See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/273811700

An improved Hummers method for eco-

friendly synthesis of graphene oxide

Article in Carbon November 2013

DOI: 10.1016/j.carbon.2013.07.055

CITATIONS READS

164 3,722

4 authors, including:

Ji Chen Bowen Yao

University of Maryland, College Park Tsinghua University
29 PUBLICATIONS 1,099 CITATIONS 10 PUBLICATIONS 280 CITATIONS

SEE PROFILE SEE PROFILE

Chun Li
Tsinghua University
154 PUBLICATIONS 13,868 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Controlled Synthesis of Graphene Oxide View project

graphene 3d materials View project

All content following this page was uploaded by Ji Chen on 27 June 2015.

The user has requested enhancement of the downloaded file.

 CARBON 6 4 ( 2 0 1 3 ) 2 2 5 2 2 9

Available at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/carbon

An improved Hummers method for eco-friendly

synthesis of graphene oxide

Ji Chen, Bowen Yao, Chun Li, Gaoquan Shi *

Department of Chemistry, Tsinghua University, Beijing 100084, Peoples Republic of China

A R T I C L E I N F O A B S T R A C T

Article history: An improved Hummers method without using NaNO3 can produce graphene oxide nearly
Received 4 June 2013 the same to that prepared by conventional Hummers method. This modification does not
Accepted 21 July 2013 decrease the yield of product, eliminating the evolution of NO2/N2O4 toxic gasses and sim-
Available online 27 July 2013 plifying the disposal of waste water because of the inexistence of Na+ and NO3 ions. For
the first time, we also developed a prototype method of post-treating the waste water col-
lected from the systems of synthesizing and purifying graphene oxide. The content of Mn2+
ions in the purified waste water was measured to be lower than the guideline value for
drinking water.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Graphene has a unique atom-thick two-dimensional struc-
ture, excellent electronic, mechanical, optical and thermal
properties [1]. Therefore, it has been widely explored for the
applications in electronics [2], catalysis [3], sensors [4], and
energy conversion and storage [5,6], etc. For these purposes,
the mass-production of graphene materials at low costs is
one of the essential requirements. Actually, graphene sheets
already exist in nature and we need to exfoliate them from
their precursors [7]. The exfoliation of graphite to graphene
can be realized either physically or chemically [1]. Among
the various methods, chemical reduction of graphene oxide
(GO) to reduced graphene oxide (rGO) is unique and attractive
because of its capability of producing single-layer graphene in
large scale and at relatively low cost [8]. Furthermore, GO and
rGO are processible and they can be fabricated or self-assem-
bled into macroscopic materials with controlled compositions
and microstructures for practical applications [9].
GO is the precursor of rGO; thus, it plays a crucial role in
controlling the structure, property and the application poten-
tial of rGO [10 16]. The pioneering work on the synthesis of
GO was reported by Brodie in 1859 [17]. In this method, one
equal weight of graphite was mixed with three equal weights
of KClO3 and reacted in fuming HNO3 at 60 C for 4 days. Sta-
udenmaier improved Brodie method by replacing about two
thirds of fuming HNO3 with concentrated H2SO4 and adding
KClO3 in multiple portions [18]. This small modification en-
ables the overall reaction in a single vessel; thus simplifying
the synthesis method. However, this reaction still needs a
long time of 4 days. The most important and widely applied
method for the synthesis of GO was developed by Hummers
and Offeman in 1958 (Hummers method) [19]. In this case,
the oxidation of graphite was achieved by harsh treatment
of one equal weight of graphite powders in a concentrated
H2SO4 solution containing three equal weights of KMnO4
and 0.5 equal weight of NaNO3. The Hummers method, at
least, has three important advantages over previous tech-
niques. First, the reaction can be completed within a few
hours. Second, KClO3 was replaced by KMnO4 to improve
the reaction safety, avoiding the evolution of explosive ClO2.
Third, the use of NaNO3 instead of fuming HNO3 eliminates
the formation of acid fog.
Hummers method has been paid the most intensive atten-
tion because of its high efficiency and satisfying reaction
safety. However, it still has the following two flaws: (1) the oxi-

* Corresponding author: Fax: +86 1062771149.

E-mail address: gshi@tsinghua.edu.cn (G. Shi).
0008-6223/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.07.055
226 CARBON 6 4 ( 2 0 1 3 ) 2 2 5 2 2 9
dation procedure releases toxic gasses such as NO2 and N2O4;
(2) the residual Na+ and NO3 ions are difficult to be removed
from the waste water formed from the processes of synthe-
sizing and purifying GO. Tour and co-workers improved the
Hummers method by excluding NaNO3, increasing the
amount of KMnO4, and performing the reaction in a 9:1 (by
volume) mixture of H2SO4/H3PO4 [20]. This modification is
successful in increasing the reaction yield and reducing toxic
gas evolution, while using twice as much KMnO4 and
5.2 times as much H2SO4 as those required by Hummers
method and also introducing a new component of H3PO4 to
the reaction system.
Recently, Baeks group studied the process of etching the
basal planes of highly ordered pyrolytic graphite (HOPG) with
a hot mixture of H2SO4 and HNO3 [21]. In this case, the graph-
ene layers of HOPG were effectively cut and exfoliated after a
long-term treatment. This observation indicates that the
H2SO4/HNO3 mixture used in Hummers method acts as a
chemical scissor and a chemical drill for graphene planes
to facilitate the penetration of oxidation solution. On the
other hand, KMnO4 is one of the strongest oxidants, espe-
cially in acidic media [22]. With the assistance of KMnO4, a
complete intercalation of graphite with concentrated H2SO4
can be achieved, forming graphite bisulfate in which every
single-layer graphene is sandwiched by the layers of bisulfate
ions [23,24]. This complete intercalation ensures the effective
penetration of KMnO4 solution into graphene layers for the
oxidation of graphite. Accordingly, KMnO4 can also take the
role of NaNO3 and the latter is unnecessary for the synthesis
of GO using Hummers method. In this article, we demon-
strate that GO can be produced using an improved Hummers
method without using NaNO3. This method decreases the
cost and environmental duty of GO production.
2. Experimental
2.1. Synthesis and purification of GO
GO was prepared by the oxidation of natural graphite powder
(325 mesh, Qingdao Huatai Lubricant Sealing S&T Co. Ltd.,
Qingdao, China) according to Hummers method with a modi-
fication of removing NaNO3 from the reaction formula [19].
Typically, graphite powder (3.0 g) was added to concentrated
H2SO4 (70 mL) under stirring in an ice bath. Under vigorous
agitation, KMnO4 (9.0 g) was added slowly to keep the temper-
ature of the suspension lower than 20 C. Successively, the
reaction system was transferred to a 40 C oil bath and vigor-
ously stirred for about 0.5 h. Then, 150 mL water was added,
and the solution was stirred for 15 min at 95 C. Additional
500 mL water was added and followed by a slow addition of
15 mL H2O2 (30%), turning the color of the solution from dark
brown to yellow. The mixture was filtered and washed with
1:10 HCl aqueous solution (250 mL) to remove metal ions.
The resulting solid was dried in air and diluted to 600 mL,
making a graphite oxide aqueous dispersion. Finally, it was
purified by dialysis for one week using a dialysis membrane
(Beijing Chemical Reagent Co., China) with a molecular weight
cut off of 8000 14,000 g mol 1 to remove the remaining metal
species. The resultant graphite oxide aqueous dispersion was
then diluted to 1.2 L, stirred overnight and sonicated for
30 min to exfoliate it to GO. The GO dispersion was then cen-
trifuged at 3000 rpm for 40 min to remove the unexfoliated
graphite. For comparison, GO was also prepared by conven-
tional Hummers method [19], and purified using the same pro-
cedures described above. The GO products prepared by the
improved and conventional Hummers methods are nomi-
nated as GO1 or GO2, respectively.
2.2. Instruments and characterizations
GO dispersions were freeze-dried and used for morphological
and structural characterizations. Raman spectra were re-
corded on a Renishaw Raman spectrometer with a 514 nm la-
ser at a power of 4.7 mW. X-ray photoelectron spectra (XPS)
were recorded on an ESCALAB 250 photoelectron spectrome-
ter (ThermoFisher Scientific) with Al Ka (1486.6 eV) as the X-
ray source set at 150 W and a pass energy of 30 eV for high
resolution scan. UVvisible spectra were taken out by the
use of a U-3010 UVvisible spectrometer (Hitachi, Japan).
Scanning electron micrographs (SEM) were taken out on a
field-emission scanning electron microscope (Sirion-200, Ja-
pan). The atomic force microscopic (AFM) images of GO
sheets were measured using a scanning probe microscope
(SPM-9600, Shimadzu). The samples used for SEM and AFM
characterizations were deposited on silicon wafers and mica
sheets, respectively. Fourier transform infrared spectros-
copy-attenuated total reflectance (FTIR-ATR) spectra were re-
corded on a Fourier transform infrared spectrometer (Bruker
Vertex V70). The zeta potentials of GO aqueous dispersions
were measured by the use of HORIBA Nano particle analyzer
SZ-100. X-ray diffraction (XRD) was carried out on a D8 Ad-
vance X-ray diffractometer with Cu Ka radiation
(k = 0.15418 nm, Bruker, Germany).
2.3. The removing of Mn2+ ions from waste water
Typically, waste water was collected from the process of fil-
trating GO from the reaction system of improved Hummers
method. Successively, 20 mL of waste water was diluted and
neutralized by a 0.2 g mL 1 KOH solution. The pH of the solu-
tion was adjusted to 10 and a precipitate was formed. Then,
this system was kept undisturbed overnight to age the precip-
itate. Finally the sediment was filtrated. The Mn2+ ions in the
purified waste water (or filtrate) was test by adding it for sev-
eral drops into a 3 mL aqueous solution of Na2S2O8
(0.1 g mL 1) followed by boiling the mixture for 1 min.
3. Results and discussion
GO samples were synthesized by using Hummers method
without (GO1) or with (GO2) using of NaNO3 and purified by
dialysis and centrifugation. The yields (the weight of GO di-
vided by the weight of graphite powder) of GO1 and GO2 were
measured to be 92% 3% and 96% 2%, respectively. This re-
sult indicates that the solution of concentrated H2SO4 con-
taining KMnO4 is capable of oxidizing graphite to GO in a
yield close to that of Hummers method even without the
assistance of NaNO3.
 CARBON 6 4 (2 0 1 3) 2 2 522 9
The composition, structure and morphology of GO1 were
characterized to be nearly the same to those of GO2. Fig. 1a
is the UVvisible spectrum of the aqueous dispersion of GO1.
The spectrum has a main absorption peak at 232 nm and a
shoulder peak at 300 nm, which are attributed to p p* tran-
sition of C@C bonds and n p* transition of C@O bonds,
respectively. The overall feature of this spectrum is identical
to that of the GO synthesized using conventional Hummers
method (GO2, Fig. S1a) and its adsorption peaks are also
similar to those of the GO samples reported in literature
[20]. The dispersion of GO1 shows a clear yellow color, indi-
cating asuccessful oxidation of graphite to GO [19]. The C/O
atomic ratios of GO1 (Fig. 1b) and GO2 (Fig. S1b) were mea-
sured by XPS to be 2.36 and 2.23, respectively, reflecting their
similar degrees of oxidation. These values are among the
range of 2.1 2.9 for the GO products reported previously
[19]. The C 1s spectrum of GO1 (Fig. 1c) demonstrates four
types of carbon bonds: CC/C@C (284.6 eV), CO (286.6 eV),
C@O (287.8 eV), and OC@O (289.0 eV). The peak intensities
of intact carbon (CC/C@C) and oxygenated carbon atoms
in this XPS spectrum were calculated to be 47.9%and 52.1%
(Fig. 1c), correspondingly. Those values in the spectrum of
GO2 were measured to be 46.5% and 53.5%, respectively
(Fig. S1c). This result further confirms that they have compa-
rable oxidization degrees. It should be noted here that the
oxidation degrees of GO products vary with their synthesis
conditions [11,15,20]. Either GO1 or GO2 has a medium oxi-
dation degree compared with those of less [15] and highly
oxidized counterparts [20]. The zeta potentials of GO1 and
GO2 suspensions were measured to be 43.8 1.3 and
45.6 0.6 mV, respectively, indicating they are negatively
charged because of the presence ofcarboxyl groups.
Although GO1 has a slightly higher zeta potential than that
of GO2, its value is still lower than 30 mV, providing it with
a good dispersibility in aqueous media [25].
The thickness of GO1 and GO2 sheets were measured to be
0.8 nm by AFM (Fig. 2a and S2a), indicating they have a sin-
gle-layer structure [8]. The GO sheets of both samples have
comparable lateral dimensions in the range of several hun-
dreds of nanometers to several micrometers according to
their AFM (Fig. 2a and S2a) and SEM (Fig. 2b and S2b) images.
The XRD pattern of freeze-dried GO1 gives a (001) reflection
Fig. 1 (a) UVVis spectrum of a 0.01 mg mL 1 GO1 aqueous dispersion, inset is a photograph of a 0.5 mg mL
dispersion. (b) XPS survey spectrum of freeze-dried GO1. (c) C 1s XPS spectrum of GO1.
227
peak at 2h = 10.9 (Fig. 2c), corresponding to a d-space of
0.81 nm, and this value is in consistent with that of freeze-
dried GO2 (Fig. S2c). The large interlayer spacing of GO1
sheets can be attributed to its oxygenated functional groups
introduced by the harsh oxidation treatment of graphite [26].
Raman and infrared spectral studies also demonstrate that
both GO products are structurally the same. The Raman spec-
trum of GO1 (Fig. 2d) or GO2 (Fig. S2d) shows a G-band at
1590 cm 1 and a D-band at 1350 cm 1. The G-band is asso-
ciated with graphitic carbons and the D-band is related to the
structural defects or partially disordered graphitic domains
[27]. The D-bands in both spectra are strong, confirming the
lattice distortions of graphene basal planes. Furthermore,
the FTIR ATR spectra of GO1 and GO2 papers (Fig. 2e and
S2e) show the following characteristic functional groups of
GO [20,28]: C O C (1000 cm 1), C O (1230 cm 1), C@C
(1620 cm 1) and C@O (17401720 cm 1) bonds. The O H
stretching vibrations in the region of 36003300 cm 1 are
attributed to the hydroxyl and carboxyl groups of GO and
residual water between GO sheets. These hydrophilic oxy-
gen-containing functional groups provide GO sheets with a
good dispersibility in water [9].
Thermalgravimetric analysis (TGA) curves of GO1 and GO2
are compared in Fig. 3. Both curves exhibit similar character-
istics: the weight loss before 100 C is caused by the release of
trapped water between GO sheets [28]; the distinct weight loss
between 200 and 230 C is attributed to the decomposition of
less stable oxygenated functional groups on GO sheets [29]. A
weaker mass loss in the range of 230700 C is related to the
removal of more stable functional groups. The nearly identi-
cal TGA curves of both GO samples reflect their close contents
of oxygenated groups.
Post-treatment of the waste water collected from the pro-
cesses of GO synthesis and purification is crucial for commer-
cializing GO. Unfortunately, to our best knowledge, little
attention has been paid to this issue. The improved Hummers
method described here does not use NaNO3, implying Na+ and
NO3 ions are excluded, and the waste water contains only
K+, H+, Mn2+, and SO42 ions. The Mn2+ ions can be readily re-
moved by converting them into a precipitate upon the addi-
tion of KOH and adjusting the pH value of solution to
around 10 (Fig. 4). The sediment was characterized by XRD
1
GO1 aqueous
228 CARBON 6 4 ( 2 0 1 3 ) 2 2 5 2 2 9
Fig. 2 (a) Tapping mode AFM and (b) SEM images of GO1. (c) XRD pattern, (d) 514.5 nm excited Raman spectrum and (e)
FTIR ATR spectrum of freeze-dried GO1.
Fig. 3 TGA curves of freeze-dried GO1 and GO2.
Fig. 4 Photographs and illustration of the post-treatment of
waste water. Insets show the pictures of color test of Mn2+
ions.
to be Mn3O4 containing a small amount of Mn(OH)2 (Fig. 5).
The efficiency of removing Mn2+ ions from the waste water
has been tested by the addition of the purified supernatant
Fig. 5 XRD pattern of the precipitation containing Mn.
into a solution of Na2S2O8 to oxidize Mn2+. As shown in
Fig. 4, the test solution remained colorless, indicating the ab-
sence of detectable Mn2+ ions in the supernatant. Actually,
the concentration of Mn2+ ions in the purified water was
quantitatively analyzed to be as low as 120 lg L 1 by induc-
tively coupled plasma mass spectrometry, and this value is
even lower than the guideline value (400 lg L 1) for Mn in
drinking water suggested by World Health Organization [30].
The residual K2SO4 in the supernatant can be further sepa-
rated from solution by successive neutralization and evapora-
tion of water.
4. Conclusions
We developed an improved Hummers method without using
NaNO3 for the synthesis of GO. This improved method elimi-
nates the generation of toxic gasses and simplifies the proce-
dure of purifying waste liquid, thus decreases the cost of GO
synthesis. The GO products prepared by both the improved
and conventional Hummers methods are nearly the same in
 CARBON 6 4 (2 0 1 3) 2 2 522 9
their dispersibility, chemical structures, thicknesses, and lat-
eral dimensions. Furthermore, the exclusion of NaNO3 does
not affect the yield of the overall reaction. The improved
Hummers method described here can be used to prepare GO
in large scale and it is one-step towards the synthesis of
graphene and its derivatives through environmentally
friendly approaches.
Acknowledgements
This work was supported by national basic research program
of China (973 Program, 2012CB933402), natural science foun-
dation of China (91027028, 51161120361, 21274074).
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.carbon.
2013.07.055.
R E F E R E N C E S
[1] Novoselov KS, Falko VI, Colombo L, Gellert PR, Schwab MG,
Kim K. A roadmap for graphene. Nature
2012;490(7419):192200.
[2] Weiss NO, Zhou H, Liao L, Liu Y, Jiang S, Huang Y, et al.
Graphene: an emerging electronic material. Adv Mater
2012;24(43):5782825.
[3] Huang C, Li C, Shi G. Graphene based catalysts. Energy
Environ Sci 2012;5(10):884868.
[4] Liu Y, Dong X, Chen P. Biological and chemical sensors based
on graphene materials. Chem Soc Rev 2012;41(6):2283307.
[5] Sun Y, Wu Q, Shi G. Graphene based new energy materials.
Energy Environ Sci 2011;4(4):111332.
[6] Wassei JK, Kaner RB. Oh, the places youll go with graphene.
Acc Chem Res 2013. http://dx.doi.org/10.1021/ar300184v.
[7] Segal M. Selling graphene by the ton. Nat Nanotechnol
2009;4(10):6124.
[8] Bai H, Li C, Shi G. Functional composite materials based on
chemically converted graphene. Adv Mater
2011;23(9):1089115.
[9] Li C, Shi G. Three-dimensional graphene architectures.
Nanoscale 2012;4(18):554963.
[10] Zhu Y, Murali S, Cai W, Li X, Suk JW, Potts JR, et al. Graphene
and graphene oxide: synthesis, properties, and applications.
Adv Mater 2010;22(35):390624.
[11] Wu Z-S, Ren W, Gao L, Liu B, Jiang C, Cheng H-M. Synthesis of
high-quality graphene with a pre-determined number of
layers. Carbon 2009;47(2):4939.
[12] Zhang L, Liang J, Huang Y, Ma Y, Wang Y, Chen Y. Size-
controlled synthesis of graphene oxide sheets on a large
View publication stats
229
scale using chemical exfoliation. Carbon 2009;47(14):
33658.
[13] Zhang L, Li X, Huang Y, Ma Y, Wan X, Chen Y. Controlled
synthesis of few-layered graphene sheets on a large scale
using chemical exfoliation. Carbon 2010;48(8):236771.
[14] Zhao J, Pei S, Ren W, Gao L, Cheng H-M. Efficient Preparation
of large-area graphene oxide sheets for transparent
conductive films. ACS Nano 2010;4(9):524552.
[15] Xu Y, Sheng K, Li C, Shi G. Highly conductive chemically
converted graphene prepared from mildly oxidized graphene
oxide. J Mater Chem 2011;21(20):737680.
[16] Li Y, Umer R, Samad YA, Zheng L, Liao K. The effect of the
ultrasonication pre-treatment of graphene oxide (GO) on the
mechanical properties of GO/polyvinyl alcohol composites.
Carbon 2013;55:3217.
[17] Brodie BC. On the atomic weight of graphite. Philos Trans R
Soc London 1859;14:24959.
[18] Staudenmaier L. Verfahren zur Darstellung der Graphitsaure.
Ber Dtsch Chem Ges 1898;31(2):14817.
[19] Hummers WS, Offeman RE. Preparation of graphitic oxide. J
Am Chem Soc 1958;80(6):1339.
[20] Marcano DC, Kosynkin DV, Berlin JM, Sinitskii A, Sun Z,
Slesarev A, et al. Improved synthesis of graphene oxide. ACS
Nano 2010;4(8):480614.
[21] Shin Y-R, Jung S-M, Jeon I-Y, Baek J-B. The oxidation
mechanism of highly ordered pyrolytic graphite in a nitric
acid/sulfuric acid mixture. Carbon 2013;52:4938.
[22] Dreyer DR, Park S, Bielawski CW, Ruoff RS. The chemistry of
graphene oxide. Chem Soc Rev 2010;39(1):22840.
[23] Avdeev VV, Monyakina LA, Nikolskaya IV, Sorokina NE,
Semenenko KN. The choice of oxidizers for graphite
hydrogenosulfate chemical synthesis. Carbon
1992;30(6):81923.
[24] Sorokina NE, Khaskov MA, Avdeev VV, Nikolskaya IV.
Reaction of graphite with sulfuric acid in the presence of
KMnO4. Russ J Gen Chem 2005;75(2):1628.
[25] Li D, Mueller MB, Gilje S, Kaner RB, Wallace GG. Processable
aqueous dispersions of graphene nanosheets. Nat
Nanotechnol 2008;3(2):1015.
[26] Chen C, Yang Q-H, Yang Y, Lv W, Wen Y, Hou P-X, et al. Self-
assembled free-standing graphite oxide membrane. Adv
Mater 2009;21(29):300711.
[27] Kudin KN, Ozbas B, Schniepp HC, Prudhomme RK, Aksay IA,
Car R. Raman spectra of graphite oxide and functionalized
graphene sheets. Nano Lett 2008;8(1):3641.
[28] Eigler S, Dotzer C, Hirsch A, Enzelberger M, Mueller P.
Formation and decomposition of CO2 intercalated graphene
oxide. Chem Mater 2012;24(7):127682.
[29] McAllister MJ, Li J-L, Adamson DH, Schniepp HC, Abdala AA,
Liu J, et al. Single sheet functionalized graphene by oxidation
and thermal expansion of graphite. Chem Mater
2007;19(18):4396404.
[30] World Health Organization (WHO). Manganese in Drinking
WaterBackground Document for Development of WHO
Guidelines for Drinking-Water Quality. Geneva: WHO; 2011.