ADAMA SCIENCE AND TECHNOLOGY UNIVERSITY

SCHOOL OF APPLIED NATURAL SCIENCE

DEPARTMENT OF APPLIED CHEMISTRY
MATERIALS CHEMISTRY PhD PROGRAM

GRAPHENE QUANTUM DOTS [GQDs]

A Seminar Presented for the Course: Material Synthesis
Endale Kebede Feyie
Wednesday June 19, 2019
Presentation outline
 INTRODUCTION

 PROPERTIES

 SYNTHESIS

 APPLICATION

 CHALLENGES
GRAPHENE QUANTUM DOTS
[GQDs]
PROPERTIES, SYNTHESIS STRATEGIES, AND
APPLICATION
1. INTRODUCTION

 Graphenequantum dots (GQDs) represent single-layer to tens of layers of

graphene of a size less than 30 nm.
 The GQDs are different from CQDs because they possess graphene lattice
inside the dots, which are smaller than 100 nm in size and less than 10 layers
thick
 CQDs are usually quasi-spherical carbon nanoparticles having a size of less than 10 nm
 Compared to the quantum dots of a traditional semiconductor, the GQDs
possess many advantages
stable fluorescence properties
low toxicity
good water solubility
 Among them, the fluorescence properties are the most important feature of the
GQDs.
2. PROPERTIES
 In addition to quantum confinement
and edge effects, GQDs exhibited
many important characteristics, such
as: stable photoluminescenc (PL),
non-toxicity, good solubility,
surface grafting, biocompatibility,
inertness
 Some of these characteristics are
overwhelmingly superior to
traditional semiconductor
quantum dots, hence prompted many
potential applications of GQDs in solar
cells, photodetectors, bioimagings,
fluorescent agents, light-emitting
diodes (LEDs), batteries, sensors, drug
carriers, photo-/electro-catalytic
3. SYNTHESIS OF GQDs
 Based on the GQDs preparation methods
developed in recent years, these
methods can be classified into two
categories, namely
 top-down
 bottom-up
 top-down method refers to direct
cutting of graphene-related
materials such as graphene, graphene
oxide, carbon nanotubes, carbon fibers,
carbon black , graphite powder and coal
into quantum size via various processes.
 In bottom-up approach, graphene-like
smaller polycyclic aromatic hydrocarbons
(PAHs) molecular precursors (such as
benzene, hexaperi-hexabenzocoronene,
glucose and fullerene are converted to
GQDs by stepwise chemical reaction.
3.1. TOP-DOWN APPROACH

 The top-down strategy involves cutting

Precursor carbonaceous materials are:
carbonaceous materials containing graphene
sheets into smaller nanosheets through  carbon fibers,
chemical and physical approaches, including  graphene,
 hydrothermal, solvothermal,  Graphene oxide (GO)
 ultrasonic, Microwave  graphite,
 Chemical oxidation  carbon black,
 electrochemical treatment,  carbon nanotubes,
 electron-beam lithography,  Coal

Advantages
• abundant raw materials
• produce oxygen containing functional groups at the edge,
• facilitating their solubility and functionalization.
Disadvantages
• low yield,
• large density of defects,
• Little control of size and shape
3.1.1. Electron-beam lithography

 GQDs were prepared first by electron-beam lithography in 2008.

 graphene was peeled off from graphite by mechanical exfoliation,
 deposited onto the n-Si substrate that was coated with 300 nm SiO 2 and 90 nm
poly(methyl methacrylate) (PMMA) as a protective layer.
 Subsequently, Ar/O2 (9:1) plasma as reactive ion etchant (RIE) was introduced to eliminate
unprotected graphene.
 After removing the residual PMMA, single GQDs with the thickness of about 0.5 nm was
obtained.
 Although this method could be difficult to obtain smaller GQDs, it paves a way for
further studies on GQDs.
3.1.2. Hydrothermal treatment

 the earliest chemical method reported for preparing GQDs with the size down below
10 nm by cutting oxidized graphene sheets into nanosize GQDs
 The graphite oxide was thermally deoxidized in tube furnace to give graphene sheets (GSs).
 the GSs were re-oxidized in the mixture of H2SO4 and HNO3 (volume ratio = 1:3) under mild
sonication and the oxidized GSs were dispersed in water to form a pH = 8 suspension.
 The solution was then treated at 200°C for a period of time to yield GQDs.
 Fluorescence spectra prove that the as-synthesized GQDs emit bright blue fluorescence
even in the neutral solution.
3.1.3. Chemical oxidation

 Chemical oxidation is widely used to synthesize GQDs

 highly depends on different carbon sources, such as carbon fibers, coal, carbon nanotubes,
graphite and carbon black in the mixture of strong acids (sulfuric acid and nitric acid).
 The oxygen-containing groups such as C=O, C–O, O–H are introduced to the surface of GQDs
during the oxidation.
 provides a simple approach to synthesize GQDs using cheap, abundant precursors.
 The fluorescence of synthesized products can also be tuned by changing reaction temperature
and time
3.1.4. Electrochemical cleavage
 electrochemical cleavage of precursors such
as carbon nanotubes, graphite, reduced GO.
 OH• and O• generated in the anodic oxidation
of water act as “scissors” to cut precursors
into GQDs.
 Oxygen-containing groups or heteroatoms are
typically introduced to the resulting GQDs.
 Heteroatoms doping in GQDs can be achieved
by a precursors approach, that is, heteroatom
containing precursors were used as carbon
sources.
 For example, Li et al. produced N-doped GQDs
by such a simple, effective electrochemical
strategy.
 Unlike the N-free counterparts, N-doped GQDs
exhibit a superior electrocatalytic activity for
the oxygen reduction reaction in alkaline
solutions.
3.1.5. Microwave irradiation
 microwave irradiation can heat reaction
media in a fast, uniform manner,
contributing to shorten the reaction time,
enhance the yield and purity of products.
 microwave is also used to synthesize
GQDs from graphite or GO.
 The reaction media are usually prepared
by dissolving strong oxidants (such as
nitric acid and potassium permanganate)
with sulfuric acid.
 During the microwave treatment, the
oxidation cleavage of precursors occurs
quickly.
 The resulting GQDs usually have more
uniform size distribution compared with
those products obtained through other
routes.
3.1.6. Other methods
 Because of the unique structure and
excellent properties of GQDs, more and
more preparation methods have been
reported, such as the
 chemical vapor deposition (CVD)
 pulsed laser ablation (PLA)
 electron-beam irradiation
 Grinding of graphite in ionic liquid
 oxygen plasma
 For instance, Lee et al. reported the size-
controlled fabrication of uniform GQDs
using self-assembled polystyrene-b-
polydimethylsiloxane (PS-PDMS) block
copolymers (BCPs) as an etch mask on
graphene films grown by chemical
vapor deposition (CVD).
3.2. BOTTOM UP METHODS

 In bottom-up approach, graphene-like smaller polycyclic aromatic hydrocarbons (PAHs)

molecular precursors such as benzene, hexaperi-hexabenzocoronene, glucose and
fullerene are converted to GQDs by stepwise chemical reaction.
Advantages,
 fewer defects and controllable of size and morphology;
Disadvantage
 poor solubility,
 small dot size
 aggregation issue
 this method can be subdivided into four main routes, which cover
 hydrothermal method,
 microwave-assisted hydrothermal method,
 soft-template method
 metal-catalysed method,
3.2.1. Hydrothermal method

 involves various techniques of crystallizing 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 research groups.
 Dong et al. successfully fabricated GQDs, having a size of ~15 nm, using citric acid (CA) as
source with height in the range of 0.5-2.0 nm.
 Yang's group Using CA and ethylenediamine (EDA) as carbon source materials, successfully
produced nitrogen doped GQDs (N-GQDs) with a size of 5-10 nm,
 Chen and co-workers fabricated amine-functionalized N-GQDs using CA and tris(hydroxymethyl)
aminomethane (Tris-HMA)
 The GQDs emitting bright green fluorescence with high yield of 63% were synthesized
with pyrene via hydrothermal method by Wang et al.
 Guo's group prepared GQDs with tunable PL emission using 1,5-dinitronaphthalene as raw
the amine-functionalized GQDs exhibited a distinct tunable PL emission from bluish green
to yellow by changing the pH level from 5 to 10
3.2.2. Microwave-assisted hydrothermal method

 Hydrothermal growth of GQDs usually takes long time and is not ideal for industrial mass
production of GQDs.
 Thus, a fast and effective method was exploited by assisting with microwave, so-called
microwave-assisted hydrothermal (MAH) method.
 Yang co-author reported the fabrication of fluorine-doped GQDs by using MAH method and the
growth of F-GQDs , the size of F-GQDs was 2.38 ± 0.04 nm
3.2.3. Soft-template method/controlled pyrolysis

 developed for facile, low-cost and environmental friendly fabrication of GQDs.

 It provides nanoscale reaction cavity without complicated separation and purifying
processes. Therefore, this route is in favour for mass production.
 Yang and co-author prepared GQDs by the soft-template approach.
 The TATB which is a planar and highly symmetric molecule with six strong intramolecular
hydrogen bonds between -NH2 and -NO2 functional groups, and possesses a graphitic-like
layered structure was used as the carbon source and template
 Müllen's research group achieved monodispersed disk-like GQDs of ~60 nm using HBC as
precursor via the soft-template method.
 Gao and co-workers utilized small molecular carbon disulphide as template to fabricate GQDs
doped with sulphur.
 Do et al. [86] used CA as the template to synthesize GQDs, which demonstrated high-
quantum yield of 83%.
 the soft-template can be a candidate for solving at least one of the challenges of GQDs, such
as low-product yield.
3.2.4. Metal-catalyzed method
 Metal-catalyzed method is a scarce route for preparation of GQDs.
 Loh et al. utilized ruthenium as metal catalyst and used C60 as a precursor to synthesize GQDs
 However, special structure of raw material and metal-catalyst were necessary for the
fabrication of GQDs using this method, thus this route is uncommon.
4. FUNCTIONALIZATION OF GQDs
 Pure GQDs have many limitations which
restrict its application.
 In order to expand its application in a variety
of fields, GQDs can be functionalized by
various methods to customize its properties
for specific applications.
 Functionalization of GQDs could modify its
optical, chemical and electronic properties,
which allow the materials to be used in wide-
ranging applications.
 doping with heteroatoms, forming composites
with inorganic materials or polymers, and the
controlling of size and shape of GQDs can be
considered as functionalization.
 The basic properties of GQDs are changed via
those means, which could potentially address
some of the challenges faced by GQDs.
4.1. Doping of GQDs

 functionalization of GQDs by means of doping

can modify its optical, electronic and
chemical properties for novel applications.
 In general, we can categorize the doping
method into three groups depending on the
number of doping atoms
 To date, the heteroatoms used in the doping
of GQDs include potassium (K), sodium (Na),
boron (B), nitrogen (N), phosphorus (P),
oxygen (N), sulphur (S), selenium (Se),
fluorine (F) and chlorine (Cl)
Doping of GQDs
Graphene quantum dot composites

 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 the
performances of the material, thus leading to many novel applications.
 polymer materials and nano-materials can be used to form composite with GQDs.
 Organic materials have a lot of merits, such as easy to form film, high carrier mobility and so on.
These virtues could complement the performances of GQDs.
 Wen and co-workers fabricated fluorescent organosilane-functionalized GQDs (Si-GQDs) and
subsequently embedding them into mesoporous hollow silica spheres as bio-label
 Chen and co-workers developed composite of GQDs and polypyrrole (PPy) as counter
electrode of dye-sensitized solar cells (DSSCs) to optimize the performances of the solar cells.
 Zor et al. prepared a novel multifunctional composite consisting of magnetic silica beads,
GQD and molecularly imprinted polypyrrole. The composite exhibited enhanced optical and
magnetic properties.
 Malik's group prepared nanofiber composite, which consisted of GQDs and polyaniline, as
supercapacitor electrode materials.
4.2. Composites

 Apart from the composites of GQDs and organic materials, many inorganic materials have
been used to form GQD composites to improve the performances of devices.
 Dhar and co-workers demonstrated the composite of ZnO and GQDs can enhance the
performance of UV photodetector
 TiO2 and GQDs nanocomposites were fabricated by Bu. The nanocomposites were used as
photocatalysts, which exhibited extremely high photocatalytic activity due to the larger energy
barrier between NGQDs and BeTiO2, resulting in enhanced light absorption and higher electron
density.
 Ji et al. assembled lithium ion battery using composite of MnV 12 and GQDs. The bar shaped
composites can maximize the interfacial contact area and improve charging/discharging
behavior, thus optimizing the performances of the lithium ion battery.
 Many inorganic materials have been used in forming composites with GQDs, such as
SnO2, ZnS, MoS2, ferroelectric liquid crystal, ceria, Zn, Fe2O3 etc.
APPLICATIONS

• Major applications
are:
 Optics
 Medicine
 energy
5. APPLICATION

MEDICAL APPLICATIONS
 Biological imaging
 Drug delivery
 Photodynamic therapy: a form of phototherapy involving the use of light and a photosensitizing
chemical substance that applied in conjunction to elicit cell death by molecular oxygen (phototoxicity).
 Photothermal therapy
 Antimicrobial materials
OPTICAL APPLICATIONS
 Optoelectrical detector
 Light emitting diodes
 Photocatalysis
ENERGY-RELATED APPLICATIONS
 Solar cells
 Energy storage battery
 Fuel cell
CHALLENGES
6. CHALLENGES

 Although there are many important advantages and potential applications of GQDs, further
research to enhance the properties of the material is required in order to meet the
application requirements.
 Therefore, the studies of GQDs have been on-going to address the five urgent issues as
stated in Fig
 Low product yield
 Low quantum yield
 Control of size and shape
 Mechanism of photoluminescence
 Narrow spectral coverage