity of a GO thin film was changed after each incremental
were cut into small sheets by controlled oxidation in a mixture hydrazine-vapor exposure (from 20 s up to 60 min).45 It is
of sulfuric acid and nitric acid under mild ultrasonication. immediately clear that in contrast to the broad absorption
The oxidized small graphene sheets were then reduced features, a relatively narrow PL peak centered around 390 nm
under hydrothermal conditions in a Teflon lined autoclave at is observed. One possible origin of the blue PL is the radiative
elevated temperature. The obtained GQDs had an average recombination of e–h pairs generated within localized states.
diameter of 9.6 nm (Fig. 4a) consisting of 1–3 layers of The energy gap between the p and p* states generally depends
graphene, and exhibited a quantum yield of 6.9% using on the size of sp2 clusters or conjugation length.46 While the
quinine sulfate as a reference. Shen et al. prepared GQDs PL intensity was weak for as-deposited GO films, short
surface-passivated by polyethylene glycol (GQDs-PEG) exposure to hydrazine vapor results in a dramatic increase in
by a one-pot hydrothermal reaction, using small graphene
oxide (GO) sheets and polyethylene glycol (PEG) as starting
materials.40 The collected GQDs-PEG were nearly mono-
disperse with a uniform diameter of ca. 5–25 nm (Fig. 4b).
By comparing the GQDs-PEG and the GQDs, the prepared
GQDs-PEG show excellent luminescence properties, the PL
quantum yield of the GQDs-PEG with 360 nm emission was
about 28.0% using rhodamine B as a reference. Zhu et al.
synthesized smaller GQDs with strong green photoluminescence Fig. 5 Representation of GQDs containing an oligomeric PEG diamino-
by a one-step solvothermal method.43 The average diameters surface passivating agent. Reprinted with permission from ref. 44.
of GQDs were 5.3 nm, and their average height was 1.2 nm, Copyright 2011.

3688 Chem. Commun., 2012, 48, 3686–3699 This journal is c The Royal Society of Chemistry 2012
 View Article Online

the PL intensities. Interestingly, this trend was reversed after

43 min exposure to hydrazine vapor. Longer exposure leaded
to eventual quenching of the PL signal.

2.1.2. Electrochemical synthesis. Zhou et al. first demon-

strated the electrochemical synthesis of C-dots from multi-
walled carbon nanotubes (MWCNTs) formed from scrolled
graphene layers on carbon paper by CVD.16 Another research
group produced C-dots electrochemically by oxidizing a graphitic
column electrode at 3 V (vs. saturated calomel electrode) with
a Pt wire counter-electrode in 0.1 M NaH2PO4 aqueous
solution.47 Chi and co-workers also produced C-dots electro-
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

chemically from a graphite rod working electrode, a Pt mesh

counter-electrode, and a Ag/AgCl reference electrode assembly
immersed in pH 7.0 phosphate buffer solution.48 Although
graphite was used as a raw material, spherical dots were
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produced with sizes of about 2 to 20 nm, which were not

considered as GQDs.13 Loh and co-workers generated fluor-
escent carbon nanoribbons, nanoparticles and graphene from
graphite electrode by ionic liquid (IL) assisted electrochemical
exfoliation using the water-soluble IL 1-butyl-3-methyl-
imidazolium tetrafluoroborate [bmim][BF4] containing up to Fig. 6 (a) Illustration of the exfoliation process showing the attack of
90 wt% water as the electrolyte.49 The mechanism of the the graphite edge planes by hydroxyl and oxygen radicals, which
exfoliation was due to a complex interplay of anodic oxidation facilitate the intercalation of BF4 anion. The dissolution of hydroxylated
of water and anionic intercalation from the ionic liquid. Using carbon nanoparticles gives rise to fluorescent carbon nanoparticles.
ILs with high water content (410% water) as the electrolyte, Oxidative cleavage of the expanded graphite produces graphene
water-soluble, oxidized carbon nanomaterials were generated. nanoribbons. (b) UV-vis absorption and fluorescence spectra (inset
In the case of electrolyte using concentrated ILs (o10% water), figure) obtained for 8–10 nm carbon nanoparticles (red curve) and
carbon nanoribbons (blue curve). The emission spectrum was obtained
IL-functionalized carbon nanomaterials were generated
using 260 nm excitation. Reprinted with permission from ref. 49.
instead. Carbon nanoribbons, which have a similar structure
Copyright 2009.
to GQDs, could be produced directly from graphite by
the concerted action of anionic intercalation and oxidative
cleavage (Fig. 6).
Later, Li et al. reported an electrochemical means of
synthesizing green-luminescent functional GQDs with a
uniform size of 3–5 nm (Fig. 7).50 GQDs were formed by
electrochemical oxidation of a graphene electrode in phosphate
buffer solution. The oxygen containing groups on the surface of
the GQDs provided aqueous solubility and facilitated further
surface functionalization. Their topographic heights were
between 1 and 2 nm, GQDs produced by electrochemical
oxidation were made of 1–3 graphene layers, attributed to
strong intergraphene attraction.51

2.1.3. Oxygen plasma treatment. Another top-down

method was discovered by Gokus et al., who claimed that Fig. 7 TEM images of green-luminescent GQDs prepared by electro-
strong PL could be induced in single-layer graphene (SLG) chemical oxidation of a graphene electrode in phosphate buffer solution,
using an oxygen plasma.52 The PL was spatially uniform inset is a photo of a GQD aqueous solution under UV irradiation (365 nm).
across the flakes and connected to elastic scattering spectra Reprinted with permission from ref. 50. Copyright 2011.
distinctly different from those of gapless pristine graphene.
Oxygen plasma could be used to selectively convert the top- that confocal PL maps revealed bright, pointlike PL features
most layer when multilayer samples were treated. Briefly, for short treatment times (1–3 s), whereas for slightly longer
graphene samples produced by microcleavage of graphite on exposures (5–6 s) spatially uniform broadband visible PL was
a silicon substrate were exposed to oxygen : argon (1 : 2) RF observed across SLG flakes (Fig. 8a and b). Moreover,
plasma (0.04 mbar, 10 W) for increasing time (1–6 s). The another group discovered that the GO nanosheets possessed
structural and optical changes were monitored by Raman visible and near-infrared (vis-NIR) fluorescene.55 Further, the
spectroscopy and elastic light scattering.53,54 The PL decay fluorescence intensity was dependent on the ionic strength and
dynamics was recorded by time-correlated single photon counting pH (Fig. 8c and d). Extracellular pH evolution during the
(TCSPC) upon pulsed excitation at 530 nm. The results showed growth and metabolism of normal and cancer cells has been

This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 3686–3699 3689
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Fig. 9 Comparison of the growth mechanism of GQDs using C60.

(a) The majority of C60 molecules adsorb on the terraces and these
decompose to produce carbon clusters with restricted mobility.
Fig. 8 (a) Confocal PL image excited at 473 nm (2.62 eV) for a (b) Temperature-dependent growth of GQDs with different equilibrium
graphene sample oxidized for 3 s. Scale bar = 5 mm. The bright PL spots shapes from the aggregation of surface diffused carbon clusters.
are spatially localized. (b) Uniform emission after 5 s; scale bar = 10 mm. (c, d) Corresponding STM images for the well-dispersed triangular
(c) Reversibility of the salt effect (inset: photograph of a reversible vis-NIR and hexagonal equilibrium shaped GQDs produced from C60-derived
fluorescence change between acidic and salt conditions). (d) Reversibility carbon clusters. Tunnelling parameters (c, d): V = 0.5 V, I = 1 nA.
of the pH effect (inset: photograph of a reversible vis-NIR fluorescence Reprinted with permission from ref. 58. Copyright 2011.
change between acidic and alkaline conditions). Reprinted with permission
from refs. 52 and 55. Copyright 2009 and 2011. showed that it originated from the combination of three flower-
shaped dots, which were joined at a central protrusion spot.
monitored by GO nanosheets while vis-NIR fluorescence
of GO has been further applied in bioimaging and optical 2.2.2. Solution chemistry methods. For the bottom-up
chemo/biosensing. approach, solution-phase chemical methods by oxidative
condensation of aryl groups have been successfully applied
2.2. Bottom-up approaches
to produce GQDs.51,59–65 Although it had been demonstrated
2.2.1. Cage-opening of fullerene. At present, some groups that intramolecular oxidative cyclodehydrogenation was useful for
have independently reported appealing methods for graphene the synthesis of large polycyclic aromatic hydrocarbons (PAHs)
nanoribbons production by the gradual unzipping of the from dendritic arene precursors, the solubility of such GQDs was
carbon nanotubes.56,57 Graphitic carbon layers can be derived unfortunately low and they exhibited a tendency to aggregate due
from the surface-catalysed decomposition of fullerene adlayers to strong intergraphene attraction.66–68 Li et al. reported the
on reactive transition metals. Loh et al. reported a mechanistic synthesis of stabilized GQDs with uniform and tunable size by
approach to the synthesis of a series of atomically defined multiple 20 ,40 ,60 -trialkyl phenyl groups covalently attached to the
GQDs by metal-catalysed cage-opening of C60 (Fig. 9).58 The edges of the graphene moieties.59 Their as-prepared GQDs consist
fragmentation of the embedded molecules at elevated temperatures of graphene moieties containing 168, 132 or 170 conjugated carbon
produced carbon clusters that underwent diffusion and aggregation atoms, respectively (Fig. 10a). The formation of 3-D protection
to form graphene quantum dots. The equilibrium shape of was attributed to the strong covalent binding and twisted phenyl
the graphene could be tailored by optimizing the annealing groups due to crowdedness at the edge of the graphene moieties.
temperature and the density of the carbon clusters. Loh et al. They reported a stepwise solution chemistry route for the synthesis
tracked the evolution of a lone C60 molecule on Ru(0001). When of these GQDs, which is illustrated in Fig. 10b.
the substrate covered with 0.03 ML C60 was gently heated to Very recently, Liu et al. prepared multicolor GQDs with a
450 K for 10 min, the C60 transformed into structures with three- uniform size of B60 nm diameter and 2–3 nm thickness by using
fold rotational symmetry. After flash annealing for 2 min at unsubstituted hexa-peri-hexabenzocoronene (HBC) as the precursor
725 K, numerous bright spots that were distinctly different from (Fig. 11a and b).65 The as-prepared GQDs with ordered
the starting C60 were found on the surface. The apparent height for morphology were obtained by pyrolysis and exfoliation of large
these bright spots was 2.7 Å, representing a decrease of 60% from PAHs, and the morphology of the GQDs were influenced by the
the initial height of 6.5 Å for C60 under a similar bias voltage. pyrolysis temperature. Fig. 11c shows the scheme of the overall
Annealing to 725 K produced flower-shaped dots with a threefold procedure for the preparation of GQDs. The as-made powder of
symmetry (0.7 nm), which constituted B23% of the decomposition HBC was first pyrolyzed at a high temperature. Then the
products. Hexagonal mushroom-shaped dots with a lateral width artificial graphite was oxidized and exfoliated with a modified
of 0.9 nm were also observed with a 67% yield. After annealing at Hummers method.69 Finally, aqueous solutions of the resultant
825 K, the smaller flower-shaped dots appeared to have merged GOs were heated to reflux for 48 h with oligomeric PEG1500N
into larger ones (1.2 nm). The magnified view of a 1.2 nm dot and then reduced with hydrazine.

3690 Chem. Commun., 2012, 48, 3686–3699 This journal is c The Royal Society of Chemistry 2012
 View Article Online

to longer wavelengths with a maximum intensity as the

excitation wavelength was changed from 300 to 470 nm; the
strongest peak was excited at 360 nm which emitted bright
blue photoluminescence (Fig. 12a).40,42,44,45 The PL spectrum
can be considered as a transition from the lowest unoccupied
molecular orbital (LUMO) to the highest occupied molecular
orbital (HOMO). Fig. 12b shows the dependence of the
HOMO–LUMO gap on the size of the graphene frag-
ments.45,70 Since the gap decreases gradually as the size of
GQDs increases, sample mixtures of different particle size
GQDs have different excitation and emission spectra, which
is in agreement with previous reports. Some groups have
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

prepared smaller GQDs (3–5 nm average diameter), which

possess strong green fluorescence (Fig. 12c).43,50
In addition to the size of the graphene fragments, the pH of
the GQDs solution will also influence the PL intensity. As Pan
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et al. reported,42 under alkaline conditions, the GQDs emitted

strong PL whereas, under acidic conditions, the PL was nearly
completely quenched. If pH was switched repeatedly between
13 and 1, the PL intensity varies reversibly. However, this
bahaviour may limit the applications of GQDs. Shen et al.
presented GQDs surface passivated by PEG to solve this
problem. They exhibited bright PL in a water solution of
Fig. 10 (a) Schemes of colloidal GQDs with tunable size. (b) Synthesis neutral pH44 while the intensity of the PL peaks decreased by
of GQDs via a wet chemistry approach. Reprinted with permission from
only about 25% under both acidic and alkaline conditions.
ref. 59. Copyright 2010.
They further found that as-prepared GQDs-PEG showed
excellent luminescence properties, and the PL quantum yield
with 360 nm emission was 28.0%, which was two times higher
than for the pure GQDs. Due to the surface-passivation agent,

Fig. 11 (a) AFM topography images of GQD-1200 on mica substrates.

(b) TEM images of GQD-1200. (c) Processing diagram for the preparation
of photoluminescent GQDs using HBC as the carbon source. Reprinted
with permission from ref. 65. Copyright 2011.
Fig. 12 (a) UV-vis absorption (Abs) and PL spectra of GQDs at
different excitation wavelengths. Inset: photograph of a GQD aqueous
3. Physical and chemical properties
solution taken under visible light and 365 nm UV light, from left to
3.1. Optical properties right, respectively. (b) Energy gap of p–p* transitions calculated based
on DFT as a function of the number (N) of fused aromatic rings. The
3.1.1. Photoluminescence. GQDs typically show strong inset shows the structures of the graphene molecules used for calcula-
optical absorption in the UV region, with a tail extending tion. (c) PL (at 375 nm excitation) spectra of a GQD aqueous solution
out into the visible range. The PL spectra are generally broad (inset: photograph taken under UV light). Reprinted with permission
and dependent on excitation wavelength, the PL peaks shifted from refs. 44, 45 and 43. Copyright 2010 and 2011.

This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 3686–3699 3691
 View Article Online

there must be a higher quantum confinement of emissive respectively (Fig. 14b). Remarkably, the shifting between the
energy trapped to the GQDs surface so that the GQDs with energy of upconverted emission light (Em) and excitation light
surface-passivation exhibit stronger PL.71 (Ex) was almost unchanged, about 1.1 eV. To further confirm
Besides the factors described above, there are other factors and explain these experimental observations, an energy level
that can influence the PL performance. As Chhowalla reported structural model of the GQDs was proposed to investigate the
the PL intensity was found to vary with reduction treatment UCPL properties. UCPL was speculated as due to anti-Stokes
by hydrazine vapor, which can be correlated to the evolution photoluminescence (ASPL), where DE between the p and s
of very small sp2 clusters.45 Gokus et al. discovered the PL orbitals was near 1.1 eV. The energy levels of p and s orbitals
intensity and thickness of graphene were directly correlated, as were determined by the carbene ground-state multiplicity.73–75
seen in Fig. 13 for flakes of different thickness.52 The single- As shown in Fig. 14c, when a number of low-energy photons
layer graphene showed pronounced PL, but a different behavior excite the electrons of the p orbital, the p electrons would
was observed for multilayer graphene. Oxygen plasma etching undergo transition to a higher energy state such as the LUMO,
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

proceeds layer-by-layer, and bi- and multilayer flakes remained and then the electrons would relax back to a lower energy
nonluminescent, thus implying that emission from the topmost state. Thus, an upconverted PL is emitted when the electrons
layer was quenched by subjacent untreated layers. return back to the s orbital. Although the electrons of the
s orbital can also undergo transition they only can emit
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3.1.2. Upconversion luminescence. Upconversion fluores- normal PL.

cence materials have attracted much recent attention for their
many promising applications, especially in the growing field 3.2. Cytotoxicity
of biomedical imaging. However, the upconversion photo-
As reported, C-dots have low toxicity12,76,77 and the cyto-
luminescence (UCPL) of GQDs were little researched until
toxicity of GQDs has been studied by various research groups.
recently. In 2008, Sun and co-workers discovered the C-dots
Dai and co-workers have also studied the cytotoxicity of
were found to be strongly emissive in the visible region with
nanographene oxide sheet-PEG composites by incubating Raji
either argon-ion laser excitation (458 nm) or a femtosecond
cells in various concentrations for 72 h, as shown in Fig. 15a.41
pulsed laser for two-photon excitation in the near-infrared
They observed slight reductions of cell viability only for
(800 nm).72 In addition, available results from exploratory
extremely high concentrations (4100 mg L1). Additionally,
experiments of luminescence imaging in vitro suggested that
Yang and co-workers performed studies using MG-63 cells43
the C-dots were internalized into human breast cancer cells
and also found GQDs possessed low cytotoxicity. Adding up
likely through endocytosis, demonstrating the potential of the
to 400 mg of GQDs to 150 mL of culture medium (104 cells)
C-dots in cell imaging with two-photon luminescence micro-
did not weaken the cell activity significantly, as shown by
scopy. After this, Lee et al. prepared C-dots by an alkali-
MTT assay (Fig. 15b). The result indicated the as-prepared
assisted electrochemical method, which possessed size-dependent
GQDs could be used in bioimaging and other biomedical
PL and excellent upconversion luminescence (UCPL) properties.70
applications at high concentration.
They also proposed that the UCPL property of C-dots should
All the evidence shows that GQDs have great potential for
be attributed to the multiphoton active process similar to that
in vitro and in vivo imaging studies. Although further toxicity
reported above, and that combining C-dots with catalytic
studies need to be carried out, such as LD50 (median lethal dose)
TiO2 in a composite system for photocatalysis would realize
measurements, some researchers predict that the biocompatibility
the efficient usage of the full spectrum of sunlight. However,
Shen et al. proposed that the multiphoton active process was
not sufficient to explain their experimental phenomenon.44 As
shown in Fig. 14a, the PL spectrum of GQDs excited by a
980 nm laser showed upconverted green light emission. Upon
changing the excitation wavelength from 600 to 800 nm, the
upconverted emissions peak shifted from 390 to 468 nm,

Fig. 14 (a) PL spectrum excited by 980 nm laser. Inset: Photograph of

the GQD aqueous solution taken under 980 nm laser. (b) Upconverted
Fig. 13 Correlation between PL and layer thickness. (a) Confocal PL PL properties of GQDs, inset is the energy of the excitation light as a
image; (b) elastic scattering image of the same sample area; (c, d) function of the emission according to Em = 1.00Ex + DE (R2 = 0.9983)
corresponding cross-sections taken along the dashed lines in (a, b). PL with DE = 1.1 eV. (c) A schematic illustration of various typical
is only observed from treated SLG (marked 1 L here); 3–4 L denotes a electronic transition processes of GQDs. Reprinted with permission
multilayer. Reprinted with permission from ref. 52. Copyright 2009. from ref. 44. Copyright 2011.

3692 Chem. Commun., 2012, 48, 3686–3699 This journal is c The Royal Society of Chemistry 2012
 View Article Online

large conjugated systems.62 The prolonged lifetimes of hot

carriers would further make it likely to be competitive against
internal conversion. More interestingly, the reduced hot-carrier
cooling rates could increase the efficiency of processes such as
hot electron extraction or multiexciton generation, to improve
the efficiency of photovoltaic devices.82,83
Graphene is metallic, leading to the possibility of modes
where the structural and electronic degrees of freedom are
Fig. 15 (a) Dosage-dependent cellular toxicity of NGO PEG to Raji entangled84 and is thus an excellent candidate material for the
cells. Relative cell viabilities vs. untreated control were plotted against manipulation of spins.85 Although the mechanisms responsible
NGO PEG concentrations. No obvious toxicity was observed except a for spin diffusion are not yet fully understood, graphene
slight delay of cell growth at the highest NGO PEG concentration spintronics has been studied by many research groups.85,86
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

(150 mg L1). (b) Effect of GQDs on MG-63 cell viability. Reprinted The presence of adatoms or corrugations is found to modify
with permission from refs. 41 and 43. Copyright 2008 and 2011. the spin–orbit coupling in GQDs.87,88 It could also be altered
into multilayered graphene.89 Recent measurements consistent
of the carbon fluorescent materials will lead to replacement of with the presence of local moments in graphene have been
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current FDA-approved dyes used as optical imaging agents, reported and magnetism in GQDs has been the subject of
such as indocyanine green (LD50 = 60 mg kg1 body extensive studies in recent years.90–93 For example, Viana-Gomes
weight).77 et al. has studied magnetism in GQDs of particular geometries
with and without zigzag edges. Similarly to what had been
3.3. Other physical properties
proposed in the context of graphene nanoribbons, the magnetism
Besides the properties described above, there are other displayed by these systems may be used in spin filters.90 A large
excellent properties of GQDs due to the physical structure of number of theoretical works suggested that the formation of
graphene.78–80 GQDs were shown to be both excellent electron local moments were at GQD edges and other defects. The
donors and acceptors.40,81 Li et al. prepared GQDs with a interactions between these local moments could be modified by
uniform and tunable size by solution chemistry methods, and gate voltages, dopants and other sources of disorder, and strains.
showed some special properties of GQDs and their opto- The expected distribution of local moments at GQDs and
electronic applications such as in photodetectors and solar graphene ribbon edges are shown in Fig. 16.
cells.59–64 They synthesized disk-shaped nanostructures materials
by assembly the colloidal GQDs on polar surfaces and the
4. Applications
control of their orientations. They showed that the orientations
of the GQDs could be determined, either in- or out-of-plane 4.1. Bioimaging
with the substrate, by chemical functionalization that intro-
Traditional semiconductor quantum dots such as CdSe or CdS
duces orientation-dependent interactions between the quantum
and their core–shell nanoparticles have been used in various
dots and the surfaces.60 The orientation control of the GQDs
in vitro or in vivo optical imaging experiments.94,95 However,
could have practical significance in determining their perfor-
these QDs dots have prompted serious health and environ-
mance in devices. For example, for use as sensitizers in dye-
mental concerns due to the heavy metal elements in them.95 As
sensitized solar cells, orientation control through chemical
a consequence of their tunable and strong PL properties,
functionalization could also be applied to aligning graphene
established low toxicity and eco-friendly nature, GQDs are
nanoribbons to take advantage of their outstanding charge
an attractive alternative for bioimaging applications.
transport properties for electro-optical applications. In addition,
Zhu and co-workers reported the use of a coaxial electro-
Li et al. first reported on the studies of electronic energy
spray method to the one-step fabrication of multifunctional
relaxation pathways in colloidal GQDs with uniform size.62
core–shell structured capsules, which possessed magnetic
They discovered that the photoexcited GQDs had a significant
targeting and fluorescence imaging functions.96 The TiO2 shell
probability of relaxing into triplet states and emitted both
suppressed the initial burst release of paclitaxel while Fe3O4
phosphorescence and fluorescence at room temperature, with
and GQDs inside the oil core functioned successfully for
relative intensities depending on the excitation energy. Because
magnetic targeting and fluorescence imaging, respectively.
of the long lifetime and reactivity of triplet electronic states,
they predicted that their results could have significant implica-
tions for applications of graphenes. Then, they showed that
carrier cooling in GQDs could be two orders of magnitude
slower than in bulk materials, which could enable harvesting
of hot charge carriers to improve the efficiency of solar energy
conversion.64 The slow hot-carrier relaxation in GQDs made it
possible to reveal other normally slow relaxation pathways
that were otherwise difficult to observe. Intersystem crossing
is generally much slower than internal conversion since it Fig. 16 (a) Sketch of the magnetization in a graphene ribbon with
involves a change in spin multiplicity. It could be enhanced zigzag edges. (b) Magnetization near the edges of a graphene quantum
in GQDs due to the reduced singlet–triplet splitting in such dot. Reprinted with permission from ref. 84. Copyright 2011.

This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 3686–3699 3693
 View Article Online

Furthermore, paclitaxel in capsules was trigger released by

ultrasound stimulation, and the release profile could be
controlled by the length of the repeatable ultrasound time.
In order to achieve the integration of targeted, therapy and
imaging, the capsules were designed in a multifunctional
core–shell structure as shown in Fig. 17.
Dai and co-workers also reported the first study on nano-
graphene oxide sheet cellular imaging and drug delivery
capabilities.41 The nanographene oxide sheets were found to
be PL in the visible and infrared regions. They demonstrated
intrinsic PL could be used for live cell imaging in the near-
infrared (NIR) with little background. They also found that
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

simple physisorption via p-stacking could be used for loading

doxorubicin, a widely used cancer drug onto nanographene Fig. 18 Nanographene for targeted NIR imaging of live cells.
oxide sheets functionalized with antibodies for selective killing (a) A schematic drawing illustrating the selective binding and cellular
of cancer cells in vitro. As shown in Fig. 18a, Dai and imaging of NGO PEG conjugated with anti-CD20 antibody, Rituxan.
Downloaded by University of Illinois - Urbana on 19 March 2013

co-workers covalently conjugated a B-cell specific antibody (b) NIR fluorescence image of CD20 positive Raji B-cells treated with
Rituxan (anti-CD20) to nanographene oxide PEG in order to the nanographene oxide PEG–Rituxan conjugate. The scale bar shows
the intensity of total NIR emission (in the range 1100–2200 nm).
selectively recognize and bind to B-cell lymphoma cells. B- and
Images are false-colored green. (c) NIR fluorescence image of CD20
T-cells were incubated in solutions of nanographene oxide–PEG
negative CEM T-Cells treated with nanographene oxide PEG-Rituxan
Rituxan conjugates at 4 1C to allow the conjugates to interact conjugate. (d) Mean NIR fluorescence intensities in the image area for
with the cell surface but block internalization via endocytosis.97 the both the positive (Raji) and negative (CEM) cells treated by nano-
The cells were imaged by detecting NIR PL in the range graphene oxide PEG Rituxan conjugate. Reprinted with permission
1100–2200 nm using a InGaAs detector under 658 nm laser from ref. 41. Copyright 2008.
excitation (laser spot size B1 mm, Fig. 18b and c). This confirmed
selective nanographene oxide-PEG-Ab binding to B- over T-cells
(Fig. 18d). Owing to its small size, intrinsic optical properties,
large specific surface area, low cost, and useful non-covalent
interactions with aromatic drug molecules, nanographene
oxide is a promising new material for biological and medical
applications.
Zhu et al. also used GQDs for conventional bioimaging by
incubating a 104 cells/150 mL solution of MG-63 (human
osteosarcoma) cells with suspensions (2.5 mg mL1) of GQDs Fig. 19 Cellular imaging of GQDs; (a–c) are washed cells imaged
from a stock solution with Dulbecco’s phosphate buffer saline under bright field, 405 and 488 nm excitations, respectively. Reprinted
(DPBS).43 MG-63 cells were cultured in Dulbecco’s modified with permission from ref. 43. Copyright 2011.
Eagle’s medium supplemented with 10% fetal bovine serum
and 1% penicillin/streptomycin (DMEM). The GQDs were the excess GQDs were removed by washing three times with
produced by a one-step solvothermal method with PL quantum warm DPBS. GQDs uptake and bioimaging experiments were
yield as high as 11.4%. Then, after sonication for 10 min to performed by the confocal fluorescence microscope as shown
ensure complete dispersion, an aliquot (typically 0.01 mL) of in Fig. 19. Observation of the bright green area inside the cells
the suspension was added to the well of a chamber slide indicated translocation of GQDs through the cell’s membrane
containing the cells cultured for 24 h. The chamber slide was (405 nm excitation). The excitation-dependent PL behavior of
then incubated at 37 1C in a CO2 incubator for 12 h for GQDs the GQDs gave rise to impressive visible results. When the
uptake (only 10 mg of GQDs to 150 mL of culture medium excitation light was changed to 488 nm a green–yellow color
(104 cells) was added). Prior to fixation of the cells on the was observed (Fig. 19c).
slide for inspection with a confocal fluorescence microscope, As shown in previous publications, cellular toxicity data
showed high biocompatibility and low toxicity of GQDs.
However, further experiments should be provided for in vitro
and in vivo applications, and for actual applications in the
human body.

4.2. Electrochemical biosensors

Due to the excellent conductivity of GQDs, Li et al. had
designed a simple but smart platform to fabricate electro-
chemical biosensors by using GQD-modified electrodes coupled
Fig. 17 Schematic illustration for procedures of shell cracking leading with specific sequence ssDNA molecules as probes.98 The probe
to drug release from capsules with increasing ultrasound time. Reprinted ssDNA inhibited electron transfer between electrochemically
with permission from ref. 96. Copyright 2011. active species [Fe(CN)6]3/4 and the electrode after the probe

3694 Chem. Commun., 2012, 48, 3686–3699 This journal is c The Royal Society of Chemistry 2012
 View Article Online

molecules were strongly bound to the surface of the modified

electrode via their interaction with GQDs. However, when the
target molecules such as target ssDNA or target protein were
also present in the test solution, the probe ssDNA bound with
the target instead of GQDs if the sequence of the probe
ssDNA was designed as complementary to the target DNA
or as the aptamer of the target protein. The obtained peak
currents of [Fe(CN)6]3/4 increased with the target molecules,
thus various electrochemical biosensors can be readily developed
with this proposed platform. The fabricated electrochemical
biosensors may also have high sensitivity and selectivity, which
may have potential applications in the future.
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

4.3. Catalyst for the oxygen reduction reaction

Very recently, Qu et al. prepared nitrogen-doped GQDs (N-GQDs)
Downloaded by University of Illinois - Urbana on 19 March 2013

with oxygen-rich functional groups by an electrochemical

method using tetrabutylammonium perchlorate (TBAP) in Fig. 20 (a, b) CVs of (a) N-GQD/graphene and (b) commercial Pt/C
acetontrile as electrolyte to introduce N atoms into the resultant on a GC electrode in N2-saturated 0.1 M KOH, O2-saturated 0.1 M
KOH, and O2-saturated 3 M MeOH solutions. (c) Rotating-disk
GQDs in situ.99 The doping of GQDs with heteroatoms
electrode (RDE) curves for N-GQD/graphene in O2-saturated 0.1 M
provides an attractive means of effectively tuning their intrinsic
KOH with different speeds. The inset shows Koutecky–Levich plots
properties and exploiting new phenomena for advanced device derived from the RDE measurements. (d) Electrochemical stability of
applications. Qu et al. reported that their as-prepared N-GQD/graphene as determined by continuous cyclic voltammetry in
N-GQDs showed luminescent and electrocatalytically active O2-saturated 0.1 M KOH. Reprinted with permission from ref. 99.
properties. Unlike their N-free counterparts, the produced Copyright 2011.
N-GQDs with a N/C atomic ratio of ca. 4.3% emitted blue
luminescence and possessed an electrocatalytic activity com-
Fig. 21c compares the current density–voltage (J–V) charac-
parable to that of a commercially available Pt/C catalyst for
teristics of a typical undoped P3HT device with those of one
the oxygen reduction reaction (ORR) in alkaline medium
blended with GQDs before and after annealing in the dark and
(Fig. 20). In addition to their use as metal-free ORR catalysts
under illumination.
in fuel cells, the linear-sweep voltammetry (LSV) curves of the
Yan et al. also reported that GQDs have high optical
ORR for NGQD/graphene in an O2-saturated 0.1 M KOH
absorptivity and nearly optimized absorption in the visible
solution were measured by a rotating disk electrode (RDE).
and near-IR region.63 Moreover, the calculated energy level in
The measured current density showed the typical increase
GQDs suggested the possibility of electron injection from
with increasing rotation rate due to the enhanced diffusion
GQDs to the large bandgap of TiO2 upon photoexcitation
of electrolytes.100,101 Apart from the use of N-GQDs as a
and regeneration of GQDs by accepting an electron from I.
metal-free catalyst for ORR, their unique luminescence properties
GQDs thus provide unique opportunities for the development
indicate their potential for use in bioimaging and light-emitting
of inexpensive, high efficiency GQD-sensitized solar cells by
diodes, among many other potential applications.
substituting GQDs for metal-organic dyes as photosensitizers.
Remarkably, since GQDs also were shown to possess UCPL
4.4. Organic photovoltaic devices
properties, they would find significant applications in photo-
Owing to their attractive optoelectronic properties and solution electrochemical cells, especially for use in near-infrared light
processibility, colloidal GQDs show promise of applications in absorption. Zhu et al. studied the photon-to-electron conver-
low cost, upconversion PL and high performance photovoltaic sion capability of GQDs.40 The photocurrents generated by
devices (e.g., organic/inorganic hybrid solar cells, GQD-sensitized GQDs-PEG and GQDs on ITO electrodes were measured by a
solar cells and organic light emitting diodes). three-electrode system. As demonstrated in Fig. 22, the
Li et al. applied colloidal GQDs with green luminescence GQDs-PEG photoelectrode generated photocurrent with both
as electron-acceptor materials in conjugated polymer, poly- 365 nm UV light and 808 nm NIR laser, while the pure GQD
(3-hexylthiophene) (P3HT)-based thin film solar cells.50 photoelectrode showed less than half of the photocurrent of
Although without device optimization in this primary study, the GQDs-PEG. It is speculated that GQDs can be a new solar
a power conversion efficiency of 1.28% was achieved. As cell dopant material and the light of the photon-to-electron
shown in Fig. 21a, polymer photovoltaic cells with the structure conversion may be extended from the ultraviolet to the near
of ITO|PEDOT:PSS|P3HT:GQDs|Al were fabricated (ITO, infrared.
PEDOT, PSS and P3HT correspond to indium tin oxide, Gupta et al. demonstrated that GQDs blended with regioregu-
poly(3,4-ethylenedioxythiophene), poly(styrenesulfonate) and lar P3HT or poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-
poly(3-hexylthiophene), respectively). The GQDs (10 wt%) vinylene) (MEH-PPV) polymer results in a significant
provided an effective interface for charge separation and a improvement in the efficiency of solar cells or organic light
pathway for electron transport, and the energy level diagram emitting diode (OLED) characteristics as compared to graphene
for the GQD-based photovoltaic cells is shown in Fig. 21b. nanosheets (GS) blended conjugated polymers.81 The GQDs were

This journal is c The Royal Society of Chemistry 2012 Chem. Commun., 2012, 48, 3686–3699 3695
 View Article Online

J–V curves of the different OLEDs and the corresponding

band diagrams are given in the inset. The turn-on voltage for
the pure MEHPPV sample was about 6 V and was decreased to
4 V for MEHPPV|MB-GQDs (1 wt%). MEHPPV|MB-GQDs
(1 wt%) exhibited strong yellow emission as compared to the
bright orange emission of MEHPPV. The MB-GQDs dispersed
in the MEHPPV provided more electrical transport paths,
which results in an enhancement of charge injection and hence
caused increase in the carrier density, thus requiring lower
turn-on voltage and much higher efficiency.

5. Outlook
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

Although much research for GQDs has been done the detailed
mechanism and chemical species responsible for PL in GQDs
Downloaded by University of Illinois - Urbana on 19 March 2013

derivatives still further understanding. Throughout these studies,

some interesting questions arise such as the factors affecting the
energy band of GQDs, whether significant inhomogeneity of the
oxidation profile exists within the GO plane, and whether energy
relaxation and spectral diffusion in GO-type materials are
altered by aggregation and interlayer coupling. GQDs have
received much attention as they may gradually replace tradi-
tional quantum semiconductors applied in bioimaging, disease
Fig. 21 Schematic (a) and energy band (b) diagrams of the detection, drug delivery and photovoltaic devices, due to their
ITO|PEDOT:PSS|P3HT:GQDs|Al device. (c) J–V characteristic curves
superiority in terms of chemical inertness, biocompatibility and
for the ITO|PEDOT:PSS|P3HT|Al, ITO|PEDOT:PSS|P3HT:GQDs|Al
low toxicity. However, GQDs also have some disadvantages,
and ITO|PEDOT:PSS|P3HT:GQDs|Al devices after annealing at 140 1C
for 10 min (single log scale). Reprinted with permission from ref. 50.
Copyright 2011.

synthesized from graphene nanosheets by the hydrothermal

approach, which were functionalized with aniline (ANI) or
methylene blue (MB) (ANI-GQDs and MB-GQDs). J–V
curves of the ANI-GQD and ANI-GS (optimized) photovoltaic
devices are plotted in Fig. 23a and corresponding band
diagrams are given in the inset. A maximum Z of 1.14, Voc
of 0.61 V, Jsc of 3.51 mA cm2 and FF of 0.53 were obtained
for 1 wt% ANI-GQD in P3HT. As shown in the inset, the
LUMO and HOMO of GQDs were 3.55 and 5.38 eV,
respectively, as determined by cyclic voltammetry. The position of
the LUMO of GQDs in between that of P3HT1 and Al suggested
their suitability for solar cell applications. Fig. 23b shows the

Fig. 23 (a) J–V characteristics of photovoltaic devices based on

ANI-GQD with different GQD content and ANI-GS (under optimized
condition) annealed at 160 1C for 10 min, in AM 1.5 G 100 mW
illumination. (b) Measured current density of MEHPPV with MB-GQD:
a: 0%, b: 0.5%, c: 1% and d: 3% as a function of the applied voltage (V).
The inset plots the electroluminescence spectrum of MEHPPV (red) and
MEHPPV|MB-GQD (1%) (black). The inset also shows the band
Fig. 22 Photocurrent response of GQDs-PEG and GQDs photo- diagram of MEHPPV|MB-GQD and the recorded brightness of
electrodes under 365 nm UV light or 808 nm NIR laser. Reprinted MEHPPV LED and MEHPPV|MB-GQD(1%) LED. Reprinted with
with permission from ref. 40. Copyright 2011. permission from ref. 81. Copyright 2011.

3696 Chem. Commun., 2012, 48, 3686–3699 This journal is c The Royal Society of Chemistry 2012
 View Article Online

such as generally presenting a blue luminescence which was not 5.4. Newer quantum dot materials
conducive to biological imaging, and other luminescence including
In addition to C-dots and GQDs, many newer quantum dots
UCPL which is relatively weaker. In addition, solar cells with
have been discovered and researched recently, such as h-BN
GQDs usually have relatively lower efficiency (o2%). However
nanosheets or BCNO nanoparticles,106 nanodiamonds,107
the initial work on GQDs for solar cells or bioimaging are very
fluorescent silicon quantum dots (SiQDs)108–110 and so on.
promising. As discussed below, future research efforts towards
He et al. presented a microwave-assisted method for one-pot
better controlled synthesis, surface functionalization, metal
synthesis of water-dispersible SiQDs using silicon nanowires
enhanced fluorescence and new quantum dot materials are
and glutaric acid as precursors.110 Their prepared SiQDs,
expected to result in even higher performance.
which feature excellent aqueous dispersibility, robust photo-
5.1. New methods for the synthesis of GQDs and pH-stability, strong fluorescence (about 15%), and favor-
able sizes (about 4 nm), were readily and rapidly prepared in
Synthesis of high quality GQDs with well controlled size, short reaction times. We speculate that the new quantum dot
Published on 21 February 2012 on http://pubs.rsc.org | doi:10.1039/C2CC00110A

shape and surface functionalization needs to be further explored. materials may provide biological probes for long-term and
GQDs prepared by the top-down approaches are usually difficult real-time immunofluorescent cellular imaging, which can over-
to control in terms of size and shape. Therefore, we speculate the come the disadvantages of GQDs.
Downloaded by University of Illinois - Urbana on 19 March 2013

bottom-up methods will become the dominant development

direction for the synthesis of GQDs. The concepts of confined
reaction and nanoreactors, which has been used to prepare
Acknowledgements
nanoparticles, may well be a useful area for research. We thank the National Natural Science Foundation of China
(20925621, 20976054, and 21176083), the Special Projects for
5.2. Surface engineering on GQDs Nanotechnology of Shanghai (11nm0500800) the Fundamental
In contrast, the surface engineering of GQDs has been studied Research Funds for the Central Universities, and the Program
relatively less. The surface modification on GQDs has a great for Changjiang Scholars and Innovative Research Team in
influence on their performance. Zhou et al. have introduced University (IRT0825), and the Shanghai Leading Academic
different shaped GQDs functioning as conjugated bridges in Discipline Project (project number: B502) for financial support.
the donor–bridge–acceptor (NH2-GQD-NO2) systems.102
They found that the shape effect and singlet diradical or References
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