Graphene Quantum Dots From Chemistry To Applications 2018

Materials Today Chemistry 10 (2018) 221e258
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Materials Today Chemistry

journal homepage: www.journals.elsevier.com/materials-today-chemistry/
Graphene quantum dots from chemistry to applications

P. Tian a, L. Tang a, **, K.S. Teng b, S.P. Lau c, *
a
Kunming Institute of Physics, Kunming, 650223, People's Republic of China
b
College of Engineering, Swansea University, Bay Campus, Fabian Way, Swansea, SA1 8EN, United Kingdom
c
Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong
a r t i c l e i n f o a b s t r a c t
Article history: Graphene quantum dots (GQDs) have been widely studied in recent years due to its unique structure-
Received 7 August 2018 related properties, such as optical, electrical and optoelectrical properties. GQDs are considered new
Received in revised form kind of quantum dots (QDs), as they are chemically and physically stable because of its intrinsic inert
20 September 2018
carbon property. Furthermore, GQDs are environmentally friendly due to its non-toxic and biologically
Accepted 21 September 2018
Available online 9 November 2018
inert properties, which have attracted worldwide interests from academic and industry. In this review, a
number of GQDs preparation methods, such as hydrothermal method, microwave-assisted hydrothermal
method, soft-template method, liquid exfoliation method, metal-catalyzed method and electron beam
Keywords:
Nanostructured graphene
lithography method etc., are summarized. Their structural, morphological, chemical composition, optical,
Graphene quantum dots electrical and optoelectrical properties have been characterized and studied. A variety of elemental
Optical properties dopant, such as nitrogen, sulphur, chlorine, fluorine and potassium etc., have been doped into GQDs to
Electrical properties diversify the functions of the material. The control of its size and shape has been realized by means of
Optoelectronics preparation parameters, such as synthesis temperature, growth time, source concentration and catalyst
etc. As far as energy level engineering is concerned, the elemental doping has shown an introduction of
energy level in GQDs which may tune the optical, electrical and optoelectrical properties of the GQDs.
The applications of GQDs in biological imaging, optoelectrical detectors, solar cells, light emitting diodes,
fluorescent agent, photocatalysis, and lithium ion battery are described. GQD composites, having opti-
mized contents and properties, are also discussed to extend the applications of GQDs. Basic physical and
chemical parameters of GQDs are summarized by tables in this review, which will provide readers useful
information.
© 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
1. Introduction Bernal using single-crystal diffraction measurements [3] in 1924. As

the characterization technology enhances, the electronic properties
1.1. History of graphene quantum dots development of graphite were first investigated by Wallace [4] and he introduced
the idea of graphene in 1947. One year later, Ruess and Vogt [5]
Carbon, which is one of the most abundant elements, has been successfully detected a few layers graphite via transmission elec-
widely researched since 19th century and has experienced a tron microscopy (TEM). In 1957, Hummers and Offeman [6]
continuous surge in its studies. The entire development of carbon developed a new method, which is safer and more efficient than
material to date is shown in Fig. 1. In the year 1859, Brodie [1] Brodie's method, in the preparation of graphite oxide. The idea of a
synthesized the graphite oxide to ascertain the molecular weight single layer graphite sheet, which was initially described by Boehm
of graphite via some hazardous experiments, and coined its name [7] in 1962 and by some theoretical physicists [8], having a massless
‘Graphon’. At that time, the properties of graphite oxide were not Dirac equation in 1984 was considered implausible in that era.
described until 1918 by Kohlschütter and Haenni [2]. Further study During the development of carbon materials, a football-shaped
on the structural property of graphite oxide was carried out by fullerene was discovered by Smally [9] in 1985, which repre-
sented eureka moment in the scientific world, leading to the award
of the Nobel Prize in 1996. This is the first carbon allotropy which
inspires scientists around the world in exploiting carbon materials.
* Corresponding author.
** Corresponding author. In 1987, Mouras [10] introduced the word ‘graphene’ to represent
E-mail addresses: scitang@163.com (L. Tang), apsplau@polyu.edu.hk (S.P. Lau). single sheets of graphite although stable single-layer graphite sheet
https://doi.org/10.1016/j.mtchem.2018.09.007
2468-5194/© 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
222 P. Tian et al. / Materials Today Chemistry 10 (2018) 221e258
Fig. 1. The history of carbon materials development.
still remained non-existent by theoretical calculations. Another functional groups, unlike the CNTs that are limited by its one
carbon allotropy so-called carbon nanotubes (CNTs) was later dimensional characteristics.
discovered by Iijima [11] in 1991. More than a decade later, an Graphene exhibits an infinite exciton Bohr radius [18]. However,
astonishing experiment on graphene was carried out by Geim and GQD is a zero-dimensional material by converting two-dimensional
Novoslov [12] in Manchester University, where a monolayer gra- graphene. This resulted in quantum confinement and edge effects,
phene was developed using a Scotch tape technique in 2004. Their which the crystal boundary significantly modifies electron distri-
work has led to many exciting scientific researches into the two bution due to the reduced dimension of the crystal to nanometer
dimensional material, which could offer many novel applications. scale. Additionally, GQDs have non-zero bandgap, which is different
In 2010, a Nobel Prize was awarded to Geim and Novoslov for their from graphene. Previous theoretical calculations as well as optical
experimental work on graphene. It was again awarded to re- and electrical experiments have demonstrated the existence of
searchers working on carbon materials. To date, the different bandgap in GQDs. The semi-metal graphene can turn into either
graphitic forms, such as 0D fullerene, 1D carbon nanotubes, 2D semiconductor or insulator GQDs. The broadening of the optical
graphene and 3D graphite, had successfully been discovered. absorption of graphene has led to higher energy spectral due to the
Since the discovery of graphene, the properties and applications opening of the bandgap in GQDs. GQDs also exhibit different
of graphene have been extensively studied and exploited. However, chemical and physical properties when compared with other
researchers have realized many limitations of graphene, such as carbon-based materials, such as CD, CNTs, fullerene and graphene
zero bandgap and low absorptivity etc. Structural modification of etc., due to its special edge and quantum confinement effects. In the
graphene was subsequently investigated to overcome the short- field of nanomaterials, many of the physical and chemical proper-
comings. Graphene quantum dots (GQDs) were fabricated by ties of nanomaterials are usually determined by the fabrication
Ponomarenko and Geim [13] in 2008 based on the previous work methods. Based on the GQDs preparation methods developed in
on carbon dots (CDs) by Xu [14] et al., in 2004. The GQDs are recent years, these methods can be classified into two categories,
different from CDs because they possess graphene lattice inside the namely top-down and bottom-up, according to the precursor ma-
dots, which are smaller than 100 nm in size and less than 10 layers terial. As shown in the central part of Fig. 2, top-down method
thick [15]. CDs are usually quasi-spherical carbon nanoparticles refers to direct cutting of graphene-related materials (such as
having a size of less than 10 nm [15]. The GQDs have many novel graphene [16], graphene oxide [19], carbon nanotubes [20], carbon
properties, such as its unique fluorescent properties discovered by fibers [21], carbon black [22], graphite powder [23] and coal [24]
Pan [16] et al., in 2010, due to its quantum confinement effect. The etc.) into quantum size via various processes. In bottom-up
ability to modulate the properties of GQDs is important if the approach, graphene-like smaller polycyclic aromatic hydrocar-
material is to be used in diverse applications. Modification of GQDs bons (PAHs) molecular precursors (such as benzene [25], hexa-
properties by means of doping was first investigated by Zhao [17] peri-hexabenzocoronene [26], glucose [27] and fullerene [28]
and collaborators in 2012 involving the use of nitrogen as dopant etc.) are converted to GQDs by stepwise chemical reaction. In
in GQDs. Besides, GQDs exhibit better solubility than CNTs. This is addition to quantum confinement and edge effects, GQDs exhibited
due to the large edge effect of GQDs, which can be modified by many important characteristics, such as stable PL, non-toxicity,
P. Tian et al. / Materials Today Chemistry 10 (2018) 221e258 223
Fig. 2. The graphene quantum dots (GQDs) related inherent effects, preparation methods, properties and applications.
good solubility, surface grafting, biocompatibility and inertness

[29], as shown in middle rings in Fig. 2. Some of these character-
istics are overwhelmingly superior to traditional semiconductor
quantum dots, hence prompted many potential applications of
GQDs in solar cells [30e34], photodetectors [35e40], bioimagings
[41e44], fluorescent agents [45e48], light-emitting diodes [49]
(LEDs), batteries [50], sensors [51,52], drug carriers [53e58] and
photo-/electro-catalytic [59] and so forth, as shown in marginal
ring of Fig. 2.
The two effects, namely edge and quantum confinement effects,
belong to the basic characteristics of GQDs. The unique chemical
and physical properties of GQDs, such as non-toxicity, solubility,
surface grafting, biocompatibility, inertness and stable PL, are re-
sults of its basic characteristics. Based on these properties, a series
of applications are developed.
1.2. The outlooks of graphene quantum dots
The research on GQDs is still at an early stage, and many chal-

lenges of GQDs have yet to be addressed, as shown in Fig. 3.
Fig. 3. The challenges of GQDs according to the recent researches.
Although there are many important advantages and potential ap-
plications of GQDs, further research to enhance the properties of
the material is required in order to meet the application re- reaction method (highest yield of 45% [60]) and facile fabrication
quirements. Therefore, the studies of GQDs have been on-going to technique using coals [24], that can improve the product yield need
address the five urgent issues as stated in Fig. 3. to be exploited. Besides, the reported quantum yields (QYs) of GQDs
To meet the industry requirements, it is necessary to mass are mostly at a range between 2% and 22.9% [60], which is much
produce GQDs at relatively low cost. However, the product yield of lower than the traditional semiconductor QDs. Thus the low QYs
GQDs using current preparation methods [60] is considerably low presented a challenge. Recent researches showed that the QYs of
(<10% mostly), therefore new methods, such as photo-Fenton GQDs can be enhanced by surface modifications, such as the
formation of carbon-metal nano-composites [61]. In addition, the shape and so on. While as the bottom-up approach is based on the
electronic and optical properties of GQDs, such as band gap [62] growth of appropriate molecular precursors, such as small mole-
and fluorescence [63,64] etc., are dependent on their sizes and cules and polymers, into nano-sized GQDs by hydrothermal,
shapes. Therefore, the modulation of the intrinsic properties of microwave-assisted hydrothermal, soft-template and metal-
GQDs is dependent on the accuracy in controlling its sizes and catalyzed methods etc. Such bottom-up approach possesses ad-
shapes etc. Conditions of fabrication methods are keys to solving vantages, such as fewer defects and controllable of size and
this issue. GQDs have displayed various unique phenomena, such as morphology; contrary to the top-down approach. However, the
up-conversion PL [65e67]. However, the current mechanisms were bottom-up approach has suffered from poor solubility, small dot
mainly acquired according to the optical behaviors leading to size and aggregration issue etc. In the next context, detailed prep-
confusing results due to the different preparation conditions, hence aration methods are presented. Bottom-up methods will be pre-
there is a lack of understanding on the exact PL mechanism. sented first and then followed by top-down.
Consequently, some forms of standard measurements coupled with
theoretical studies should be carried out to better understand the 2.1. Bottom-up methods
PL phenomenon. To date, most of the reported PL colors of GQDs
were ranged from blue to yellow [60]. The narrow spectral coverage As previously mentioned, bottom-up methods are based on
of GQDs is limiting its applications in optoelectronic devices. The growth of the sources including graphene-like smaller polycyclic
expanding of the spectral coverage of GQDs to all visible wave- aromatic hydrocarbons (PAHs) and appropriate molecules into
lengths and even near-infrared (NIR) is an important area of GQDs. However, this method can be subdivided into four main
research in the future. Some groups [27,68,69] have obtained the routes, which cover hydrothermal method, microwave-assisted
NIR PL spectrum by doping nitrogen into GQDs. hydrothermal method, soft-template method and metal-catalyzed
The future of GQDs is more promising once the above challenges method, according to the way external energy is provided and
have been solved. In this review, we discuss the current preparation the characteristics of fabrication.
methods of GQDs in Section 2, and the functionalization of GQDs,
such as heteroatoms doping, sizes and shapes controlling and
forming its composite with other functional materials, in Section 3. 2.1.1. Hydrothermal method
In Section 4, some applications related to GQDs will be reviewed. Hydrothermal method involves various techniques of crystal-
Finally, a conclusion will be presented. lizing substances from high-temperature aqueous solutions to high
vapor pressures. The fabrication of single-crystalline GQDs through
the hydrothermal method has been demonstrated by many
2. Preparation methods for graphene quantum dots research groups. In early 2012, Dong et al. [69] successfully fabri-
cated GQDs, having a size of ~15 nm, using citric acid (CA) as source
According to the current fabrication methods of GQDs as re- in the hydrothermal method that produced a photoluminescence
ported in literatures, the syntheses of GQDs can be classified into (PL) quantum yield (PLQY) of 9.0%. The mechanism of synthesizing
two main categories, namely top-down and bottom-up preparation GQDs using CA via hydrothermal method is depicted in Fig. 5a. The
approaches. As shown in Fig. 4, top-down approach involves direct atomic force microscopy (AFM) image of GQDs prepared by Dong
cleaving of bulk carbon materials into nanoscale GQDs via liquid and co-workers is displayed in Fig. 5b, which indicated that the
exfoliation and electron beam lithography techniques etc. Such GQDs were mostly nano-sheets of ~15 nm in size with height in the
approach has the advantages of abundant raw materials and would range of 0.5e2.0 nm. Using CA and ethylenediamine (EDA) as car-
usually produce oxygen-containing functional groups at the edge, bon source materials, Yang's group [70] successfully produced ni-
thus facilitating their solubility and functionalization. However, this trogen doped GQDs (N-GQDs) with a size of 5e10 nm, which
approach has also suffered from some disadvantages, such as low exhibited relatively high PLQY of 75.2%. They suggested that the
yield, large density of defects, and non-controllable of size and high PLQY was possibly due to two factors: the higher production
yield (60%e70%), and the large number of surface defects, groups
and edges from N-doping using EDA. Below is an equation related
to the PLQY, which is expressed as [75,76]:
.
Fc ¼ Fst Kc Kst hc hst (1)
where F is QY, K is the slope determined by the curves, h is the

refractive index of the solvent, st refers to a standard with known
quantum yield and c indicates unknown samples. For the aqueous
solution, hc/hst was 1. Besides, Dong [71] et al. also prepared the N-
GQDs using CA as precursor, and the resultant size was between 2
and 8 nm as indicated by the TEM image of the N-GQDs shown in
Fig. 5d. The fringes of the carbon lattice can be clearly seen in the
inset of Fig. 5d. Additionally, Chen and co-workers [77] fabricated
amine-functionalized N-GQDs using CA and tris(hydroxymethyl)
aminomethane (Tris-HMA), and its PLQY was 59.2%. CA as precur-
sor has been widely adopted in the growth of GQDs using hydro-
thermal method [78,79].
Apart from CA, some graphene-like smaller polycyclic aro-
matic hydrocarbons (PAHs) can also be used as precursors in the
preparation of GQDs. The GQDs emitting bright green fluores-
cence with high yield of 63% were synthesized with pyrene via
Fig. 4. The categorized illustrations on the various preparation methods of GQDs. hydrothermal method by Wang et al. [72]. Fig. 5e depicts the
Fig. 5. The hydrothermal method based multifarious precursors. (a) The schematic diagram of the preparation of GQDs via hydrothermal method with certain time and tem-
perature based on the source of citric acid (CA); (b) The AFM of the GQDs synthesized by using the CA [69]; (c) Fluorescence (FL) intensity and UVevis intensity of the N-GQDs
fabricated by using CA (excited at 365 nm), the inset shows photography of the N-GQDs in aqueous solution under visible light (left) and 365 nm UV light (right) [70]; (d) TEM image
of N-GQDs prepared by using CA, inset is high-resolution transmission electron microscopy (HRTEM) [71]; (e) Synthetic procedure of OH-functionalized GQDs (OH-GQDs) based on
the source of pyrene via hydrothermal treatment [72]; (f) and (g) show the TEM and HRTEM image of GQDs prepared by using pyrene, respectively. The insets of (f) and (g) are
lateral size distribution and fast Fourier transform (FFT) pattern, respectively [72]; (h) Schematic illustration of the hydrothermal synthesis of GQDs with bifunctional groups based
on the source of 1,5-dinitronaphthalene [73]; (i) Digital photography of the GQDs solutions synthetized by using 1,5-dinitronaphthalene at different pH conditions under 365 nm UV
irradiation [73]; (j) and (k) present the schematic diagram and the TEM image of GQDs which was synthetized through the pyrolysis of L-glutamic acid, respectively. The inset of (k)
is the typical single GQDs with a lattice parameter of 0.246 nm [74].
entire procedures. The dispersion showed highly uniform lateral Fig. 5k. The lattice spacing was 0.246 nm similar to the charac-
size as indicated in TEM of GQDs in Fig. 5f. Fig. 5g showed the teristic spacing of graphene.
defect-free GQDs with spacing of 0.21 nm corresponding to that
of graphene (100) planes. Furthermore, distinguishable benzene 2.1.2. Microwave-assisted hydrothermal method
rings, which were well arranged in a hexagonal honeycomb Hydrothermal growth of GQDs usually takes long time. Thus, a
carbon network, can be seen in the inset of Fig. 5g. Guo's group fast and effective method was exploited by assisting with micro-
[73] prepared GQDs with tunable PL emission by hydrothermal wave, so-called microwave-assisted hydrothermal (MAH) method.
approach using 1,5-dinitronaphthalene as raw material as shown The previously mentioned hydrothermal usually takes several
in Fig. 5h. Interestingly, the amine-functionalized GQDs exhibited hours, thus the method is not ideal for industrial mass production
a distinct tunable PL emission from bluish green to yellow by of GQDs. It is possible to shorten the growth duration of GQDs to a
changing the pH level from 5 to 10, as shown in Fig. 5i. This few minutes or even seconds by assisting with microwave.
phenomenon can be attributed to the protonation and deproto- Yang [80] co-author reported the fabrication of fluorine-doped
nation of the amine-groups in acid or alkaline solutions. Broad- GQDs by using MAH method and the growth of F-GQDs is depicted
ening of the PL emission has been a challenge for previous in Fig. 6a. The high crystallinity of the F-GQDs with an in-plane lattice
materials. However, Zhao et al. [74] addressed the challenge by spacing of 0.214 nm is shown in the HRTEM image (Fig. 6c). According
the formation of GQDs through pyrolysis of L-glutamic acid and to the size distribution, the size of F-GQDs was 2.38 ± 0.04 nm by
the fabrication process is shown in Fig. 5j. The PL emission of Gaussian fitted calculation. The PL of F-GQDs was shifted to green
GQDs fabricated by the raw material was tunable to NIR in the (seen in Fig. 6b) as compared to simple GQDs, though the size of the
range from 800 to 850 nm. The morphology of the GQDs is shown prepared F-GQDs was much smaller than that of most GQDs. Ac-
in Fig. 5k, and high crystallinity of the GQDs is shown in inset of cording to their analysis, the red-shifted PL might be ascribed to the
Fig. 6. Preparation and related analysis of GQDs prepared by microwave-assisted hydrothermal. (a) Microwave-assisted hydrothermal growth process of GQDs [80]; (b) Digital
photography of the aqueous F-GQDs under the 360 nm UV illumination [81]; (c) HRTEM image with observed lattice fringe of GQDs prepared by MAH route [80]; (d) and (e) show the
growth mechanism of GQDs with the heating time and the GQDs solutions irradiated by ambient light (top) and 365 nm UV lamp (bottom), respectively [81]; (f) The diameter of the GQDs
as a function of microwave heating time, the top inset shows the photographs of the GQD solutions prepared at various heating times irradiated by ambient light (top left) and 365 nm UV
lamp (top right). The bottom inset shows the corresponding TEM images of the GQDs prepared at various heating times [63]; (g) and (h) present the TEM and the diameter distribution of
GQDs, respectively [81]; (i) Schematic and the corresponding photographs of the interface separation process and detailed structures of the obtained A- and O-GQDs [82].
doping of fluorine. The relationship between size of GQDs prepared Hence, the MAH method combined the advantages of both hy-
by MAH method and the heating time was studied by Tang [63,81] drothermal and microwave techniques. The microwave heating
et al. As shown in Fig. 6d, the glucose molecules dehydrated to provides simultaneous, homogeneous and fast heating, which has
form nucleation crystal of GQDs in the first step, and then the glucose led to uniform size distribution of quantum dots and non-surface
and chemically active functional groups attached at the edges or the passivation.
surface of growing GQDs. Finally, as-grown GQDs with certain size
were prepared at different duration of microwave heating. Fig. 6e 2.1.3. Soft-template method
shows a series of GQD solutions, which were prepared by various A novel method, known as soft-template, was developed for
heating times, irradiated by the ambient (top) and UV lamp (bottom). facile, low-cost and environmental friendly fabrication of GQDs. It
The emission color of the solutions are obviously changed. To un- provides nanoscale reaction cavity without complicated separation
derstand this phenomenon, the diameter of the GQDs as a function of and purifying processes. Therefore, this route is in favor for mass
heating time was characterized using TEM and the curve plotted in production.
Fig. 6f. The diameter of the GQDs increased monotonically from 1.5 to Yang and co-author [84] prepared GQDs by the soft-template
3.9 nm when the heating time increased from 1 to 9 min, therefore approach. The TATB which is a planar and highly symmetric
increasing the heating times would lead to further growth of the molecule with six strong intramolecular hydrogen bonds between
GQDs. Moreover, the MAH method provided GQDs with uniform size eNH2 and eNO2 functional groups, and possesses a graphitic-like
distribution as shown in Fig. 6g and h. Feng et al. [82] also synthe- layered structure was used as the carbon source and template.
sized the GQDs and separated the A- (aqueous phase) and O- (organic Firstly, the TATB was annealed in the thermal process, which
phase) GQDs) by inducing the solvent. The whole separation of GQD resulted in breaking down of various chemical bonds, along with
solution and related structure of A- and O-GQDs is represented in the generation of expanding gases (e.g., NO, NO2, and H2O). Sub-
Fig. 6i. Zhao and co-workers [83] obtained the oxygen-rich GQDs by sequently, the graphitic-like TATB multilayer developed into single
MAH method and the level of doping with nitrogen was at 5.7%. layers as a result of the expanding gas. Finally, oxidative exfoliation
was employed to obtain dispersed N-GQDs. The preparation pro- were characterized by TEM (seen in Fig. 7h) showing an average
cess of GQDs using TATB is displayed in Fig. 7a. Morphology and size diameter of 2.46 nm according to statistic calculation from Fig. 7i.
of GQDs via the soft-template route using TATB is as shown in Besides, Do et al. [86] used CA as the template to synthesize GQDs,
Fig. 7b. The AFM image shows well-dispersed and few-layer GQDs. which demonstrated high-quantum yield of 83%. It is worth
One of the main advantages of soft-template method is controllable mentioning that the PL intensity in a long-wavelength range
uniform size of GQDs. Müllen's [26] research group achieved (>500 nm) was observed to increase with increasing nitrogen
monodispersed disk-like GQDs of ~60 nm using HBC as precursor content.
via the soft-template method. Detailed steps on the preparation are In brief, the soft-template can be a candidate for solving at least
shown in Fig. 7c. The HBC molecules were condensedly stacked one of the challenges of GQDs, such as low-product yield.
followed by the formation of a graphitic framework with fewer
defects during the pyrolysis step. Subsequently, the artificial 2.1.4. Metal-catalyzed method
graphite was oxidized and exfoliated with a modified Hummers Metal-catalyzed method is a scarce route for preparation of
method, and then reduced with hydrazine. Finally, the GQDs pre- GQDs. Loh et al. [28] utilized ruthenium as metal catalyst and used
pared by using HBC as template was obtained. Homogeneous C60 as a precursor to synthesize GQDs (seen in Fig. 8a). Interestingly,
nanodisks of ~60 nm in diameter and 2e3 nm in thickness were this method can modify the shape of GQDs by the annealing tem-
observed from the AFM image (seen in Fig. 7d and e). These GQDs perature, as shown in Fig. 8bec. The scanning tunnelling micro-
demonstrated strong blue PL emission under excitation at 365 nm scopy (STM) measurement was carried out on the GQDs grown on
as shown in Fig. 7f. Apart from using the polymer as template, some the surface of Ru (0001) at different annealing temperature for
small molecules were also used. For instance, Gao and co-workers certain duration. The triangular and hexagonal shaped GQDs were
[85] utilized small molecular carbon disulphide as template to obtained by annealing at 725 K and 825 K for 2 min respectively, as
fabricate GQDs doped with sulphur. As shown in Fig. 7g, the shown in Fig. 8deg. However, special structure of raw material and
mixture liquid was burnt to form the carbon powder, which was metal-catalyst were necessary for the fabrication of GQDs using this
then exfoliated to GQDs. The uniformity and dispersity of the GQDs method, thus this route is uncommon.
Fig. 7. Schematic diagrams and related characterized results of GQDs by using soft-template approach. (a) Illustration of the formation process of GQDs from single-layer 1,3,5-Tri-
amino-2,4,6-trinitrobenzene (TATB) intermolecular condensation by soft-template route [84]; (b) AFM image of GQDs which was synthesized by using TATB deposited on a freshly
cleaved mica surface. Inset: height profile along the dark line in the AFM image [84]. (c) Processing diagram for fabrication of GQDs via soft-template method based on the carbon
source of Hexa-peri-hexabenzocoronene (HBC) [26]; (dee) and (f) AFM topography images of GQD prepared by using HBC and height profiles along the line in the images, and
optical photograph obtained under excitation at 365 nm UV lamp, respectively [87]; (g) Schematic representation of the GQDs prepared by soft-template route [85]; (h) and (i) show
the TEM and diameter distribution of GQDs fabricated by former method, respectively [85].
Fig. 8. Illustration and STM image of transformation of GQDs through C60 by metal-catalyzed method. (a) Schematic diagram of Ru metal catalyzed cage-opening for C60 under
different temperatures; (bec) The majority of C60 molecules adsorbed on the terrace and temperature-dependent growth of GQDs with different equilibrium shapes from the
aggregation of the surface diffused carbon clusters; (d) STM image of C60/Ru sample after annealing at 725 K, inset shows magnified view of mushroom-shaped dots. (e) Magnified
views of triangular from (d); (feg) Hexagon-shaped GQDs obtained after further annealing the sample at 825 K [28].
2.2. Top-down methods synthesis temperature. Besides, Tour et al. [24] managed to in-
crease the product yield of GQDs through the use of coal via the
An opposite route of the bottom-up method is top-down same method as shown in Fig. 9d.
method, according to the relationship between precursors and Similarly, Li [92] used coal for the preparation of GQDs. Fig. 9e
products. Top-down approach usually fabricates the GQDs by shows the morphology and single crystalline of the GQDs. However,
breaking down the bulk material by physical or chemical means. there was nonuniformity in the size distribution of the GQDs as
The first GQDs was developed using this approach, thus top-down observed from the TEM image, which could be caused by the
routes is very effective in the discovery of new materials and fabrication conditions. On the other hand, graphite [97,98] has been
research of its structure and properties. Among top-down routes, considered the best source in the preparation of GQDs. Wang and
liquid exfoliation method, by means of hydrothermal, electro- co-authors [93] fabricated GQDs by sonication of graphite in liquid.
chemical, oxidation and ultrasonic etc., and electron beam lithog- Fig. 9f shows the complete preparation process of the GQDs based
raphy method are commonly used routes. There are other less on the use of graphite as source. The TEM image of the GQDs
common routes, such as magnetron sputtering technique, which showed an average lateral size of 2.5 nm (Fig. 9g), and the HRTEM
will also be described in this section. indicated good crystallinity of the GQDs with lattice spacing of
0.335 nm corresponding to the c-axis orientation, as shown in
2.2.1. Liquid exfoliation method Fig. 9h. Similar experiment was also carried out by Pei et al. [96] A
Nowadays liquid-phase exfoliation is often used for the prep- more facile route was recently developed by Zuo and co-workers
aration of graphene, where intercalation of graphite was per- [94]. As shown in Fig. 9i, cotton was first annealed and then fol-
formed using strong oxidizing agents, followed by expansion of lowed by liquid exfoliation. GQDs doped with fluorine were sub-
graphite layers via thermal or chemical techniques. Such synthesis sequently obtained. Similar shape of PGNFs to the CF can also be
approach has increasingly been used in the preparation of GQDs used as the source for GQDs in liquid exfoliation method, as
by many groups [87e91]. The preparation of GQDs usually demonstrated by Li's [95] group. The SEM image in Fig. 9j shows
required the use of acid in cutting graphene, as shown in Fig. 9a. high-purity platelet graphite nanofibers (PGNFs) with diameters of
Wu and co-workers [16] produced GQDs that demonstrated blue ~10e40 nm and zigzag-like surfaces. The TEM images of the pre-
luminescent via the liquid exfoliation route. The GQDs exhibited pared GQDs are shown in Fig. 9k and l. The CeC bond length in the
uniform size distribution with new PL results. Bulk carbon ma- GQDs was 0.146 nm which is close to the ideal CeC bond length for
terials have been used in the synthesis of GQDs. For instance, graphite (0.142 nm). The GQDs also exhibited good crystallinity as
carbon fibers (CF) was used as the precursor in the preparation of indicated in the inset of Fig. 9l. Similar to Zuo’ work, Zhao and co-
GQDs by Peng's [21] liquid exfoliation approach, as shown in authors [99] also used the cotton as the carbon source in the
Fig. 9b. AFM measurement indicated that the GQDs were con- preparation of GQDs. The difference was the use of chlorine as
sisting of 1e3 graphene layers (seen in Fig. 9c). Their results also dressing agent, thus the GQDs were doped with chlorine (Cl-GQDs)
showed that the PL emission color was influenced by the showing many distinctive properties from pure GQDs, such as the
Fig. 9. Diagram and corresponding measured image of the GQDs by using different sources via liquid exfoliation approach. (a) Illustration on the formation of GQDs by cutting
graphene in the acid environment, commonly used the mixture of H2SO4 and HNO3; (b) Representation scheme of the transformation of GQDs through oxidation cutting of carbon
fibers (CF) [21]; (c) AFM image of GQDs by cutting CF [21]; (d) Schematic illustration of the synthesis of GQDs by using coal [24]; (e) TEM image of the GQDs by using coal via liquid
exfoliation method, the inset is the HRTEM image of the GQDs [92]; (f) Schematic presentation of the preparation of GQDs by sonication-assisted liquid exfoliating graphitic carbon
precursor [93]; (g) and (h) show TEM and HRTEM images of GQDs prepared by sonication-assisted exfoliation route, respectively (the inset in panel (g) is the magnified TEM image
of GQDs) [93]; (i) Illumination of entire fabricated process of GQDs through the cotton [94]; (j) SEM image of platelet graphite nanofibers (PGNFs) [95]; (k) and (l) display the TEM of
GQDs by using PGNFs, the inset of (l) represents a FFT pattern [95].
intensity and peak of UVevis absorption. The overall fabrication flakes rapidly broke apart due to the harsh electrochemical exfoli-
process of GQDs is shown in Fig. 10a. Apart from 3D graphite, 2D ation conditions in the strong electrolyte system, hence leading to
graphene and 0D fullerene, the 1D carbon nanotube can also be cut the low yield of GQDs. However, in a weak electrolyte environment,
into GQDs. In the reported work of Dong et al. [20], SWCTs with an the relatively prolonged oxidation interaction and suppressed
average diameter less than 2 nm and a length of 5e15 mm were cut intercalation induced exfoliation resulted in the continuous and
by means of chemical oxidation using a three-step sediment to efficient formation of GQDs, as displayed in Fig. 10d. Fig. 10e shows
form the GQDs1 and GQDs2 respectively, as shown in Fig. 10b. the TEM image of GQDs using electrochemical route, which pro-
Interestingly, the aqueous solutions of GQDs1 and GQDs2 were duced homogeneous and good crystallinity GQDs. Kun and collab-
yellow under white light, but their UVevis absorption spectra are orators [101] also synthesized GQDs doped with boron (B-GQDs) by
dissimilar (seen in Fig. 10h). Among the optical properties of GQDs1 using CF as anode and Pt as cathode in the electrochemical work-
and GQDs2, their PL characteristics were obviously different. station, as shown in the left of Fig. 10f. Their preparation process of
However, the former liquid exfoliation assisted both the hydro- GQDs and a detailed diagram showing the formation mechanism is
thermal and chemical oxidation. A new technique, known as elec- represented on the right of Fig. 10f. The UVevisible absorption
trochemical exfoliation, was recently introduced to the liquid spectra of the above GQDs synthesized with different ratios of H2O/
exfoliation method. Huang and co-workers [100] used the electro- IL (e.g. 0-a, 15%-b and 30%-c) is shown in Fig. 10g. A clear red shift
chemical workstation to prepare GQDs with higher product yield by from 265 to 348 nm was observed when the ratio of H2O/IL
using graphene paper as anode and platinum (Pt) sheet as counter increased from 0% to 30%, this was attributed to a new hydrogen-
electron. During the electrochemical oxidation and cutting process, bonded network formed that resulted in a change to the internal
the colorless electrolyte solution quickly turned black with product organization and the liquid structure of the ILs. The inset of Fig. 10g
yield of 28% (after 120 min) in an ammonia solution because of the shows the fluorescence of GQDs solutions at different concentra-
rapid generation of GQDs, as shown in Fig. 10c. A possible mecha- tions under the 365 nm lamp illumination. It showed that the PL
nism was proposed suggesting the graphene sheets or graphite properties were influenced by the ratio of H2O/IL. Graphene oxide
Fig. 10. Schematic illustration and corresponding measurements of the GQDs by different liquid exfoliation method. (a) Diagram illustration on the preparation process of GQDs
derived from cotton [99]; (b) Schematic representation of preparation of GQDs from single-walled carbon nanotubes (SWCNTs) [20]; (c) Digital photography of the electrolytic
process of graphene paper in ammonia (top) and NaOH (bottom) solutions under different reaction times [100]; (d) Mechanism illustration of the preparation of GQDs in strong and
weak electrolyte solutions [100]; (e) TEM display of the GQDs derived from graphene paper via electrochemical cutting approach, the inset is the HRTEM image of the GQDs [100];
(f) Schematic diagram of the preparation of B-GQDs by using CF as precursor via the electrochemical exfoliation [101]; (g) UVevis spectrum of the B-GQDs solution with different
ratio of H2O/1L:a-0%, b-15%,c-30%, the inset shows the photography of corresponding GQDs under UV Light with 365 nm irradiation [101]; (h) UVevis absorption and PL emission
spectra (recorded for progressively longer excitation wavelengths in 20 nm increments) of GQDs1 (top) and GQDs2 (down) in water solution. Inset: Optical photographs of GQD
solutions under visible light (left) and a UV beam of 365 nm (right) [20].
has also been used as carbon source in the preparation of GQDs as requirement of expensive equipment. Besides, the size of GQDs was
shown by the work of Teng et al. [102]. The TEM image, as shown in limited by the processable scale of lithography technology and the
Fig. 11aec, indicates homogenous GQDs with good crystallinity diameter of GQDs was arbitrary modified. Nevertheless, this
were prepared by the liquid exfoliation method. method opened up an important field of 0D carbon materials, which
Generally, the liquid exfoliation route occurs in the liquid and have so far generated great excitement within the scientific world.
the properties of products are often determined by the process Table 1 provides a summary on the related properties of GQDs
environment and conditions. Therefore, the chemical and physical produced by current state-of-the-art bottom-up and top-down
properties of the GQDs can be precisely controlled by modifying the methods. It is worth noting that the product yield of GQDs via
fabrication parameters. bottom-up approach is generally higher than the top-down
A novel technique, different from liquid exfoliation, was approach. Furthermore, the physical and chemical properties of
exploited in the fabrication of GQDs by Liu's [103] research group GQDs can be easily modified when prepared using bottom-up
via the use of magnetron sputtering. As shown in Fig. 11d, a com- approach as compared to the top-down. Also, the choice of source
posite film comprising of GQDs and ZnO is formed at the substrate for bottom-up route is wider than the opposite route. In any case,
after magnetron sputtering on the target of graphite and ZnO the selected method would very much depend on your applications.
composite. Subsequently, the composite film is treated with acid
and then dialyzed to separate the GQDs from ZnO. Fig. 11e shows 3. Functionalization of graphene quantum dots
the TEM image of the highly crystalline and uniform GQDs.
Pure GQDs have many limitations which restrict its application.
2.2.2. Electron beam lithography method In order to expand its application in a variety of fields, GQDs can be
Electron beam lithography method was first used in the prepa- functionalized by various methods to customize its properties for
ration of GQDs [13]. However, it was not widely used due to the specific applications. Functionalization of GQDs could modify its
Fig. 11. Novel preparation routes of GQDs. (aeb) TEM of GQDs prepared by using graphene oxide (GO) as carbon source [102]; (c) Selected area electron nanobeam diffraction
pattern of GQDs in plane (b) [102]; (d) Schematic of fabrication process of GQDs via magnetron sputtering technique [103]; (e) TEM and HRTEM images of GQDs fabricated by
magnetron sputtering route, the left top inset shows the selected area electron diffraction (SAED) pattern in the red cycle of (e) [103].
Table 1
Related properties of GQDs by using the bottom-up and top-down method in state-of-the-art.
Main-methods Sub-method Source Diameter (nm) PLQY Color of PL Product yield Advantages Disadvantages Ref.
Bottom-up Hydrothermal CA ~15 9.0% blue d high yield, easy to dope small size, [69]
Hydrothermal CAþEDA 5e10 75.2% blue 60%e70% long period [70]
Hydrothermal CA 2e8 34% blue d [71]
Hydrothermal Pyrene 3.5 ± 0.6 23% green 63% [72]
Hydrothermal 1,5-dinitronaphthalene 1.5 d Green- yellow d [73]
Hydrothermal L-glutamic acid 4.66 ± 1.24 54.5% NIR d [74]
Hydrothermal CAþTris-HMA 0.5e4 59.2% blue d [77]
MAH glucose 2.38 ± 0.04 d green d short period, uniform size, small size [80]
MAH glycerol 1e5 d green/blue 9.8% [82]
MAH glucose ~3 5.2% green d [83]
Soft-template TATB 2e5 d green d low-cost, environmentally aggregration [84]
Soft-template HBC 59.6 ~3.8% blue d friendly [26]
Soft-template CA 2.0 83% blue d [86]
Top-down Liquid exfoliation graphite 6.0 3.6% blue d precisely controlled environmental [88]
Liquid exfoliation GO 3.3 ± 0.7 0.9% green d disruption, non- [89]
Liquid exfoliation graphite 3e4 22.3% blue d uniform size [90]
Liquid exfoliation graphite 5.6 13.6% blue d [91]
Liquid exfoliation coal 2.30 ± 0.78 51% blue 20% [24]
Liquid exfoliation coal 4.7 47.0% blue 25.6% [92]
Liquid exfoliation graphite 2e6 2.4% blue 3.8 mg/ml [96]
Liquid exfoliation GO 2e6 12.8% d d [102]
Electrochemical graphene paper 3e8 46% cyan 28% short period, homogenous low yield [100]
exfoliation and good crystallinity
optical, chemical and electronic properties, which allow the ma- functionalization of GQDs remains a hot-topic in the study of car-
terials to be used in wide-ranging applications. As shown in Fig. 12, bon nanomaterials. In this section, we will introduce the various
doping with heteroatoms, forming composites with inorganic functionalization methods in the following sequence: doping with
materials or polymers, and the controlling of size and shape of a variety of heteroatoms in Section 3.1, the controlling of size and
GQDs can be considered as functionalization. The basic properties shape to tune the properties of GQDs in Section 3.2, and lastly the
of GQDs are changed via those means, which could potentially improved performances of GQDs via forming composites will be
address some of the challenges faced by GQDs. Research into the described in Section 3.3.
Fig. 12. Schematic diagram on the functionalization of GQDs via various methods and the improvement of GQDs properties.
3.1. Doping of graphene quantum dots via a variety of heteroatoms 3.1.1. GQDs doped with single heteroatom
Single heteroatom doping of GQDs has shown to alter the
Doping of semiconducting materials is an essential process in properties of the GQDs. This section will describe the changes in the
the semiconductor industry as it can modulate the basic physical, properties of GQDs by doping with single atom and less emphasis is
chemical and electronic properties of the materials, hence making given to the doping methods.
them useful in device applications. Similarly, functionalization of Boron atom is near by the carbon in the periodic table, hence it
GQDs by means of doping can modify its optical, electronic and can be easily introduced into the GQDs. Wang and co-workers [104]
chemical properties for novel applications. In general, we can demonstrated the doping of B into GQDs via MAH method, as
categorize the doping method into three groups depending on the shown in Fig. 13b. TEM images reveal non-uniform dispersion of B-
number of doping atoms, as shown in Fig. 13a. An effective doping GQDs and high-quality crystalline structure as shown in Fig. 13c
can tune the optical, chemical, electrochemical and electronic etc. and d respectively. Interestingly, obvious absorption peaks ocurred
properties of GQDs. It is possible to characterize the effect of at 230 nm, 260 nm and 320 nm, which was different from un-
doping, for example, through determining the change in the color doped GQDs, are shown in Fig. 13e. The prominent peaks at
of PL, the conductivity and water solubility of the doped GQDs. The 230 nm was ascribed to the transition of the p-p* aromatic sp2
various heteroatoms doping and doping methods will be intro- domains, while the other two weaker peaks were attributed to C]
duced in this section. The effect of doping GQDs resulting in the O n-p* transition. The B-doped GQDs have shown to enhance its PL
change of its basic properties will be described as well. To date, the intensity as demonstrated by Yang et al. [105]. They obtained high
heteroatoms used in the doping of GQDs include potassium (K), quantum yield of 95% from their B-GQDs, which were fabricated by
sodium (Na), boron (B), nitrogen (N), phosphorus (P), oxygen (N), evaporating B-GQDs borax aqueous solution. Highly intensive
sulphur (S), selenium (Se), fluorine (F) and chlorine (Cl), as shown fluorescence of their B-GQDs under 405 nm excitation is shown in
in top-left diagram of Fig. 12. Besides, these atoms can be co-doped Fig. 13feh. The B-GQDs were also synthesized by means of bottom-
into the GQDs, which can enhance certain properties of GQDs. The up approach as demonstrated by Tam and co-authors [106], as
change in properties could cause by the electronegativity and shown in Fig. 13i. The electrocatalytic activity has been enhanced by
other basic properties of the dopant atoms. The doping of GQDs B doping into GQDs. Apart from doping GQDs with B element, Qian
with single, double and multiple heteroatoms will be presented as et al. [107] doped GQDs with K atom and the resultant absorption
follows. spectrum is shown in Fig. 13j. Two peaks were apparent at 222 nm
Fig. 13. Schematic diagrams of the different doping methods and results, and related proposed mechanism of single atoms doping. (a) Illustration of three kinds of doping
techniques. (b) Preparation process of B doped into GQDs (B-GQDs) through GO and borax as carbon and boron source, respectively. The right picture is optical digital image [104];
(c), (d) and (e) show TEM image of B-GQDs, individual B-GQDs and UVevis absorption spectra of B-GQDs, respectively [104]; (feh) Fluorescence microscopy image of B-GQDs
crystals obtained by evaporating aqueous B-GQDs at room temperature with different rotation directions and solutions under lighting at laser of 405 nm [105]; (i) Diagram of
preparation of B-GQDs through hydrothermal route [106]; (j) and (k) show UVevis absorption and TEM image of K doped into GQDs (K-GQDs), respectively. The inset of (j) is optical
image of aqueous K-GQDs solution under UV 365 nm excitation [107].
and 274 nm, which indicated blue-shift due to K doping. The PL of controlling the preparation conditions, such as doping concentra-
K-GQDs is shown in the inset of Fig. 13j under 365 nm radiation. tion, preparation temperature and pH level. The band gap structure
Similar results were also obtained by doping GQDs with Na atom as of N-GQDs prepared by the solid-to-solid method is displayed in
studied by Yazdi and co-workers [108]. They reported blue-shift of Fig. 14e. The double plotted graphs showing the dependent of band
the absorption peaks from their Na-doped GQDs. Hence, the doping gap on doping concentration and synthesis temperature is shown
of B, K and Na into GQDs can tune the optical absorption to short in Fig. 14f. From the graphs, we can deduce that the doping con-
wavelength and enhance its PL intensity. centration decreased with the synthesis temperature, while the
Apart from the above-mentioned elements, other elements band gap was significantly influenced by the doping concentration
were also widely researched. Among all the elements, N atom due to the high electronegativity. Furthermore, when the N-GQDs
doping of GQDs is considered the earliest [17] and widest were in an acidic environment, the graphitic N was gradually
[70,77,85,109e134] studies performed on doped GQDs. The N- protonated and then showed a weaker negative induction effect
GQDs were fabricated by solid-to-solid process through using than that of un-protonated graphitic N. This resulted in a high p
melamine as carbon and nitrogen sources which were carried out electron cloud density, which led to a narrowed band gap. This
by Zhu et al. [135]. The preparation process is shown in Fig. 14a. phenomenon is represented in Fig. 14g, which shows the
Interestingly, this method of preparation has produced high quality decreasing band gap of N-GQDs by reducing the pH level in the N-
N-GQDs, as shown in Fig. 14bec. Fig. 14c shows a lattice spacing of GQDs at a doping concentration of 5.5 at%. In addition, Sun and co-
0.24 nm from the TEM image. In addition, UVevis absorption workers [136] fabricated high-crystalline N-GQDs via cutting gra-
spectra of N-GQDs were studied, as represented in Fig. 14d. The phene oxide (GO) precursor (refer to Fig. 14h), and the quantum
observed three absorption peaks were due to the aromatic sp2 yield was significantly improved to 74% through controlling the size
domains around 210 nm, n-p* transition absorption peak around and nitrogen doping. Microwave-assisted hydrothermal technique
240 nm and band-gap transition absorption peak around 270 nm, was used by Tang and co-workers [27] in the preparation of N-
while the long tail extending to the visible range spectrum. It is GQDs (refer to Fig. 14i), the resultant absorption peak was modified
important to note that the band gap can be tuned through and exhibited at near-infrared region instead of situating at yellow
Fig. 14. Diagram of fabricated and measured results of N and P doped into GQDs. (a) and (bec) show the preparation process schematic and TEM images of N doped GQDs (N-GQDs)
[135]; (d) and (feg) represent the UVevis spectra and the energy band gap tuneable of N-GQDs [142]; (h) TEM display of N-GQDs via cutting graphene oxide (GO) precursor [136];
(i) Diagram illustration of N-GQDs by using microwave-assisted hydrothermal routine [27]; (j) Optical characters of N-rich GQDs, UVevis absorption (black line), PLE spectrum
(green line) and PL spectrum (red line), inset shows photograph of N-rich GQDs under UV 365 nm lighting [137]; (k) The illustration on the formation of N-GQDs by utilizing
hydrothermal treatment [138]; (l) Up-conversion PL spectrum of N-GQDs at different excitation wavelength [139]; (m) Synthetic process and structural illustration for P doped
GQDs (P-GQDs) [140]; (n) UVevis absorption of the 2,2-diphenyl-1-picrylhydrazyl (DPPH) with water P-GQDs which is fabricated by electrochemical routine before (1d) and after
(5d) the scavenging period, inset is the color of the DPPH before and after the scavenging period [141].
[142,143] or blue [144,145] regions. A novel metal catalytic strategy and is shown in Fig. 14n. The inset represents the change in color of
was also used to prepare N-rich GQDs by Lv's research group [137]. the DPPH solution from purple to yellowish which indicated the
Fig. 14j displays the optical properties of their N-rich GQDs, which excellent scavenging ability of P-GQDs.
revealed excellent luminescence behavior. Huang [138] demon- Group Ⅵ and Ⅶ elements were also studied for doping of the
strated the formation of N-GQDs via hydrothermal method using GQDs. Li et al. [147] doped the GQDs with S atom using hydrother-
CA and dicyandiamide as carbon and nitrogen sources. Their mal method and the preparation process is shown in Fig. 15a. TEM
technique demonstrated a high quantum yield of 36.5%. The image, shown in Fig. 15b, indicates S-GQDs with uniform size were
strategy is illustrated in Fig. 14k. Up-conversion of PL was observed prepared. The electron diffraction pattern of the S-GQD indicates
in N-GQDs prepared using hydrothermal method. This means that both in-plane (d2 ¼ 0.213 nm) and basal plane (d1 ¼ 0.344 nm)
the emission wavelength of the N-GQDs was shorter than the diffractions, as shown in Fig. 15c. Jin et al. [148] analyzed the optical
excitation wavelength as studied by Li et al. [139]. The resultant PL variation of S-GQDs. Fig. 15d shows the fluorescence of S-GQDs at
curves for the N-GQDs are shown in Fig. 14l. An excellent quantum different preparation temperatures. Strong luminescence was
yield of 94% for N-GQDs was achieved by Sun and co-workers [146]. observed for S-GQDs prepared at a temperature of 170 C. Their
Apart from the N doping, P-doped GQDs was also studied [93]. finding suggested that the excessively high temperature introduced
Liu [140] fabricated P-doped GQDs (P-GQDs) having good stability a large number of S atoms, which subsequently covered the surface
and dispersion, and exhibited wide visible-light absorption region. of S-GQDs resulting in the decrease of the fluorescence intensity.
Fig. 14m shows the synthesis process of P-GQDs. It is possible to Moreover, the UVeVis absorption spectra of S-GQDs were compared
tailor the electronic properties of P-GQDs via the process. P-GQDs with undoped GQDs, as shown in Fig. 15e. For S-GQDs, there existed
can also be prepared using an electrochemical route as performed a new absorption peak at 350 nm, which was absent from the
by Ma and co-workers [141] to investigate the free radical scav- undoped GQDs. In addition, the intensity of the overall absorption
enging ability of P-GQDs. UVevis absorption of the DPPH in water wavelength of S-GQDs was larger than the undoped GQDs. Inter-
with P-GQDs before and after the scavenging period was measured estingly, Wang and co-workers [149] prepared S-GQDs using durian
Fig. 15. Representations and resultant image of Ⅵ and Ⅶ elements doped into GQDs. (a), (b) and (c) show preparation process schematic diagram, typical TEM and electron
diffraction pattern of GQDs doped with S (S-GQDs) via hydrothermal approach, respectively [147]; (d) and (e) represent the optical image of S-GQDs aqueous solution under sunlight
(top) and UV 365 nm (bottom) radiation and the UVevis absorption spectra of S-GQDs (black line) and undoped GQDs (green line), respectively [148]; (f) Diagram and some
corresponding results of S-GQDs prepared by using durian as carbon and sulphur source via bottom-up method [149]; (g) and (h) are the TEM or AFM images and digital picture of
PL under 365 nm excitation of Se doped GQDs (Se-GQDs) [150]; (i), (k) and (l) display the TEM image, proposed preparation process and emission spectra under different excitation
wavelengths of 300e750 nm of Cl doped GQDs (Cl-GQDs) [151]; (j) UVevis absorption spectra of Cl-GQDs and undoped GQDs solutions [99].
flesh as precursor in a bottom-up approach. TEM image of the S- 3.1.2. GQDs doped with double heteroatom
GQDs and its preparation process are shown in top part of Fig. 15f. The doping of double atoms was initiated to utilize the advan-
Importantly, the PL characteristics of the S-GQDs were strongly tages of various doped elements and has been performed by re-
determined by the doping concentration, as shown in bottom part of searchers around world [160e172]. UVevis absorption spectra of S
Fig. 15f. The color of PL from the S-GQDs can be tuned from blue to and N co-doped GQDs (S, N-GQDs), which were prepared by Qu et al.
yellow, which is distinctively different from other elemental doping. [152], is shown in Fig. 16a. Three absorption bands were found at
Besides, the quantum yield was high and can reach up to 79% for S- 338 nm, 467 nm and 557 nm, which were different from previous
GQDs exhibiting yellow PL. Group Ⅵ elemental doping of GQDs, report. The extending absorption bands were attributed by the
such as O and Se doped GQDs, were also prepared to form GOQDs introduction of S and N atoms. The PL quantum yields for S, N-GQDs
and Se-GQDs. Yang and co-workers [150] prepared Se-GQDs by were 61%, 45% and 8% at wavelength of 340 nm, 440 nm and 540 nm,
using GOQDs as precursors. Fig. 15g shows the uniform size and which represented blue, green and red emission, respectively. They
high-quality crystalline of their Se-GQDs, which displayed yellow explained the PL process of S, N-GQDs using the proposed mecha-
luminescence with a quantum yield of 29% (shown in Fig. 15h). nism shown in Fig. 16b. There were O, N, S states, which could relate
Group Ⅶ elements, such as Cl and F, were also investigated for to the p* orbital of the C]O (excitation energy was above 3.10 eV),
doping GQDs. Li and co-workers [151] prepared Cl doped GQDs (Cl- C]N (excitation energy was above 2.75 eV) and C]S (excitation
GQDs) using the process shown in Fig. 15k. TEM image of the Cl- energy was above 1.90 eV) bonds in the S, N-GQDs. The observed
GQDs is shown in Fig. 15i. Multicolor light emission was demon- cyan light under excitation wavelength of 440 nm could due to the
strated from the Cl-GQDs as shown in Fig. 15l. Besides, Zhao et al. overlapping of the N and O states in some degree. Moreover, the S p*
[99] reported the optical absorption peaks of Cl-GQDs occurred in orbital and S state, which were formed by introducing S doping,
deep-UV unlike the undoped GQDs. Zuo and co-workers [94] pre- contributed to a weaker electronegativity. As a result, S, N-GQDs can
pared F-doped GQDs, however its properties were rarely studied. absorb lower energy and emit light with longer wavelength. A high
In brief, single elemental doping route has been studied exten- quantum yield of 87.8% for S, N-GQDs had been realized by using
sively and in great depth, but most studies have been focussed on the one-step bottom-up molecular fusion in a hydrothermal process
N-GQDs. It would be of interest to explore other doping elements. [153] as shown in the diagram of Fig. 16c. The S, N-GQDs prepared by
Fig. 16. Diagram, proposed mechanism and characterized results of double elements doped GQDs. (a) and (b) show UVevis absorption and proposed energy-level diagram of S and
N co-doped GQDs (S,N-GQDs) through solvothermal synthetic approach [152]; (c) Schematic illustration of the prepared S,N-GQDs by hydrothermal routine [153]; (d) Diagram of N-
GQDs and S,N-GQDs by using microwave-assisted hydrothermal method [154]; (eef) and (g) represent the TEM image of S,N-GQDs and the comparison of N-GQDs (left) with S,N-
GQDs (right) under the irradiation with 385 nm wavelength, respectively [155]; (h) and (i) display the schematic diagram and UVevis absorption spectra of S,N-GQDs with tuneable
fluorescence, respectively. The inset of (i) shows the photographs of S,N-GQDs prepared with different temperatures under UV lamp lighting with 365 nm [156]; (j), (l) and (m) are
illustration of the synthesis procedure, TEM image and absorption spectrum of P and N co-doped GQDs (P,N-GQDs), respectively. The inset of (m) displays the optical image of an
aqueous solution of P,N-GQDs under visible (left) and UV lamp (right) lighting [157]; (k) UVevis spectra of S,N-GQDs, the insets are digital picture of concentrated S,N-GQDs water
solution and diluted solution excited at different wavelengths of light [158].
this method displayed bright blue fluorescence with quantum yield 150 C and 180 C as shown in Fig. 16i. Qu et al. [158] demonstrated
of 23.2%. They have successfully demonstrated the co-doping of S that the introduction of S atom could alter the surface states of GQDs
and N atoms into the lattice of GQDs. Kim's group [154] fabricated resulting in the extension of the absorption band to visible region
various doped GQDs by dissolving organic materials in different (refer to Fig. 16k). S, N co-doped GQDs showed different emission
solvents. As shown in Fig. 16d, catecholamine was first dissolved in colors under excitation of 420e520 nm as shown in the insets of
water and N, N-dimethyl sulfoxide (DMSO). N-GQDs and S, N-GQDs Fig. 16k. To date, the main researches have been focussed on the S, N
were then synthesized using microwave-assisted hydrothermal co-doped GQDs, but P, N co-doped has been less studied. Chen's
method. Besides, Li et al. [155] fabricated N, S-GQQDs via a facile, [157] research group synthesized N and P co-doped GQDs from a
cheaper, and environmental friendly hydrothermal method using single biomolecule precursor via a simple strategy, as illustrated in
ammonia, S powder as dopant and GQDs mixed precursor. A rela- Fig. 16j. Such P, N-GQDs exhibited high quality structure and
tively high QY of 41% was obtained from the S, N-GQDs and the TEM excellent optical characteristics (refer to Fig. 16l and m respectively).
image on the materials showed uniform size as well as high- As shown in Fig. 16m, the absorption band was extended and the
crystalline structure (refer to Fig. 16eef). In addition, the PL prop- prominent PL peak occurred at 460 nm while a shoulder peak was
erties of N-GQDs and S, N-GQDs were investigated. PL emission of found at 360 nm. Such optical characteristic was attributed to the
the NS-GQDs exhibited a clear blue shift of 54 nm as compared to a introduction of S atoms. Limited work was reported on N, B co-
red shift observed from the N-GQDs (refer to Fig. 16g). However, doped into GQDs. However, Favaro [159] and co-authors prepared
such findings have been debated. Interestingly, Xu and co-workers N, B co-doped GQDs to enhance the electrochemical activity and
[156] used a porous polythiophene-derived carbon as the sulphur they noted a clear decrease in the overpotential as a function of
source, while HNO3 vapor was presented as the scissor and the ni- dopant concentration according to the sequence: N> B > B,N.
trogen source, to prepare the S, N-GQDs using the novel method, as In summary, the co-doped technique was indeed able to control
shown in Fig. 16h. The color of PL can be modified from blue to the properties of GQDs. However, the choice of the doping elements
yellowish-green by varying the synthesis temperature between usually depends on the application of GQDs.
3.1.3. GQDs doped with multiple atoms size using density-functional theory (DFT) and time-dependent
In addition to the double heteroatom doped GQDs, multiple DFT calculations as shown in Fig. 19b. It was suggested that the
atom doping also paly important role in some field such as bat- PL of a large GQD, consisting of heterogeneously hybridized carbon
teries, solar cells and so forth. Pillai and co-workers [173] fabri- network, was essentially determined by the embedded small sp2
cated F, S, N-doped GQDs, the QY could reach up to 70%. The clusters isolated by sp3 carbons. There was a slight difference be-
fabrication procedure and TEM images are presented in Fig. 17 tween theoretical prediction and experimental work in the degree
(aec). Another group [174] also prepared F, S, N-doped GQDs of tuning the band gap by changing the size of GQDs, however the
(see Fig. 17 (def)) and utilized them to optimize the performance trend was in good agreement as studied by Ye and co-workers
of dye-sensitized solar cells with power conversion efficiency [176]. The band gap of GQDs, which influences its photo-
(PCE) of 11.7% ± 0.22 and a fill factor (FF) of 71 %, and a QY of 70%. luminescent, can be tuned by tailored GQDs size via chemical
The tested properties of the solar cells can be seen in Fig. 17 (g). In a methods.
word, the multiple atom doped GQDs is an interesting approach, it
should be extensively studied in the future. Fig. 18 is a plot to
3.2.2. Modification of GQDs bandgap via controlling size and shape
present the absorption peaks of various doped GQDs in the liter-
Based on the above-mentioned theoretical studies, numerous
ature and the electronegativity of the dopant. It is noted that the
experimental studies have been performed to investigate the
absorption peaks are mostly concentrate on the blue region. The
modification of GQDs bandgap. As shown in Fig. 19c, GQDs were
absorption peak can be extended from deep UV to red t by using S,
capable of emitting light ranging from blue-green (2.9 eV) to
N or N doping.
orange-red (2.05 eV), depending on its size, functionalities and
defects. Kim's [19] research group studied the relationship be-
3.2. Tunable properties of graphene quantum dots by controlling tween PL and size of GQDs. Anomalous size dependences on the
size and shape visible PL was also found in their experiment, which could due to
shape and edge-state variations in the GQDs, as shown in
Another strategy to tune the optical, physical and chemical Fig. 19dee. Both the size and morphology of GQDs were inves-
properties of GQDs is via controlling the size and shape of the tigated to study their effect on tunable bandgaps. For example,
GQDs. Several methods have been applied to modify the size and studies were performed on GQDs with different shapes (e.g.
morphology of GQDs. circular to polygonal) and the corresponding edge-state varia-
tions as the size of GQD increases suggested that the PL behaviors
3.2.1. Theoretical study of GQDs bandgap were attributed to the novel feature of GQDs. Furthermore,
Fig. 19a shows a decrease of the energy band gap with increasing morphology of GQDs can solely influence its band gap. Sarkar
size of the GQDs, hence demonstrating a relationship between and co-workers [177] performed theoretical studies on the
energy band gap and size of the materials. Besides, Chen and co- relationship between the shape of GQD and its band gap, as
workers [175] studied the relationship between the band gap and shown in Fig. 19f. Besides, they also explored the possibility of
Fig. 17. Diagram and characterized images of multiple atoms doped GQDs. (a) schematic diagram indicating the formation of co-doped GQDs; inset shows a comparison of the same
concentration of co-doped GQDs in DMF under visible light and UV light respectively (left: co-doped GQDs in DMF and right: DMF) [173]; (bec) TEM image of N, F and S co-doped
into GQDs (N, F, S-GQDs), inset of (b) and (c) are the particle size distribution and fast Fourier transform (FFT) pattern, respectively [173]; (def) TEM image of N,F,S-GQDs and (g)
shows the properties of dye-sensitized solar cells with or without N, F, S-GQDs [174].
of the density of states of different functionalized GQDs. The

theoretical analysis is in agreement with recently reported
experimental work.
The properties of GQDs modified by its size and shape have been
investigated using different methodologies, such as Raman scat-
tering [178], density of states [179], magnetic properties [180,181],
faraday optical rotation (FOR) [182] and optical characterizers
[130,183,184]. This topic on band gap engineering of GQDs via
tailoring its size and shape has attracted great interests from both
theoretical [185,186] and experimental [18,187] researchers. This is
a promising technique in extending the application of GQDs in the
near future.
3.3. Graphene quantum dot composites to optimize performances
Fig. 18. Statistical plot of absorption peak and electronegativity of the doped element. There are several drawbacks of GQDs, such as difficult to
assemble into film and poor conductivity etc. The formation of GQD
composites could overcome some of the challenges and enhance
tuning the band gap by functionalizing the GQDs with different the performances of the material, thus leading to many novel ap-
organic groups, and the fact that the covalent functionalization plications. As shown in Fig. 20a, polymer materials [191,192] and
shifted both the HOMO and LUMO energies without significantly nano-materials [193e198] can be used to form composite with
changing the HOMOeLUMO gap were explained by the analysis GQDs. Follow the sequence of organic and inorganic materials
Fig. 19. Schematic illustration, corresponding measured results and analysis of GQDs depended on size and morphology. (a) Modulation of band gap for GQDs via size variation; (b)
Calculated emission wavelength (nm) using TDDFT method in vacuum as a function of the diameter of GQDs. The solid line is the linear fitting of zigzag-edged GQDs with various
sizes [175]; (c) The curves of band gap with the increase with the size of GQDs, inset shows the color of PL tuneable with the size of GQDs [176]; (d) and (e) represent the UVevis
spectra and PL of GQDs with various sizes, inset is digital picture of different luminescence of GQDs with different sizes [19]; (f) The energy gap as a function of total number of
conjugated carbon atoms (N) and various morphologies for type-1 GQD (dash line with black circle), type-2 GQD (dash line with red square), type-3 GQD (dash line with green
triangle) and type-4 (dash line with blue star), insets represent GQDs with different morphologies [177].
Fig. 20. Diagrams and related measured images of GQDs composites with organic and inorganic materials. (a) Illustration on the formation of GQDs composites with polymer or
inorganic (nano-rods/wires, nano-flakes and nanoparticles) materials; (b) and (c) represent fabrication process and TEM image of the composite of GQDs with hollow mesoporous
silica spheres, inset of (c) shows the HRTEM image of individual Si-GQDs [188]; (d) and (e) are scheme of the preparation process of GQDs-polypyrrole (PPy) film and the SEM image
of composites with PPy and GQDs (10%) [189]; (f) and (g) display the schematic representation of the magnetic silica beads/graphene quantum dots/molecularly imprinted pol-
ypyrrole (mSGP) composites and spectroscopic characterization of the mSGP composites, inset of (g) is the optical picture of water solutions of GQDs (left) and mSGP (right) [190].
composites, the forming of composites with GQDs and other ma- wavelength, as displayed in Fig. 20g. Whereas, the inset of Fig. 20g
terials will be described. indicates the obvious difference in the color of aqueous solution of
Organic materials have a lot of merits, such as easy to form film, GQDs and mSGP. The enhanced properties of GQD composite would
high carrier mobility and so on. These virtues could complement benefit many applications. There has been a growing interest in
the performances of GQDs. Wen and co-workers [188] fabricated developing new GQD composites in recent years. Malik's [199]
fluorescent organosilane-functionalized GQDs (Si-GQDs) and sub- group prepared nanofiber composite, which consisted of GQDs
sequently embedding them into mesoporous hollow silica spheres and polyaniline, as supercapacitor electrode materials. The com-
as bio-label for the first time. The entire preparation process is posite material led to an enhanced current density of 1 Ag-1 as well
shown in Fig. 20b. TEM image, shown in Fig. 20c, displays the high as cyclic stability. The preparation process of the composite is
crystalline quality of Si-GQDs and the characteristic of GQDs. Chen shown in Fig. 21a. Qu et al. [200] fabricated composite of 0D GQDs
and co-workers [189] developed composite of GQDs and poly- and 3D graphene (3DG) by assembling them via a novel benign
pyrrole (PPy) as counter electrode of dye-sensitized solar cells electrochemical method, as shown in Fig. 21b. The GQDs-3DG
(DSSCs) to optimize the performances of the solar cells. The fabri- composite material was then used to develop supercapacitor with
cation procedure is presented in Fig. 20d. The composite formed a enhanced performances, which relied on the high surface area and
compact and uniform electrode as shown in Fig. 20e. As the com- increased active sites of the GQDs.
posite film of GQD and PPy consisted of porous structures, there Apart from the composites of GQDs and organic materials, many
were more active sites resulting in higher charge transfer rate. The inorganic materials have been used to form GQD composites to
performance of DSSCs was greatly enhanced by the composite film improve the performances of devices. Dhar and co-workers [201]
and achieved the highest PCE of 5.27%, which was ~20% higher than demonstrated the composite of ZnO and GQDs can enhance the
that of plain PPy (4.46%) based DSSCs. There is no doubt that the performance of UV photodetector with superior external quantum
composites of GQDs and organic materials have enormous poten- efficiency (EQE) of ~57681% (at -1 V bias) at wavelength of ~340 nm.
tial in future. Interestingly, Zor et al. [190] prepared a novel The device structure is shown in Fig. 21c. The composite of ZnO
multifunctional composite consisting of magnetic silica beads, GQD nanorods/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
and molecularly imprinted polypyrrole. The formation of the (PEDOT:PSS) and GQDs exhibited far better performances than GQD
fabricated composite material is shown in Fig. 20f. The composite modified ZnO NRs and pure ZnO NRs. Other shape of ZnO, such as
exhibited enhanced optical and magnetic properties. For example, leaf-shaped ZnO (L-ZnO) [202], was also used in forming composite
the absorption spectrum of the composite was extended to greater with GQDs. TEM image of the L-ZnO and GQDs composite is as
Fig. 21. Illustration and corresponding images of the GQDs composites with organic and inorganic materials. (a) Schematic diagram of the fabrication process of GQDs composites
with polyaniline (PANI) [199]; (b) Cartoon representation of fabricating a symmetrical supercapacitor based on the GQDse3DG composite material [200]; (c) Schematic diagram on
the structure of UV photodetector using composites of ZnO and GQDs as active layer [201]; (d) and (e) show SEM image and UVevis absorption of composites of leaf-templated ZnO
and GQDs, respectively [202]; (f) TEM image of black TiO2 [203]; (g) Schematic illustration of the fabrication of composite of a manganese vanadium oxide and (GQDs) using a
molecular manganese vanadate precursor [204]; (h) The synthesis route for the GQDeMn3O4 nanocomposite using MWCNTs as the precursor of GQDs [205]; (i) and (j) represent
TEM image and the structure of composites of Au nanoparticles and GQDs [206].
shown in Fig. 21d. UVevis absorption of the composite showed an frequently used as catalysts. Wu et al. [206] fabricated the com-
increase in the absorbance intensity as well as extended spectrum posites of GQDs and Au nanoparticles as catalysts. TEM image and
(refer to Fig. 21e). In the same manner, TiO2 and GQDs nanostructure of the composites are displayed in Fig. 21i and j,
composites were fabricated by Bu [203]. TEM image of the nano- respectively.
composites is shown in Fig. 21f. The nanocomposites were used as Many inorganic materials have been used in forming composites
photocatalysts, which exhibited extremely high photocatalytic ac- with GQDs, such as SnO2 [207], ZnS [208], MoS2 [209], ferroelectric
tivity due to the larger energy barrier between NGQDs and BeTiO2, liquid crystal [210], ceria [211], Zn [212] and Fe2O3 [213] etc.
resulting in enhanced light absorption and higher electron density. In brief, GQD composites have shown to improve and optimize
Ji et al. [204] assembled lithium ion battery using composite of the performances of devices. Novel functionalities of GQDs can be
MnV12 and GQDs. The fabrication process is shown in Fig. 21g. The developed using techniques, such as doping, controlling size/shape
bar shaped composites can maximize the interfacial contact area and composites, which would open up new applications for GQDs.
and improve charging/discharging behavior, thus optimizing the
performances of the lithium ion battery. Another interesting
experiment [205] was performed by assembling Mn3O4 and GQDs 4. The applications of graphene quantum dots
into nanocomposites, which can change the energy level of the
materials instead of doping with heteroatoms or controlling the The extensive properties of GQDs (and functionalized GQDs)
size and shape of GQDs. As shown in Fig. 21h, the multi-walled would benefit many applications in a variety of fields. As shown in
carbon nanotubes (MWCNTs), acted as the GQDs' precursor, were Fig. 22, GQDs have found many potiential applications in fields,
mixed with the Mn3O4 to form the composites which exhibited such as medical [214e219], optical [85,220e224] and energy
intensive Raman scattering. This could be used in bioimaging to [139,225e229], which will impact our quality of life and attract
discriminate cancer cells and normal cells. Due to the large surface significant commercial interests. Much research has been carried
area to volume ratio of the GQDs, the composite materials are out to understand the unique properties of GQDs and tailoring its
Fig. 22. The extensive applications of the GQDs on medicine, optics and energy. The red-carp represent the vitality of the GQDs.
properties using different techniques, such as doping, controlling of highly selective detection. The entire fabrication process is shown
size/shape and developing composite material and so forth. in Fig. 23a. Firstly, the GQDs were stripped from graphene oxide
In the next decade, GQDs may become a popular material for sheets and amine-modified. Anti-human IgG antibodies were
advanced technology. They have already been exploited in a conjugated with Fe3O4 nanoparticles to detect casts in urine. The
number of applications, such as biological imaging [230,231], drug modified GQDs were then linked on to the surface of anti-IgG
delivery [232,233], photodetector [234,235], LEDs [236e238] and functionalized Fe3O4 nanoparticles. Finally, the Fe3O4/GQDs fluo-
battery [239] etc. In this section, we will present the current ap- rescent probes were added into the sample to detect casts through
plications of GQDs in medical, optical and energy-related fields. fluorescent imaging. For comparing the efficiency of fluorescent
Each of these fields will be subdivided into detailed applications. probe using GQDs and Fe3O4/GQDs, a series of pre-quantitative
casts (2, 4, 8, and 10 casts/ml) were analyzed by microscopy and
4.1. Medical applications fluorescent imaging assay, and the results are shown in Fig. 23bed.
At the same concentration of casts, the counts of fluorescent im-
Due to the biocompatibility and nontoxicity of the GQDs, the aging assay from Fe3O4/GQDs (Fig. 23d) were approximately 10
nanomaterials have been exploited for medical applications and times higher than that of microscopy (Fig. 23b) and GQDs only
demonstrated some excellent performances, which could poten- (Fig. 23c). Their results indicated the detection efficiency of this
tially replace some traditional materials in this field. There have fluorescent imaging assay was higher than microscopy mainly due
been continuous efforts in exploiting GQDs for other novel medical to the magnetic enrichment of Fe3O4/GQDs nanocomposites. Such
applications due to the recent promising outcomes in the field. magnetic enrichment was efficient and simple.
Yang and co-workers [241] demonstrated that GQDs can be
4.1.1. Biological imaging widely utilized for biological imaging in different kinds of cells.
GQDs have been used in biological imaging for medical diag- They prepared GQDs with uniform size and strong yellow emission
nostic as they can assist in locating cancerous cells and determining by using top-down method. Three different kinds of stem cells,
if drugs have been delivered to targeted cells as well as locating the namely neurospheres cells (NSCs), pancreas progenitor cells (PPCs)
drugs within cells [242]. The strong and tunable PL of GQDs allow and cardiac progenitor cells (CPCs), were used in the studied and
the materials to be used in biological imaging. Pu and co-workers cultured in different mediums. On the day of treatment, the cells
[240] used the modified GQDs as efficient fluorescent probes for were incubated with GQDs at a final concentration of 25 mg mL1
Fig. 23. Preparation process of the fluorescent probe and biological imaging of the GQDs. (a) Preparation of Fe3O4/GQDs fluorescent probe [240]; (b) is microscopy of cast (control
method), (c) and (d) are detection efficiency of fluorescent imaging assay by using GQDs and Fe3O4/GQDs probes, respectively [240]; (e), (g) and (i) are micrographs of stem cells
under bright field, (f), (h) and (j) show the fluorescent image of stem cells via using fluorescent agents with NSCs, PPCs and CPCs incorporated with GQDs at 405 nm excitation,
respectively [241]; (k) Cell viability for the stem cells of NSCs, CPCs and PPCs as a function of the added GQDs concentration [241].
for 24 h at 37 C. Subsequently, the cells were washed three times interactions and easy functionalization via the oxygen functional
with PBS and then fixed with 4% paraformaldehyde for 20 min at groups [243].
room temperature. Fig. 23f, h and j show the confocal fluorescent Hu and co-workers [243] fabricated SCNAs by employing GQDs
images of NSCs, PPCs and CPCs with an excitation wavelength of as the substrate of the vehicles, as shown in Fig. 24a. Both GQDs and
405 nm, respectively. As shown in Fig. 23e, g and i, the morphology SCNAs were incubated with RG2 cells (a rat glioma cell line) at
of the cells can be discerned from the internalized GQDs. These various concentrations for 24 h in order to evaluate the effects of
results demonstrated that the GQDs can be used in different cells the particles on cell viability. As shown in Fig. 24bee, CLSM images
for biological imaging. However, there was slight cytotoxicity of of RG2 cells incubated for 0.5 h showed the presence of SCNAs in
GQDs in these cells as observed in Fig. 23k. The average cell viability the cytoplasm, and with increasing incubation time to 4 h, most of
of NSCs and CPCs was above 80% after 3 days culturing with GQDs the particles were surrounding the cell nuclei. In addition to the
at a concentration of 100 mg mL1, and was about 65% for PPCs. fluorescence signal from DOX, the fluorescence of the GQDs could
In summary, the biocompatibility, strong fluorescence and also be observed in RG2. When comparing the fluorescence signals
nontoxicity of the GQDs have been investigated and they are an between DOX and GQDs, most of them actually overlapped, which
excellent choice for biological imaging in medical applications. indicated good affinity in the cell. A detailed schematic illustration
of the drug delivery is represented in Fig. 24f. The effectiveness of
4.1.2. Drug delivery GQDs as drug delivery was studied by Some [244] et al. They used
Compact drug delivery nanosystems with multifunctional fea- graphene-derivatives (such as DGO and GQD) as nanovectors for
tures are currently of considerable interest for cancer therapy the delivery of the hydrophobic anticancer drug Cur and performed
owing to their improved dose tolerance and therapeutic efficacy clinical studies using the technique. As shown in Fig. 24g, while
[243]. GQDs have many attractive properties, such as sp2 carbons, tumor growth was initially inhibited to some extent (blue line) in
rich in p electrons and having a variety of functional groups (e.g. the control group treated with free Cur, the tumor size did even-
carboxyl, hydroxyl, carbonyl and epoxy). tually increase. In stark contrast, the DGO-Cur and GQD-Cur groups
This is in addition to the reduced size of GQDs and different exhibited a remarkable inhibition of tumor growth. Both GQD-Cur
chemical reactivity as compared to other graphene based materials, and DGO-Cur treated mice survived more than 14 days with almost
such as GO or CNTs [245]. These characteristics would make GQDs no observable increase in tumor size (yellow and green lines). The
an ideal candidate for drug delivery platform through p-p photographic images showing the size of the tumor in response to
Fig. 24. Schematic and some clinical results on the application of GQDs on drug delivery. (a) Schematic illustration on the key steps in the size-changeable nanoaircraft (SCNA)
synthesis process [243]; (bee) Confocal laser scanning microscope (CLSM) image of cellular uptake after 24 h, doxorubicin (DOX) appears in red, and GQDs appears in cyan [243]; (f)
Size-changeable nanoaircrafts (SCNAs) for hierarchical tumor targeting through an aggregation transition in the weak acidity of the tumor environment and photopenetrating drug/
GQD delivery. i) The SCNAs delivered DOX/GQD to the tumor through intravenous injection. ii) The aggregation transition of the SCNAs in the weak acidity of the tumor envi-
ronment enhanced tumor accumulation. iii) NIR-activated disassembly of SCNAs into DOX/GQDs facilitated penetration deep into tumors [243]; (g) Relative tumor volumes of mice
(n ¼ 6) treated with PBS (control sample), double-oxidize graphene oxide (DGO), GQD, DGO-Cur, GQD-Cur, and curcumin (Cur), top planar and bottom section of inset show
photographs of mice and tumors treated with PBS, DGO, GQD, DGO-Cur, GQD-Cur, and Cur after 14 days, respectively [244].
the treatments can be seen in the inset. Besides, GQDs can also be [247] as shown in Fig. 25bee. Their findings suggested GQDs as
used in gene delivery due to its favorable properties. For instance, anti-oxidants and pro-oxidants upon irradiation because they have
Zhang's [248] and Guo's [249] team demonstrated such delivery by the potential to become potent anti-oxidants for controlling ROS-
using GQDs. induced cell damage.
In brief, the preliminary work on using GQDs as drug delivery
system demonstrated the superior stability, good biocompatibility 4.1.4. Photothermal therapy
and excellent therapeutic performance of the material, which is a Apart from the above-mentioned PDT, another therapeutic
promising candidate for in-vivo therapeutic agent. technique has been performed using GQDs. Photothermal therapy
(PTT) refers to the use of electromagnetic radiation (e.g. often in
4.1.3. Photodynamic therapy infrared wavelengths) for the treatment of various medical condi-
Photodynamic therapy (PDT), also known as photo- tions, such as cancer. This approach is an extension of photody-
chemotherapy, is a form of phototherapy involving the use of light namic therapy, in which a photosensitizer is excited with a specific
and a photosensitizing chemical substance that applied in band of light. This activation brings the sensitizer to an excited state
conjunction to elicit cell death by molecular oxygen (phototoxicity). where it then releases vibrational energy in the form of heat that
An interesting phenomenon that GQDs can generate the reactive kills the targeted cells.
oxygen species (ROS) in tumor cells was observed [250]. In addi- Unlike photodynamic therapy, PTT does not require oxygen to
tion, the upconversion characteristic of GQDs can convert low en- interact with the target cells or tissues. Current studies on PTT are
ergy NIR light to UVevisible light, which has been widely examined investigating the use of longer wavelength light, which is less en-
for biological applications. Therefore, GQDs can be considered ergetic, and therefore less harmful to surrounding cells and tissues.
excellent materials for photodynamic therapy. Xing and co-workers For instance, Zhu and co-workers [58] fabricated DOX-MMSN/GQDs
[246] explained the mechanism of PDT (refer to Fig. 25a). The which were used as multifunctional platform for controlled drug
effectiveness of PDT using GQDs was investigated through clinical delivery, magnetic hyperthermia and photothermal therapy, as
evaluation as shown in Fig. 25g. Furthermore, photoinduced cyto- shown in Fig. 25f. Many more studies have recently been carried
toxicity and oxidative stress of GQDs were also studied by Yin et al. out, such as from Lee's [253] and Yang's [254] research group. In
Fig. 25. Representation and clinical results on the photodynamic therapy application of GQDs. (a) Schematic illustration on the fabrication of upconversion nanoparticles-GQDs/
Tetramethylrhodamine-5-isothiocyanate (UCNP-GQDs/TRITC) with mitochondria-targeting potency [246]. (bee) A549 cells fluorescence-based LIVE/DEAD assays (b) after 24 h
under irradiation at 405 nm excited [247]. (f) Schematic illustration of the preparation process of the doxorubicin loading GQDs-capped magnetic mesoporous silica (DOX-MMSN/
GQDs) nanoparticles and synergistic therapy combined with controlled drug release, magnetic hyperthermia, and photothermal therapy [58]; (g) Growth curves of mouse
mammary tumor cell (4T1 tumors) in each group, inset is typical photographs of tumor tissue after each treatment [246].
short, GQDs has enormous prospect in medicine therapy and re- There remain much potential of GQDs in this field that has yet to be
searchers are working tirelessly to develop advanced and novel fully explored, which could lead to many more exciting applica-
therapeutic technologies based on the materials. tions. Many of the above-mentioned applications are still at its
early stage of development however they have given us some ideas
4.1.5. Antimicrobial materials on the future of nanomedicine based on GQDs.
Infectious diseases caused by bacteria continue to be one of the
greatest health problems worldwide, afflicting millions of people 4.2. Optical applications
annually. Antibacterial materials are widely used in daily life and
can effectively protect the public health [255]. GQDs have some Due to the unique optical properties of the GQDs, different opto-
remarkable behavior, which has been exploited as antimicrobial devices have been developed, such as photodetector [265,266],
materials. For example, GQDs can produce toxicity under special light emitting diodes [267e270] and photocatalysis [271e274] etc.
wavelength irradiation. This is based on some special characteristics of GQDs, for example,
This was demonstrated by Wang et al. [251] as they fabricated upconversion, strong photoluminescence and tuning of energy gap
antimicrobial materials using GQDs. The clinical results of N-GQDs by controlling size/shape, which are different from traditional
(5.1%)-AbLPS-treated-bacteria in E. coli under 670 nm laser photo- quantum dots, such as ZnO QDs and TiO2 QDs etc. Different func-
excitation are shown in Fig. 26aec, which indicated the GQDs tionalization techniques of the GQDs were studied and achieved
played an important role in killing the bacteria. Qu and co-workers excellent performances in related applications. There are many
[252] designed an antibacterial system based on GQDs and low potiential applications of GQDs in the optical field, which will be
dose of H2O2. The system, represented in Fig. 26d, benefitted from the topic for the following sections. Following the main lines of
the peroxidase-like activity and excellent biocompatibility of GQDs. optoelectrical detector, LEDs and photocatalysis, many interesting
Clinical studies were performed to assess the efficacy of the researches related to these applications will be described.
designed antibacterial system (shown in Fig. 26eei) in wound
disinfection. GQDs band-aids were prepared and showed excellent 4.2.1. Optoelectrical detector
antibacterial property in-vivo with the assistance of low concen- Photodetectors or photosensors are sensors of light or electro-
tration of H2O2, which indicated that GQDs band-aids have po- magnetic energy [275], and they play an important role in national
tential use for wound disinfection. defense, real-time monitoring and space exploration and so on. Due
As shown, GQDs have been studied for use in the medical ap- to the ease of functionalization and uncommon optical properties
plications due to the many unique properties of the materials. of GQDs, many research groups have worked on the nanomaterials
Fig. 26. Mechanism and clinical photos of antimicrobial materials using GQDs. (aec) Images and viability of E. coli [251]; (dei) The designed system is based on GQDs and low level
of H2O2 for the antibacterial application, the photography of wound disinfection [252].
and developed various methods to enhance the performance of 4.2.2. Light emitting diodes
photodetectors by utilizing GQDs. Among these methods, GQDs Luminescence is a phenomenon where light is emitted from a
composited with traditional materials, such as silicon, ZnO or P3HT, material excited by an external energy. Such phenomenon has
with different dimensions, for example, Si nanowire [256] major scientific and technological roles in a variety of applications
(Fig. 27a), Si nanoparticles [257] (Fig. 27b), Si pyramid [258] [275e277]. With a significant portion of global energy consump-
(Fig. 27dee), ZnO nanorods [259,260] (Fig. 27c and f) and P3HT tion going towards lighting, it is important to develop efficient
[261] (Fig. 27g), have been investigated for use in photodetectors. In illumination-grade lighting technologies [278]. The excellent opti-
addition, GQDs have also been used to form hybrid composites with cal properties of GQDs have been exploited in LEDs. There are two
other 2D materials, such as graphene [35,38,263,264] (Fig. 27i, j, m main approaches in the application of GQDs in LEDs. The first
and n), MoS2 [262] (Fig. 27h) and WSe2 [133] (Fig. 27l) etc. It is rare approach is to coat LEDs with GQDs to modify its lighting intensity
to use pure GQDs as an active layer, even though they have been and emitting wavelength (Fig. 28a) [279e282]. Second approach is
attempted by some groups, due to the absorption peak position of to develop emitting layer using GQDs within the structure of LEDs
GQDs is mainly located at the ultraviolet range, hence the photo- (Fig. 28b) [283,284].
detector would generally respond to short wavelength range, as GQDs have been frequently used as phosphors coated on to the
shown in Fig. 27k, which led to deep ultraviolet photodetector [39] surface of LEDs, which led to the modification of color [285] (refer
using pure GQDs. Interestingly, Tang and co-workers [27] devel- to Fig. 28c) as well as enhancement in intensity of emitting lights
oped a photodetector that exhibited photoresponse over UV to NIR [286,287] (refer to Fig. 28feh). Besides, the GQDs can also be used
range by doping pure GQDs with nitrogen. Such novel technique is as the active layer by forming composite with other emitting ma-
generally known as Tang-Lau method. terials to improve the performance of LEDs. The intensity of LEDs
Table 2 provides a detailed list of merits of the different GQDs irradiation can be controlled by changing the content of GQDs in
based photodetectors. According to the listed merits, it is apparent the composites [49] (refer to Fig. 28d and e). Furthermore, the color
that there is a great prospect in using GQDs based photodetector in of GQDs based LEDs can be tuned by functionalizing the GQDs with
the near future. It has indeed inspired researchers to perform different functional group agents [288e290] (refer to Fig. 28iem).
further research and development work in using GQDs as an active The recent research has demonstrated that GQDs can be applied
layer in the photodetector. in LEDs using different approaches, namely as phosphors or active
Fig. 27. Schematic and performance of various photodetectors based on GQDs. (a) Photodetector based the shell structure of GQDs sensitive Si nanowires (SiNWs) [256]; (b)
Schematic of photodetector composed of the GQDs/Si nanoparticle (GQDs/SiNPs) [257]; (c) Illustration of photodetector based on ZnO nanorod array sensitized with GQDs [258];
(dee) Schematic and SEM image of the photodetector by hybridization with GQDs and Si [259]; (f) Representation of photodetector consisting of ZnO nanorods and GQDs [260]; (g)
Diagram of photovoltaic detector based P3HT/GQDs [261]; (h) Schematic of a MoS2-GQDs heterostructure phototransistor [262]; (i) Schematic representation of a graphene/NGQDs
hybrid phototransistor [263]; (j) Diagram of photodetector hybridization with GQDs and graphene [38]; (k) Schematic illustration of the pure GQDs photodetector with asymmetric
AgeAu electrodes [39]; (l) Schematic illustration of an ML WSe2/N-GQDs photodetector [133]; (m) Schematics of a typical GQDs photodetector device [264]; (n) Photoresponsivity
and specific detectivity versus laser wavelengths of 254e940 nm for the GQDs/Graphene hybrid photodetector [35]; (o) Schematic diagram of the N-GQDs photodetector [27].
Table 2
The related merits of photodetectors based on active layer with GQDs.
Active materials Performance Structure Ref.
Detectivity Responsivity Response EQE (%) Tested Cover spectral

(cmHz1/2W1) (AW1) time temperature range
GQDs/SiNW 11.9 1012 40.6 d 8150 RT UV-NIR Vertical [256]

GQDs/SiNP d 0.31 d d d UV-NIR Vertical [257]
GQDs/Si 8.0 1011 1.02 80 ms d d Visible Vertical [259]
GQDs/ZnOND d d 150e200 s d d UV Vertical [258]
GQDs/ZnOND 1.3 1012 36 d 13161 d UV Vertical [260]
GQDs/ZnOND 2.4 1011 247 0.94 s 90063 d` UV Vertical [265]
GQDs/MoS2 d 1.6 104 1.23 s d RT Visible Planar [262]
GQDs/Graphene 1.2 1012 3.5 104 0.61 s d d UV-NIR Planar [263]
GQDs/Graphene 5.5 1013 2.3 106 0.69 s d RT UV-NIR Planar [35]
GQDs/WSe2 d 2578 d d RT Visible Planar [133]
GQDs 9.6 1011 2.1 103 64 ms d RT UV Planar [39]
GQDs d 14.1 (VW1) 50 s d RT UV-NIR Planar [27]
GQDs >1011 0.2e0.5 2m s d RT UV-NIR Vertical [264]
(Notes: SiNW, SiNP, ZnOND and RT represents Si nanowire, Si nanoparticle, ZnO nanorod and room temperature, respectively.).
Fig. 28. Illustrative diagrams and results on the application of GQDs in LEDs. (a) Schematic of covering on LEDs route with GQDs; (b) Diagram of using the GQDs as emitting layer;
(c) Top and bottom plane show fluorescence image of the GQDs phosphors/PDMS composites under 365 nm irradiation and photos of single color GQDs-covering LEDs operating
under the voltage of 3.0 V, respectively [285]; (d) Schematic illustration of the GQD-LEDs structure and the corresponding band diagram (top plane), electroluminescent image of
GQDs-LEDs, consisting of five emitting areas (bottom plane) [49]; (e) Luminous efficiencies and emission spectra of the devices, inset shows the emission spectra of LEDs composed
of pure PVK (red dot line) and with 3 wt % (dark dot line) [49]; (f) and (g) show schematic cross section of the InGaN/InAlGaN UV LEDs coated with the GQDs and optical mi-
crographs of the InGaN/InAlGaN LEDs without (top) and with (bottom) deposition of GQDs under an injection current of 100 mA, respectively [286]; (h) Photographs of the
fabricated white LED lamp with no coating (left) and coated (middle) with GQDs as well as LEDs coated with GQDs ON states (right) [287]; (i) Structure of LEDs with GQDs as active
layer [288]; (jem) Electroluminescence spectra of the LEDs with different functionalized GQDs, each inset show the photos of LEDs [288].
layers. Another important aspect of GQDs based LEDs is that the edge chemistry. Moreover, they exhibit large surface area, high
color and intensity of the emitting light can be tuned by modifying electron mobility and can provide a direct path for the transport of
the GQDs and its composite materials. In brief, the application of photo- generated charge carriers, which will increase the lifetime
the GQDs on LEDs is fast becoming a reality in the near future. of electronehole pairs and upconversion behavior. Different
methods to enhance photocatalysis performances have been
4.2.3. Photocatalysis investigated recently [77,297e302]. Photocatalysts comprising of
Photocatalysis, which is the acceleration of a chemical reaction GQDs composites with other inorganic materials in different
by light in the presence of a catalyst, has attracted considerable shapes, such as nanoparticle [308e310], nanobelt [307] and
attention due to its application in renewable energy source. For nanowire [310,311] have been synthesized and studied. As shown
example, clean energy can be generated by water-splitting into H2 in Fig. 29b, the composites of GQDs and CdS were fabricated, where
and O2 using sunlight [291e295]. A visible light sensitive material the GQDs were attached on to the surface of CdS nanoparticles. This
capable of splitting water into H2 and O2 is critical in photocatalytic resulted in enhancing the intensity of absorption for visible light
water-splitting [296], as shown in Fig. 29a. Another important and the mechanism was explained in detail by Lei and co-workers
criterion for such application is the use of low-cost, scalable and [303]. Titanium dioxide (TiO2), which has been frequently used as
sustainable materials as photocatalysts. Carbon materials, which catalyst, was hybridized with GQDs and the hybridization mecha-
are low-cost, abundant and environmentally friendly, have been nism was proposed by Yang and co-workers [304], as shown in
investigated as photocatalysts for cost-effective hydrogen produc- Fig. 29c. Li [172] et al. explained the possible mechanism for the
tion. Among the carbon materials, GQDs stand out as the best photocatalytic H2 evolution of S,N-GQD/TiO2 composites under
candidate for photocatalysis applications due to its many UVevis light irradiation using the band gap diagram shown in
outstanding properties. For example, GQDs are 0D semiconductors Fig. 29d. Composites of GQDs and ZnO NWs were also prepared for
with a bandgap that can be tailored by varying its size/shape and used as photocatalysts under solar irradiation [311], as illustrated in
Fig. 29. Schematic illustration and mechanism of photocatalysis composed of GQDs. (a) Illustration of photocatalysts consisting of GQDs with different catalysts shapes; (b)
Representation of preparation process of CdS/GQDs nanohybrids, inset shows the photography of GQDs and solution of GQDs under irradiation of 365 nm lamp [303]; (c) Simulation
model of the cross-interaction in TiO2 between carbon atoms and lattice oxygen (TieO) [304]; (d) Proposed mechanism for the photocatalytic H2 evolution of S,N-GQD/TiO2
composites under UVevis light irradiation [172]; (e) Schematic illustration of splitting mechanism over the N-GQDs/ZnO NW heterostructure under simulated solar light irradiation
[305]; (f) Photocatalytic mechanism for hydrogen evolution over NGQDs/g-C3N4 under visible light irradiation [306]; (g) Schematic for a plausible decomposition mechanism of
GQDs/ZnS nanocomposite under light irradiation [307].
Fig. 29e. Moreover, the upconversion behavior of GQDs can also be renewable energy that can be converted in to electrical energy to
observed in the composites of GQDs and g-C3N4 [306]. It can support our daily life. However, solar energy is only available in the
enhance the intensity of visible light by converting the NIR spectra day but not at night. Therefore, energy storage is an important topic
to visible range, as shown in Fig. 29f. Nanobelts possess greater in energy applications and it remains one of the major challenges in
surface areas, as compared to nanowire, hence increasing the renewable energy. In the following sections, the use of GQDs in
loading of GQDs to enhance photocatalytic performances. Jang et al. solar cells and energy storage battery are presented.
[307] prepared ZnS nanobelts decorated with GQDs for photo-
degradation reaction of rhodamine B, as shown in Fig. 29g.
4.3.1. Solar cells
The unique properties of GQDs have been exploited in the
Solar cells, which can covert sunlight to electricity, provide clean
above-mentioned optical applications. With the continuous efforts
and renewable energy source. It is also an essential energy source
in understanding the properties of GQDs and developing new
for society which has scarce resources to generate electricity using
functionalities of the nanomaterials, it is anticipated that new and
conventional methods. The characteristics of GQDs, such as the
novel optical applications will continue to be developed in the near
downconversion, strong fluorescence, intensive absorption at UV
future.
range and easily-functionalization etc., have led to development of
different solar cells using GQDs to enhance the performances of the
4.3. Energy-related applications cells. Some of the solar cells were based on traditional silicon solar
cells [322], polymer solar cells [31,323e332] and other novel solar
As the growth of population and the reduction of resources cells [183,333e345] etc.
continue, it becomes an urgent quest to explore new and sustain- Hybrid of Si and GQDs remain the leader in all solar cells as its
able energy for the future. As carbon is one of the most abundant power conversion efficiency was significantly enhanced to 16.55%
materials in the world, it can be considered as an excellent candi- via utilizing the properties of GQDs, such as strong absorption at UV
date for energy-related applications. Solar energy is clean and range [32,312] (Fig. 30a and e), down-shift energy [33,313] (Fig. 30b
Fig. 30. Diagrams on the different structures of solar cells based on GQDs. (a) Schematic illustration of the GQDs/Si heterojunction solar cell with graphene film on top as the
transparent electrode [312]; (b) [33], (e) [313] and (f) [32] show the GQDs/Si solar cells by taking advantage of downconversion of GQDs [32,33]; (c) Diagram of a typical quantum
dot sensitized solar cells (QDSSC) based ZnO/GQDs device [314]; (d) Schematic structure of TiO2/CdS/GQDsnS2/Sn2eSb2Se3/NiO/C-fabric cell [315]; (g) The schematic device
structure of NCQDs-sensitized TiO2 solar cell [316]; (h) Diagram of all-weather GQDs solar cell [30]; (i) Schematic of a BHJ solar cell based on GQDs with different edge functional
groups [317]; (j) Representation of the formation process of the GQDs@PEDOT coreshell nanostructure (CSNS) [203]; (k) Schematic structure of typical polymer solar cells based on
GQDs [318]; (l) Normalized PCEs of the Ag NWs mixed with GQDs/graphene transparent conductive electrodes/flexible organic solar cells (TCE/FOSCs) as functions of bending
radius. The inset shows real images of the FOSCs at different radium [319]; (m) Schematic structure of an inverted polymer solar cell with GQDsCs2CO3 buffer layer, inset shows
the molecular structure of Cs2CO3 [320]; (n) Schematic of organic photovoltaic (OPV) device with a GQDs-incorporated PEDOT:PSS layer [321].
and f) and so on. Besides, the GQDs composites with other inor- Generally, the GQDs and organic materials were utilized to form the
ganic materials, such as ZnO [137,171,314,346e348], TiO2 bulk heterojunction (BHJ) in organic solar cells [319,321], as shown
[315,316,349] and some classical solar materials [350e356], have in Fig. 30k and n.
also been reported, the power conversion efficiency of optimized In summary, GQDs have been applied as hybrid materials in
devices were enhanced to 1.26%, 7.19% and 35% respectively. The both inorganic and organic solar cells. Besides, the performance of
structures of these solar cells are shown in Fig. 30c, d and g. Apart solar cells was enhanced by the special properties of the GQDs.
from using GQDs as active materials, they have been exploited for Thus, the exploration of novel characteristics of GQDs will continue
other functional layers, such as fluorescent layer of all-weather to make contribution towards the solar cells technology.
solar cells [30,357,358] (Fig. 30h), transporting layer [203]
(Fig. 30j) and buffer layer [320] (Fig. 30m) etc. Organic materials
were also used to form composites with GQDs [318] [359,360] 4.3.2. Energy storage battery
(Fig. 30k) due to the ease of functionalization of the GQDs. Most renewable energy sources, especially those harvested from
Different functionalized types of the GQDs were investigated by nature, require storage via battery, thus it is important to develop
Kim and co-workers [317] (refer to Fig. 30i). Their findings showed supercapacitor battery technology that exhibit high efficiency,
that enhanced optical absorptivity by rich functional groups in long-term cycling life, low weight, high energy density, and long-
GQDs increased short-circuit current, while the improved con- term stability to deal with the energy demand. The excellent
ductivity of reduced GQDs led to an increase of fill factors and properties of GQDs, such as large surface area and ease of func-
power conversion efficiency of up to 7.6%. The merit of organic solar tionalization, provide many advantages for energy storage appli-
cells is its flexibility, thus related research were studied by Shin and cations. As shown in Fig. 31a, the environmentally friendly and high
co-workers [319]. They have found that the GQDs enhanced the performance battery is composed of GQDs and the GQDs play vital
bending flexibility of the organic solar cells, as shown in Fig. 30l. role in the enhancement of battery performances.
Fig. 31. Diagrams and performances of the different batteries with GQDs. (a) Schematic of battery based on GQDs; (b) Diagram of the GF supported GQD-anchored VO2 arrays
electrode.
Li ion and Na ion batteries have been widely investigated due to and co-workers [50] coated both carbon black and GQDs on sodium
their high capacity, long cycle life and low cost. However, GQDs can thiosulfate (Fig. 31e and f) and investigated their characteristics, as
be used as transporting materials to enhance the electrical prop- well as demonstrated an excellent performance on discharge ca-
erties of the battery [361] by introducing them into the electrolytes, pacity of ~1000 mAhg1 even after 100 cycles. They discussed the
as shown in Fig. 31b. In Li ion battery, TiO2 has frequently been used structure of the cathode has a significant impact on the irreversible
as anodes. Wei and co-workers [362] fabricated hierarchical TiO2 loss of high-order polysul-fides (HOPSs) during repeated battery
imbedded with GQDs (Fig. 31c), which were then applied to Li ion operations, as shown in Fig. 31i. Furthermore, Teng et al. [364]
battery, and they reported a high specific capacity and excellent demonstrated that GQDs can enhance the Li ion mobility in a gel
rate capability (160.1 mAhg1 at 10 C after 500 cycles). In addition, polymer electrolyte (GPE) for Li ion batteries (LIBs) (delivering
Li [363] at el synthesized GQDs composites with Si nanoparticles, as discharge capacity of 155 mAhg1) and the proposed mechanism of
shown in Fig. 31d. They reported that the GQDs coated surface the enhancement is represented in Fig. 31g and h. Another exper-
resulted in an improved with bicontinuous electron and Li/Na ion iment that can clearly account for the important role of GQDs in
transfer channels [361]; (c) Schematic illustration of the electro- enhancing the performance of Li ion battery (having specific ca-
chemical reaction process of TiO2/GQDs [362]; (d) The process for pacity of 780 mAhg1) was performed by Fan and co-workers [365].
synthesis of GQDs/Si nanoparticles [363]; (e) and (f) show the The preparation process of their electrodes is shown in Fig. 31j. The
structure and magnified structure of GQDs-sodium thiosulfate/ plot, shown in Fig. 31k, reveals the different battery performances
carbon black (GQDs-S/CB), respectively [50]; (g) and (h) Conceptual due to the different electrode structures.
illustrations of liquid electrolyte and Gel polymer electrolytes- a As reported, the use of GQDs in batteries has led to improved
polymer framework comprising PAV and incorporated PMMA: performances in the battery. Importantly, such improvement in
Quantum Dots (GPE-PAVM:QD), respectively [364]; (i) Schematic performances using GQDs is very cost-effective. Therefore the
configuration of S/CB (left) and GQDs-S/CB (right) employed as a application of GQDs in battery to provide better energy storage is
cathode in a LieS battery [50]; (j) Schematics of the fabrication practical and commercially viable.
process of CuO-based nanowire electrodes [365]; (k) Rate perfor-
mance with coulombic efficiency of CuO, Cu, and GQDs (CCG) and 4.3.3. Fuel cell
CuO, Cu nanowires (CC) anodes [365]. electrical conductivity as Fuel cell can generate electricity through an electrochemical
well as effectively prevented (the capacity remained at reaction of hydrogen fuel with oxygen. Unlike battery, fuel cell can
3068 mAhg1 after 100 cycles at 100 mAg1) the direct contact of provide a continuous supply of electricity as long as there is a
silicon surface with the electrolyte molecules. Interestingly, Park constant source of fuel and oxygen (usually from air) to sustain the
chemical reaction. Such energy technology is sustainable and [6] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem.
Soc. 80 (1958) 1339.
environmentally friendly. There are different types of fuel cell
[7] H.P. Boehm, A. Clauss, G.O. Fischer, U. Hofmann, Das adsorptionsverhalten
[366e368] but they all consist of an anode and a cathode, which are sehr dünner Kohlenstoff-Folien, Z. Anorg. Allg. Chem. 316 (1962)
essential components of the fuel cell. In the past, the electrode 119e127.
materials were mainly made of precious metals, such as Pd, Pt, Ag [8] D. DiVincenzo, E. Mele, Self-consistent effective-mass theory for intralayer
screening in graphite intercalation compounds, Phys. Rev. B 29 (1984)
and Au etc, hence leading to expensive fuel cell. Recent studies have 1685e1694.
demonstrated the use of functionalized GQDs as fuel cell electrodes [9] H.W. Kroto, J.R. Heath, S.C. O'Brien, R.F. Curl, R.E. Smalley, C60: buckmin-
[369,370]. Inner charge transfer of the functionalized GQDs has sterfullerene, Nature 318 (1985) 162e163.
[10] S. Mouras, A. Hamm, D. Djurado, J.-C. Cousseins, Synthesis of first stage
resulted in the enhancement of the catalytic activity and stability. graphite intercalation compounds with fluorides, Rev. Chim. Miner. 24
Since then, there has been an increase in research activities to (1987) 151.
exploit functionalized GQDs as cathode materials for fuel cell. [11] S. Lijima, Helical microtubules of graphitic carbon, Nature 354 (1991) 56e58.
[12] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos,
I.V. Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
5. Conclusions Science 306 (2004) 666e669.
[13] L.A. Ponomarenko, F. Schedin, M.I. Katsnelson, R. Yang, E.W. Hill,
K.S. Novoselov, A.K. Geim, Chaotic dirac billiard in graphene quantum dots,
In this review, the history of the GQDs is introduced. Most of the Science 320 (2008) 356e358.
work performed so far indicates that the applications of GQDs are [14] X.Y. Xu, R. Ray, Y.L. Gu, H.J. Ploehn, L. Gearheart, K. Raker, W.A. Scrivens,
Electrophoretic analysis and purification of fluorescent single-walled carbon
still at the early stage of development and have been progressing nanotube fragments, J. Am. Chem. Soc. 126 (2004) 12736e12737.
rapidly. Numerous methods in fabricating the GQDs have been [15] D. Wang, J.-F. Chen, L. Dai, Recent Advances in graphene quantum dots for
reviewed. The different unique properties of the GQDs have been fluorescence bioimaging from cells through tissues to animals, Part. Part.
Syst. Char 5 (2015) 515e523.
discussed. This included various functionalization routes of the [16] D. Pan, J. Zhang, Z. Li, M. Wu, Hydrothermal route for cutting graphene
GQDs to optimize or enhance its properties, such as water solubi- sheets into blue-Luminescent graphene quantum dots, Adv. Mater. 6 (2010)
lity, optical absorption and conductivity etc. Since the discovery of 734e738.
[17] Y. Zhao, C.G. Hu, Y. Hu, H.H. Cheng, G.Q. Shi, L.T. Qu, A versatile, ultralight,
graphene, limited progress on the application of graphene has been
nitrogen-doped graphene framework, Angew. Chem. Int. Ed. 51 (2012)
achieved. It was understood that this is due to some practical 11371e11375.
problems of graphene, such as zero band gap and low absorptivity [18] X. Yan, X. Cui, L.-S. Li, Synthesis of large, stable colloidal graphene quantum
and so forth. The development of GQDs has therefore become an dots with tunable Size, J. Am. Chem. Soc. 17 (2010) 5944e5945.
[19] S. Kim, S.W. Hwang, M.-K. Kim, D.Y. Shin, D.H. Shin, C.O. Kim, S.B. Yang,
important catalyst for the application of graphene. Undoubtedly, J.H. Park, E. Hwang, S.-H. Choi, G. Ko, S. Sim, C. Sone, H.J. Choi, S. Bae,
this has led to significant research efforts in GQDs. As demonstrated B.H. Hong, Anomalous behaviors of visible luminescence from graphene
by previous work, GQDs are becoming imperative functional ma- quantum dots: interplay between size and shape, ACS Nano 9 (2012)
8203e8208.
terials that can find applications in medical, optical and energy- [20] Y. Dong, H. Pang, S. Ren, C. Chen, Y. Chi, T. Yu, Etching single-wall carbon
related fields. However, understanding of the mechanism in some nanotubes into green and yellow single-layer graphene quantum dots,
of the GQDs applications remains unclear and requires further in- Carbon 64 (2013) 245e251.
[21] J. Peng, W. Gao, B.K. Gupta, Z. Liu, R. Romero-Aburto, L. Ge, L. Song,
vestigations. Nevertheless, this area of research has received much L.B. Alemany, X. Zhan, G. Gao, S.A. Vithayathil, B.A. Kaipparettu, A.A. Marti,
attention by researchers due to the enormous benefits of the GQDs T. Hayashi, J.-J. Zhu, P.M. Ajayan, Graphene quantum dots derived from
can bring in the different applications. carbon fibers, Nano Lett. 2 (2012) 844e849.
[22] Y. Dong, C. Chen, X. Zheng, L. Gao, Z. Cui, H. Yang, C. Guo, Y. Chi, C.M. Li, One-
In conclusion, this review has provided the developments, step and high yield simultaneous preparation of single- and multi-layer
fabrication methods, different functionalization routes and appli- graphene quantum dots from CX-72 carbon black, J. Mater. Chem. 18
cations of the GQDs with detailed discussions in those contexts. It (2012) 8764.
[23] Y. Sun, S. Wang, C. Li, P. Luo, L. Tao, Y. Wei, G. Shi, Large scale preparation of
also suggested the future direction for the development of GQDs.
graphene quantum dots from graphite with tunable fluorescence properties,
Phys. Chem. Chem. Phys. 24 (2013) 9907.
[24] R.Q. Ye, C.S. Xiang, J. Lin, Z.W. Peng, K.W. Huang, Z. Yan, N.P. Cook,
Acknowledgements E.L.G. Samuel, C.C. Hwang, G.D. Ruan, G. Ceriotti, A.R.O. Raji, A.A. Marti,
J.M. Tour, Coal as an abundant source of graphene quantum dots, Nat.
This work was supported by National Natural Science Founda- Commun. 4 (2013) 2943.
[25] K. Habiba, V.I. Makarov, J. Avalos, M.J.F. Guinel, B.R. Weiner, G. Morell,
tion of China (Grant Nos. 61106098, 51201150, and 11374250), the
Luminescent graphene quantum dots fabricated by pulsed laser synthesis,
Key Project of Applied Basic Research of Yunnan Province, China Carbon 64 (2013) 341e350.
(Grant No. 2012FA003), PolyU grant (1-ZVGH) and the Research [26] R. Liu, D. Wu, X. Feng, K. Müllen, Bottom-up fabrication of photoluminescent
Grants Council (RGC) of Hong Kong (Project Nos. PolyU 153030/15P graphene quantum dots with uniform morphology, J. Am. Chem. Soc. 39
(2011) 15221e15223.
and PolyU 153271/16P). [27] L. Tang, R. Ji, X. Li, G. Bai, C.P. Liu, J. Hao, J. Lin, H. Jiang, K.S. Teng, Z. Yang,
S.P. Lau, Deep ultraviolet to near-infrared emission and photoresponse in
layered N-doped graphene quantum dots, ACS Nano 6 (2014) 6312e6320.
Appendix A. Supplementary data [28] J. Lu, P.S.E. Yeo, C.K. Gan, P. Wu, K.P. Loh, Transforming C-60 molecules into
graphene quantum dots, Nat. Nanotechnol. 4 (2011) 247e252.
Supplementary data to this article can be found online at [29] S.Y. Lim, W. Shen, Z. Gao, Carbon quantum dots and their applications, Chem.
Soc. Rev. 44 (2015) 362e381.
https://doi.org/10.1016/j.mtchem.2018.09.007. [30] Q. Tang, W. Zhu, B. He, P. Yang, Rapid conversion from carbohydrates to
large-scale carbon quantum dots for all-weather solar cells, ACS Nano 11
(2017) 1540e1547.
References [31] Y. Li, Y. Hu, Y. Zhao, G. Shi, L. Deng, Y. Hou, L. Qu, An Electrochemical avenue
to green-luminescent graphene quantum dots as potential electron-
[1] B.C. Brodie, On the atomic weight of graphite, Phil. Trans. Roy. Soc. Lond. 149 acceptors for photovoltaics, Adv. Mater. 6 (2011) 776e780.
(1859) 249e259. [32] M.-L. Tsai, W.-R. Wei, L. Tang, H.-C. Chang, S.-H. Tai, P.-K. Yang, S.P. Lau, L.-
[2] V. Kohlschütter, P. Haenni, Zur Kenntnis des Graphitischen Kohlenstoffs und J. Chen, J.-H. He, Si Hybrid solar cells with 13% efficiency via concurrent
der Graphitsa €ure, Z. Anorg. Allg. Chem. 105 (1919) 121e144. improvement in optical and electrical properties by employing graphene
[3] J.D. Bernal, The structure of graphite, Proc. R. Soc. Lond. Ser. A Contain. Pap. quantum dots, ACS Nano 1 (2015) 815e821.
Math. Phys. Character 106 (1924) 749e773. [33] M.-L. Tsai, W.-C. Tu, L. Tang, T.-C. Wei, W.-R. Wei, S.P. Lau, L.-J. Chen, J.-H. He,
[4] P.R. Wallace, The band theory of graphite, Phys. Rev. 71 (1947) 622e634. Efficiency enhancement of silicon heterojunction solar cells via photon
[5] G. Ruess, F. Vogt, Ho € chstlamellarer Kohlenstoff aus Graphitoxyhydroxyd, management using graphene quantum dot as downconverters, Nano Lett. 1
Monatsh. Chem. 78 (1948) 222e242. (2015) 309e313.
[34] J. Ryu, J.W. Lee, H. Yu, J. Yun, K. Lee, J. Lee, D. Hwang, J. Kang, S.K. Kim, J. Jang, multifunctional platform for controlled drug delivery, magnetic hyperther-
Correction: size effects of a graphene quantum dot modified-blocking TiO2 mia, and photothermal yherapy, Small 2 (2017) 1602225.
layer for efficient planar perovskite solar cells, J. Mater. Chem. A 34 (2017) [59] M. Arvand, S. Hemmati, Analytical methodology for the electro-catalytic
18276. determination of estradiol and progesterone based on graphene quantum
[35] H. Tetsuka, A. Nagoya, S.-I. Tamura, Graphene/nitrogen-functionalized gra- dots and poly(sulfosalicylic acid) co-modified electrode, Talanta 174 (2017)
phene quantum dot hybrid broadband photodetectors with a buffer layer of 243e255.
boron nitride nanosheets, Nanoscale 47 (2016) 19677e19683. [60] L. Li, G. Wu, G. Yang, J. Peng, J. Zhao, J.-J. Zhu, Focusing on luminescent
[36] G. Haider, P. Roy, C.-W. Chiang, W.-C. Tan, Y.-R. Liou, H.-T. Chang, C.-T. Liang, graphene quantum dots: current status and future perspectives, Nanoscale 5
W.-H. Shih, Y.-F. Chen, Electrical-polarization-induced ultrahigh responsivity (2013) 4015e4039.
photodetectors based on graphene and graphene quantum dots, Adv. Funct. [61] L. Tian, D. Ghosh, W. Chen, S. Pradhan, X. Chang, S. Chen, Nanosized carbon
Mater. 4 (2016) 620e628. particles from natural gas soot, Chem. Mater. 13 (2009) 2803e2809.
[37] T. Yu, F. Wang, Y. Xu, L. Ma, X. Pi, D. Yang, Graphene coupled with silicon [62] G. Eda, Y.-Y. Lin, C. Mattevi, H. Yamaguchi, H.-A. Chen, I.-S. Chen, C.-W. Chen,
quantum dots for high-performance bulk-silicon-based Schottky-junction M. Chhowalla, Blue photoluminescence from chemically derived graphene
photodetectors, Adv. Mater. 24 (2016) 4912e4919. oxide, Adv. Mater. 4 (2010) 505e509.
[38] C.-W. Chiang, G. Haider, W.-C. Tan, Y.-R. Liou, Y.-C. Lai, R. Ravindranath, H.- [63] L. Tang, R. Ji, X. Li, K.S. Teng, S.P. Lau, Size-dependent structural and optical
T. Chang, Y.-F. Chen, Highly stretchable and sensitive photodetectors based characteristics of glucose-derived graphene quantum dots, Part. Part. Syst.
on hybrid graphene and graphene quantum dots, ACS Appl. Mater. Interfaces Char. 6 (2013) 523e531.
1 (2016) 466e471. [64] S.K. Das, C.M. Luk, W.E. Martin, L. Tang, D.Y. Kim, S.P. Lau, C.I. Richards, Size
[39] Q. Zhang, J. Jie, S. Diao, Z. Shao, Q. Zhang, L. Wang, W. Deng, W. Hu, H. Xia, and dopant dependent single particle fluorescence properties of graphene
X. Yuan, S.-T. Lee, Solution-processed graphene quantum dot deep-UV quantum dots, J. Phys. Chem. C 31 (2015) 17988e17994.
photodetectors, ACS Nano 2 (2015) 1561e1570. [65] S. Zhu, J. Zhang, X. Liu, B. Li, X. Wang, S. Tang, Q. Meng, Y. Li, C. Shi, R. Hu,
[40] G. Konstantatos, M. Badioli, L. Gaudreau, J. Osmond, M. Bernechea, B. Yang, Graphene quantum dots with controllable surface oxidation, tunable
F.P.G. Arquer, F. Gatti, F.H.L. Koppens, Hybrid graphene-quantum dot pho- fluorescence and up-conversion emission, RSC Adv. 2 (2012) 2717e2720.
totransistors with ultrahigh gain, Nat. Nanotechnol. 6 (2012) 363e368. [66] S. Zhu, J. Zhang, S. Tang, C. Qiao, L. Wang, H. Wang, X. Liu, B. Li, Y. Li, W. Yu,
[41] S. Zhu, J. Zhang, C. Qiao, S. Tang, Y. Li, W. Yuan, B. Li, L. Tian, F. Liu, R. Hu, X. Wang, H. Sun, B. Yang, Surface chemistry routes to modulate the photo-
H. Gao, H. Wei, H. Zhang, H. Sun, B. Yang, Strongly green-photoluminescent luminescence of graphene quantum dots: from fluorescence mechanism to
graphene quantum dots for bioimaging applications, Chem. Commun. 24 up-conversion bioimaging applications, Adv. Funct. Mater. 22 (2012)
(2011) 6858. 4732e4740.
[42] H. Shen, L. Zhang, M. Liu, Z. Zhang, Biomedical applications of graphene, [67] L.-L. Feng, Y.-X. Wu, D.-L. Zhang, X.-X. Hu, J. Zhang, P. Wang, Z.-L. Song, X.-
Theranostics 3 (2012) 283e294. B. Zhang, W. Tan, Near infrared graphene quantum dots-based two-photon
[43] P.-C. Wu, J.-Y. Wang, W.-L. Wang, C.-Y. Chang, C.-H. Huang, K.-L. Yang, J.- nanoprobe for direct bioimaging of endogenous ascorbic acid in living cells,
C. Chang, C.-L.L. Hsu, S.-Y. Chen, T.-M. Chou, W.-S. Kuo, Efficient two-photon Anal. Chem. 7 (2017) 4077e4084.
luminescence for cellular imaging using biocompatible nitrogen-doped [68] T. Gao, X. Wang, L.-Y. Yang, H. He, X.-X. Ba, J. Zhao, F.-L. Jiang, Y. Liu, Red,
graphene quantum dots conjugated with polymers, Nanoscale 1 (2018) yellow, and blue luminescence by graphene quantum dots: syntheses,
109e117. mechanism, and cellular imaging, ACS Appl. Mater. Interfaces 29 (2017)
[44] K. Li, W. Liu, Y. Ni, D. Li, D. Lin, Z. Su, G. Wei, Technical synthesis and 24846e24856.
biomedical applications of graphene quantum dots, J. Mater. Chem. B 5 [69] Y. Dong, J. Shao, C. Chen, H. Li, R. Wang, Y. Chi, X. Lin, G. Chen, Blue lumi-
(2017) 4811e4826. nescent graphene quantum dots and graphene oxide prepared by tuning the
[45] Q. Xu, Q. Zhou, Z. Hua, Q. Xue, C. Zhang, X. Wang, D. Pan, M. Xiao, Single- carbonization degree of citric acid, Carbon 12 (2012) 4738e4743.
particle spectroscopic measurements of fluorescent graphene quantum dots, [70] J. Gu, X. Zhang, A. Pang, J. Yang, Facile synthesis and photoluminescence
ACS Nano 12 (2013) 10654e10661. characteristics of blue-emitting nitrogen-doped graphene quantum dots,
[46] P. Nuengmatcha, P. Sricharoen, N. Limchoowong, R. Mahachai, S. Chanthai, Nanotechnology 27 (16) (2016) 165704.
The use of S2O2- 8 and H2O2 as novel specific masking agents for highly se- [71] A.B. Ganganboina, A.D. Chowdhury, R.-A. Doong, N-Doped graphene quan-
lective “turn-on” fluorescent switching recognition of CN- and I- based on tum dots-decorated V2O5 nanosheet for fluorescence turn offeon detection
þ
Hg2 egraphene quantum dots, RSC Adv. 8 (2018) 1407e1417. of cysteine, ACS Appl. Mater. Interfaces 1 (2017) 614e624.
[47] M. Mehrzad-Samarin, F. Faridbod, A.S. Dezfuli, M.R. Ganjali, A novel metro- [72] L. Wang, Y. Wang, T. Xu, H. Liao, C. Yao, Y. Liu, Z. Li, Z. Chen, D. Pan, L. Sun,
nidazole fluorescent nanosensor based on graphene quantum dots M. Wu, Gram-scale synthesis of single-crystalline graphene quantum dots
embedded silica molecularly imprinted polymer, Biosens. Bioelectron. 92 with superior optical properties, Nat. Commun. 5 (2014) 5357.
(2017) 618e623. [73] Z. Guo, B. Cai, Q. Cao, Y. Su, M. Li, J. Hu, Z. Yang, Y. Zhang, Facile synthesis of
[48] L. Zhou, F. Wu, J. Yu, Q. Deng, F. Zhang, G. Wang, Titanium carbide (Ti3C2Tx) amine-functionalized graphene quantum dots with highly pH-sensitive
MXene: a novel precursor to amphiphilic carbide-derived graphene quan- photoluminescence, Fullerenes, Nanotub. Carbon Nanostruct. 25 (2017)
tum dots for fluorescent ink, light-emitting composite and bioimaging, 704e709.
Carbon 118 (2017) 50e57. [74] X. Wu, F. Tian, W. Wang, J. Chen, M. Wu, J.X. Zhao, Fabrication of highly
[49] S.H. Song, M.-H. Jang, J. Chung, S.H. Jin, B.H. Kim, S.-H. Hur, S. Yoo, Y.-H. Cho, fluorescent graphene quantum dots using L-glutamic acid for in vitro/in vivo
S. Jeon, Highly efficient light-emitting diode of graphene quantum dots imaging and sensing, J. Mater. Chem. C 31 (2013) 4676e4684.
fabricated from graphite intercalation compounds, Adv. Opt. Mater. 11 [75] J. Gu, M.J. Hu, Q.Q. Guo, Z.F. Ding, X.L. Sun, J. Yang, High-yield synthesis of
(2014) 1016e1023. graphene quantum dots with strong green photoluminescence, RSC Adv. 4
[50] J. Park, J. Moon, C. Kim, J.H. Kang, E. Lim, J. Park, K.J. Lee, S.-H. Yu, J.-H. Seo, (2014) 50141e50144.
J. Lee, J. Heo, N. Tanaka, S.-P. Cho, J. Pyun, J. Cabana, B.H. Hong, Y.-E. Sung, [76] S. Zhuo, M. Shao, S.-T. Lee, Upconversion and downconversion fluorescent
Graphene quantum dots: structural integrity and oxygen functional groups graphene quantum dots: ultrasonic preparation and photocatalysis, ACS
for high sulfur/sulfide utilization in lithium sulfur batteries, NPG Asia Mater. Nano 6 (2012) 1059e1064.
5 (2016) 272. [77] L. Lin, M. Rong, S. Lu, X. Song, Y. Zhong, J. Yan, Y. Wang, X. Chen, Facile
[51] D. Raeyani, S. Shojaei, S. Ahmadi-Kandjani, Optical graphene quantum dots synthesis of highly luminescent nitrogen-doped graphene quantum dots for
gas sensors: theoretical study, Superlattice. Microst. 114 (2018) 321e330. the detection of 2,4,6-trinitrophenol in aqueous solution, Nanoscale 7 (2015)
[52] S. Benitez-Martinez, M. Valcarcel, Graphene quantum dots as sensor for 1872e1878.
phenols in olive oil, Sensor. Actuator. B Chem. 197 (2014) 350e357. [78] Y. Yin, Q. Liu, D. Jiang, X. Du, J. Qian, H. Mao, K. Wang, Atmospheric pressure
[53] J. Qiu, R. Zhang, J. Li, Y. Sang, W. Tang, P.R. Gil, H. Liu, Fluorescent graphene synthesis of nitrogen doped graphene quantum dots for fabrication of BiOBr
quantum dots as traceable, pH-sensitive drug delivery systems, Int. J. nanohybrids with enhanced visible-light photoactivity and photostability,
Nanomed. 10 (2015) 6709e6724. Carbon 96 (2016) 1157e1165.
[54] H. Chen, Z. Wang, S. Zong, P. Chen, D. Zhu, L. Wu, Y. Cui, A graphene quantum [79] Y.-F. Chen, C.-L. Kao, P.-C. Huang, C.-Y. Hsu, C.-H. Kuei, Facile synthesis of
dot-based FRET system for nuclear-targeted and real-time monitoring of multi-responsive functional graphene quantum dots for sensing metal cat-
drug delivery, Nanoscale 7 (2015) 15477e15486. ions, RSC Adv. 6 (2016) 103006e103011.
[55] Z. Wang, J. Xia, C. Zhou, B. Via, Y. Xia, F. Zhang, Y. Li, L. Xia, J. Tang, Synthesis [80] M. Yousaf, H. Huang, P. Li, C. Wang, Y. Yang, Fluorine functionalized graphene
of strongly green-photoluminescent graphene quantum dots for drug Car- quantum dots as inhibitor against hIAPP amyloid aggregation, ACS Chem.
rier, Colloids Surfaces B Biointerfaces 112 (2013) 192e196. Neurosci. 8 (2017) 1368e1377.
[56] J. Dong, K. Wang, L. Sun, B. Sun, M. Yang, H. Chen, Y. Wang, J. Sun, L. Dong, [81] L. Tang, R. Ji, X. Cao, J. Lin, H. Jiang, X. Li, K.S. Teng, C.M. Luk, S. Zeng, J. Hao,
Application of graphene quantum dots for simultaneous fluorescence im- S.P. Lau, Deep ultraviolet photoluminescence of water-soluble self-passiv-
aging and tumor-targeted drug delivery, Sensor. Actuator. B 256 (2017) ated graphene quantum dots, ACS Nano 6 (2012) 5102e5110.
616e623. [82] Z. Huang, Y. Shen, Y. Li, W. Zheng, Y. Xue, C. Qin, B. Zhang, J. Hao, W. Feng,
[57] H. Ding, F. Zhang, C. Zhao, Y. Lv, G. Ma, W. Wei, Z. Tian, Beyond a Carrier: Facile synthesis of analogous graphene quantum dots with sp2 hybridized
graphene quantum dots as a probe for programmatically monitoring anti- carbon atom dominant structures and their photovoltaic application,
cancer drug delivery, release, and response, ACS Appl. Mater. Interfaces 33 Nanoscale 6 (2014) 13043e13052.
(2017) 27396e27401. [83] X. Hou, Y. Li, C. Zhao, Microwave-assisted synthesis of nitrogen-doped multi-
[58] X. Yao, X. Niu, K. Ma, P. Huang, J. Grothe, S. Kaskel, Y. Zhu, Graphene layer graphene quantum dots with oxygen-rich functional groups, Aust. J.
quantum dots-capped magnetic mesoporous silica nanoparticles as a Chem. 3 (2016) 357.
[84] R. Li, Y. Liu, Z. Li, J. Shen, Y. Yang, X. Cui, G. Yang, Bottom-up fabrication of [109] Q. Li, S. Zhang, L. Dai, L.-S. Li, Nitrogen-doped colloidal graphene quantum
single-layered nitrogen-doped graphene quantum dots through intermo- dots and their size-dependent electrocatalytic activity for the oxygen
lecular carbonization arrayed in a 2D plane, Chem. Eur. J. 1 (2016) 272e278. reduction reaction, J. Am. Chem. Soc. 134 (2012) 18932e18935.
[85] S. Gao, L. Tang, J. Xiang, R. Ji, S.K. Lai, S. Yuan, S.P. Lau, Facile preparation of [110] B. Zheng, Y. Chen, P. Li, Z. Wang, B. Cao, F. Qi, J. Liu, Z. Qiu, W. Zhang, Ul-
sulphur-doped graphene quantum dots for ultra-high performance ultravi- trafast ammonia-driven, microwave-assisted synthesis of nitrogen-doped
olet photodetectors, New J. Chem. 18 (2017) 10447e10451. graphene quantum dots and their optical properties, Nnaophotics 6 (2017)
[86] S. Do, W. K, S.-W. Rhee, Soft-template synthesis of nitrogen-doped carbon 259e267.
nanodots: tunable visible-light photoluminescence and phosphor-based [111] X. Deng, J. Sun, S. Yang, H. Shen, W. Zhou, J. Lu, G. Ding, Z. Wang, The
light-emitting diodes, J. Mater. Chem. C 2 (2014) 4221e4226. emission wavelength dependent photoluminescence lifetime of the N-doped
[87] A. Ciesielski, S. Haar, A. Aliprandi, M.E. Garah, G. Tregnago, G.F. Cotella, graphene quantum dots, Appl. Phys. Lett. 107 (2015) 241905.
M.E. Gemayel, F. Richard, H. Sun, F. Cacialli, F. Bonaccorso, P. Samori, [112] M. Fan, C. Zhu, J. Yang, D. Sun, Facile self-assembly N-doped graphene
Modifying thesSize of ultrasound-induced liquid-phase exfoliated graphene: quantum dots/graphene for oxygen reduction reaction, Electrochim. Acta
from nanosheets to nanodots, ACS Nano 10 (2016) 10768e10777. 216 (2016) 102e109.
[88] E. Blanco, G. Blanco, J.M. Gonzalez-Leal, M.C. Barrera, M. Dominguez, [113] Y. Bian, B. He, J. Li, A One-step hydrothermal method of nitrogen-doped
M. Ramirez-del-Solar, Green and fast synthesis of amino-functionalized graphene quantum dots decorated graphene for fabrication of paper-based
graphene quantum dots with deep blue photoluminescence, J. Nanopart. fluorescent composite, BioResources 11 (2016) 6299e6308.
Res. 17 (2015) 214. [114] S.B. Aoun, Nanostructured carbon electrode modified with N-doped gra-
[89] J.P. Guin, S.K. Guin, T. Debnath, H.N. Ghosh, Chemically clean single-step phene quantum dots-chitosan nanocomposite: a sensitive electrochemical
oxido-reductive synthesis of green luminescent graphene quantum dots as dopamine sensor, Roy. Soc. Open Sci. 4 (2017) 171199.
impending electrocatalyst, Carbon 109 (2016) 517e528. [115] S. Kumar, S.K.T. Aziz, O. Girshevitz, G.D. Nessim, One-step synthesis of N-
[90] D.K. Nguyen, T.Y. Kim, Graphene quantum dots produced by exfoliation of doped graphene quantum dots from chitosan as a sole precursor using
intercalated graphite nanoparticles and their application for temperature chemical vapor deposition, J. Phys. Chem. C 122 (2018) 2343e2349.
sensors, Appl. Surf. Sci. 427 (2018) 1152e1557. [116] Y. Deng, L. Tang, C. Feng, G. Zeng, J. Wang, Y. Lu, Y. Liu, J. Yu, S. Chen, Y. Zhou,
[91] S. Maiti, S. Kundu, C.N. Roy, T.K. Das, A. Saha, Synthesis of excitation inde- Construction of plasmonic Ag and nitrogen-doped graphene quantum dots
pendent highly luminescent graphene quantum dots through perchloric acid codecorated ultrathin graphitic carbon nitride nanosheet composites with
oxidation, Langmuir 33 (2017) 14634e14642. enhanced photocatalytic activity: full-spectrum response ability and mech-
[92] M. Li, C. Yu, C. Hu, W. Yang, C. Zhao, S. Wang, M. Zhang, J. Zhao, X. Wang, anism insight, ACS Appl. Mater. Interfaces 9 (2017) 42816e42828.
J. Qiu, Solvothermal conversion of coal into nitrogen-doped carbon dots with [117] J. Ju, R. Zhang, S. He, W. Chen, Nitrogen-doped graphene quantum dots-
singlet oxygen generation and high quantum yield, Chem. Eng. J. 320 (2017) based fluorescent probe for the sensitive turn-on detection of glutathione
570e575. and its cellular imaging, RSC Adv. 4 (2014) 52583e52589.
[93] Z. Luo, G. Qi, K. Chen, M. Zou, L. Yuwen, X. Zhang, W. Huang, L. Wang, Mi- [118] Y. Li, Y. Zhao, H. Cheng, Y. Hu, G. Shi, L. Dai, L. Qu, Nitrogen-doped graphene
crowave-assisted preparation of white fluorescent graphene quantum dots quantum dots with oxygen-rich functional groups, J. Am. Chem. Soc. 134
as a novel phosphor for enhanced white-light-emitting diodes, Adv. Funct. (2012) 15e18.
Mater. 26 (2016) 2739e2744. [119] S. Kundu, B. Malik, D.K. Pattanayak, P. Ragupathy, V.K. Pillai, Role of specific
[94] W. Zuo, L. Tang, J. Xiang, R. Ji, L. Luo, L. Rogee, S.P. Lau, Functionalization of N-containing active sites in interconnected graphene quantum dots for the
graphene quantum dots by fluorine: preparation, properties, application, and enhanced electrocatalytic activity towards oxygen evolution reaction,
their mechanisms, Appl. Phys. Lett. 110 (2017) 221901. Chemisteryselect 2 (2017) 9943e9946.
[95] Y.-W. Shih, G.-W. Tseng, C.-Y. Hsieh, Y.-Y. Li, A. Sakoda, Graphene quantum [120] T.V. Tam, N.B. Trung, H.R. Kim, J.S. Chung, W.M. Choi, One-pot synthesis of N-
dots derived from platelet graphite nanofibers by liquid-phase exfoliation, doped graphene quantum dots as a fluorescent sensing platform for Fe3þ
Acta Mater. 78 (2014) 314e319. ions detection, Sensor. Actuator. B 202 (2014) 568e573.
[96] L. Lu, Y. Zhu, C. Shi, Y.T. Pei, Large-scale synthesis of defects-selective gra- [121] U. Saleem, F.A. Permatasari, F. Iskandar, T. Ogi, K. Okuyama, Y. Darma,
phene quantum dots by ultrasonic assisted liquid-phase exfoliation, Carbon M. Zhao, K.P. Loh, A. Rusydi, P. Coquet, M.D. Birowosuto, H. Wang, Surface
109 (2016) 373e383. plasmon enhanced nitrogen-doped graphene quantum dot emission by
[97] S. Sarkar, D. Gandla, Y. Venkatesh, P.R. Bangal, S. Ghosh, Y. Yang, S. Misra, single bismuth telluride nanoplates, Adv. Opt. Mater. 5 (2017) 1700176.
Graphene quantum dots from graphite by liquid exfoliation showing [122] T. Pillar-Little, D.Y. Kim, Differentiating the impact of nitrogen chemical
excitation-independent emission, fluorescence upconversion and delayed states on optical properties of nitrogen-doped graphene quantum dots, RSC
fluorescence, Phys. Chem. Chem. Phys. 18 (2016) 21278e21287. Adv. 7 (2017) 48263e48267.
[98] M. Xu, W. Zhang, Z. Yang, F. Yu, Y. Ma, N. Hu, D. He, Q. Liang, Y. Su, Y. Zhang, [123] Y. Dai, H. Long, X. Wang, Y. Wang, Q. Gu, W. Jiang, Y. Wang, C. Li, T.H. Zeng,
One-pot liquid-phase exfoliation from graphite to graphene with carbon Y. Sun, J. Zeng, Versatile graphene quantum dots with tunable nitrogen
quantum dots, Nanoscale 7 (2015) 10527e10534. doping, Part. Part. Syst. Char. 31 (2014) 597e604.
[99] J. Zhao, L. Tang, J. Xiang, R. Ji, J. Yuan, J. Zhao, R. Yu, Y. Tai, L. Song, Chlorine [124] W.A. Saidi, Oxygen reduction electrocatalysis using N-doped graphene
doped graphene quantum dots: preparation, properties, and photovoltaic quantum-dots, J. Phys. Chem. Lett. 23 (2013) 4160e4165.
detectors, Appl. Phys. Lett. 105 (2014) 111116. [125] S.R.M. Santiago, Y.A. Wong, T.-N. Lin, C.-H. Chang, C.-T. Yuan, J.-L. Shen, Effect
[100] H. Huang, S. Yang, Q. Li, Y. Yang, G. Wang, X. You, B. Mao, H. Wang, Y. Ma, of nitrogen doping on the photoluminescence intensity of graphene quan-
P. He, Z. Liu, G. Ding, X. Xie, Electrochemical cutting in weak aqueous elec- tum dots, Opt. Lett. 42 (2017) 3642e3645.
trolytes: the strategy for efficient and controllable preparation of graphene [126] N.D. Anh, M.O. Hye, T.D. Ngoc, S. Bang, S.J. Yoon, M.S. Jeong, Highly enhanced
quantum dots, Langmuir 34 (2018) 250e258. photoresponsivity of a monolayer WSe2 photodetector with nitrogen-doped
[101] Y. Yan, H. Li, Q. Wang, H. Mao, W. Kun, Controllable ionic liquid-assisted graphene quantum dots, ACS Appl. Mater. Interfaces 10 (2018)
electrochemical exfoliation of carbon fibers for the green and large-scale 10322e10329.
preparation of functionalized graphene quantum dots endowed with [127] X. Xu, F. Gao, X. Bai, F. Liu, W. Kong, M. Li, Tuning the photoluminescence of
multicolor emission and size tenability, J. Mater. Chem. C 5 (2017) graphene quantum dots by photochemical doping with nitrogen, Materials
6092e6100. 10 (2017) 1328.
[102] T.-F. Yeh, S.-J. Chen, H. Teng, Synergistic effect of oxygen and nitrogen [128] L. Lin, X. Song, Y. Chen, M. Rong, T. Zhao, Y. Jiang, Y. Wang, X. Chen, One-pot
functionalities for graphene-based quantum dots used in photocatalytic H2 synthesis of highly greenish-yellow fluorescent nitrogen-doped graphene
production from water decomposition, Nano Energy 12 (2015) 476e485. quantum dots for pyrophosphate sensing via competitive coordination with
[103] H. Zhu, A. Liu, Y. Xu, F. Shan, A. Li, J. Wang, W. Yang, C. Barrow, J. Liu, Gra- Eu3þ ions, Nanoscale 7 (2015) 15427e15433.
phene quantum dots directly generated from graphite via magnetron sput- [129] Q. Liu, B. Guo, Z. Rao, B. Zhang, J.R. Gong, Strong two-photon-induced fluo-
tering and the application in thin-film transistors, Carbon 88 (2015) rescence from photostable, biocompatible nitrogen-doped graphene quan-
225e232. tum dots for cellular and deep-tissue imaging, Nano Lett. 13 (2013)
[104] X. Hai, Q.-X. Mao, W.-J. Wang, X.-F. Wang, X.-W. Chen, J.-H. Wang, An acid- 2436e2441.
free microwave approach to prepare highly luminescent boron-doped gra- [130] T. Majumder, K. Debnath, S. Dhar, J.J.L. Hmar, S.P. Mondal, Nitrogen-doped
phene quantum dots for cell imaging, J. Mater. Chem. B 3 (2015) 9109e9114. graphene quantum dot-decorated ZnO nanorods for improved electro-
[105] Z. Fan, Y. Li, X. Li, L. Fan, S. Zhou, D. Fang, S. Yang, Surrounding media sen- chemical solar energy conversion, Energy Technol. 4 (2016) 1e10.
sitive photoluminescence of boron-doped graphene quantum dots for highly [131] B. Zhang, C. Xiao, Y. Xiang, B. Dong, S. Ding, Y. Tang, Nitrogen-doped gra-
fluorescent dyed crystals, chemical sensing and bioimaging, Carbon 70 phene quantum dots anchored on thermally reduced graphene oxide as an
(2014) 149e156. electrocatalyst for the oxygen reduction reaction, ChemElectroChem 3
[106] T.V. Tam, S.G. Kang, K.F. Babu, E.-S. Oh, S.G. Lee, W.M. Choi, Synthesis of B- (2016) 864e870.
doped graphene quantum dots as a metal-free electrocatalyst for the oxygen [132] B.J. Moon, D. Jang, Y. Yi, H. Lee, S.J. Kim, Y. Oh, S.H. Lee, M. Park, S. Lee, S. Bae,
reduction reaction, J. Mater. Chem. A 5 (2017) 10537e10543. Multi-functional nitrogen self-doped graphene quantum dots for boosting
[107] F. Qian, X. Li, L. Tang, S.K. Lai, C. Lu, S.P. Lau, Potassium doping: tuning the the photovoltaic performance of BHJ solar cells, Nano Energy 34 (2017)
optical properties of graphene quantum dots, AIP Adv. 6 (2016) 075116. 36e46.
[108] N.-U. Ain, M.O. Eriksson, S. Schmidt, M. Asghar, P.-C. Lin, P.O. Holtz, [133] L. Sun, Y. Luo, M. Li, G. Hu, Y. Xu, T. Tang, J. Wen, X. Li, L. Wang, Role of
M. Syv€ aj€
arvi, G.R. Yazdi, Tuning the emission energy of chemically doped pyridinic-N for nitrogen-doped graphene quantum dots in oxygen reaction
graphene quantum dots, Nanomaterials (Basel) 6 (2016) 198. reduction, J. Colloid Interface Sci. 508 (2017) 154e158.
[134] L. Li, L. Li, C. Wang, K. Liu, R. Zhu, H. Qiang, Y. Lin, Synthesis of nitrogen- quantum dots: unraveling the origin of selectivity in the oxygen reduction
doped and amino acid-functionalized graphene quantum dots from reaction, ACS Catal. 5 (2015) 129e144.
glycine, and their application to the fluorometric determination of ferric ion, [160] R.S. Li, B. Yuan, J.H. Liu, M.L. Liu, P.F. Gao, Y.F. Li, M. Li, C.Z. Huan, Boron and
Microchim. Acta 182 (2015) 763e770. nitrogen co-doped single-layered graphene quantum dots: a high-affinity
[135] C. Zhu, S. Yang, G. Wang, R. Mo, P. He, J. Sun, Z. Di, N. Yuan, J. Ding, G. Ding, platform for visualizing the dynamic invasion of HIV DNA into living cells
X. Xie, Negative induction effect of graphite N on graphene quantum dots: through fluorescence resonance energy transfer, J. Mater. Chem. B 5 (2017)
tunable band gap photoluminescence, J. Mater. Chem. C 3 (2015) 8719e8724.
8810e8816. [161] R. Liu, J. Zhao, Z. Huang, L. Zhang, M. Zou, B. Shi, S. Zhao, Nitrogen and
[136] J. Sun, S. Yang, Z. Wang, H. Shen, T. Xu, L. Sun, H. Li, W. Chen, X. Jiang, G. Ding, phosphorus co-doped graphene quantum dots as a nano-sensor for highly
Z. Kang, X. Xie, M. Jiang, Ultra-high quantum yield of graphene quantum sensitive and selective imaging detection of nitrite in live cell, Sensor.
dots: aromatic-nitrogen doping and photoluminescence mechanism, Part. Actuator. B Chem. 240 (2017) 604e612.
Part. Syst. Char. 32 (2015) 434e440. [162] J.J.L. Hmar, T. Majumder, S. Dhar, S.P. Mondal, Sulfur and Nitrogen Co-
[137] W. Zhu, H. Song, L. Zhang, Y. Weng, Y. Su, Y. Lv, Fabrication of fluorescent doped graphene quantum dot decorated ZnO nanorod/polymer hybrid
nitrogen-rich graphene quantum dots by tin (IV) catalytic carbonization of flexible device for photosensing applications, Thin Solid Films 612 (2016)
ethanolamine, RSC Adv. 5 (2015) 60085e60089. 274e283.
[138] Z.L. Wu, M.X. Gao, T.T. Wang, X.Y. Wan, L.L. Zheng, C.Z. Huang, A general [163] H. Xie, C. Hou, H. Wang, Q. Zhang, Y. Li, S, N co-doped graphene quantum
quantitative pH sensor developed with dicyandiamide N-doped high quan- dot/TiO2 composites for efficient photocatalytic hydrogen generation,
tum yield graphene quantum dots, Nanoscale 6 (2014) 3868e3874. Nanoscale Res. Lett. 12 (2017) 400.
[139] M. Li, W. Wu, W. Ren, H.-M. Cheng, N. Tang, W. Zhong, Y. Du, Synthesis and [164] H. Tian, K. Shen, X. Hu, L. Qiao, W. Zheng, N, S co-doped graphene quantum
upconversion luminescence of N-doped graphene quantum dots, Appl. Phys. dots-graphene-TiO2 nanotubes composite with enhanced photocatalytic
Lett. 101 (2012) 103107. activity, J. Alloy. Comp. 691 (2017) 369e377.
[140] J. Qian, C. Shen, J. Yan, F. Xi, X. Dong, J. Liu, Tailoring the electronic properties [165] M. Mahyari, Y. Bide, J.N. Gavgani, Iron(III) porphyrin supported on S and N
of graphene quantum dots by P doping and their enhanced performance in co-doped graphene quantum dot as an efficient photocatalyst for aerobic
metal-free composite photocatalyst, J. Phys. Chem. C 122 (2018) 349e358. oxidation of alcohols under visible light irradiation, Appl. Catal. Gen. 517
[141] Y. Li, S. Li, Y. Wang, J. Wang, H. Liu, X. Liu, L. Wang, X. Liu, W. Xue, N. Ma, (2016) 100e109.
Electrochemical synthesis of phosphorus-doped graphene quantum dots for [166] T.K. Mondal, D. Dinda, S.K. Saha, Nitrogen, sulphur co-doped graphene
free radical scavenging, Phys. Chem. Chem. Phys. 19 (2017) 11631e11638. quantum dot: an excellent sensor for nitroexplosives, Sensor. Actuator. B 207
[142] D. Qu, M. Zheng, J. Li, Z. Xie, Z. Sun, Tailoring color emissions from N-doped (2018) 586e593.
graphene quantum dots for bioimaging applications, Light Sci. Appl. 4 (2015) [167] Y. Dong, H. Pang, H.B. Yang, C. Guo, J. Shao, Y. Chi, C.M. Li, T. Yu, Carbon-
364. based dots co-doped with nitrogen and sulfur for high quantum yield and
[143] Z. Liu, Y. Gong, Z. Fan, Cysteine detection using a high-fluorescence sensor excitation-independent emission, Angew. Chem. Int. Ed. 52 (2013)
based on a nitrogen-doped graphene quantum dotemercury (II) system, 7800e7804.
J. Lumin. 175 (2016) 129e134. [168] Z. Luo, D. Yang, G. Qi, J. Shang, H. Yang, Y. Wang, L. Yuwen, T. Yu, W. Huang,
[144] Y. Zhang, X. Su, Q. Ma, Novel formaldehyde sensor based on hydrogen L. Wang, Microwave-assisted solvothermal preparation of nitrogen and
peroxide/melamine modulated photoluminescence of nitrogen-doped gra- sulfur co-doped reduced graphene oxide and graphene quantum dots hy-
phene quantum dots, J. Wuhan Univ. Technol. 32 (2017) 1481e1486. brids for highly efficient oxygen reduction, J. Mater. Chem. A 2 (2014)
[145] S. Kim, D.H. Shin, C.O. Kim, S.S. Kang, K.W. Lee, J. Kim, S.-H. Choi, S.W. Hwang, 20605e20611.
Effect of nitrogen doping on the structural and the optical variations of [169] N.T.N. Anh, A.D. Chowdhury, R.-A. Doong, Highly sensitive and selective
graphene quantum dots by using hydrazine treatment, J. Kor. Phys. Soc. 67 detection of mercury ions using N, S-codoped graphene quantum dots and
(2015) 746e751. its paper strip based sensing application in wastewater, Sensor. Actuator. B
[146] D. Qu, M. Zheng, L. Zhang, H. Zhao, Z. Xie, X. Jing, R.E. Haddad, H. F, Z. Sun, 252 (2017) 1169e1178.
Formation mechanism and optimization of highly luminescent N-doped [170] M. Wang, Y. Sun, M. Yang, CdS QDs amplified electrochemiluminescence of
graphene quantum dots, Sci. Rep. 4 (2014) 5294. N,S co-doped graphene quantum dots and its application for Pb(II) deter-
[147] X. Li, S.P. Lau, L. Tang, R. Ji, P. Yang, Sulphur doping: a facile approach to tune mination, Chem. Lett. 47 (2018) 44e47.
the electronic structure and optical properties of graphene quantum dots, [171] O.J. Achadu, J. Britton, T. Nyokong, Graphene quantum dots functionalized
Nanoscale 6 (2014) 5323e5328. with 4-amino-2, 2, 6, 6-tetramethylpiperidine-N-oxide as fluorescence
[148] K. Jin, H. Gao, L. Lai, Y. Pang, S. Zheng, Y. Niu, X. Li, Preparation of highly “turn-on” nanosensors, J. Fluoresc. 26 (2016) 2199e2212.
fluorescent sulfur doped graphene quantum dots for live cell imaging, [172] M. Dinari, M.M. Momeni, M. Goudarzirad, Nanocomposite films of polyani-
J. Lumin. 197 (2018) 147e152. line/graphene quantum dots and its supercapacitor properties, Surf. Eng. 32
[149] G. Wang, G. Guo, D. Chen, Z. Liu, X. Zheng, A. Xu, S. Yang, G. Ding, Facile and (2016) 535e540.
highly effective synthesis of controllable lattice sulfur-doped graphene [173] S. Kundu, R.M. Yadav, T.N. Narayanan, M.V. Shelke, R. Vajtai, P.M. Ajayan,
quantum dots via hydrothermal treatment of durian, ACS Appl. Mater. In- V.K. Pillai, Synthesis of N, F and S co-doped graphene quantum dots,
terfaces 10 (2018) 5750e5759. Nanoscale 7 (2015) 11515e11519.
[150] S. Yang, J. Sun, P. He, X. Deng, Z. Wang, C. Hu, G. Ding, X. Xie, Selenium doped [174] S. Kundu, P. Sarojinijeeva, R. Karthick, G. Anantharaj, G. Saritha, R. Bera,
graphene quantum dots as an ultrasensitive redox fluorescent switch, Chem. S. Anandan, A. Patra, P. Ragupathy, M. Selvaraj, D. Jeyakumar, K.V. Pillai,
Mater. 27 (2015) 2004e2011. Enhancing the efficiency of DSSCs by the modification of TiO2 photoanodes
[151] X. Li, S.P. Lau, L. Tang, R. Ji, P. Yang, Multicolour light emission from chlorine- using N, F and S, co-doped graphene quantum dots, Electrochim. Acta 242
doped graphene quantum dots, J. Mater. Chem. C 1 (2013) 7308e7313. (2017) 337e343.
[152] D. Qu, Z. Sun, M. Zheng, J. Li, Y. Zhang, G. Zhang, H. Zhao, X. Liu, Z. Xie, Three [175] M.A. Sk, A. Ananthanarayanan, L. Huang, K.H. Lim, P. Chen, Revealing the
colors emission from S,N co-doped graphene quantum dots for visible light tunable photoluminescence properties of graphene quantum dots, J. Mater.
H2 production and bioimaging, Adv. Opt. Mater. 3 (2015) 360e367. Chem. C 2 (2014) 6954e6960.
[153] C. Shen, S. Ge, Y. Pang, F. Xi, J. Liu, X. Dong, P. Chen, Facile and scalable [176] R. Ye, Z. Peng, A. Metzger, J. Lin, J.K. Mann, K. Huang, C. Xiang, X. Fan,
preparation of highly luminescent N,S co-doped graphene quantum dots and E.L.G. Samuel, L.B. Alemany, A.A. Marti, J.M. Tour, Bandgap engineering of
their application for parallel detection of multiple metal ions, J. Mater. Chem. coal-derived graphene quantum dots, ACS Appl. Mater. Interfaces 7 (2015)
B 5 (2017) 6593e6600. 7041e7048.
[154] S.-J. Jeon, T.-W. Kang, J.-M. Ju, M.-J. Kim, J.H. Park, F. Raza, J. Han, H.-R. Lee, J.- [177] B. Mandal, S. Sarkar, P. Sarkar, Exploring the electronic structure of graphene
H. Kim, Modulating the photocatalytic activity of graphene quantum dots via quantum dots, J. Nanoparticle Res. 14 (2012) 1317.
atomic tailoring for highly enhanced photocatalysis under visible light, Adv. [178] S. Kim, D.H. Shin, C.O. Kim, S.S. Kang, S.S. Joo, S.-H. Choi, S.W. Hwang, C. Sone,
Funct. Mater. 26 (2016) 8211e8219. Size-dependence of Raman scattering from graphene quantum dots: inter-
[155] Y. Luo, M. Li, L. Sun, Y. Xu, G. Hu, T. Tang, J. Wen, X. Li, Tuning the photo- play between shape and thickness, Appl. Phys. Lett. 102 (2013) 053108.
luminescence of graphene quantum dots by co-doping of nitrogen and sul- [179] T. Espiosa-Ortega, I.A. Luk'Yanchuk, Y.G. Rubo, Density of states in randomly
fur, J. Nanopart. Res. 19 (2017) 363. shaped graphene quantum dots, Superlattice. Microst. 49 (2011) 283e287.
[156] H. Xu, S. Zhou, L. Xiao, Q. Yuan, W. Gan, Time-efficient syntheses of nitrogen [180] J.S. Nascimento, D.R.D. Costa, M. Zarenia, A. Chaves, J.J.M. Pereira, Magnetic
and sulfur co-doped graphene quantum dots with tunable luminescence and properties of bilayer graphene quantum dots in the presence of uniaxial
their sensing applications, RSC Adv. 6 (2016) 36554e36560. strain, Phys. Rev. B 96 (2017) 115428.
[157] A. Ananthanarayanan, Y. Wang, P. Routh, M.A. Sk, A. Than, M. Lin, J. Zhang, [181] T. Espinosa-Ortega, I.A. Luk’yanchuk, Y.G. Rubo, Magnetic properties of
J. Chen, H. Sun, P. Chen, Nitrogen and phosphorus co-doped graphene graphene quantum dots, Phys. Rev. B 87 (2013) 205434.
quantum dots: synthesis from adenosine triphosphate, optical properties, [182] J. Vahakangas, P. Lantto, J. Vaara, Faraday rotation in graphene quantum
and cellular imaging, Nanoscale 7 (2015) 8159e8165. dots: interplay of size, perimeter type, and functionalization, J. Phys. Chem. C
[158] D. Qu, M. Zheng, P. Du, Y. Zhou, L. Zhang, D. Li, H. Tan, Z. Zhao, Z. Xie, Z. Sun, 118 (2014) 23996e24005.
Highly luminescent S, N co-doped graphene quantum dots with broad [183] R. Zhang, S. Qi, J. Jia, B. Torre, H. Zeng, H. Wu, X. Xu, Size and refinement
visible absorption bands for visible light photocatalysts, Nanoscale 5 (2013) edge-shape effects of graphene quantum dots on UV-visible absorption,
12272e12277. J. Alloy. Comp. 623 (2015) 186e191.
[159] M. Favaro, L. Ferrighi, G. Fazio, L. Colazzo, C.D. Vaentin, C. Durante, F. Sedona, [184] F. Liu, M.-H. Jang, H.D. Ha, J.-H. Kim, Y.-H. Cho, T.S. Seo, Facile synthetic
A. Gennaro, S. Agnoli, G. Granozzi, Single and multiple doping in graphene method for pristine graphene quantum dots and graphene oxide quantum
dots: origin of blue and green luminescence, Adv. Mater. 25 (2013), 3657- [209] J. Guo, H. Zhu, Y. Sun, L. Tang, X. Zhang, Doping MoS2 with graphene
3622. quantum dots: structural and electrical engineering towards enhanced
[185] P. Zhang, Q. Hu, X. Yang, X. Hou, J. Mi, L. Liu, M. Dong, Size effect of oxygen electrochemical hydrogen evolution, Electrochim. Acta 211 (2016)
reduction reaction on nitrogen-doped graphene quantum dots, RSC Adv. 8 603e610.
(2018) 531e536. [210] V. Kumar, A. Kumar, A.M. Biradar, G.B. Reddy, D. Sachdev, R. Pasricha,
[186] P. Elvati, E. Baumeister, A. Violi, Graphene quantum dots: effect of size, Enhancement of electro-optical response of ferroelectric liquid crystal: the
composition and curvature on their assembly, RSC Adv. 7 (2017) role of graphene quantum dots, Liq. Cryst. 41 (2014) 1719e1725.
17704e17710. [211] P.R. Kharangarh, S. Umapathy, G. Singh, Synthesis and luminescence of ceria
[187] H. Yang, K.H. Ku, J.M. Shin, J. Lee, C.H. Park, H.-H. Cho, S.G. Jang, B.J. Kim, decorated graphene quantum dots (GQDs): evolution of band gap, Integr.
Engineering the shape of block copolymer particles by surface-modulated Ferroelectr. 184 (2017) 114e123.
graphene quantum dots, Chem. Mater. 28 (2016) 830e837. [212] Z. Protich, P. Wong, K.S.V. Santhanam, Composite of zinc Using graphene
[188] T. Wen, B. Yang, Y. Guo, J. Sun, C. Zhao, S. Zhang, M. Zhang, Y. Wang, quantum dot bath: a prospective material for energy storage, ACS Sustain.
Organosilane-functionalized graphene quantum dots and their encapsula- Chem. Eng. 4 (2016) 6177e6185.
tion into bi-layer hollow silica spheres for bioimaging applications, Phys. [213] T. Hu, X. Chu, F. Gao, Y. Dong, W. Sun, L. Bai, Trimethylamine sensing
Chem. Chem. Phys. 16 (2014) 23188e23195. properties of graphene quantum dots/a-Fe2O3 composites, J. Solid State
[189] L. Chen, C.X. Guo, Q. Zhang, Y. Lei, J. Xie, S. Ee, G. Guai, Q. Song, C.M. Li, Chem. 237 (2016) 284e291.
Graphene quantum-dot-doped polypyrrole counter electrode for high- [214] H. Liu, W. Na, Z. Liu, X. Chen, X. Su, A novel turn-on fluorescent strategy for
performance dye-sensitized solar cells, ACS Appl. Mater. Interfaces 5 sensing ascorbic acid using graphene quantum dots as fluorescent probe,
(2013) 2047e2052. Biosens. Bioelectron. 92 (2017) 229e233.
[190] E. Zor, E. Morales-Narvaez, A. Zamora-Galvez, H. Bingol, M. Ersoz, A. Merkoci, [215] Z.S. Qian, X.Y. Shan, L.J. Chai, J.R. Chen, H. Feng, Dual-colored graphene
Graphene quantum dots-based photoluminescent sensor: a multifunctional quantum dots-labeled nanoprobes/graphene oxide: functional carbon ma-
composite for pesticide detection, ACS Appl. Mater. Interfaces 7 (2015) terials for respective and simultaneous detection of DNA and thrombin,
20272e20279. Nanotechnology 25 (2014) 415501.
[191] H.C. Lim, S.H. Min, E. Lee, J. Jang, S.H. Kim, J.-I. Hong, Self-assembled poly(3,4- [216] S. Xiao, D. Zhou, P. Luan, B. Gu, L. Feng, S. Fan, W. Liao, W. Fang, L. Yang,
ethylene dioxythiophene):poly(styrenesulfonate)/graphene quantum dot E. Tao, R. Guo, J. Liu, Graphene quantum dots conjugated neuroprotective
organogels for efficient charge transport in photovoltaic devices, ACS Appl. peptide improve learning and memory capability, Biomaterials 106 (2016)
Mater. Interfaces 7 (2015) 11069e11073. 98e110.
[192] C.M. Luk, L.B. Tang, W.F. Zhang, S.F. Yu, K.S. Teng, S.P. Lau, An efficient and [217] L. Chen, G. Yang, P. Wu, C. Cai, Real-time fluorescence assay of alkaline
stable fluorescent graphene quantum dot-agar composite as a converting phosphatase in living cells using boron-doped graphene quantum dots as
material in white light emitting diodes, J. Mater. Chem. 22 (2012) fluorophores, Biosens. Bioelectron. 96 (2017) 294e299.
22378e22381. [218] S. Radhakrishnan, A. Samanta, P.M. Sudeep, K.L. Maldonado, S.A. Mani,
[193] M.L. Lam, N.D. Nguyen, Q.T. Tran, Synthesis and characterization of poly- G. Acharya, C.S. Tiwary, A.K. Singh, P.M. Ajayan, Metal-free dual modal
meric graphene quantum dots based nanocomposites for humidity sensing, contrast agents based on fluorographene quantum dots, Part. Part. Syst. Char.
J. Nanomater. 2016 (2016) 5849018. 34 (2017) 1600221.
[194] X. Zhou, X. Gao, F. Song, C. Wang, F. Chu, S. Wu, A sensing approach for [219] Z.M. Markovic, B.Z. Ristic, K.M. Arsikin, D.G. Klisic, L.M. Harhaji-Trajkovic,
dopamine determination by boronic acid-functionalized molecularly B.M. Todorovic-Markovic, D.P. Kepic, T.K. Kravic-Stevovic, S.P. Jovanovic,
imprinted graphene quantum dots composite, Appl. Suf. Sci. 423 (2017) M.M. Milenkovic, D.D. Milivojevic, V.Z. Bumbasirevic, M.D. Dramicanin,
810e816. V.S. Trajkovic, Graphene quantum dots as autophagy-inducing photody-
[195] X. Chu, P. Dai, Y. Dong, W. Sun, L. Bai, W. Zhang, The acetic acid gas sensing namic agents, Biomaterials 33 (2012) 7084e7092.
properties of graphene quantum dots (GQDs)-ZnO nanocomposites prepared by [220] M. Zubair, M. Mustafa, A. Ali, Y.H. Doh, K.H. Choi, Improvement of solution
hydrothermal method, J. Mater. Sci. Mater. Electron. 28 (2017) 19164e19173. based conjugate polymer organic light emitting diode by ZnO-graphene
[196] X. Wu, Y. Zhang, T. Han, H. Wu, S. Guo, J. Zhang, Composite of graphene quantum dots, J. Mater. Sci. Mater. Electron. 26 (2015) 3344e3351.
quantum dots and Fe3O4 nanoparticles: peroxidase activity and application [221] D.H. Kim, T.W. Kim, Ultrahigh current efficiency of light-emitting devices
in phenolic compound removal, RSC Adv. 4 (2014) 3299e3305. based on octadecylamine-graphene quantum dots, Nano Energy 32 (2017)
[197] J. Liu, L. Qin, S.-Z. Kang, G. Li, X. Li, Gold nanoparticles/glycine derivatives/ 441e447.
graphene quantum dots composite with tunable fluorescence and surface [222] W. Zhang, X. Zhang, X. Dong, H. Ma, G. Wang, Synthesis of N-doped graphene
enhanced Raman scattering signals for cellular imaging, Mater. Des. 123 oxide quantum dots with the internal P-N heterojunction and its photo-
(2017) 32e38. catalytic performance under visible light illumination, J. Adv. Oxid. Technol.
[198] D.K.L. Chan, P.L. Cheung, J.C. Yu, A visible-light-driven composite photo- 21 (2018) 201700331.
catalyst of TiO2 nanotube arrays and graphene quantum dots, Beilstein J. [223] Y. Yan, J. Chen, N. Li, J. Tian, K. Li, J. Jiang, J. Liu, Q. Tian, P. Chen, Systematic
Nanotechnol. 5 (2014) 689e695. bandgap engineering of graphene quantum dots and applications for pho-
[199] S. Mondal, U. Rana, S. Malik, Graphene quantum dot-doped polyaniline tocatalytic water splitting and CO2 reduction, ACS Nano 12 (2018)
nanofiber as high performance supercapacitor electrode materials, Chem. 3523e3532.
Commun. 51 (2015) 12365e12368. [224] T.T. Do, K.B. Ko, Z. Khurelbaatar, C.-J. Choi, C.-H. Hong, V.C. Tran, Transparent
[200] Q. Chen, Y. Hu, C. Hu, H. Cheng, Z. Zhang, H. Shao, L. Qu, Graphene quantum and flexible ultraviolet photoconductors based on solution-processed gra-
dots-three-dimensional graphene composites for high-performance super- phene quantum dots on reduced graphene oxide films, Mater. Res. Bull. 91
capacitors, Phys. Chem. Chem. Phys. 16 (2014) 19307e19313. (2017) 49e53.
[201] S. Dhar, T. Majumder, S.P. Mondal, Phenomenal improvement of external [225] P. Sudhagar, I. Herraiz-Cardona, H. Park, T. Song, S.H. Noh, S. Gimenez,
quantum efficiency, detectivity and responsivity of nitrogen doped graphene I.M. Sero, F. Fabregat-Santiago, J. Bisquert, C. Terashima, U. Paik, Y.S. Kang,
quantum dot decorated zinc oxide nanorod/polymer Schottky junction UV A. Fujishima, T.H. Han, Exploring graphene quantum dots/TiO2 interface in
detector, Mater. Res. Bull. 95 (2017) 198e203. photoelectrochemical reactions: solar to fuel conversion, Electrochim. Acta
[202] A. Cai, X. Wang, Y. Qi, Z. Ma, Hierarchical ZnO/S,N:GQD composites: bio- 187 (2016) 249e255.
templated synthesis and enhanced visible-light-driven photocatalytic ac- [226] Z. Zhu, J. Ma, Z. Wang, C. Mu, Z. Fan, L. Du, Y. Bai, L. Fan, H. Yan, D.L. Phillips,
tivity, Appl. Surf. Sci. 391 (2017) 484e490. S. Yang, Efficiency enhancement of perovskite solar cells through fast elec-
[203] X. Bu, S. Yang, Y. Bu, P. He, Y. Yang, G. Wang, H. Li, P. Wang, X. Wang, G. Ding, tron extraction: the role of graphene quantum dots, J. Am. Chem. Soc. 136
J. Yang, X. Xie, Highly active black TiO2/N-doped graphene quantum dots (2014) 3760e3763.
nanocomposites for sunlight driven photocatalytic sewage treatment, [227] X. Yan, X. Cui, B. Li, L.-S. Li, Large, Solution-processable graphene quantum
ChemistrySelect 3 (2018) 12260e12265. dots as light absorbers for photovoltaics, Nano Lett. 10 (2010) 1869e1873.
[204] Y. Ji, J. Hu, J. Biskupek, U. Kaiser, Y.-F. Song, C. Streb, Polyoxometalate-based [228] H. Wang, Y. Yang, X. Zhou, R. Li, Z. Li, NiCo2S4/tryptophan-functionalized
bottom-up fabrication of graphene quantum dot/manganese vanadate graphene quantum dot nanohybrids for high-performance supercapacitors,
composites as lithium ion battery anodes, Chem. Eur J. 23 (2017) New J. Chem. 41 (2017) 1110e1118.
16637e16643. [229] M. Wang, Z. Fang, K. Zhang, J. Fang, F. Qin, Z. Zhang, J. Li, Y. Liu, Y. Lai,
[205] C. Lan, J. Zhao, L. Zhang, C. Wen, Y. Huang, S. Zhao, Self-assembled nano- Synergistically enhanced activity of graphene quantum dots/graphene
porous graphene quantum dot-Mn3 O4 nanocomposites for surface- hydrogel composites: a novel all-carbon hybrid electrocatalyst for metal/air
enhanced Raman scattering based identification of cancer cells, RSC Adv. 7 batteries, Nanoscale 8 (2016) 11398e11402.
(2017) 18658e18667. [230] Z. Su, H. Shen, H. Wang, J. Wang, J. Li, G.U. Nienhaus, L. Shang, G. Wei, Motif-
[206] X. Wu, S. Guo, J. Zhang, Selective oxidation of veratryl alcohol with com- designed peptide nanofibers decorated with graphene quantum dots for
posites of Au nanoparticles and graphene quantum dots as catalysts, Chem. simultaneous targeting and imaging of tumor cells, Adv. Funct. Mater. 25
Commun. 51 (2015) 6318e6321. (2015) 5472e5478.
[207] X. Chu, J. Wang, J. Zhang, Y. Dong, W. Sun, W. Zhang, L. Bai, Preparation and [231] J. Zhang, Y.-Q. Ma, N. Li, J.-L. Zhu, T. Zhang, W. Zhang, B. Liu, Preparation of
gas-sensing properties of SnO2/graphene quantum dots composites via sol- graphene quantum dots and their application in cell imaging, J. Nanomater.
vothermal method, J. Mater. Sci. 52 (2017) 9441e9451. 2016 (2016) 9245865.
[208] Z. Zhang, C. Fang, X. Bing, Y. Lei, Graphene quantum dots-ZnS nanocomposites [232] D. Wu, Y. Liu, Y. Wang, L. Hu, H. Ma, G. Wang, Q. Wei, Label-free electro-
with improved photoelectric performances, Materials 11 (2018) 512. chemiluminescent immunosensor for detection of prostate specific antigen
based on aminated graphene quantum dots and carboxyl graphene quantum [257] S. Kim, D.H. Shin, J. Kim, C.W. Jang, S.S. Kang, J.M. Kim, J.H. Kim, D.H. Lee,
dots, Sci. Rep. 6 (2016) 20511. J.H. Kim, S.-H. Choi, S.W. Hwang, Energy transfer from an individual silica
[233] M. Thakur, A. Mewada, S. Pandey, M. Bhori, K. Singh, M. Sharon, M. Sharon, nanoparticle to graphene quantum dots and resulting enhancement of
Milk-derived multi-fluorescent graphene quantum dot-based cancer thera- photodetector responsivity, Sci. Rep. 6 (2016) 27145.
nostic system, Mat. Sci. Eng. C Mater. 67 (2016) 468e477. [258] B. Yang, J. Chen, L. Cui, W. Liu, Enhanced photocurrent of a ZnO nanorod
[234] V.T. Tran, S.H. Hur, J.S. Chung, W.M. Choi, Ultraviolet light sensor based on array sensitized with graphene quantum dots, RSC Adv. 5 (2015)
graphene quantum dots/reduced graphene oxide hybrid film, Sensor. Actuat. 59204e59207.
A. Phys. 233 (2015) 368e373. [259] M.-L. Tsai, D.-S. Tsai, L. Tang, L.-J. Chen, S.P. Lau, J.-H. He, Omnidirectional
[235] S.D. Zhuang, Y. Chen, W.C. Zhang, Z. Chen, Z.L. Wang, Humidity sensor and harvesting of weak light using a graphene quantum dot-modified organic/
ultraviolet photodetector based on Carrier trapping effect and negative silicon hybrid device, ACS Nano 11 (2017) 4564e4570.
photoconductivity in graphene quantum dots, Sci. Chin. Phys. Mech. 61 [260] S. Dhar, T. Majumder, S.P. Mondal, Graphene quantum dot-sensitized ZnO
(2018) 0142111. nanorod/polymer Schottky junction UV detector with superior external
[236] C. Xu, S. Yang, L. Tian, T. Guo, G. Ding, J. Zhao, J. Sun, J. Lu, Z. Wang, quantum efficiency, detectivity, and responsivity, ACS Appl. Mater. Interfaces
Fabrication of centimeter-scale light-emitting diode with improved per- 8 (2016) 31822e31831.
formance based on graphene quantum dots, Appl. Phys. Express 10 (2017) [261] J. Zhao, L. Tang, J. Xiang, R. Ji, Y. Hu, J. Yuan, J. Zhao, Y. Tai, Y. Cai, Fabrication
032102. and properties of a high-performance chlorine doped graphene quantum dot
[237] J. Zhu, X. Bai, J. Bai, G. Pan, Y. Zhu, Y. Zhai, H. Shao, X. Chen, B. Dong, H. Zhang, based photovoltaic detector, RSC Adv. 5 (2015) 29222e29229.
H. Song, Emitting color tunable carbon dots by adjusting solvent towards [262] C. Chen, H. Qiao, S. Lin, C.M. Luk, Y. Liu, Z. Xu, J. Song, Y. Xue, D. Li, J. Yuan,
light-emitting devices, Nanotechnology 29 (2018) 085705. W. Yu, C. Pan, S.Pi Lau, Q. Bao, Highly responsive MoS2 photodetectors
[238] J. Joseph, A.A. Anappara, White-light emitting carbon dots prepared by the enhanced by graphene quantum dots, Sci. Rep. 5 (2015) 11830.
electrochemical exfoliation of graphite, ChemPhysChem 18 (2017) 292e298. [263] H. Tetsuka, A. Nagoya, T. Fukusumi, T. Matsui, Molecularly designed,
[239] J. Guo, H. Zhu, Y. Sun, L. Tang, X. Zhang, Boosting the lithium storage per- nitrogen-functionalized graphene quantum dots for optoelectronic devices,
formance of MoS2 with graphene quantum dots, J. Mater. Chem. A 4 (2016) Adv. Mater. 28 (2016) 4632e4638.
4783e4789. [264] C.O. Kim, S.W. Hwang, S. Kim, D.H. Shin, S.S. Kang, J.M. Kim, C.W. Jang,
[240] D. Jiang, D. Ni, F. Liu, L. Zhang, L. Liu, X. Pu, A fluorescent imaging assay of cast J.H. Kim, K.W. Lee, S.-H. Choi, E. Hwang, High-performance graphene-
in renal disease based on graphene quantum dots and Fe3O4 nanoparticles, quantum-dot photodetectors, Sci. Rep. 4 (2014) 5603.
Clin. Chim. Acta 454 (2016) 94e101. [265] S. Dhar, T. Majumder, P. Chakraborty, S.P. Mondal, DMSO modified PEDOT:
[241] M. Zhang, L. Bai, W. Shang, W. Xie, H. Ma, Y. Fu, D. Fang, H. Sun, L. Fan, PSS polymer/ZnO nanorods Schottky junction ultraviolet photodetector:
M. Han, C. Liu, S. Yang, Facile synthesis of water-soluble, highly fluorescent photoresponse, external quantum efficiency, detectivity, and responsivity
graphene quantum dots as a robust biological label for stem cells, J. Mater. augmentation using N doped graphene quantum dots, Org. Electron. 53
Chem. 22 (2012) 7461e7467. (2018) 101e110.
[242] K.L. Schroeder, R.V. Goreham, T. Nann, Graphene quantum dots for thera- [266] K. Rahimi, A. Yazdani, M. Ahmadirad, Graphene quantum dots enhance UV
nostics and bioimaging, Pharm. Res. 33 (2016) 2337e2357. photoresponsivity and surface-related sensing speed of zinc oxide nanorod
[243] Y.-L. Su, T.-W. Yu, W.-H. Chiang, H.-C. Chiu, C.-H. Chang, C.-S. Chiang, S.- thin films, Mater. Des. 140 (2018) 222e230.
H. Hu, Hierarchically targeted and penetrated delivery of drugs to tumors by [267] F. Zhang, X. Feng, Y. Zhang, L. Yan, Y. Yang, X. Liu, Photoluminescent carbon
size-changeable graphene quantum dot nanoaircrafts for photolytic therapy, quantum dots as a directly film-forming phosphor towards white LEDs,
Adv. Funct. Mater. 27 (2017) 1700056. Nanoscale 8 (2016) 8618e8632.
[244] S. Some, A.-R. Gwon, E. Hwang, G.-H. Bahn, Y. Yoon, Y. Kim, S.-H. Kim, S. Bak, [268] G.S. Kumar, U. Thupakula, P.K. Sarkar, S. Acharya, Easy extraction of water-
J. Yang, D.-G. Jo, H. Lee, Cancer therapy using ultrahigh hydrophobic drug- soluble graphene quantum dots for light emitting diodes, RSC Adv. 5
loaded graphene derivatives, Sci. Rep. 4 (2014) 6314. (2015) 27711e27716.
[245] D. Iannazzo, I. Ziccarelli, A. Pistone, Graphene quantum dots: multifunctional [269] J.K. Kim, S. Bae, Y. Yi, M.J. Park, S.J. Kim, N.S. Myoung, C.-L. Lee, B.H. Hong,
nanoplatforms for anticancer therapy, J. Mater. Chem. B 5 (2017) J.H. Park, Origin of white electroluminescence in graphene quantum dots
6471e6489. embedded host/guest polymer light emitting diodes, Sci. Rep. 5 (2015)
[246] D. Zhang, L. Wen, R. Huang, H. Wang, X. Hu, D. Xing, Mitochondrial specific 11032.
photodynamic therapy by rare-earth nanoparticles mediated near-infrared [270] D.H. Kim, T.W. Kim, Highly-efficient organic light-emitting devices based on
graphene quantum dots, Biomaterials 153 (2018) 14e26. poly(N,N '-bis-4-butylphenyl-N,N '-bisphenyl)benzidine: octadecylamine-
[247] M.J. Birnkrant, K. Bell, S. Coreth, P.R. Harris, A.M. Vincitore, J.M. Alexander, graphene quantum dots, Org. Electron. 57 (2018) 305e310.
Detection system for measuring presence of multiple conditions in pre- [271] H. Li, C. Sun, M. Ali, F. Zhou, X. Zhang, D.R. MacFarlane, Sulfated carbon
determined area of aircraft, has control system to analyze more than one quantum dots as efficient visible-light switchable acid catalysts for room-
signal and wavelength of scattered light associated with node to determine temperature ring-opening reactions, Angew. Chem. Int. Ed. 54 (2015)
presence and magnitude, ACS Nano 10 (2016) 8690e8699. 8420e8424.
[248] H. Dong, W. Dai, H. Ju, H. Lu, S. Wang, L. Xu, S.F. Zhou, Y. Zhang, X. Zhang, [272] S. Chinnusamy, R. Kaur, A. Bokare, F. Erogbogbo, Incorporation of graphene
Multifunctional poly(L-lactide)polyethylene glycol-grafted graphene quantum dots to enhance photocatalytic properties of anatase TiO2, MRS
quantum dots for intracellular microRNA imaging and combined specific- Commun. 8 (2018) 137e144.
gene-targeting agents delivery for improved therapeutics, ACS Appl. Mater. [273] J. Xia, J. Di, H. Li, H. Xu, H. Li, S. Guo, Ionic liquid-induced strategy for carbon
Interfaces 7 (2015) 11015e11023. quantum dots/BiOX (X¼Br, Cl) hybrid nanosheets with superior visible light-
[249] C. Luo, Y. Li, L. Guo, F. Zhang, H. Liu, J. Zhang, J. Zheng, J. Zhang, S. Guo, driven photocatalysis, Appl. Catal. B Environ. 181 (2016) 260e269.
Graphene quantum dots downregulate multiple multidrug-resistant genes [274] A. Cai, Q. Wang, Y. Chang, X. Wang, Graphitic carbon nitride decorated with
via interacting with their C-rich promoters, Adv. Healthcare Mater. (2017) S,N co-doped graphene quantum dots for enhanced visible-light-driven
1700328. photocatalysis, J. Alloy. Comp. 692 (2017) 183e189.
[250] K. Hola, Y. Zhang, Y. Wang, E.P. Giannelis, R. Zboril, A.L. Rogach, Carbon dots- [275] G. Bai, M.-K. Tsang, J. Hao, Luminescent ions in advanced composite mate-
Emerging light emitters for bioimaging, cancer therapy and optoelectronics, rials for multifunctional applications, Adv. Funct. Mater. 26 (2016)
Nano Today 9 (2014) 590e603. 6330e6350.
[251] W.-S. Kuo, H.-H. Chen, S.-Y. Chen, C.-Y. Chang, P.-C. Chen, Y.-I. Hou, Y.- [276] X. Qin, X. Liu, W. Huang, M. Bettinelli, X. Liu, Lanthanide-activated phosphors
T. Shao, H.-F. Kao, C.-L.L. Hsu, Y.-C. Chen, S.-J. Chen, S.-R. Wu, J.-Y. Wang, based on 4f-5d optical transitions: theoretical and experimental aspects,
Graphene quantum dots with nitrogen-doped content dependence for Chem. Rev. 117 (2017) 4488e4527.
highly efficient dual-modality photodynamic antimicrobial therapy and [277] B. Wang, H. Lin, F. Huang, J. Xu, H. Chen, Z. Lin, Y. Wang, Non-rare-earth
bioimaging, Biomaterials 120 (2017) 185e194. BaMgAl10e2xO17:xMn4þ,xMg2þ: a narrow-band red phosphor for use as a
[252] H. Sun, N. Gao, K. Dong, J. Ren, X. Qu, Graphene quantum dots-band-aids high-power warm w-LED, Chem. Mater. 28 (2016) 3515e3524.
used for wound disinfection, ACS Nano 8 (2014) 6202e6210. [278] W. Dai, Y. Lei, M. Xu, P. Zhao, Z. Zhang, J. Zhou, Rare-earth free self-activated
[253] A. Tayyebi, O. Akhavan, B.-K. Lee, M. Outokesh, Supercritical water in top- graphene quantum dots and copper-cysteamine phosphors for enhanced
down formation of tunable-sized graphene quantum dots applicable in white light-emitting-diodes under single excitation, Sci. Rep. 7 (2017)
effective photothermal treatments of tissues, Carbon 130 (2018) 267e272. 12872.
[254] S. Li, S. Zhou, Y. Li, X. Li, J. Zhu, L. Fan, S. Yang, Exceptionally high payload of [279] J. Zhu, X. Bai, X. Chen, Z. Xie, Y. Zhu, G. Pan, Y. Zhai, H. Zhang, B. Dong,
the IR780 iodide on folic acid-functionalized graphene quantum dots for H. Song, Carbon dots with efficient solid-state red-light emission through the
targeted photothermal therapy, ACS Appl. Mater. Interfaces 9 (2017) step-by-step surface modification towards light-emitting diodes, Dalton T 47
22332e22341. (2018) 3811e3818.
[255] L. Rizzello, P.P. Pompa, Nanosilver-based antibacterial drugs and devices: [280] P. Dong, B.-P. Jiang, W.-Q. Liang, Y. Huang, Z. Shi, X.-C. Shen, Synthesis of
mechanisms, methodological drawbacks, and guidelines, Chem. Soc. Rev. 43 white-light-emitting graphene quantum dots via a one-step reduction and
(2014) 1501e1518. their interfacial characteristics-dependent luminescence properties, Inorg.
[256] I. Mihalache, A. Radoi, R. Pascu, C. Romanitan, E. Vasile, M. Kusko, Engi- Chem. Front. 4 (2017) 712e718.
neering graphene quantum dots for enhanced ultraviolet and visible light p- [281] Q. Liu, D. Li, Z. Zhu, S. Yu, Y. Zhang, D. Yu, Y. Jiang, N-doped carbon dots from
Si nanowire-based photodetector, ACS Appl. Mater. Interfaces 9 (2017) phenol derivatives for excellent colour rendering WLEDs, RSC Adv. 8 (2018)
29234e29247. 4850e4856.
[282] X.-F. Wang, G.-G. Wang, J.-B. Li, Z. Liu, W.-F. Zhao, J.-C. Han, Towards high- [308] X. Hao, Z. Jin, J. Xu, S. Min, G. Lu, Functionalization of TiO2 with graphene
powered remote WLED based on flexible white-luminescent polymer com- quantum dots for efficient photocatalytic hydrogen evolution, Superlattice.
posite films containing S, N co-doped graphene quantum dots, Chem. Eng. J. Microst. 94 (2016) 237e244.
336 (2018) 406e415. [309] D. Pan, J. Jiao, Z. Li, Y. Guo, C. Feng, Y. Liu, L. Wang, M. Wu, Efficient separation
[283] R. Sekiya, Y. Uemura, H. Murakami, T. Haino, White-light-emitting edge- of electron-hole pairs in graphene quantum dots by TiO2 heterojunctions for
functionalized graphene quantum dots, Angew. Chem. Int. Ed. 53 (2014) dye degradation, ACS Sustain. Chem. Eng. 3 (2015) 2405e2413.
5619e5623. [310] B. De, J. Balamurugan, N.H. Kim, J.H. Lee, Enhanced electrochemical and
[284] X. Guo, C.-F. Wang, Z.-Y. Yu, L. Chen, S. Chen, Facile access to versatile photocatalytic performance of coreshell CuS@carbon quantum dots@
fluorescent carbon dots toward light-emitting diodes, Chem. Commun. 48 carbon hollow nanospheres, ACS Appl. Mater. Interfaces 9 (2017)
(2012) 2692e2694. 2459e2468.
[285] Z. Tian, X. Zhang, D. Li, D. Zhou, P. Jing, D. Shen, S. Qu, R. Zboril, A.L. Rogach, [311] M. Ebrahimi, M. Samadi, S. Yousefzadeh, M. Soltani, A. Rahimi, T.-C. Chou, L.-
Full-color inorganic carbon dot phosphors for white-light-emitting diodes, C. Chen, K.-H. Chen, A.Z. Moshfegh, Improved solar-driven photocatalytic
Adv. Opt. Mater 5 (2017) 1700416. activity of hybrid graphene quantum dots/ZnO nanowires: a direct Z-scheme
[286] T.-N. Lin, S.R.M. Santiago, C.-T. Yuan, K.-P. Chiu, J.-L. Shen, T.-C. Wang, H.- mechanism, ACS Sustain. Chem. Eng. 5 (2017) 367e375.
C. Kuo, C.-H. Chiu, Y.-C. Yao, Y.-J. Lee, Enhanced performance of GaN-based [312] S. Diao, X. Zhang, Z. Shao, K. Ding, J. Jie, X. Zhang, 12.35% efficient graphene
ultraviolet light emitting diodes by photon recycling using graphene quan- quantum dots/silicon heterojunction solar cells using graphene transparent
tum dots, Sci. Rep. 7 (2017) 7108. electrode, Nano Energy 31 (2017) 359e366.
[287] D. Pan, L. Wang, Z. Li, B. Geng, C. Zhang, J. Zhan, L. Yin, L. Wang, Synthesis of [313] K.D. Lee, M.J. Park, D.-Y. Kim, S.M. Kim, B. Kang, S. Kim, H. Kim, H.-S. Lee,
graphene quantum dot/metal-organic framework nanocomposites as yellow Y. Kang, S.S. Yoon, B.H. Hong, D. Kim, Graphene quantum dot layers with
phosphors for white light-emitting diodes, New J. Chem. 42 (2018) energy-down-shift effect on crystalline-silicon solar cells, ACS Appl. Mater.
5083e5089. Interfaces 7 (2015) 19043e19049.
[288] W. Kwon, Y.-H. Kim, J.-H. Kim, T. Lee, S. Do, Y. Park, M.S. Jeong, T.-W. Lee, S.- [314] T. Majumder, S. Dhar, P. Chakraborty, K. Debnath, S.P. Mondal, Advantages of
W. Rhee, High color-purity green, orange, and red light-emitting didoes ZnO nanotaper photoanodes in photoelectrochemical cells and graphene
based on chemically functionalized graphene quantum dots, Sci. Rep. 6 quantum dot sensitized solar cell applications, J. Electroanal. Chem. 813
(2016) 24205. (2018) 92e101.
[289] T. Feng, Q. Zeng, S. Lu, X. Yan, J. Liu, S. Tao, M. Yang, B. Yang, Color-tunable [315] A. Kolay, R.K. Kokal, A. Kalluri, I. Macwan, P.K. Patra, P. Ghosal, M. Deepa,
carbon dots possessing solid-state emission for full color light-emitting di- New Antimony selenide/nickel oxide photocathode boosts the efficiency of
odes applications, ACS Photonics 5 (2018) 502e510. graphene quantum-dot co-sensitized solar cells, ACS Appl. Mater. Interfaces
[290] H. Tetsuka, A. Nagoya, R. Asahi, Highly luminescent flexible amino- 9 (2017) 34915e34926.
functionalized graphene quantum dots@cellulose nanofibereclay hybrids [316] Y.-Q. Zhang, D.-K. Ma, Y.-G. Zhang, W. Chen, S.-M. Huang, N-doped carbon
for white-light emitting diodes, J. Mater. Chem. C 3 (2015) 3536e3541. quantum dots for TiO2-based photocatalysts and dye-sensitized solar cells,
[291] O. Khaselev, A Monolithic photovoltaic-photoelectrochemical device for Nano Energy 2 (2013) 545e552.
hydrogen production via water splitting, Science 280 (1998) 425e427. [317] J.K. Kim, M.J. Park, S.J. Kim, D.H. Wang, S.P. Cho, S. Bae, J.H. Park, B.H. Hong,
[292] M. Gra €tzel, Photoelectrochemical cells, Nature 414 (2001) 338e344. Balancing light absorptivity and Carrier conductivity of graphene quantum
[293] K. Maeda, K. Teramura, D.L. Lu, T. Takata, N. Saito, Y. Inoue, K. Domen, dots for high-efficiency bulk heterojunction solar cells, ACS Nano 7 (2013)
Photocatalyst releasing hydrogen from water - enhancing catalytic perfor- 7207e7212.
mance holds promise for hydrogen production by water splitting in sunlight, [318] Y. Dang, X. Zhang, X. Chen, B. Kang, S.R.P. Silva, Heterojunction solar cells
Nature 440 (2006) 7082. with improved power conversion efficiency using graphene quantum dots,
[294] F.E. Osterloh, Inorganic materials as catalysts for photochemical splitting of RSC Adv. 6 (2016) 110493e110498.
water, Chem. Mater. 20 (2008) 35e54. [319] D.H. Shin, S.W. Seo, J.M. Kim, H.S. Lee, S.-H. Choi, Graphene transparent
[295] Akihiko Kudo, Yugo Miseki, Heterogeneous photocatalyst materials for water conductive electrodes doped with graphene quantum dots-mixed silver
splitting, Chem. Soc. Rev. 38 (2009) 253e278. nanowires for highly-flexible organic solar cells, J. Alloy. Comp. 744 (2018) 1e6.
[296] T.-F. Yeh, C.-Y. Teng, S.-J. Chen, H. Teng, Nitrogen-doped graphene oxide [320] H.B. Yang, Y.Q. Dong, X. Wang, S.Y. Khoo, B. Liu, Cesium carbonate func-
quantum dots as photocatalysts for overall water-splitting under visible light tionalized graphene quantum dots as stable electron-selective layer for
illumination, Adv. Mater. 26 (2014) 3297e3303. improvement of inverted polymer solar cells, ACS Appl. Mater. Interfaces 6
[297] B.K. Gupta, G. Kedawat, Y. Agrawal, P. Kumar, J. Dwivedi, S.K. Dhawan, (2014) 1092e1099.
A novel strategy to enhance ultraviolet light driven photocatalysis from [321] J.K. Kim, S.J. Kim, M.J. Park, S. Bae, S.-P. Cho, Q.G. Du, D.H. Wang, J.H. Park,
graphene quantum dots infilled TiO2 nanotube arrays, RSC Adv. 5 (2015) B.H. Hong, Surface-engineered graphene quantum dots incorporated into
10623e10631. polymer layers for high performance organic photovoltaics, Sci. Rep. 5
[298] D. Pan, C. Xi, Z. Li, L. Wang, Z. Chen, B. Luc, M. Wu, Electrophoretic fabrication (2015) 14276.
of highly robust, efficient, and benign heterojunction photoelectrocatalysts [322] P. Gao, K. Ding, Y. Wang, K. Ruan, S. Diao, Q. Zhang, B. Sun, J. Jie, Crystalline
based on graphene-quantum-dot sensitized TiO2 nanotube arrays, J. Mater. Si/graphene quantum dots heterojunction solar cells, J. Phys. Chem. C 118
Chem. A 1 (2013) 3551e3555. (2014) 5164e5171.
[299] S. Bian, C. Zhou, P. Li, J. Liu, X. Dong, F. Xi, Graphene quantum dots decorated [323] Z. Ding, Z. Hao, B. Meng, Z. Xie, J. Liua, L. Dai, Few-layered graphene quantum
titania nanosheets heterojunction: efficient charge separation and enhanced dots as efficient hole-extraction layer for high-performance polymer solar
visiblelight photocatalytic performance, ChemCatChem 9 (2016) cells, Nano Energy 15 (2015) 186e192.
3349e3357. [324] H.B. Yang, Y.Q. Dong, X. Wang, S.Y. Khoo, B. Liu, C.M. Li, Graphene quantum
[300] S. Wang, I.S. Cole, Q. Li, Quantum-confined bandgap narrowing of TiO2 dots-incorporated cathode buffer for improvement of inverted polymer solar
nanoparticles by graphene quantum dots for visible-light-driven applica- cells, Sol. Energy Mater. Sol. Cell. 117 (2013) 214e218.
tions, Chem. Commun. 52 (2016) 9208e9211. [325] Y. Yang, X. Lin, W. Li, J. Ou, Z. Yuan, F. Xie, W. Hong, D. Yu, Y. Ma, Z. Chi,
[301] S. Yu, Y.-Q. Zhong, B.-Q. Yu, S.-Y. Cai, L.-Z. Wu, Y. Zhou, Graphene quantum X. Chen, One-pot large-scale synthesis of carbon quantum dots: efficient
dots to enhance the photocatalytic hydrogen evolution efficiency of anatase cathode interlayers for polymer solar cells, ACS Appl. Mater. Interfaces 9
TiO2 with exposed {001} facet, Phys. Chem. Chem. Phys. 18 (2016) (2017) 14953e14959.
20338e20344. [326] F. Li, L. Kou, W. Chen, C. Wu, T. Guo, Enhancing the short-circuit current and
[302] K.-A. Tsai, Y.-J. Hsu, Graphene quantum dots mediated charge transfer of power conversion efficiency of polymer solar cells with graphene quantum
CdSe nanocrystals for enhancing photoelectrochemical hydrogen produc- dots derived from double-walled carbon nanotubes, NPG Asia Mater. 5
tion, Appl. Catal. B Environ. 164 (2015) 271e278. (2013) 60.
[303] Y. Lei, C. Yang, J. Hou, F. Wang, S. Min, X. Ma, Z. Jin, J. Xu, G. Lu, K.-W. Huang, [327] M. Li, W. Ni, B. Kan, X. Wan, L. Zhang, Q. Zhang, G. Long, Y. Zuo, Y. Chen,
Strongly coupled CdS/graphene quantum dots nanohybrids for highly effi- Graphene quantum dots as the hole transport layer material for high-
cient photocatalytic hydrogen evolution: unraveling the essential roles of performance organic solar cells, Phys. Chem. Chem. Phys. 15 (2013)
graphene quantum dots, Appl. Catal. B Environ. 216 (2017) 59e69. 18973e18978.
[304] J. Tang, Y. Liu, Y. Hu, G. Lv, C. Yang, G. Yang, Carbothermal reduction induced [328] V. Gupta, N. Chaudhary, R. Srivastava, G.D. Sharma, R. Bhardwaj, S. Chand,
Ti3þ self-doped TiO2/GQD nanohybrids for high-performance visible light Luminescent graphene quantum dots for organic photovoltaic devices, J. Am.
photocatalysis, Chem. Eur J. 24 (2018) 4390e4398. Chem. Soc. 133 (2011) 9960e9963.
[305] Z. Zeng, F.-X. Xiao, X. Gui, R. Wang, B. Liu, T.T. Yang Tan, Layer-by-layer [329] D.H. Wang, J.K. Kim, S.J. Kim, B.H. Hong, J.H. Park, Efficient solution-
assembly of nitrogen-doped graphene quantum dots monolayer decorated processed small-molecule solar cells by insertion of graphene quantum
one dimensional semiconductor nanoarchitectures for solar-driven water dots, Nanoscale 6 (2014) 15175e15180.
splitting, J. Mater. Chem. A 4 (2016) 16383e16393. [330] T.H. Nhu, N.T. Huynh, S.-J. Jang, V. Senthilkumar, Y.C. Park, S. Cho, Y.S. Kim,
[306] J.-P. Zou, L.-C. Wang, J. Luo, Y.-C. Nie, Q.-J. Xing, X.-B. Luo, H.-M. Du, S.-L. Luo, Enhancement of recombination process using silver and graphene quantum
S.L. Suib, Synthesis and efficient visible light photocatalytic H2 evolution of a dot embedded intermediate layer for efficient organic tandem cells, Sci. Rep.
metal-free g-C3N4/graphene quantum dots hybrid photocatalyst, Appl. 6 (2016) 30327.
Catal. B Environ. 193 (2016) 103e109. [331] Z. Yang, J. Xie, V. Arivazhagan, K. Xiao, Y. Qiang, K. Huang, M. Hu, C. Cui, X. Yu,
[307] S. Ham, Y. Kim, M.J. Park, B.H. Hong, D.-J. Jang, Graphene quantum dots- D. Yang, Efficient and highly light stable planar perovskite solar cells with
decorated ZnS nanobelts with highly efficient photocatalytic performances, graphene quantum dots doped PCBM electron transport layer, Nano Energy
RSC Adv. 6 (2016) 24115e24120. 40 (2017) 345e351.
[332] T.G. Novak, J. Kim, S.H. Song, G.H. Jun, H. Kim, M.S. Jeong, S. Jeon, Fast P3HT wrapped with graphene quantum dots, Electrochim. Acta 168 (2015)
exciton dissociation and absorption enhancement of organic solar cells by 116e124.
PEG-functionalized graphene quantum dots, Small 12 (2016) 994e999. [352] Y. Zhong, H. Zhang, D. Pan, L. Wang, X. Zhong, Graphene quantum dots
[333] Q. Chang, Z. Ma, J. Wang, P. Li, Y. Yan, W. Shi, Q. Chen, Y. Huang, L. Huang, assisted photovoltage and efficiency enhancement in CdSe quantum dot
Hybrid graphene quantum dots@graphene foam nanosheets for dye- sensitized solar cells, J. Energy Chem. 24 (2015) 722e728.
sensitized solar cell electrodes, Energy Technol. 4 (2016) 256e262. [353] J. Wang, X. Xin, Z. Lin, Cu2ZnSnS4 nanocrystals and graphene quantum dots
[334] X. Fang, J. Ding, N. Yuan, P. Sun, M. Lv, G. Ding, C. Zhu, Graphene quantum dot for photovoltaics, Nanoscale 3 (2011) 3040e3048.
incorporated perovskite films: passivating grain boundaries and facilitating [354] C. Yu, Z. Liu, Y. Chen, X. Meng, M. Li, J. Qiu, CoS nanosheets-coupled graphene
electron extraction, Phys. Chem. Chem. Phys. 19 (2017) 6057e6063. quantum dots architectures as a binder-free counter electrode for high-
[335] P. Wang, S. Lin, G. Ding, X. Li, Z. Wu, S. Zhang, Z. Xu, S. Xu, Y. Lu, W. Xu, performance DSSCs, Sci. Chin. Mater. 59 (2016) 104e111.
Z. Zheng, Enhanced monolayer MoS2/InP heterostructure solar cells by [355] M. Dinari1, M.M. Momeni1, M. Goudarzirad, Dye-sensitized solar cells based
graphene quantum dots, Appl. Phys. Lett. 108 (2016) 163901. on nanocomposite of polyaniline/graphene quantum dots, J. Mater. Sci. 51
[336] B. Mandal, S. Sarkar, P. Sarkar, Theoretical studies on understanding the (2016) 2964e2971.
feasibility of porphyrin-sensitized graphene quantum dot solar cell, J. Phys. [356] T.-N. Lin, S.R.M.S. Santiago, J.-A. Zheng, Y.-C. Chao, C.-T. Yuan, J.-L. Shen, C.-
Chem. C 119 (2015) 3400e3407. H. Wu, C.-A.J. Lin, W.-R. Liu, M.-C. Cheng, W.-C. Chou, Enhanced conversion
[337] X. Fang, M. Li, K. Guo, J. Li, M. Pan, L. Bai, M. Luoshan, X. Zhao, Graphene efficiency of III-V triple-junction solar cells with graphene quantum dots, Sci.
quantum dots optimization of dye-sensitized solar cells, Electrochim. Acta Rep. 6 (2016) 39163.
137 (2014) 634e638. [357] Q. Tang, All-weather solar cells: a rising photovoltaic revolution, Chem. Eur J.
[338] B. Cui, L. Yan, H. Gu, Y. Yang, X. Liu, C.-Q. Ma, Y. Chen, H. Jia, Fluorescent 23 (2017) 8118e8127.
carbon quantum dots synthesized by chemical vapor deposition: an alter- [358] Y. Meng, Y. Zhang, W. Sun, M. Wang, B. He, H. Chen, Q. Tang, Biomass
native candidate for electron acceptor in polymer solar cells, Opt. Mater. 75 converted carbon quantum dots for all-weather solar cells, Electrochim. Acta
(2018) 166e173. 257 (2017) 259e266.
[339] E. Lee, J. Ryu, J. Jang, Fabrication of graphene quantum dots via size-selective [359] C.-P. Lee, K.-Y. Lai, C.-A. Lin, C.-T. Li, K.-C. Ho, C.-I. Wu, S.-P. Lau, J.-H. He,
precipitation and their application in upconversion-based DSSCs, Chem. A paper-based electrode using a graphene dot/PEDOT:PSS composite for
Commun. 49 (2013) 9995e9997. flexible solar cells, Nano Energy 36 (2017) 260e267.
[340] H. Teymourinia, M. Salavati-Niasari, O. Amiri, M. Farangi, Facile synthesis of [360] C.-P. Leea, C.-A. Lin, T.-C. Wei, M.-L. Tsai, Y. Meng, C.-T. Li, K.-C. Ho, C.-I. Wu,
graphene quantum dots from corn powder and their application as down S.-P. Lau, J.-H. He, Economical low-light photovoltaics by using the Pt-free
conversion effect in quantum dot-dye-sensitized solar cell, J. Mol. Liq. 251 dye-sensitized solar cell with graphene dot/PEDOT:PSS counter electrodes,
(2018) 267e272. Nano Energy 18 (2015) 109e117.
[341] Y. Zhang, Y. Zhao, J. Duan, Q. Tang, S-doped CQDs tailored transparent [361] D. Chao, C. Zhu, X. Xia, J. Liu, X. Zhang, J. Wang, P. Liang, J. Lin, H. Zhang,
counter electrodes for high-efficiency bifacial dye-sensitized solar cells, Z.X. Shen, H.J. Fan, Graphene quantum dots coated VO2 arrays for highly
Electrochim. Acta 261 (2018) 588e595. durable electrodes for Li and Na ion batteries, Nano Lett. 15 (2015)
[342] I. Mihalache, A. Radoi, M. Mihaila, C. Munteanu, A. Marin, M. Danila, 565e573.
M. Kusko, C. Kusko, Charge and energy transfer interplay in hybrid sensitized [362] W. Zhang, T. Xu, Z. Liu, N.-L. Wu, M. Wei, Hierarchical TiO2-x imbedded with
solar cells mediated by graphene quantum dots, Electrochim. Acta 153 graphene quantum dots for high-performance lithium storage, Chem.
(2015) 306e315. Commun. 54 (2018) 1413e1416.
[343] T. Majumder, S.P. Mondal, Advantages of nitrogen-doped graphene quantum [363] L. Kong, Y. Yang, R. Li, Z. Li, Phenylalanine-functionalized graphene quantum
dots as a green sensitizer with ZnO nanorod based photoanodes for solar dot-silicon nanoparticle composite as an anode material for lithium ion
energy conversion, J. Electroanal. Chem. 769 (2016) 48e52. batteries with largely enhanced electrochemical performance, Electrochim.
[344] F. Gao, C.-L. Yang, M.-S. Wang, X.-G. Ma, Computational studies on the ab- Acta 198 (2016) 144e155.
sorption enhancement of nanocomposites of tetraphenylporphyrin and [364] Y.-M. Chen, S.-T. Hsu, Y.-H. Tseng, T.-F. Yeh, S.-S. Hou, J.-S. Jan, Y.-L. Lee,
graphene quantum dot as sensitizers in solar cell, J. Mater. Sci. 53 (2018) H. Teng, Minimization of ion-solvent clusters in gel electrolytes containing
5140e5150. graphene oxide quantum dots for lithium-ion batteries, Small 14 (2018)
[345] Wei, Q. Li, Top-down strategy toward versatile graphene quantum dots for 1703571.
organic/inorganic hybrid solar cells, ACS Sustain. Chem. Eng. 3 (2015) [365] C. Zhu, D. Chao, J. Sun, I.M. Bacho, Z. Fan, C.F. Ng, X. Xia, H. Huang, H. Zhang,
637e644. Z.X. Shen, G. Ding, H.J. Fan, Enhanced lithium storage performance of CuO
[346] M. Dutta, S. Sarkar, T. Ghosh, D. Basak, ZnO/graphene quantum dot solid- nanowires by coating of graphene quantum dots, Adv. Mater. Interface. 2
state solar cell, J. Phys. Chem. C 116 (2012) 20127e20131. (2015) 1400499.
[347] S. Tamandani, G. Darvish, Charge transfer modeling in monolayer circular [366] S. Bose, T. Kuila, T.X.H. Nguyen, N.H. Kim, K.-T. Lau, J.H. Lee, Polymer
graphene quantum dots-ZnO nanowires system for application in photo- membranes for high temperature proton exchange membrane fuel cell:
voltaic devices, Int. J. Mod. Phys. B 31 (2017) 1650253. recent advances and challenges, Prog. Polym. Sci. 36 (2011) 813e843.
[348] G. Zamiri, S. Bagheri, Fabrication of green dye-sensitized solar cell based on [367] S.C. Singhal, Advances in solid oxide fuel cell technology, Solid State Ionics
ZnO nanoparticles as a photoanode and graphene quantum dots as a photo- 135 (2000) 305e313.
sensitizer, J. Colloid Interface Sci. 511 (2018) 318e324. [368] T. Burchardt, P. Goue rec, E. Sanchez-Cortezon, Z. Karichev, J.H. Miners,
[349] Q. Zhang, G. Zhang, X. Sun, K. Yin, H. Li, Improving the power conversion Alkaline fuel cells: contemporary advancement and limitations, Fuel 81
efficiency of carbon quantum dot-sensitized solar cells by growing the dots (2002) 2151e2155.
on a TiO2 photoanode in situ, Nanomaterials 130 (2017) 7060130. [369] H. Fei, R. Ye, G. Ye, Y. Gong, Z. Peng, X. Fan, E.L.G. Samuel, P.M. Ajayan,
[350] Q. Liu, Y. Yin, N. Hao, J. Qian, H. Mao, K. Wang, Self-templating synthesis of J.M. Tour, Boron- and nitrogen-doped graphene quantum dots/graphene
nitrogen doped graphene quantum dots/3D bismuth oxyiodine hybrid hol- hybrid nanoplatelets as efficient electrocatalysts for oxygen reduction, ACS
low microspheres with improved visible-light excited photocurrent gener- Nano 8 (2014) 10837e10843.
ation: simultaneous electron transfer acceleration and bandgap narrowing, [370] A. Dhand, S. Suresh, A. Jain, O.N. Varadan, M.A.K. Kerawalla, P. Goswami,
J. Alloy. Comp. 729 (2017) 27e37. Advances in materials for fuel cell technologies-a review, Int. J. Res. Appl. Sci.
[351] X. Zhang, R. Ke, S. Zhang, H. Niu, J. Song, C. Mao, B. Jin, Y. Tian, One-step Eng. Technol. 5 (2017) 1672e1682.
electrosynthesis and photoelectric conversion of selenium nanowires

Graphene Quantum Dots From Chemistry To Applications 2018

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What are some of the methods used to prepare graphene quantum dots?

How have graphene quantum dots been characterized and what properties have been studied?

Materials Today Chemistry 10 (2018) 221e258

Contents lists available at ScienceDirect

Materials Today Chemistry

Graphene quantum dots from chemistry to applications

1. Introduction Bernal using single-crystal diffraction measurements [3] in 1924. As

Fig. 1. The history of carbon materials development.

good solubility, surface grafting, biocompatibility and inertness

1.2. The outlooks of graphene quantum dots

The research on GQDs is still at an early stage, and many chal-

where F is QY, K is the slope determined by the curves, h is the

of the density of states of different functionalized GQDs. The

3.3. Graphene quantum dot composites to optimize performances

Active materials Performance Structure Ref.

Detectivity Responsivity Response EQE (%) Tested Cover spectral

GQDs/SiNW 11.9 1012 40.6 d 8150 RT UV-NIR Vertical [256]

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