View Article Online

View Journal

Journal of

Materials Chemistry C
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: Z. Wang, H. Zeng
and L. Sun, J. Mater. Chem. C, 2014, DOI: 10.1039/C4TC02536A.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journals
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/materialsC

Journal of Materials Chemistry C

Journal Name

View Article Online

DOI: 10.1039/C4TC02536A

RSCPublishing

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

ARTICLE

Cite this: DOI: 10.1039/x0xx00000x

Graphene Quantum Dots: Versatile

Photoluminescence for Energy, Biomedical, and
Environmental Applications
Zhaofeng Wang, a Huidan Zeng b and Luyi Sun a,*

Received 00th January 2012,

Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/

Photoluminescence is one of the most outstanding features of graphene quantum dots. Because of their
versatile photoluminescence, large surface area, high photostability, low cytotoxicity, and excellent
biocompatibility, graphene quantum dots are showing promising application in various fields, and
herein they have become the research focus in recent years. In this r eview article, we summarized the
latest research progress of graphene quantum dots, focusing on their photoluminescence features and
promising applications. This article also summarized the most recent researches on the upconversion by
use of femtosecond laser. Perspectives on this topic were presented on the basis of the current research
status. We hope this article could help gain an in-depth understanding of photoluminescent graphene
quantum dots, and herein stimulate continued interests and endeavors in this research area.

1. Introduction
Graphene, a two-dimensional (2D) lattice of sp2-hybridized
carbon, presents many unique properties and has attracted
intensive research interest since its discovery in 2004.1-8
Because of the linear energy dispersion relation of charge
carriers, graphene is proven to be a specific type of zero band
gap semiconductor with an infinite exciton Bohr radius. 9
However, the zero band gap of graphene strongly limits its
applications in optoelectronics and photonics.10 Surface
modification, doping, as well as reducing the lateral dimensions
of graphene into nanoribbon and/or quantum dots (QDs), are
considered the main effective approaches to contribute to its
band gap engineering.11-15 In addition to remarkably enhanced
quantum confinement effect (QCE), edge effect will be
prominent when graphene is converted to graphene quantum
dots (GQDs), whose lateral dimensions are less than 100 nm. 16
These two outstanding effects endow GQDs new physical
properties with widespread application, and herein they have
become the research focus in recent years.17
Photoluminescence (PL) of GQDs is one of the most
outstanding features extended from graphene, which can be
easily tailored by controlling their size and shape, doping
nonmetallic ions, and modifying their surfaces and edges.18 In
addition to the tunable PL, GQDs exhibit large surface area,
ease of surface modification, high photostability, low
cytotoxicity, and excellent biocompatibility. 19 As a
consequence of their special structure and unique properties,
photoluminescent GQDs are expected to be more viable than

This journal is The Royal Society of Chemistry 2013

the conventional semiconductor QDs and other carbon-based

luminescent nanomaterials.
The prerequisite for the investigation of photoluminescent
GQDs is the controllable synthesis of high quality GQDs. To
date, a variety of synthetic methods have been developed,20
which can be classified into two categories: one is to directly
cut graphene- or graphite-related materials (graphene,21
graphene oxide,22 carbon nanotube,23 carbon fiber,24 carbon
black,25 nanosized graphite,19 graphite powder,26 coal,27 etc.)
into quantum size through a series of physical, chemical, and
electrochemical processes, which is commonly referred to as
top-down method. The other strategy lies in chemical
synthesis, typically called bottom-up method, in which
molecular precursors (such as hexa-peri-hexabenzocoronene,28
4-bromobenzene carboxylic acid,29 3-iodo-4-bromoaniline,30,31
citric acid,32 glucose,33 benzene,34 etc.) were controllably
converted to GQDs by stepwise chemical reactions. Such rich
synthetic methods allow us to investigate the PL features of
GQDs with a desired size and structure. Herein, abundant
meaningful achievements, associated with the PL mechanisms
and expanded applications, have been made during recent years.
In this article, we provide an overview of photoluminescent
GQDs, focusing on their PL features, underlying mechanisms,
and promising applications. Since there are a large number of
publications on the subject of photoluminescent GQDs,17,18,35
we emphasize to clearly elucidate the PL mechanisms that
could be applied to explain both the normal and abnormal PL
properties of GQDs, as well as covering the latest applications
in the fields of energy, biomedicine, and environment. The

J. Name., 2013, 00, 1-3 | 1

Journal of Materials Chemistry C Accepted Manuscript

Page 1 of 9

Journal of Materials Chemistry C

latest researches on the UC in GQDs by use of femtosecond

laser are also summarized. We hope this article could provide a
concise overview of photoluminescent GQDs and stimulate
new ideas for further research.

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

2. General description of PL of GQDs

Photoluminescence refers to the phenomenon of light emission
after the excitation of photons. The PL spectrum of GQDs
usually presents a broad emission band, covering from UV to
visible light regions. The corresponding photoluminescence
excitation (PLE) spectra are composed of two or more peaks,
corresponding to the excitations of size/edge-related intrinsic
states in higher energy and vacancy/functional groups
associated defect states in lower energy. 19 For instance, Figure
1a shows the representative PL and PLE spectra of the
hydrothermally synthesized GQDs. It is worth noting that
GQDs could exhibit bright emission with tunable color by
simply adjusting the experimental conditions (Figure 1b).36

Figure 1. (a) Representative PLE, PL spectra, and luminescent photograph of

GQDs; Reproduced by permission of Wiley-VCH.21 (b) Emission images of
different kinds of GQDs under excitation of a 365 nm UV lamp. Reproduced by
permission of Wiley-VCH.36

3. Versatile PL features
3.1 Internal factor-dependent PL
The intrinsic structures of GQDs, including size/edge,22,37,38
functional groups,39,40 and chemical doping,41-45 can be easily
varied by using different synthesis methods and subsequent
treatments, leading to the tailoring of the electronic structure of
GQDs. As a result, versatile PL properties can be achieved.
Generally, the band gap of GQDs has been demonstrated to
increase as the size decreases, leading to blue shift on their PL
emission (Figure 2a). 24,33 However, Kim et al. obtained an
anomalous PL evolution of GQDs with various sizes.22 As
shown in Figure 2b, the PL peak energy exhibited red-shift first
and then blue-shift with an increasing lateral dimension of

2 | J. Name., 2012, 00, 1-3

Page 2 of 9

Journal Name
GQDs. This unusual PL behavior could be attributed to the
corresponding edge structure variations of GQDs with different
sizes, in addition to QCE. The above size-dependent PL
features were based on GQDs without surface passivation.
However, GQDs will not exhibit such behaviors if there is a
self-passivated layer on the surface, such as the GQDs prepared
by glucose carbonization. 46
Functionalization of GQDs is another common factor to
shift PL emission. Jin et al.47 observed that the amine
functionalized GQDs exhibited a redshift of PL emission (ca.
28 nm) compared to the un-functionalized GQDs, as depicted in
Figure 2c. They ascribed it to the charge transfer from amine
functional groups to GQDs, which could increase the electron
density on the carbon framework, subsequently lowering band
gap. Zhu et al.39 compared the PL spectra of graphene oxide
quantum dots (GOQDs), reduced GQDs, and alkylamine
functionalized GQDs. With reducing and replacing the carboxyl
and epoxy groups in GOQDs, PL intensities were greatly
enhanced because carboxyl and epoxy groups could induce
non-radiative recombination. Moreover, PL color was changed
from green to blue during the above processes. Since carboxyl
and epoxy groups act as the non-radiative luminescent centers,
the removal of these oxygen-containing groups, either by
reduction or surface passivation, is beneficial to achieve a
higher quantum yield. 18,36
Doping foreign atoms is another effective method to adjust
the PL of GQDs. Li et al. 41 observed that the PL peak of GQDs
was shifted to higher energy when N atoms were introduced
into the structure. This phenomenon could be attributed to the
relatively strong electron affinity of N atoms, inducing the
modulation of the chemical and electronic characteristics of
GQDs. Tang et al.42 found a clear red shift (~10 nm) when
fluorine was doped in GQDs, which may be attributed to the
trapping of excitons in shallow trap states associated with
charge separation between carbon backbone and high
electronegative F atoms.
3.2 External factor-dependent PL
In addition to the internal parameters, PL of GQDs is readily
affected by the external experimental conditions. Like most
luminescent carbon nanoparticles, 48,49 GQDs can exhibit an
excitation-dependent PL behavior. 21,28,50 In general, the PL
peak of GQDs will shift to longer wavelengths with an
increasing excitation wavelength (Figure 2d). At the same time,
the PL intensity will vary rapidly, with the most intense peak
excited at the absorption band. Another remarkable feature of
GQDs is the pH-dependent PL, and the pH-dependence varies
contingent to their size and structure. For example, Pan et al.
observed that GQDs emitted strong PL under basic conditions
while completely quenching under acidic conditions. 21 The PL
intensity was reversible if pH value was switched repeatedly
between 1 and 13 (Figure 2e). Jeon and coworkers47 observed
that their GQDs showed enhanced PL without peak shift when
pH value was tuned from 7 to 1, while the PL intensity greatly
decreased with emission peak red-shift when pH value was
changed from 7 to10. They continued to functionalize the

This journal is The Royal Society of Chemistry 2012

Journal of Materials Chemistry C Accepted Manuscript

ARTICLE

View Article Online

DOI: 10.1039/C4TC02536A

Journal of Materials Chemistry C

Journal Name

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

GQDs with amine and obtained a different pH-dependent result

(Figure 2f). In addition to the excitation- and pH- dependent
features, PL of GQDs also depends on the types of solvents.39

View Article Online

DOI: 10.1039/C4TC02536A

ARTICLE
penetration depth, low destruction to tissues or organisms, and
reduced autofluorescence. 54 However, it should be pointed out
that the UCPL of GQDs by monochromatic light from a
Xenon lamp should be normal PL (NPL).55,56 Gan et al.
presented a systematic study to explain the origin of the blue
emission in GQDs by the excitation of monochromatic lights.
Based on the comparisons of PL (Figure 3a), PLE spectra
(Figure 3b), and decay lifetimes (Figure 3c) between
upconversion luminescence (excited by ) and normal
luminescence (excited by /2), they confirmed that the
previously claimed UCPL in GQDs excited by
monochromatic light was actually originated from the coexistence of second-order diffraction light of wavelength /2 in
the excitation wavelength . Such UCPL would vanish if a
cut filter was applied as shown in Figure 3d. Likely, under the
excitation of a Xenon lamp, nitrogen doped GQDs (N-GQDs)
did not exhibit UCPL either. Besides the above evidences,
Wen et al.57 measured the excitation intensity dependence of
fluorescence of GQDs, and found the slope value to be
approximately 1, further verifying the UCPL in GQDs by the
excitation of monochromatic light should be NPL.

Figure 2. Factors that affect the PL of GQDs: (a, b) Size; Reproduced by

permission of American Chemical Society.22,33 (c) Functionalization; Reproduced
by permission of American Chemical Society.47 (d) Excitation wavelength;
Reproduced by permission of The Royal Society of Chemistry.50 (e, f) pH values.
Reproduced by permissions of Wiley-VCH21 and American Chemical Society.47

The surrounding micro-environment of GQDs also shows

great influence to their PL properties. When GQDs were
encapsulated into zeolitic imidazolate framework (ZIF)
nanocrystals, their PL spectra could be red shifted by ca. 32 nm,
attributing to the interaction between the carboxylic acids in
GQDs and the Zn ions in ZIF.51 Furthermore, Wang and
coworkers52 theoretically speculated that the PL color of GQDs
could also be precisely adjusted from blue to green by
designing a single silver nano-octahedron (SNO) in the vicinity
of GQDs. The SNO was predicted to act as a multifrequency
plasmonic antenna with multiple plasmon resonance modes,
covering multiple emission peaks of GQDs. Although this
novel modulating strategy could facilitate the potential
applications of GQDs, great efforts are still required to achieve
it in experiments.
Detailed mechanisms of the above factor-dependent PL of
GQDs will be discussed in the next section.
3.3 Upconversion
In some recent researches, 42,53 GQDs were reported to exhibit
upconversion photoluminescence (UCPL). This was significant
for GQDs to be practically applied in biomedical
imaging/labeling, as the excitation photons possess a high

This journal is The Royal Society of Chemistry 2012

Figure 3. (a) Normalized PL spectra of GQDs excited at 320 and 640 nm; (b) PLE
spectra and (c) Time resolved PL of GQDs; (d) PL spectra of GQDs with and
without a cutoff filter; (e) UCPL spectra of GQDs under the excitation of a
femtosecond pulsed laser at 800 nm; (f) UCPL integrated intensity as a function
of laser power. Reproduced by permission of Wiley-VCH.56

It is interesting and imperative to explore whether there is

real UCPL in GQDs when using a high power density laser.
Gan et al.56 experimentally observed the UCPL under excitation
of a femtosecond 800 nm pulsed laser as presented in Figures
3e and 3f. The UCPL can be further shifted to green emission,
when the GQDs were oxidized 58 or doped with nitrogen
atoms.59 The appearance of UCPL under femtosecond laser

J. Name., 2012, 00, 1-3 | 3

Journal of Materials Chemistry C Accepted Manuscript

Page 3 of 9

Journal of Materials Chemistry C

should be attributed to the abundant energy levels in GQDs,

which can be directly reflected from the excitation wavelengthdependent PL features. 56 In the recent reports,58,59 the main UC
mechanism of GQDs should be the excited-state absorption.
More efficient UC approaches need to be further explored, like
the energy transfer upconversion, cooperative sensitization
upconversion, and photon avalanche in lanthanide-doped
materials.60

4. PL mechanisms
Currently, various mechanisms have been proposed to explain
the PL phenomena of GQDs with different sizes, shapes, edges,
and surface structures. At first, the PL of GQDs was simply
suggested to originate from free zigzag sites with a carbene-like
triplet ground state.21 Subsequently, a more complete PL
mechanism, involving intrinsic and defect emissions, was
proposed.19,39,61,62 The exhibited PL emission depends on the
competition of these emission centers. A clear evidence to
support this mechanism was reported by Liu et al. 19 They found
that the pristine GQDs exhibited a blue PL emission band.
However, for GOQDs under the same excitation wavelength,
PL emission band was shifted to green with intensity greatly
decreased. The PLE (Figures 4a-b) and decay lifetime curves
(Figures 4c-d) suggested that GQDs possessed both intrinsic
and defect states while the intrinsic state in GOQDs almost
disappeared. Therefore, the reduction of intrinsic state emission
and increase of defect state emission should be responsible for
the PL evolution of GOQDs. This mechanism could well
explain most of the PL features of GQDs. As the intrinsic
emission of GQDs is generated by QCE and edge effect, the
variation of size and edge structure will change the above two
effects, leading to different PL features, which is called
size/edge-dependent PL. The QCE will arouse the discrete
feature of the intrinsic excitation band. 62 With the increase of
excitation wavelength, the gradual evolution from discrete
intrinsic excitation band to the defect state band causes the
excitation wavelength-dependent PL. In addition, the size
distribution in GQDs should also be one of the possible reasons
for the excitation-dependent PL. In this case, GQDs with a
smaller size will be excited by shorter wavelength, while GQDs
with a larger size will be excited by longer wavelength.
Therefore, along with the increase of excitation wavelength,
red-shift will be observed according to QCE. Since both the
size of sp2 carbon clusters and the defect state density in GQDs
may be altered by surface/edge functionalization, either the
defect state emission or the intrinsic state emission may
dominate, causing the widely reported functionalizationdependent PL. In some specific functionalization forms (amine,
etc.), the surface/edge modification of GQDs can also tune the
band gap through the charge transfer between the functional
groups and GQDs47 or forming an interband state,63 resulting in
the shift of PL emission.
As described in section 3.2, both the PL intensity and peak
energy of GQDs show strong dependence on surrounding pH
values. This phenomenon could be generally attributed to the

4 | J. Name., 2012, 00, 1-3

Page 4 of 9

Journal Name
protonation and de-protonation of the edge sites and functional
groups.21,47 On one hand, the free zigzag sites will be
protonated in acidic condition, which destroys the emissive
carbene-like triplet state and decreases its intrinsic PL intensity.
However, the zigzag sites can be restored under basic
environment, thereby leading to the restoration of emission
intensity. On the other hand, the functional groups grafted onto
the surface or edge will also protonate and deprotonate in acidic
and basic conditions, respectively. These processes play a key
role in suppressing or prompting the charge transfer from
GQDs to the functional groups, and thus resulting in PL peak
red or blue shift. Therefore, by combining these two
mechanisms, versatile pH dependent PL features can be
realized in various GQDs.

Figure 4. Comparison of the UV-vis absorption and PLE spectra of (a) GQDs and
(b) GOQDs; PL decay curves of (c) GQDs and (d) GOQDs. Reproduced by
permission of Wiley-VCH.19

Very recently, Yang and coworkers 64-66 employed a

combination of techniques, including femtosecond broadband
transient absorption spectroscopy, femtosecond time-resolved
fluorescence dynamics, as well as nanosecond time-correlated
single-photon counting technique, to give more detailed
information on the PL processes of GQDs. Their experimental
results revealed that the molecule-like states, composed by the
functional groups (such as carboxyl and carbonyl groups) and
carbon atoms on the edge of GQDs, were mainly responsible
for the green PL emission of GQDs. The related PL
mechanisms involved both regular absorption and excited-state
absorption processes. This is an important supplement to the
existing mechanism, binding the functional groups and carbon
atoms as a whole emissive center. The synergistic effect of
intrinsic state and molecule-like emission could endow GQDs
an enhanced resistance to photobleaching.

5. Applications
5.1 Energy-related applications
Recent reports suggest that the GQDs are promising for
applications in light emitting diodes (LED) as the luminescent

This journal is The Royal Society of Chemistry 2012

Journal of Materials Chemistry C Accepted Manuscript

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

ARTICLE

View Article Online

DOI: 10.1039/C4TC02536A

Journal of Materials Chemistry C

View Article Online

DOI: 10.1039/C4TC02536A

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

Journal Name
component.38,67 This is because that the broad PLE band of
GQDs matches well with the LED chips. Lau and co-workers
coated a layer of GQDs onto the surface of a commercial blue
LED chip.46,68 After applying voltage, the chip exhibited
intense blue emission centered at ~410 nm, which further
excited GQDs to show the characteristic broad emission peaked
at ~510 nm. As a result, the whole LED emitted white light as
illustrated in Figure 5. 46 Furthermore, they employed
GQDs@agar composites to replace raw GQDs for the
fabrication of LED. 68 The luminous efficiency of the
GQDs@agar composite coated LED reached 42.2 lm/W under
20 mA, which was almost constant during continuous operation
for over 100 hours. These kinds of LED using GQDs and
GQDs composites were suggested to have higher luminous
efficiency and better light conversion stability than those of the
conventional semiconductor QDs based LED.

Figure 5. Luminescence spectra, optical photographs, and emission color

coordinates of the blue LED with and without GQDs coating. Reproduced by
permission of American Chemical Society.46

GQDs also showed great promise in photovoltaic devices,

with respect to their size-tuned optical response, high specific
surface area, efficient multiple carrier generation, and tunable
band gaps.17,69 Gao et al.70 developed a new type of solar cells
based on the crystalline silicon/GQDs heterojunction.
Compared to the devices without GQDs, crystalline
silicon/GQDs heterojunction solar cells showed a significantly
enhanced photovoltaic performance, with an optimum power
conversion efficiency of 6.63%. Zhu et al.71 reported a
remarkable power conversion efficiency enhancement of
perovskite solar cells by inserting an ultrathin GQDs layer.
Such an improvement was owing to the faster electron
extraction in the presence of GQDs. Therefore, GQDs were
suggested to act as a superfast electron tunnel for optoelectronic
devices.
Like other N-doped carbon nanomaterials, N-GQDs could
exhibit electrocatalytic activity for the oxygen reduction
reaction (ORR). Qu and coworkers 41 reported that the ORR
onset potential of graphene supported N-GQDs (NGQDs/graphene) was close to that of commercial Pt/C catalyst.
Moreover, the N-GQDs/graphene electrode showed a stable

This journal is The Royal Society of Chemistry 2012

ARTICLE
ORR, indicating their remarkable tolerance to possible
crossover effects. Another work by Li et al. 72 suggested that
nitrogen doping played an important role in the electrocatalytic
activity of N-GQDs, even at a level as low as ~1%. Their
results did not show a direct correlation between the catalytic
performance and amount of nitrogen doping. Instead, sizedependent electrocatalytic activity for ORR was observed,
ascribing to the higher HOMO (highest occupied molecular
orbital) levels in larger N-GQDs leading to easier oxidation.
This feature is significant for understanding and further
improving the electrocatalytic activity of N-GQDs.
5.2 Biomedical applications for human health
Because of their tunable PL, excellent photostability, low
cytotoxicity, high biocompatibility, as well as ease of
functionalization, GQDs are attractive for applications in
biomedical field as an imaging and labeling luminescent agent
to track molecular targets in live cells or organs. 25,26,73,74 This
allows us to obtain direct evidences for the understanding of the
underlying molecular mechanisms and bio-dynamic processes.
Here, we take the imaging of stem cells as an example, as stem
cells are essential to understand native development and tissue
regeneration. The research by Zhang et al. 75 suggested that
GQDs could easily penetrate into the stem cells with little
cytotoxicity and helped generate clear and stable images
(Figure 6a, b). They also carried out the control experiments by
using CdS QDs and C60 nanoparticles. However, the stem cells
died by incubating with CdS QDs owing to the cytotoxicity of
Cd2+, while no C60 fluorescence was detected inside the stem
cells, indicating that GQDs were a much better bio-imaging and
labeling agent.
GQDs can also be employed to detect biological tissues. For
example, Zhao et al.76 adopted graphene as an acceptor and
mouse anti-human immunoglobulin G (mIgG)-conjugated
GQDs (mIgG-GQDs) as a donor to fabricate immunosensor for
detecting human mIgG. The detection mechanism was based on
the PL recovery degree of mIgG-GQDs that was first quenched
by graphene due to the - stacking interaction. Similarly, Qian
et al.77 managed to analyze a low concentration of DNA based
on the fluorescence resonance energy transfer between
biocompatible GQDs and carbon nanotubes.
Most recent results further supported the development of
GQDs as antibacterial agents. 78 The work by Qu and coworkers
demonstrated that GQDs possessed peroxidase-like activity,
allowing the conversion of H 2O2 into OH.79 Due to the fact
that OH exhibits a higher antibacterial performance than that
of H2O2, a more efficient antibacterial system in vitro could be
realized by combining GQDs with a low dose of H 2O2. This
made it possible to avoid the toxicity of H 2O2 at high
concentrations. Moreover, GQDs-Band-Aids were prepared,
which exhibited an excellent antibacterial feature in vivo when
combining with a low concentration of H2O2 (Figure 6c-e),
indicating that GQDs-Band-Aids have promising applications
for wound disinfection.

J. Name., 2012, 00, 1-3 | 5

Journal of Materials Chemistry C Accepted Manuscript

Page 5 of 9

Journal of Materials Chemistry C

Figure 6. (a) Confocal fluorescence microscopy image of stem cells with the
incorporation of GQDs; (b) The corresponding image of (a) under bright field;
Reproduced by permission of The Royal Society of Chemistry.75 (c) The cotton
fabric absorbed with (left) and without (right) GQDs; (d) The obtained GQDsBand-Aid; (e) The mouse treated with GQDs-Band-Aid. Reproduced by
permission of American Chemical Society.79

5.3 Sensors for environmental detection

The PL of GQDs can be effectively quenched by selectively
doping specific cations, anions, or chemical groups.80-84 This
feature allows GQDs to be used as sensors for quantitative and
qualitative detection. The detection method on the basis of PL
quenching is the so-called turn off model. It should be noted
that GQDs with different intrinsic structures have different
selective quenching phenomena, allowing GQDs to detect
various ions/chemical groups. For example, the N-containing
GQDs synthesized by electrochemical cutting of graphene 3D
framework could be employed to detect Fe 3+ (as illustrated in
Figure 7),85 while the photoluminescent GQDs prepared by
pyrolyzing citric acid and the amino-functionalized GQDs by
hydrothermal reaction could be used to detect Cl - and Cu2+,
respectively.32,86 Generally, the turn off luminescent model
presents a relatively high background compared with the turn
on method.87 Therefore, a novel off-to-on model, through
recovering the quenched PL, was designed to fabricate GQDs
based sensors. By use of this model, Bai et al. 88 and Liu et al.89
demonstrated that GQDs@Eu3+ and glutathione-functionalized
GQDs@Fe3+ were efficient photoluminescent probes for
phosphate sensing. Such GQDs based sensors for detecting
metal cations, nonmetal anions, and chemical groups in solution
with a high sensitivity are undoubtedly beneficial to
environment protection.

6 | J. Name., 2012, 00, 1-3

Page 6 of 9

Journal Name

Figure 7. (a) PL intensity of GQDs in the absence and presence of Fe3+ at

different pH; (b) Remaining PL percentage of GQDs after addition of different
metal ions; (c) PL emission spectra of GQDs as a function of concentrations of
Fe3+ (mM); (d) Average concentration-dependent fluorescence response in the
acetate buffer solution. Reproduced by permission of Wiley-VCH.85

6. Conclusions and outlook

In this article, we have summarized recent progress of
photoluminescent GQDs, including the versatile PL features,
key mechanisms, and promising applications. The PL behaviors
of GQDs could be readily tuned. In general, the tunable PL
could be ascribed to the competition between the intrinsic state
and the defect state emissions. Some other important PL
mechanisms, such as the charge transfer and molecule-like
states, were also discussed. Although many significant
achievements have been made, many challenges are yet to be
addressed. For example, the quantum yield of GQDs, which
varies with the fabrication method and the involved surface
chemistry, needs to be further improved. This requires
researchers to further explore the in-depth PL mechanisms,
including a thorough understanding of the formation of defect
states, and the luminescence efficiencies for both intrinsic states
and defect states. As shown in Figure 1b, GQDs can be
controlled to exhibit intense emissions from blue to yellow. Red
and near infrared emissions can be obtained by further
increasing the excitation wavelength, but their intensity is low.
Therefore, it is necessary to exploit bright longer wavelength
luminescence to expand the applications of GQDs. In addition,
the methodology to design GQDs-based materials for
environment detection should be further advanced, to ideally
eliminate the side effects originated from the external
ions/chemical groups at low concentrations. It is worth noting
that most of the optical studies of GQDs reported so far were
performed macroscopically, in which some intriguing
fluorescent phenomena were hidden. The ultimate goal is to
investigate photoluminescent GQDs on a single-particle level,
which is expected to eventually clarify the mechanism. We
wish this article would stimulate continued interests and
endeavors in the area of photoluminescent GQDs.

This journal is The Royal Society of Chemistry 2012

Journal of Materials Chemistry C Accepted Manuscript

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

ARTICLE

View Article Online

DOI: 10.1039/C4TC02536A

Journal of Materials Chemistry C

Journal Name

Acknowledgements

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

This work is sponsored by the National Science Foundation

(Partnerships for Research and Education in Materials, DMR1205670), the Air Force Office of Scientific Research (No.
FA9550-12-1-0159), and the Faculty Large Grant from the
University of Connecticut.

Notes and references

a

Department of Chemical & Biomolecular Engineering and Polymer

Program, Institute of Materials Science, University of Connecticut, Storrs,
Connecticut 06269, United States. E-mail: luyi.sun@uconn.edu; Fax:
+1(860) 486-4745; Tel: +1(860) 486-6895
b
Key Laboratory for Ultrafine Materials of Ministry of Education, School
of Materials Science and Engineering, East China University of Science
and Technology, Shanghai 200237, China

1. K. S. Novoselov, A. K. Geim, S. Morozov, D. Jiang, Y. Zhang, S.

Dubonos, I. Grigorieva and A. Firsov, Science, 2004, 306, 666-669.
2. C. Lee, X. Wei, J. W. Kysar and J. Hone, Science, 2008, 321, 385388.
3. Z. Wang, J. Liu, W. Wang, H. Chen, Z. Liu, Q. Yu, H. Zeng and L.
Sun, Chem. Commun., 2013, 49, 10835-10837.
4. H.-X. Wang, Q. Wang, K.-G. Zhou and H.-L. Zhang, Small, 2013, 9,
1266-1283.
5. Z. Luo, Y. Lu, L. A. Somers and A. C. Johnson, J. Am. Chem. Soc.,
2009, 131, 898-899.
6. Z. Luo, S. Kim, N. Kawamoto, A. M. Rappe and A. C. Johnson, ACS
Nano, 2011, 5, 9154-9160.
7. Q. Yu, L. A. Jauregui, W. Wu, R. Colby, J. Tian, Z. Su, H. Cao, Z.
Liu, D. Pandey, D. Wei, T. F. Chung, P. Peng, N. P. Guisinger, E. A.
Stach, J. Bao, S.-S. Pei and Y. P. Chen, Nat. Mater., 2011, 10, 443449.
8. W. Wu, L. A. Jauregui, Z. Su, Z. Liu, J. Bao, Y. P. Chen and Q. Yu,
Adv. Mater., 2011, 23, 4898-4903.
9. A. K. Geim, Science, 2009, 324, 1530-1534.
10. J. Park and M. Yan, Acc. Chem. Res., 2012, 46, 181-189.
11. Z. Wang, J. Wang, Z. Li, P. Gong, X. Liu, L. Zhang, J. Ren, H. Wang
and S. Yang, Carbon, 2012, 50, 5403-5410.
12. Z. Wang, J. Wang, Z. Li, P. Gong, J. Ren, H. Wang, X. Han and S.
Yang, RSC Adv., 2012, 2, 11681-11686.
13. P. Gong, Z. Wang, Z. Fan, W. Hong, Z. Yang, J. Wang and S. Yang,
Carbon, 2014, 72, 176-184.
14. P. Gong, J. Wang, W. Sun, D. Wu, Z. Wang, Z. Fan, H. Wang, X.
Han and S. Yang, Nanoscale, 2014, 6, 3316-3324.
15. Z. Luo, P. M. Vora, E. J. Mele, A. C. Johnson and J. M. Kikkawa,
Appl. Phys. Lett., 2009, 94, 111909.
16. L. Ponomarenko, F. Schedin, M. Katsnelson, R. Yang, E. Hill, K.
Novoselov and A. Geim, Science, 2008, 320, 356-358.
17. Z. Zhang, J. Zhang, N. Chen and L. Qu, Energy Environ. Sci., 2012,
5, 8869-8890.
18. L. Li, G. Wu, G. Yang, J. Peng, J. Zhao and J.-J. Zhu, Nanoscale,
2013, 5, 4015-4039.
19. F. Liu, M. H. Jang, H. D. Ha, J. H. Kim, Y. H. Cho and T. S. Seo,
Adv. Mater., 2013, 25, 3657-3662.

This journal is The Royal Society of Chemistry 2012

View Article Online

DOI: 10.1039/C4TC02536A

ARTICLE
20. M. Bacon, S. J. Bradley and T. Nann, Part. Part. Syst. Charact., 2014,
31, 415-428.
21. D. Pan, J. Zhang, Z. Li and M. Wu, Adv. Mater., 2010, 22, 734-738.
22. S. Kim, S. W. Hwang, M.-K. Kim, D. Y. Shin, D. H. Shin, C. O. Kim,
S. B. Yang, J. H. Park, E. Hwang and S.-H. Choi, ACS Nano, 2012, 6,
8203-8208.
23. Y. Dong, H. Pang, S. Ren, C. Chen, Y. Chi and T. Yu, Carbon, 2013,
64, 245-251.
24. J. Peng, W. Gao, B. K. Gupta, Z. Liu, R. Romero-Aburto, L. Ge, L.
Song, L. B. Alemany, X. Zhan, G. Gao, S. A. Vithayathil, B. A.
Kaipparettu, A. A. Marti, T. Hayashi, J.-J. Zhu and P. M. Ajayan,
Nano Lett., 2012, 12, 844-849.
25. Y. Dong, C. Chen, X. Zheng, L. Gao, Z. Cui, H. Yang, C. Guo, Y.
Chi and C. M. Li, J. Mater. Chem., 2012, 22, 8764-8766.
26. Y. Sun, S. Wang, C. Li, P. Luo, L. Tao, Y. Wei and G. Shi, Phys.
Chem. Chem. Phys., 2013, 15, 9907-9913.
27. R. Ye, C. Xiang, J. Lin, Z. Peng, K. Huang, Z. Yan, N. P. Cook, E. L.
G. Samuel, C.-C. Hwang, G. Ruan, G. Ceriotti, A.-R. O. Raji, A. A.
Martand J. M. Tour, Nat. Commun., 2013, 4, 2943.
28. Liu
u
eng and
llen J. Am. Chem. Soc., 2011, 133,
15221-15223.
29. X. Yan, X. Cui, B. Li and L.-s. Li, Nano Lett., 2010, 10, 1869-1873.
30. X. Yan, X. Cui and L.-s. Li, J. Am. Chem. Soc., 2010, 132, 59445945.
31. C. Sun, F. Figge, J. A. McGuire, Q. Li and L.-S. Li, Phys. Rev. Lett.,
2014, 113, 107401.
32. Y. Dong, G. Li, N. Zhou, R. Wang, Y. Chi and G. Chen, Anal. Chem.,
2012, 84, 8378-8382.
33. L. Tang, R. Ji, X. Li, G. Bai, C. P. Liu, J. Hao, J. Lin, H. Jiang, K. S.
Teng and Z. Yang, ACS Nano, 2014, 7, 1239-1245.
34. K. Habiba, V. I. Makarov, J. Avalos, M. J. Guinel, B. R. Weiner and
G. Morell, Carbon, 2013, 64, 341-350.
35. J. Shen, Y. Zhu, X. Yang and C. Li, Chem. Commun., 2012, 48,
3686-3699.
36. H. Tetsuka, R. Asahi, A. Nagoya, K. Okamoto, I. Tajima, R. Ohta
and A. Okamoto, Adv. Mater., 2012, 24, 5333-5338.
37. K. Lingam, R. Podila, H. Qian, S. Serkiz and A. M. Rao, Adv. Funct.
Mater., 2013, 23, 5062-5065.
38. W. Kwon, Y.-H. Kim, C.-L. Lee, M. Lee, H. C. Choi, T.-W. Lee and
S.-W. Rhee, Nano Lett., 2014, 14, 1306-1311.
39. S. Zhu, J. Zhang, S. Tang, C. Qiao, L. Wang, H. Wang, X. Liu, B. Li,
Y. Li and W. Yu, Adv. Funct. Mater., 2012, 22, 4732-4740.
40. R. Sekiya, Y. Uemura, H. Murakami and T. Haino, Angew. Chem. Int.
Ed., 2014, 53, 5619-5623.
41. Y. Li, Y. Zhao, H. Cheng, Y. Hu, G. Shi, L. Dai and L. Qu, J. Am.
Chem. Soc., 2011, 134, 15-18.
42. Q. Feng, Q. Cao, M. Li, F. Liu, N. Tang and Y. Du, Appl. Phys. Lett.,
2013, 102, 013111.
43. M. Li, W. Wu, W. Ren, H.-M. Cheng, N. Tang, W. Zhong and Y. Du,
Appl. Phys. Lett., 2012, 101, 103107.
44. X. Li, S. P. Lau, L. Tang, R. Ji and P. Yang, J. Mater. Chem. C, 2013,
1, 7308-7313.
45. P. Gong, Z. Yang, W. Hong, Z. Wang, K. Hou, J. Wang and S. Yang,
Carbon, 2015, 83, 152-161.
46. L. Tang, R. Ji, X. Cao, J. Lin, H. Jiang, X. Li, K. S. Teng, C. M. Luk,
S. Zeng and J. Hao, ACS Nano, 2012, 6, 5102-5110.

J. Name., 2012, 00, 1-3 | 7

Journal of Materials Chemistry C Accepted Manuscript

Page 7 of 9

Journal of Materials Chemistry C

47. S. H. Jin, D. H. Kim, G. H. Jun, S. H. Hong and S. Jeon, ACS Nano,

2013, 7, 1239-1245.
48. D. Tan, S. Zhou, B. Xu, P. Chen, Y. Shimotsuma, K. Miura and J.
Qiu, Carbon, 2013, 62, 374-381.
49. D. Tan, Y. Yamada, S. Zhou, Y. Shimotsuma, K. Miura and J. Qiu,
Nanoscale, 2013, 5, 12092-12097.
50. D. Pan, L. Guo, J. Zhang, C. Xi, Q. Xue, H. Huang, J. Li, Z. Zhang,
W. Yu and Z. Chen, J. Mater. Chem., 2012, 22, 3314-3318.
51. B. P. Biswal, D. B. Shinde, V. K. Pillai and R. Banerjee, Nanoscale,
2013, 5, 10556-10561.
52. W. Wang, D. He, J. Duan, M. Fu, X. Zhang, H. Wu, Y. Hu and Y.
Wang, Phys. Chem. Chem. Phys., 2014, 16, 4504-4509.
53. S. Zhuo, M. Shao and S.-T. Lee, ACS Nano, 2012, 6, 1059-1064.
54. Z. Wang, Y. Li, Q. Jiang, H. Zeng, Z. Ci and L. Sun, J. Mater. Chem.
C, 2014, 2, 4495-4501.
55. D. Tan, S. Zhou and J. Qiu, ACS Nano, 2012, 6, 6530-6531.
56. Z. Gan, X. Wu, G. Zhou, J. Shen and P. K. Chu, Adv. Optical Mater.,
2013, 1, 554-558.
57. X. Wen, P. Yu, Y.-R. Toh, X. Ma and J. Tang, Chem. Commun.,
2014, 50, 4703-4706.
58. H. D. Ha, M.-H. Jang, F. Liu, Y.-H. Cho and T. S. Seo, Carbon, 2015,
81, 367-375.
59. Q. Liu, B. Guo, Z. Rao, B. Zhang and J. R. Gong, Nano Lett., 2013,
13, 2436-2441.
60. F. Wang and X. Liu, Chem. Soc. Rev., 2009, 38, 976-989.
61. C.-T. Chien, S.-S. Li, W.-J. Lai, Y.-C. Yeh, H.-A. Chen, I. Chen, L.C. Chen, K.-H. Chen, T. Nemoto and S. Isoda, Angew. Chem. Int. Ed.,
2012, 51, 6662-6666.
62. Q. Xu, Q. Zhou, Z. Hua, Q. Xue, C. Zhang, X. Wang, D. Pan and M.
Xiao, ACS Nano, 2013, 7, 10654-10661.
63. G. S. Kumar, R. Roy, D. Sen, U. K. Ghorai, R. Thapa, N. Mazumder,
S. Saha and K. K. Chattopadhyay, Nanoscale, 2014, 6, 3384-3391.
64. L. Wang, S.-J. Zhu, H.-Y. Wang, Y.-F. Wang, Y.-W. Hao, J.-H.
Zhang, Q.-D. Chen, Y.-L. Zhang, W. Han, B. Yang and H.-B. Sun,
Adv. Optical Mater., 2013, 1, 264-271.
65. L. Wang, S.-J. Zhu, H.-Y. Wang, S.-N. Qu, Y.-L. Zhang, J.-H. Zhang,
Q.-D. Chen, H.-L. Xu, W. Han, B. Yang and H.-B. Sun, ACS Nano,
2014, 8, 2541-2547.
66. S. Zhu, L. Wang, B. Li, Y. Song, X. Zhao, G. Zhang, S. Zhang, S. Lu,
J. Zhang, H. Wang, H. Sun and B. Yang, Carbon, 2014, 77, 462-472.
67. V. Gupta, N. Chaudhary, R. Srivastava, G. D. Sharma, R. Bhardwaj
and S. Chand, J. Am. Chem. Soc., 2011, 133, 9960-9963.
68. C. Luk, L. Tang, W. Zhang, S. Yu, K. Teng and S. Lau, J. Mater.
Chem., 2012, 22, 22378-22381.
69. X. Fang, M. Li, K. Guo, J. Li, M. Pan, L. Bai, M. Luoshan and X.
Zhao, Electrochim. Acta, 2014, 137, 634-638.
70. P. Gao, K. Ding, Y. Wang, K. Ruan, S. Diao, Q. Zhang, B. Sun and J.
Jie, J. Phys. Chem. C, 2014, 118, 5164-5171.
71. Z. Zhu, J. Ma, Z. Wang, C. Mu, Z. Fan, L. Du, Y. Bai, L. Fan, H.
Yan and D. L. Phillips, J. Am. Chem. Soc., 2014, 136, 3760-3763.
72. Q. Li, S. Zhang, L. Dai and L.-s. Li, J. Am. Chem. Soc., 2012, 134,
18932-18935.
73. X. T. Zheng, A. Than, A. Ananthanaraya, D.-H. Kim and P. Chen,
ACS Nano, 2013, 7, 6278-6286.
74. P. Nigam, S. Waghmode, M. Louis, S. Wangnoo, P. Chavan and D.
Sarkar, J. Mater. Chem. B, 2014, 2, 3190-3195.

8 | J. Name., 2012, 00, 1-3

Page 8 of 9

Journal Name
75. M. Zhang, L. Bai, W. Shang, W. Xie, H. Ma, Y. Fu, D. Fang, H. Sun,
L. Fan and M. Han, J. Mater. Chem., 2012, 22, 7461-7467.
76. H. Zhao, Y. Chang, M. Liu, S. Gao, H. Yu and X. Quan, Chem.
Commun., 2013, 49, 234-236.
77. Z. S. Qian, X. Y. Shan, L. J. Chai, J. J. Ma, J. R. Chen and H. Feng,
Biosens. Bioelectron., 2014, 60, 64-70.
78. B. Z. Ristic, M. M. Milenkovic, I. R. Dakic, B. M. TodorovicMarkovic, M. S. Milosavljevic, M. D. Budimir, V. G. Paunovic, M.
D. Dramicanin, Z. M. Markovic and V. S. Trajkovic, Biomaterials,
2014, 35, 4428-4435.
79. H. Sun, N. Gao, K. Dong, J. Ren and X. Qu, ACS Nano, 2014, 8,
6202-6210.
80. L.-L. Li, J. Ji, R. Fei, C.-Z. Wang, Q. Lu, J.-R. Zhang, L.-P. Jiang
and J.-J. Zhu, Adv. Funct. Mater., 2012, 22, 2971-2979.
81. Y. Zhou, Z.-b. Qu, Y. Zeng, T. Zhou and G. Shi, Biosens.
Bioelectron., 2014, 52, 317-323.
82. F. Wang, Z. Gu, W. Lei, W. Wang, X. Xia and Q. Hao, Sens.
Actuators, B, 2014, 190, 516-522.
83. J. Ju and W. Chen, Biosens. Bioelectron., 2014, 58, 219-225.
84. H. Sun, L. Wu, W. Wei and X. Qu, Materials Today, 2013, 16, 433442.
85. A. Ananthanarayanan, X. Wang, P. Routh, B. Sana, S. Lim, D.-H.
Kim, K.-H. Lim, J. Li and P. Chen, Adv. Funct. Mater., 2014, 24,
3021-3026.
86. H. Sun, N. Gao, L. Wu, J. Ren, W. Wei and X. Qu, Chem. Eur. J.,
2013, 19, 13362-13368.
87. L. Zhang, Z.-Y. Zhang, R.-P. Liang, Y.-H. Li and J.-D. Qiu, Anal.
Chem., 2014, 86, 4423-4430.
88. J.-M. Bai, L. Zhang, R.-P. Liang and J.-D. Qiu, Chem. Eur. J., 2013,
19, 3822-3826.
89. J.-J. Liu, X.-L. Zhang, Z.-X. Cong, Z.-T. Chen, H.-H. Yang and G.-N.
Chen, Nanoscale, 2013, 5, 1810-1815.

This journal is The Royal Society of Chemistry 2012

Journal of Materials Chemistry C Accepted Manuscript

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

ARTICLE

View Article Online

DOI: 10.1039/C4TC02536A

Page 9 of 9

Journal of Materials Chemistry C

View Article Online

Graphene quantum dots have large surface area, high photostability, excellent
biocompatibility and versatile photoluminescence, promising for various applications.

Journal of Materials Chemistry C Accepted Manuscript

Published on 24 December 2014. Downloaded by University of Huddersfield on 29/12/2014 06:32:36.

DOI: 10.1039/C4TC02536A