Optical Materials 60 (2016) 204e208

Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Solvothermal method to prepare graphene quantum dots by hydrogen

peroxide
Renbing Tian a, Suting Zhong a, Juan Wu a, Wei Jiang a, Yewen Shen a, Wei Jiang a, *,
Tianhe Wang b, **
a
National Special Superfine Powder Engineering Technology Research Center, Nanjing University of Science and Technology, 210094 Nanjing, China
b
Nanjing University of Science and Technology, 210094 Nanjing, China

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 synthesized by different chemical methods in recent years.
Received 25 May 2016 For conventional chemical methods, it is inevitable to introduce a large amount of impurities in the
Received in revised form preparation process. Long time of dialysis process increases the time cost extremely. Herein, we report a
13 July 2016
one-step solvothermal method for synthesizing GQDs with the application of hydrogen peroxide in N, N-
Accepted 24 July 2016
Available online 30 July 2016
Dimethylformamide (DMF) environment, which completely avoids the use of concentrated sulphuric
acid and nitric acid to treat raw material and introduces no impurity in whole preparation process
simultaneously for the first time. Pure GQDs can be obtained after evaporation/redissolution and
Keywords:
Graphene quantum dots
filtration process with a strong blue emission at 15% quantum yield. This solvothermal method, not
Solvothermal method requiring dialysis process and complicated equipments, exhibits simple, eco-friendly and low time-cost
Hydrogen peroxide properties. Besides high quantum yields, the as-prepared GQDs also show good photoluminescence
Luminescence stability in different pH conditions. The optical properties, morphology and structure of GQDs were
studied by various equipments, implying potential application in biomedical fields and electronic device.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
When it was firstly found at 2004 [1], graphene has attracted
tremendous attention for its unique properties, such as high surface
area, electronic conductivity, chemical/thermal stability and low
toxicity [2]. These properties make graphene materials promising
candidates in electronic devices and some biological fields [3,4]. If the
lateral dimensions of graphene sheet are smaller than 100 nm, the
graphene, is converted to graphene quantum dots (GQDs) because of
prominent quantum confinement effect and edge effect [5]. GQDs
not only possess the inherent properties of graphene, but also play a
series of novel behaviors in physical and chemical environment [6,7].
One of the most significant properties of GQDs is photoluminescence
(PL). GQDs emit various PL colors with different preparation methods
[8,9], The ultra-small size, stability of PL and biocompatibility make
the GQDs an excellent application in drug delivery, cellular imaging
and fluorescent labelling in vitro or vivo [10e12].
* Corresponding author.
** Corresponding author.
E-mail addresses: superfine_jw@126.com (W. Jiang), thwang56@126.com
(T. Wang).
Over the recent years, numerous synthesis methods have been
developed to prepare GQDs. To sum up, those methods can be
divided into two categories: top-down method and bottom-up
method. Top-down method means directly cutting raw material
(such as graphite anode [13], graphene oxide [6], carbon black [9],
carbon fiber [8], coal [14], fullerene C60 [15], etc) into small gra-
phene segments via chemical, physical and electrochemical tech-
niques. Conversely, the bottom-up method refers to stepwise
synthesis of GQDs from organic precursors [16,17]. Both of the
existing methods suffer from inevitable drawbacks: the bottom-up
methods involve complex process and limited raw materials; the
top-down methods, however, are widely used in the preparation of
GQDs, have to face some notable disadvantages, such as high cost,
difficult to remove impurities and special requirement of equip-
ments. For example, graphene oxide (GO) is a common starting
material in acidic oxidation [6], hydrothermal [18] or photo-Fenton
methods [7]. However, compared with other starting materials, the
cost of GO is not low. What is more, those methods employ strong
acid as oxidant or metal ions as catalyst, which introduce a quantity
of ionic impurities. It takes a long time to remove impurities. In fact,
the remove process is often not complete because of the dynamic
equilibrium in dialysis process. Some preparation process needs

http://dx.doi.org/10.1016/j.optmat.2016.07.032
0925-3467/© 2016 Elsevier B.V. All rights reserved.
 R. Tian et al. / Optical Materials 60 (2016) 204e208
particular equipments, such as electrochemistry [19] and
microwave-assisted methods [18], which are not convenient for
some laboratories to repeat the reaction. They are also unsuitable
for mass production.
Graphite material was used in several chemical methods. Tan
et al. prepared GQDs via electrochemical exfoliation of graphite rod
in K2S2O8 solution with red fluorescent [19]. Liu et al. used graphite
nanoparticles as raw material to prepared graphene quantum dots
and graphene oxide quantum dots by exfoliation in organic solvent
and hummers' method, respectively [20]. GQDs can also be pre-
pared from graphite flakes employing potassium-sodium tartrate
(KNaC4H4O6$4H2O) as both intercalant and solvent according
Song's work [13]. Many other chemical methods prepared GO from
graphite first and then obtained GQDs. Recently, Shin et al. reported
a method using potassium monopersulfate as an oxidant, which
shows acid-free advantage [21]. Although concentrated sulphuric
acid and nitric acid have been avoided in preparing GQDs from
graphite in many methods, however, these methods also introduce
a quantity of impurities into the reaction system, which increases
the purify difficulty extremely. As far as we know, no chemical
methods have been proposed to solve this problem.
Hydrogen peroxide is one kind of cheap and eco-friendly
oxidant, to the best of our knowledge, which has never been used
in preparation GQDs from graphite materials. It is meaningful to
employ hydrogen peroxide in the preparation of GQDs for lower
cost and more environmental friendly. Herein, we report a one-step
solvothermal method to prepare GQDs with hydrogen peroxide and
expanded graphite (In fact, common graphite is also suitable for
this method with lower efficiency). This method completely avoids
the use of concentrated sulphuric acid and nitric acid to treat raw
material, and introduces no impurities into reaction system,
exhibiting simple and practical characteristics. Pure product can be
obtained by evaporation/redissolution and filtration process, and
no tedious dialysis process is used in the preparation of GQDs.
2. Experimental
High purity expandable graphite was purchased from Qingdao
Jinrilai Graphite Co., Ltd. Other reagents were purchased from
Sinopharm Chemical Reagent Co., Ltd. All reagents were used
without further purification.
Expanded graphite was prepared from expandable graphite by a
thermal expansion method. Typically, a muffle furnace was first
heated to 800  C in 5 h and then, 2 g of expandable graphite in
Alumina crucible were placed into the high temperature environ-
ment for 10 s to form expanded graphite. Expansion volume is
160 mL/g. In this step, sulphuric acid and nitric acid molecular
decompose into gas and escape from the interlayer of expanded
graphite. Afterwards, 50 mg of expanded graphite were firstly
mixed with 15 mL of N,N-Dimethylformamide (DMF) and treated
with ultrasonic for 5 min to remove air in the layered structure of
expanded graphite, which step makes a fully contact between
solvent and expanded graphite. And then, 10 mL of hydrogen
peroxide were added into the mixture and stirred for 5 min to form
homogeneous solution. The final mixture was transferred into an
autoclave and heated up to 170  C for 5 h. The product solution was
treated with vacuum fitration to obtain raw GQDs. Afterwards,
solvent was evaporated and the residue redissolved in deionized
water. Pure GQDs with strong blue PL can be finally obtained by
passing through slow filter paper and 100 nm filter membrane
because the hydrogen peroxide has been consumed completely,
and the only impurity is unreacted expanded graphite. No tedious
dialysis process was employed in the preparation process of GQDs.
UVevis absorption spectra were recorded on an UVevis spec-
trometer (Agilent Technologies Cary 100). PL and PLE spectra were
205
measured on a Fluorescence spectrometer (Horiba Jobin Yvon FL3-
TCSPC). An atomic force microscope (Dimension Icon) was used to
obtain the height information and topographic image of GQDs by
tapping mode. The morphology of product were studied by a high
resolution transmission electron microscopy (Horiba Jobin Yvon
FL3-TCSPC). X-ray photoelectron spectroscopy (XPS) was recorded
on a PHI QUANIERA II electron spectrometer using 300 W Al Ka
radiation. The FT-IR spectrum was measured using a IR Prestige-21
FT-IR spectrometer in aqueous solution. Raman spectra were ob-
tained on a Raman spectrometer system (Horiba Aramis).
3. Results and discussions
The reaction is based on the cutting function of hydroxyl radical
(OH) generated by hydrogen peroxide and the large interlayer
spacing in expanded graphite. The extremely large specific surface
of expanded graphite also contributed to the synthesis of GQDs. The
mechanism mentioned-above is similar to electrochemistry
method and the structure of expanded graphite accelerates the
reaction in a certain degree. The as-prepared GQDs show stable and
strong blue PL with a quantum yield of 15%. The average size is
35 nm and thickness is mainly 2e3 layers. In view of one-step
preparation process, low synthesis cost and almost no impurity in
the final product, this method would reduce the cost of industrial
production greatly and be widely used in the preparation of GQDs
in laboratory.
GQDs with strong blue PL were synthesized through a one-step
solvothermal method with hydrogen peroxide and expanded
graphite (Fig. 1). The layered structure and large specific surface
area of expanded graphite contributed to the low time cost and
high yield. The mechanism of the reaction is similar to electro-
chemistry exfoliation of graphite anode: water was oxidized under
high redox potential to generate oxygen and hydroxyl radicals
which acted as the “scissors” to cut down the graphite anode [22].
However, the method we proposed here needs no electrode
equipment and graphite anode. The oxygen and hydroxyl radicals
were generated in autoclave under a high temperature and high
pressure condition, and the starting material used expanded
graphite which possesses several necessary properties to synthe-
size GQDs efficiently: large interlayer spacing and specific surface
area. Finally, pure GQDs with good water solubility and strong blue
PL were obtained successfully.
The as-prepared GQDs were water soluble for the introducing of
oxygen-containing groups. Fig. S1 indicates a comparison before
and after the reaction of the water solubility. Almost all expanded
graphite dispersed in hexane layer while all GQDs dispersed in
water layer. There was no PL in the organic solvent layer while
water layer shows strong blue PL under 365 nm UV light.
The UVevis spectra of GQDs aqueous solution are seen in Fig. 2a,
a clear absorption peak is observed at 217 nm due to the pep*
transition of aromatic C]C bonds, and an absorption shoulder at
270 nm (inset 1 of Fig. 2a) assigned to the n-p* transition of the C]
O bonds. The inset 2 of Fig. 2a shows the optical photos of GQDs
under 365 nm UV light. The emission quantum yield was quantified
at 350 nm excitation wavelength (selecting quinine sulfate as a
reference), the calculated quantum yield was determined to be
about 15% (Table S2), which is higher than most GQDs reported
previously [23,24].
The PL behavior was also characterized with different excitation
wavelength. As shown in Fig. 2b, as the excitation wavelength
increased from 280 nm to 420 nm, the PL intensity increased to
maximum then decreased, while the PL peaks shifted from 398 nm
to 480 nm. The emission wavelength depends strongly on the
excitation wavelength which is similar to other luminescent carbon
materials for analogous PL mechanism [25,26]. The
206 R. Tian et al. / Optical Materials 60 (2016) 204e208

Fig. 1. Schematic representation of GQDs prepared by solvothermal method.

Fig. 2. (a) UVevis absorption and the PLE of GQDs (inset 1: detailed UVevis absorption from 240 nm to 350 nm. Inset 2: photograph of GQDs aqueous solution showing strong blue
PL under UV light at a 365 nm excitation wavelength). (b) PL spectra of GQDs in water measured at different excitation wavelength from 280 to 420 nm. (c) PL intensity of GQDs in
water at different pH, from 1 to 14. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

photoluminescence excitation (PLE) spectra of GQDs as well as
UVevis spectra are also shown in Fig. 2a. There is a strong excita-
tion peak at 350 nm and a weak excitation peak at 425 nm. These
two excitation peaks correspond to the UVevis absorption at 217
and 270 nm, respectively. The effect of pH on the PL intensity of as-
prepared GQDs was studied at different pH from 1 to 14. As shown
in Fig. 2c, the PL intensity changed a little in different pH envi-
ronment. The differences between intensity maybe induced by the
pH controlled process which changed the solution concentration a
little. This result means that the as-prepared GQDs possess good
optical stability in different pH environment, which broaden a
wider field for the application of GQDs.
Fig. 3 displays the SEM image of expanded graphite and the TEM
of as-prepared GQDs. The SEM (Fig. 3a) observation shows the
layered structure of expanded graphite, which increases the surface
area greatly. Large interlayer spacing of expanded graphite makes
the “cutting” process easier because the graphite layers and solvent
have sufficient contact. GQDs in TEM image disperse uniformly on a
carbon grid (Fig. 3b) with an average size of 35 nm. No crystal
lattice can be observed in TEM images. The atomic force microscopy
(AFM) image with a scanning scope of 1  1 mm displayed in Fig. 4a
presents the topologic morphology and height profile of the GQDs.
The diameters mainly distributed in a range of 20e40 nm which
was consistent with TEM image and the thickness mainly fell in a
range of 1e1.5 nm, corresponding to 2e3 graphene layers (Fig. 4b).
The X-ray photoelectron spectroscopy (XPS) was carried out to
illustrate the elemental composition of as-prepared GQDs. As can
be seen in Fig. 5a, the XPS results show a prominent C1s peak at
284.8 eV and an O1s peak at 532 eV. A high-resolution spectrum of
C1s indicated the presence of various oxygen functional groups of
carbon atoms, such as C]C (284.3 eV), CeO (285.8 eV) and C]O
(287.8 eV) bonds (Fig. 5b). From Fourier transform infrared
 R. Tian et al. / Optical Materials 60 (2016) 204e208 207

Fig. 3. (a) SEM image of expanded graphite. (b) TEM image of as-prepared GQDs on a carbon grid. GQDs are highlighted with solid line.

Fig. 4. (a) AFM image of the GQDs on a mica substrate by taping mode. (b) The height profile along the line from A to B in Fig. 4(a).

Fig. 5. (a) XPS spectra of GQDs. (b) High-resolution XPS C1s spectra of GQDs. (c) FT-IR spectra of GQDs and expanded graphite. (d) Raman spectra of expanded graphite and GQDs.
208 R. Tian et al. / Optical Materials 60 (2016) 204e208
Fig. 6. Schematic illustration of oxygen-containing groups modified GQD structure.
spectroscopy (FT-IR) of GQDs and expanded graphite (Fig. 5c), after
solvothermal treatment, the intensity of CeOeC bond (1064 cm 1),
eOH bond (1394 cm 1) and C]O bond (1660 cm 1) increased
obviously. According to XPS and FT-IR, carbonyl, hydroxyl and
epoxy groups were introduced to edge and onto the basal plane.
The presence of these functional groups makes the GQDs good
water solubility. It is worth-mentioning that no overt COOH group
can be found in both XPS and FT-IR, besides, the intensity of C]O
bond was also very weak. This phenomenon owed to the excess of
expanded graphite, so there was no enough OH to oxidize oxygen-
containing groups further. Consequently, we can conclude that
those oxygen-containing groups are mainly hydroxyl and epoxy
groups. A schematic illustration of oxygen-containing groups
modified GQDs structure is displayed in Fig. 6. Raman spectra of
expanded graphite and GQDs are compared in Fig. 5d. G bands arise
from the E2g vibrational modes of the aromatic domains which
reflect the crystalline degree, while D bands originate from the
breathing modes of the graphitic domains, reflecting the “disorder”
degree [22]. The Raman spectra of expanded graphite show no
obvious D bands but a strong G band at 1579 cm-1 conversely,
indicating an excellent crystalline structure in expanded graphite.
However, a D band at 1339 cm 1 and a G band at 1571 cm 1 can be
observed in GQDs. Compared with expanded graphite, the ID/IG
value of 1.01 means the decrease of the fraction of sp2 domain and
increase of defect sites for the introducing of numerous oxygen-
containing groups. This result also corresponds to the change on
the water solubility from expanded graphite to GQDs.
4. Conclusions
In summary, we have successfully prepared pure and water-
soluble GQDs with strong blue PL by a one-step solvothermal
method between hydrogen peroxide and expanded graphite in
DMF solvent. The quantum yields of 15% in neutral condition, good
photoluminescence stability in different pH conditions are
demonstrated, implying a wider application in different harsh
environment. To our best knowledge, this is the first time to
prepare GQDs from graphite materials by hydrogen peroxide
without dialysis process. The extremely low cost, good water sol-
ubility, high quantum yield, no need for dialysis to purify and easy-
obtained experiment equipment of this method, show a great
prospect in the biomedical fields and electronic device.
Acknowledgment
This work was supported by a Project Funded by the Priority
Academic Program Development of Jiangsu Higher Education In-
stitutions (PAPD).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.optmat.2016.07.032.
References
[1] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos,
I.V. Grigorieva, A.A. Firsov, Science 306 (2004) 666e669.
[2] A.K. Geim, K.S. Novoselov, Nat. Mater. 6 (2007) 183e191.
[3] C. Chung, Y.K. Kim, D. Shin, S.R. Ryoo, B.H. Hong, D.H. Min, Acc. Chem. Res. 46
(2013) 2211e2224.
[4] V. Georgakilas, M. Otyepka, A.B. Bourlinos, V. Chandra, N. Kim, K.C. Kemp,
P. Hobza, R. Zboril, K.S. Kim, Chem. Rev. 112 (2012) 6156e6214.
[5] L.A. Ponomarenko, F. Schedin, M.I. Katsnelson, R. Yang, E.W. Hill,
K.S. Novoselov, A.K. Geim, Science 320 (2008) 356e358.
[6] D. Pan, J. Zhang, Z. Li, M. Wu, Adv. Mater. 22 (2010) 734e738.
[7] X. Zhou, Y. Zhang, C. Wang, X. Wu, Y. Yang, B. Zheng, H. Wu, S. Guo, J. Zhang,
ACS Nano 6 (2012) 6592e6599.
[8] J. Peng, W. Gao, B.K. Gupta, Z. Liu, R. Romero-Aburto, L. Ge, L. Song,
L.B. Alemany, X. Zhan, G. Gao, S.A. Vithayathil, B.A. Kaipparettu, A.A. Marti,
T. Hayashi, J.J. Zhu, P.M. Ajayan, Nano Lett. 12 (2012) 844e849.
[9] Y. Dong, C. Chen, X. Zheng, L. Gao, Z. Cui, H. Yang, C. Guo, Y. Chi, C.M. Li,
J. Mater. Chem. 22 (2012) 8764e8766.
[10] M. Zhang, L. Bai, W. Shang, W. Xie, H. Ma, Y. Fu, D. Fang, H. Sun, L. Fan, M. Han,
J. Mater. Chem. 22 (2012) 7461e7467.
[11] K. Yang, S. Zhang, G. Zhang, X. Sun, S.T. Lee, Z. Liu, Nano Lett. 10 (2010)
3318e3323.
[12] S. Zhu, J. Zhang, C. Qiao, S. Tang, Y. Li, W. Yuan, B. Li, L. Tian, F. Liu, R. Hu,
H. Gao, H. Wei, H. Zhang, H. Sun, B. Yang, Chem. Commun. 47 (2011)
6858e6860.
[13] S.H. Song, M.H. Jang, J. Chung, S.H. Jin, B.H. Kim, S.H. Hur, S. Yoo, Y.H. Cho,
S. Jeon, Adv. Opt. Mater. 2 (2014) 1016e1023.
[14] R. Ye, C. Xiang, J. Lin, Z. Peng, K. Huang, Z. Yan, N.P. Cook, E.L. Samuel, C.-
C. Hwang, G. Ruan, Nat. Commun. 4 (2013).
[15] C.K. Chua, Z. Sofer, P. Simek, O. Jankovsky, K. Klimova, S. Bakardjieva,
S. Hrdlickova Kuckova, M. Pumera, ACS Nano 9 (2015) 2548e2555.
[16] X. Yan, X. Cui, B. Li, L.-s. Li, Nano Lett. 10 (2010) 1869e1873.
[17] X. Yan, X. Cui, L.S. Li, J. Am. Chem. Soc. 132 (2010) 5944e5945.
[18] Y. Huang, C. Bai, K. Cao, Y. Tian, Y. Luo, C. Xia, S. Ding, Y. Jin, L. Ma, S. Li, RSC
Adv. 4 (2014) 43160e43165.
[19] X. Tan, Y. Li, X. Li, S. Zhou, L. Fan, S. Yang, Chem. Commun. 51 (2015)
2544e2546.
[20] F. Liu, M.H. Jang, H.D. Ha, J.H. Kim, Y.H. Cho, T.S. Seo, Adv. Mater 25 (2013)
3657e3662.
[21] Y. Shin, J. Park, D. Hyun, J. Yang, J.-H. Lee, J.-H. Kim, H. Lee, Nanoscale 7 (2015)
5633e5637.
[22] J. Lu, J.X. Yang, J. Wang, A. Lim, S. Wang, K.P. Loh, ACS Nano 3 (2009)
2367e2375.
[23] L. Li, G. Wu, G. Yang, J. Peng, J. Zhao, J.J. Zhu, Nanoscale 5 (2013) 4015e4039.
[24] X.T. Zheng, A. Ananthanarayanan, K.Q. Luo, P. Chen, Small 11 (2015)
1620e1636.
[25] J. Zhou, C. Booker, R. Li, X. Zhou, T.-K. Sham, X. Sun, Z. Ding, J. Am. Chem. Soc.
129 (2007) 744e745.
[26] Y.P. Sun, B. Zhou, Y. Lin, W. Wang, K.A. Fernando, P. Pathak, M.J. Meziani,
B.A. Harruff, X. Wang, H. Wang, P.G. Luo, H. Yang, M.E. Kose, B. Chen,
L.M. Veca, S.Y. Xie, J. Am. Chem. Soc. 128 (2006) 7756e7757.