Accepted Manuscript

Graphene quantum dots and their possible energy applications: A review

Sora Bak, Doyoung Kim, Hyoyoung Lee

PII: S1567-1739(16)30100-6
DOI: 10.1016/j.cap.2016.03.026
Reference: CAP 4219

To appear in: Current Applied Physics

Received Date: 13 January 2016

Revised Date: 22 March 2016
Accepted Date: 23 March 2016

Please cite this article as: S. Bak, D. Kim, H. Lee, Graphene quantum dots and their possible energy
applications: A review, Current Applied Physics (2016), doi: 10.1016/j.cap.2016.03.026.

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Graphene Quantum Dots and Their Possible Energy

Applications: A Review

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Sora Bak1,3, Doyoung Kim1.2, and Hyoyoung Lee1,2,3,4,*

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1
IBS Center for Integrated Nanostructure Physics, Institute for Basic Science (IBS), 2Department of

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Energy Science, 3Department of Chemistry, 4SKKU Advanced Institute of Nano Technology (SAINT),

Sungkyunkwan University, Suwon, 440-746, Republic of Korea.

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Corresponding author E-mail: hyoyoung@skku.edu

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Abstract

As new carbon-based materials, graphene quantum dots (GQDs) many advantages due to the
additional unique properties that arise from their nanoscale small size. GQDs are expected to be suitable
for various applications. For use of GQDs in various fields, mass production is critically required. To

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date, many methods for preparing GQDs with good properties and high yield have been introduced. The
main synthesis strategies are known as bottom-up and top-down methods. Synthesis of GQDs from

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small organic molecules, known as the bottom-up approach, is appropriate for controlling the size of
GQDs but requires multistep organic reactions and purification at each step. However, the top-down

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approach of breaking the carbon-carbon bonds of a large carbon source is easy and simple, and therefore
suitable for mass production. Here, we briefly introduce the solution-process synthesis of GQDs using a

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top-down method and recent energy-related applications such as capacitors, lithium ion batteries, and
solar cells.
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Highlights
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Method for synthesis of GQDs in solution process to simplify the reaction steps.

Introduction of recent progress of GQDs based energy applications.
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Suggest the various unique optoelectronic properties of GQDs

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Keywords: Graphene quantum dots, capacitor, battery, solar cell, photovoltaic cell

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1. Introduction
The discovery of graphene with sp2-sp2 carbon bonds and its subsequent development proved the
way to a new generation of various devices due to its superior properties such as extremely high
mechanical stiffness, strong elasticity, high thermal stability, and electrically high conductivity.[1,2]
Intrinsically, graphene itself does not have a bandgap but can be opened by controlling the size, such as
a nano-ribbon strip, and by introduction of other hetero atoms and defects into the graphene moiety.

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On the other hand, graphene quantum dots (GQDs) that consist of nanometer-scaled graphene
particles with sp2-sp2 carbon bonds are expected to show characteristic properties such as size-
dependent general quantum dots (QDs) [41,42] or chemically modified quantum dots with sp2-sp2

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carbon bonds. In contrast to graphene, most applications of GQDs have been focused on the
photoluminescence (PL)-related fields since GQDs show a PL. In recent studies, additional excellent

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properties of GQDs such as high transparency and high surface area have been proposed for energy and
display applications.[44] Because of the large surface area, electrodes using GQDs are applied for

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capacitors[44] and batteries,[45,46] and the conductivity of GQDs is higher than that of graphene oxide
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(GO).[51] In particular, their hole transporting ability is good, therefore GQDs can be applied for hole
transport layers. In addition, due to their nm size, GQDs are well dispersed in various organic solvents
to allow many organic reactions and solution processes. Therefore, with further modifications and with
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different synthesis conditions GQDs can be modified to show different PL colors, indicating changes in
band gap. For commercially available products, the mass preparation of GQDs and simple device
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fabrication become important issues. For these purposes, the solution process with well-dispersed GQDs
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in various solvents is preferred.

Here, we introduce the solution-process synthesis of GQDs using a top-down method and energy-
related applications such as capacitors, lithium ion batteries, and solar cells. Figure 1 illustrates the
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unique properties of GQDs with energy related applications.

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2. Synthesis
There are many methods for synthesizing various quantum dots (QDs). Among them, top-down and
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bottom-up strategies are well categorized.[3] For general metal QDs, the bottom-up method is preferred
over the top-down approach because it is much easier to uniformly control the size, which is directly
related to the band gap of QDs.
In the case of GQDs, the size also can be controlled through a cage-opening of fullerene [4] and by
organic synthesis using the bottom-up method.[5,6] However, preparation of GQDs using the bottom-up
method requires very stringent conditions with specific organic materials after complicated reaction
steps.[5,6]

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On the other hand, preparation of GQDs using the top-down method that involves cutting down
bulk carbonaceous materials into small pieces is preferred, as described below. The starting materials
are abundant raw carbon materials that can be cheaply and easily prepared. In addition, due to the
simple preparation steps, researchers are trying to develop top-down methods for mass production. For
starting materials, GO is a good candidate because it contains an abundance of oxygen-containing
functional groups that can be easily broken down into nanometer sized and single-layered GQDs (Fig.

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2a).[8] However, since the preparation of GO itself involves several processes,[7] the direct use of a
natural resource without specific production processes, such as graphite, as a starting material has
recently been introduced. The yield of GQDs from graphite is not high since natural graphite does not

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have enough functional groups. To enhance the yield of GQDs various methods have been investigated,
including the use of strong acidic conditions like a modified Hummers method and the use of

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microwaves as an external power source.[29,30] In general, for controlling the size of QDs, sorting the
size of quantum dots using top-down strategies has been tried.[11,33,34] Until now, however,

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generating uniform diameter GQDs at the synthesis step by applying the top-down method has not been
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greatly successful, although separation of GQDs according to the diameter size have shown marginal
success.
In this review paper we focus on the various synthetic methods to prepare GQD, in particular with
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the top-down solution process, for a high product yield from GO, graphite, or other carbon materials as
starting materials.
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2.1. Starting materials and methods for making GQDs

2.1.1. Graphene and graphene oxide
The functional groups on graphite play an important role in breaking down the carbon-carbon bonds
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of graphite, so single or few layered GO is one of the best starting materials.[8] The GO nanosheets are
functionalized enough with oxygen-containing groups that can be easily broken down into small parts
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and also well dispersed in various solvents, especially in water. Due to these advantages, there are
numerous reports of the use of GO as the starting material for the synthesis of GQDs in solution phases.
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2.1.1.1. Hydro- and solvo-thermal methods

Pan et al. suggested a solution process for GQDs from oxidized graphene sheets (GS) involving a
hydrothermal method at 200C.[8] To increase the product yield, they oxidized the graphene sheets to
introduce more oxygen-containing groups such as ketone, carboxyl, hydroxyl, and ether groups. The
size of GS is reduced during the oxidation and reduction processes. As a result, GS becomes GQDs with
9.6 nm average diameter after hydrothermal de-oxidation with approximately 5 % yield. According to

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FTIR and XPS, particularly C=O (ketone/carboxyl) and epoxy functional groups are dramatically
reduced after hydrothermal treatment. Unlike oxidized GS, GQDs show blue luminescence with an
excitation-dependence that is similar to that of most luminescent carbon nanoparticles.
The PL peak of these GQDs is shifted from blue to green depending on the solvent (Fig. 2b). With a
hydrothermal reaction of the oxidized GS in ammonia solution, amino-functional groups are also
introduced into the edge site of GQDs.[10] In this approach the degree of functionalization and PL color

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can be controlled by different reaction temperatures and concentrations of ammonia solution (Figs. 2c
and 2d).
In addition, GQDs are easily tuned using solvothermal treatment with various solvents. GO

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ultrasonicated in DMF can be cut into GQDs, which emit a green luminescent light with high solubility
in most polar solvents due to the existence of oxygen and nitrogen atoms.[9]

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2.1.1.2. Ultrasonication methods

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Graphene derivatives can be cut down to GQDs only using mechanical force.[11] For this, graphene
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sheets can be oxidized with a ultrasonic treatment under a strong acidic condition. After multiple
purifications GQDs can be obtained that are 3-5 nm in diameter and showthe bright blue PL. Generally,
the ultrasonication methods can be combined with solvothermal and microwave treatments.
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2.1.1.3. Microwave methods

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Microwave methods utilize the heat that is emitted as a result of molecular rotation of polar solvent
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molecules with an electrical dipole moment by microwave energy.[12] This microwave method can be
applied to synthesize organic[13] and inorganic materials[14] in a short time with a high yield. Based on
microwave-assisted reduction, Li et al. reported that GO can be broken down into GQDs under strong
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acids (HNO3 and H2SO4). They also reported that the reaction time was reduced compared with that of a
solvothermal process.[15] These GQDs have green fluorescence (gGQD), but after further reduction
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with NaBH4, they change to blue PL (bGQD) and the intensity is increased. Although the PL properties
are dramatically changed, there is no detectable difference in the size before and after NaBH4 treatment
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(Fig. 3a). Similarly, carbon dots (CDs) show changes in PL after reduction.[16] Zheng el al. explained
the relationship between functional groups and PL properties by the quantity of hydroxyl groups. As the
quantity of hydroxyl groups, which are one of electron-donating groups, is increased during reduction,
the luminescence intensity is enhanced. The more hydroxyl groups on CDs, the higher the PL intensity.
Various trials to tune the optical properties with functional groups have been suggested.[17,18,19]

2.1.1.4. Radical methods

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Fluorescent carbon materials can be generated from the graphite electrode by electrochemical
methods.[20] Li et al. prepared GQDs using the electrochemical method.[21] Hydroxyl and oxygen
radicals from the oxide water can cleave the C-C bond. GQDs are generated via cyclic voltammetry
scans of reduced GO used as a working electrode in phosphate buffer solution (PBS).
Zhou et al. synthesized GQDs using a photo-Fenton reaction.[22] The hydroxyl radicals generated
from the Fenton reagent (Fe2+/Fe3+/H2O2) under UV (365nm, 500 W) can cut the GOs into GQDs. After

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the reaction, most of the oxygen groups in GOs are removed and the resulting GQDs show blue photo-
luminescence.

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2.1.2. Carbon nanotubes (CNTs) and carbon fibers (CFs)
The strategy for the preparation of GQDs using carbon nanotubes (CNTs) and carbon fibers

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(CFs) as starting carbon materials is similar to the preparation of graphene nanoribbons (GNRs) by
longitudinal unzipping of CNTs.[23,24] The functionalized sites can break the backbone structure of

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CNTs, so that the heteroatom-doped CNTs and CFs are broken into nanosized carbon materials.[25,26]
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During the exfoliation, CNTs and CFs can be turned into GQDs (Fig. 3b).[27] Potassium ions are
intercalated into the layered structure of CNTs and CFs during heating under vacuum condition. After
exposure to air, ethanol, and water, the product yields of the oxidized GQDs are 22.96% from CNT and
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9.9% from CFs.

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2.1.3. Graphite for making GQDs

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2.1.3.1. Hummers method for making GQDs

GOs can be prepared with large scales from graphite using Hummers method,[28] and after
repeated reduction and oxidation can be turned into GQDs. The preparation of GQDs from GOs has a
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strong advantage in terms of easy and effective mass production of GQDs. However, even though mass
production of GQDs from GOs is possible, the price of GOs will not be low enough for conversion of
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GOs into GQDs within the near future. Therefore, the direct conversion of graphite, which is cheap and
universally present, into GQDs has been investigated. An improved Hummers method is used for the
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solution process from the graphite.[29] The two main steps to make GQDs are oxidation and cutting of
graphite. The reaction conditions for the preparation of GQDs are more stringent than those for the
preparation of GOs due to an extra cutting step. Graphite is first oxidized in an excess amount of a
mixture of H2SO4 and NaNO3, and then cleaved into nano-sized GQD dots by heating at high
temperature with high pressure in a closed autoclave vessel. The GQDs are uniform and consist of
monolayers or few layers. The yield of GQDs is approximately 63%. Shin et al. suggest a one-pot
synthesis method for mass production of GQDs using high-powered microwave treatment.[30] The

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microwave treatment is important for a smaller size and higher product yield in a short time. First,
graphite is dispersed in a strong oxidizing agent (H2SO4 and then KMnO4). As microwave irradiation
with least power is applied, the solution becomes transparent. The resulting product yield is around 70%.
These GQDs are uniform with a diameter of 2-8 nm and show a blue luminescence, indicating removal
of the oxygen-containing functional groups with reduction. .

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2.1.3.2. Acid-free Method
As we noted, the Hummers method for GQDs with microwaving is simple and shows a high

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product yield, but it has still some drawbacks. After reaction, the strong acid has to be removed by
complicated purifications including neutralization or evaporation at high temperature.[11] Therefore, it

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is important to find the methods without any strong acids that do not require inconvenient purification
steps.

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Song et al. suggest mass-producible method for GQDs with exfoliation of graphite intercalation
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compounds (GICs).[61] In here, potassium-sodium tartrate (KNaC4H4O64H2O) is an important reagent.
It can be intercalated into the graphite to make GICs with minimal damage and be a solvent for
solvothermal treatment. After exfoliation of GICs in water, GQDs are generated with high yield (>60 %
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yield). The GQDs have near UV emission (~400 nm) which means low oxidation.
Oxone, a monosulfate compound, is suggested as a neutral oxidant that does not require the tedious
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neutralization step.[31] GO is mixed with oxone, and treatment by both sono- and photo-oxidations can
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produce GQDs. Using oxone, various GQDs are prepared directly from graphite, carbon nanotubes
(CNTs), carbon fibers (CF), and coal in acid-free conditions. Instead of sono- and photo-oxidation
treatments, a thermal reaction method also can produce GQDs.[32] Through the solvothermal redox
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reaction, all of these carbon-based materials are converted into GQDs. The properties of GQDs from
different carbon sources are not the same. The initial product yield is around 10%, and the re-collected
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product yield after the 2nd run is 6%.

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2.2. Size distribution of GQDs

2.2.1. Size sorting methods of GQDs
Size sorting of nano-sized quantum dots is one of the important factors determining their properties.
The top-down methods for GQDs are based on the introduction of defects into the carbonaceous starting
material during oxidation and reduction. However, it is not easy to control the site for functionalization
and defects, so GQDs produced by top-down strategies do not have uniform size. As a result, further
purification steps are needed to collect GQDs with uniform diameter. General and simple ways to

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classify by size are filtration and dialysis methods. Using different pore sizes, GQDs can easily be
separated[33] and the effects of size of GQDs on structural and optical parameters can be observed (Fig.
4). In general, the PL peak position is dependent on the size of the QDs, but PL peaks of GQDs that are
bigger than 17 nm show an anomalous size dependence. This result can be explained by differences in
the shape of the GQDs. The major shape of GQDs that are smaller than 17 nm is circular or elliptical with
mixed edge structure of zigzag and armchair, while that of GQDs that are bigger than 17 nm is polygonal

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mainly with armchair structure. The shape affects the major edge type and leads to the abnormal PL
properties. In addition, chromatographic separation is also possible in which the different sizes of GQDs
are separated according to different packing materials and eluent systems.[34]

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2.2.2. Size control method of GQDs

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Lee et al. suggested a new method for preparing uniform GQDs with a top-down method (Fig.
5a).[35] They have reported a technique to make well-aligned silica nanodots with uniform size, in

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which the size of silica dots can be controlled by the reaction conditions (Fig. 5b). Silica dots on CVD-
graphene act as masks during etching, so the resulting GQDs have almost same size as the nanodots,
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with diameters of 10 nm and 20 nm (Fig. 5c).
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2.3. Further development in the synthesis of GQDs

The basic concept for making GQDs is cleavage of carbonaceous starting materials through
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repeated oxidation and reduction. At the present time, the environmentally friendly approach for the
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preparation of GQDs is the hydrothermal strategy using GO as a starting material and the mass
production method is strong-acidic treatment of graphite. For further development of GQDs, we need to
find the commercially available methods for preparation and easy and effective purification methods to
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distinguish various GQDs.

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3. Energy Applications of GQDs

Electrochemical energy applications such as electrochemical capacitors, Li ion batteries, and solar
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cells have attracted much attention because of the strong demand in our society. To date, many kinds of
metal oxides[36,37], sulfides,[38] and conductive materials[39,40] have been used in the design of
energy applications. Many researchers are trying to find energy-related and environmentally friendly
products using GQDs that have unique properties such as high transparency, large surface area, strong
and PL intensity. Therefore, it is meaningful to introduce energy-related and environmental applications
of GQDs.
3.1. Capacitors

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In principal, the main characteristics of an electrochemical capacitor are charge transfer and storage
mechanisms. There are two different kinds of capacitor: the first uses ion absorption and desorption
mechanism and is called a double layer capacitor, or simply a supercapacitor, and the second uses a
surface redox reaction (Faradaic reaction) mechanism and is called a pseudocapacitor. For the
development of a high-efficiency capacitor, a high surface area of electrode material, high conductivity,
and wide potential window are required. For good capacitor materials, high power density, stable long

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cycle life, and fast absorption and desorption (charge and discharge) capability are required. To date,
many articles on GQDs and CDs have reported advantages for application in electrochemical capacitors
due to their favorable properties such as high surface area, high electrical conductivity, high mobility,

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tunable band gap, and good dispersion in various solvents.[41,42] Mondal et al. reported the excellent
specific capacitance value of a quantum dot-based supercapacitor by GQDs with pseudocapacitance

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derived from doped polyaniline composites by the chemical oxidation of aniline.[43] They successfully
synthesized ~6.0 nm sized GQDs from GO flakes. In particular, the synthesized GQDP(polyaniline)

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composites were nanofibrous or nanotubular in nature. Moreover, the inner diameter could be controlled
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by the weight ratio of GQDs to aniline. The GQDP composites showed a specific capacitance value of
~1044 Fg-1 at a current density of 1 Ag-1, with 80.1% retention of capacitance after 3,000 cycles. The
GQDP schematic diagram is shown in Fig. 6.[43] In addition, Liu et al. reported a GQD-based micro-
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supercapacitor. GQDs were synthesized from GO powder using a facile one-step solvothermal method.
They tried two different types of capacitor systems, symmetric and asymmetric. A GQD/GQD
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symmetric capacitor prepared using a simple electrodeposition approach in aqueous electrolyte and
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ionic liquid electrolyte was systematically investigated. Additionally, a GQD/metal oxide-MnO2

asymmetric capacitor was also built using MnO2 nano-needles as the positive electrode and GQD as the
negative electrode in an aqueous electrolyte in the capacitor fuel cell structure. The GQD
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electrodeposition and morphologic studies are shown in Fig. 7.[44] This special structure of the GQD-
based capacitor facilitates the transport of electrolyte ions and provides abundant surfaces for charge
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transfer behaviors. The asymmetric capacitor has shown promising properties, exhibiting specific
capacitance and energy density 2 times higher than those of the previous GQD/GQD symmetric
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capacitor in the same aqueous electrolyte. Amazingly, it shows great rate capability, with a scan rate of
up to 1000 Vs-1 and good power response with a small resistor capacitor (RC) time constant of 103.6 s,
specific capacitance of 468.1 Fcm-2, and cycle stability in 0.5 M Na2SO4 aqueous solution. Moreover,
the GQD/GQD symmetric capacitor in 2 M EMIMBF4/ACN (1-ethyl-3-methylimidazolium
tetrafluoroborate/acetonitrile) electrolyte shows a potential window of 2.7 V, a smaller RC time constant
of 53.8 s, and a 7 times higher energy density compared with that using a Na2SO4 electrolyte. The

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asymmetric capacitor showed 2 times higher specific capacitance than the symmetric capacitor (1107.4
Fcm-2) and energy density of 0.154 Whcm-2. The electrochemical properties are shown in Fig. 8.[44]

3.2. Li ion battery

At the present time only two reports are available. Chao et al. reported generation of a Li ion
battery using GQDs. First, they synthesized graphene flakes that supported a GQD-anchored VO2 array

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electrode (denoted as GVG), as shown in Fig. 9.[45] CVD-grown graphene foam was employed as the
substrate to grow VO2 arrays via a solvothermal process and then the GQDs were attached to VO2
arrays by an electrophoresis process. Generally speaking, GQDs are negatively charged with carboxyl

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groups on the surface. They can be immobilized onto the positively charged surface of a VO2 array
through a process driven by positive bias in the electrophoresis deposition process.[46] It is well known

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that VO2 is a semiconductor with low electrical conductivity, low initial Coulombic efficiency, and high
electrochemical impedance. They expected that the conductive graphene flake and GQDs coating the

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VO2 would support high electrical conductivity. Also, the homogeneous GQDs covering the VO2 can
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effectively prevent direct contact, avoiding agglomeration as well as minimizing the dissolution of
active materials. The Li ion battery based on a GVG electrode shows a ~99% initial Coulombic
efficiency and 100% efficiency during the following cycles and the specific capacity is 389 mAhg-1 at
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1C, and 36% capacitance was retained when the current density increased from 1/3 C to 120 C. And
also, GVG electrode provided 94% retention of the original capacity after 1,500 cycles at 18 Ag-1. In
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addition, Na ion battery based on a GVG electrode showed a 306 mAhg-1 of the capacity with great
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capacity retention of 88% after 1,500 cycles at 18 Ag-1.[45] Also, recently another work has been
reported about doped GQDs as an anode material. The researchers reported a facile synthesis of the
lithium titanate/nitrogen and sulfur co-doped GQDs (LTO/N.S-GQDs) as an anode material for Li-ion
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battery. They found important roles of the sulfur and nitrogen co-doped GQDs. The sulfur and nitrogen
atoms on the GQDs showed a synergetic effect. That effect enhanced the electron transfer by strong
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electronic coupling between sulfur and nitrogen co-doped GQDs and LTO anode electrode. This anode
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material exhibited the magnificent electrochemical performance for the Li-ion battery. The specific
discharge capacity was 254.2 mAhg-1 at 0.1C and 126.5 mAhg-1 at 10C. The retention test was resulted
in keeping 96.9% at least after 2,000 cycles at 2C.[57] These results clearly prove that GQDs are
effective materials for electrochemical applications compared with other less stable materials such as
semiconductors. We strongly believe that GQDs can improve the electrochemical property of Li ion
batteries and other ion batteries, especially transparent ion batteries, in the future.

3.3. Solar cell

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GQDs have very attractive benefits for applications to solar cells compared with other materials
used in ongoing research such as silicon, perovskite, and TiO2-based dye sensitized solar cells,[46]
mainly because of their low cost,[47] high chemical stability[48,49], low toxicity, and
biocompatibility.[50] The major factor for use in solar cells is a size-dependent bandgap tuning property.
Also, since GQDs have a quantum confinement and edge effect, they well suited to solar cells. To date,
many kinds of GQD-based solar cells have been reported, such as use of hole transport layer (HTL)

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material,[51] silicon/GQDs heterojunction solar cell,[52] semiconductor/GQDs solar cell,[48]
conductive polymer doped GQDs solar cell,[49] and others.[47,53] GQDs are acted as diverse roles
including hole/electron transport agents[58] and active layer additive in the donor/acceptor blends[59]

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and sensitizers. Gao et al. reported a crystalline silicon with GQD heterojunction solar cell with an
conversion efficiency of 6.63%, They focused on a special energy band structure of GQDs, yielding

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photogenerated electron-hole pairs that were effectively separated at the junction interface and served as
an electron blocking layer to further prevent carrier recombination at the anode. They found that the size

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of GQDs affected the device performance. The open circuit voltage (Voc) of the device increased, while
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the short circuit current (Jsc) decreased, as the size decreased, which means that the heterojunction
barrier increases with a decrease in size and the barrier for hole transportation increases. Many groups
trying to enhance the efficiency of the solar cell have made efforts to separate the photogenerated
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electron-hole pairs and to suppress the recombination of electron-hole pairs. However, mechanism of
enhancement the donor/acceptor blended with GQDs are still unclear. Novak et al. reported a
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dissociation and absorption enhancement of poly-3-hexyl thiophene (P3HT) blended GQDs in the
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organic solar cell system. P3HT as a donor, phenyl-C61-butyric acid methyl ester (PCBM) as an
acceptor, and polyethylene glycol (PEG) as an adhesive agent for improved the GQDs interaction
between active layers were used. They made the three different kinds of chain lengths of PEG. It was
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assumed the shorter PEG chains could give the stronger electronic effect in the active layer to fast
exciton dissociation from P3HT. First, they blended P3HT and PCBM with PEG-GQDs for fabrication
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of OPV cells, followed by general procedure for making a solar cell. As a results, 36% efficiency
improvement in the solar cell compared with general P3HT:PCBM based solar cell was achieved via the
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active layer absorption and exciton dissociation of P3HT.[60] The device and its properties are
illustrated in Fig. 10.[52] Most papers have focused on the use of GQDs as an electron-hole transfer
material and as a tuner of the band gap. These properties enhance the harvest of absorption at the
incident light area for high-performance solar cells.

4. Conclusion and Further Developments

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GQDs are expected to be applied for various applications such as FETs, capacitors, Li ion batteries,
electrodes, and solar cells. To utilize GQDs in various fields, mass production of GQDs is critically
required. Especially important aspects that are emphasized in this review are a low-cost and simple
process, uniform products with proper properties, and high yields. We have briefly introduced various
synthetic methods of making GQDs and also describe recent energy-related applications of GQDs.
In further developments, it is necessary to find easy purification methods to eliminate residual

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reagents that might cleavage the carbonaceous surface and/or find novel methods to achieve an
extremely high yield that does not require the removal of starting materials at all. Also, new strategies to
distinguish GQDs with different sizes are needed to obtain uniform properties of GQDs. One of the

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most excellent properties of GQDs is their high solubility, which means that GQDs can be used in all
device fabrication steps.

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Acknowledgments

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This work is supported by IBS-R011-D1.
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Figures:

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Fig. 1. a) Illustration of general Li ion battery.[55] b) Schematic illustration of the GVG electrode with
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bicontinuous electron and Li/Na ion transfer channels for Li/Na battery.[45] c) Illustration of

supercapacitor electrode.[54]. d) Solution processed GQDs with conducting polymer composite.[43] e)

Illustration of general mechanism of solar cell.[21] f) Schematic illustration of Si/GQDs hetero junction

solar cell.[52] Reprinted with permission from refs. 21, 43, 45, 54, and 55. Copyright 2011 and 2015.

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Figure 1. S. Bak et al.

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Fig. 2. a) General mechanism of cleavage of oxidized graphene during deoxidation. b) PL peaks

of GQDs in different solvents. c,d) Amino-functionalized GQDs with different reaction

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temperature (from the left, 150 , 120 , 70 , 90 and 90 in X2 conc. Ammonia sol
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ution). Reprinted with permission from refs. 8, 9, and 10. Copyright 2010, 2011 and 2012.
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Figure 2. S. Bak et al.

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Fig. 3. Schematic illustration of a) synthesis of GQDs with different PL colors using microwave

and b) making GQDs by the exfoliation of CNTs and graphite. Reprinted with permission from

refs. 15 and 27. Copyright 2012.

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Figure 3. S. Bak et al.
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Fig. 4. HRTEM image and PL spectra of GQDs according to their diameters. Reprinted with per
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mission from ref. 33. Copyright 2012.
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Figure 4. S. Bak et al.

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Fig. 5. a) Schematic representation to make GQDs with uniform size by etching. B) SEM imag

e of 10 nm sized silica nanodots on graphene. c) AFM image of GQDs with diameter of 10 n

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m. Reprinted with permission from ref. 35. Copyright 2012.
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Fig. 6. Schematic diagram for the preparation of GQDP composites. Reprinted with permission

from ref. 43. Copyright 2015.

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Fig. 7. a) Schematic illustration of the electrophoretic deposition of GQDs on the interdigital f

inger electrodes to prepare a GQDs//GQDs symmetric micro-supercapacitor, b) Digital photograp

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hs of GQDs//MnO2 asymmetric micro-supercapacitor built by the electro-deposition of the MnO2

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(right), and then deposited the GQDs (left), c) SEM image of the interdigital finger electrodes
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after the deposition of GQDs and MnO2, d) The digital photographs of the GQDs electrodes

with different electro-deposition times exposed to visible light (top) and ultraviolet light (bottom
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) and e,f) top-view SEM images of MnO2 coating with low and high magnifications. The insets

are photographs of a kind of pine branches native to northeast Asia. Reprinted with permissio
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n from ref. 44. Copyright 2013.

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Fig. 8. a,b,c) CV curves of GQDs//GQDs symmetric micro-supercapacitor obtained in 2.0 M E
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MIMBF4 /ACN electrolyte at different scan rates: a) 1 Vs1 , b) 100 Vs1 , and c) 1000 Vs1

. d,e,f) GQDs//MnO2 asymmetric micro-supercapacitor obtained in 0.5 M Na2SO4 electrolyte at

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different scan rates: a) 1 Vs1 , b)100 Vs1, and c) 1000 Vs1. Reprinted with permission from
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ref. 44. Copyright 2013.

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Fig. 9. Fabrication processes of GF supported GQDs-coated VO2 nanobelts array. a,b.c) Schemat
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ics of the fabrication process. d.e.f) The corresponding SEM images (fine structures in inset). g)

Schematic illustration of the GVG electrode with bicontinuous electron and Li/Na ion transfer c

hannels. h) Ragone plot based on the total mass of the whole electrode, the sloping lines indic

ate the relative time to get the charge in or out of the electrodes. Reprinted with permission fr

om ref. 45. Copyright 2014.

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Fig. 10. a) Illustration of the crystalline Si/GQDs heterojunction solar cell. b) J-V curve of sola

r cell, c) Energy band diagrams of the CH3-Si/Au schottky junction device and d) CH3-Si/GQD
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s heterojunction device. EC and EV represent the conduction band and valence band of silicon,
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respectively. EF is the Fermi level of silicon. e) J-V curves of the CH3-Si/Au, CH3-Si/GO, and

CH3-Si/GQDs solar cells in the dark. Reprinted with permission from ref. 52. Copyright 2014.

Figure 10. S. Bak et al.

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We added These authors contributed equally to this work as below;

1,3 1.2
Sora Bak , Doyoung Kim , and Hyoyoung Lee1,2,3,4,*

1
IBS Center for Integrated Nanostructure Physics, Institute for Basic Science (IBS), 2Department

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of Energy Science, 3Department of Chemistry, 4SKKU Advanced Institute of Nano Technology

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(SAINT), Sungkyunkwan University, Suwon, 440-746, Republic of Korea.

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These authors contributed equally to this work.

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