Materials Chemistry and Physics 218 (2018) 51–61

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Materials Chemistry and Physics

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

A general strategy for direct synthesis of reduced graphene oxide by T

chemical exfoliation of graphite
A.F. Betancura,∗∗, N. Ornelas-Sotob, A.M. Garay-Tapiac, F.R. Péreza, Ángel Salazara, A.G. Garcíac,∗
a
Grupo de Óptica y Espectroscopia, Universidad Pontificia Bolivariana, A. A. 56006, Campus de Laureles Circular 1 No. 70-01, Medellín, Colombia
b
Laboratorio de Nanotecnología Ambiental, Centro del Agua para América Latina y el Caribe, Instituto Tecnológico de Monterrey, C.P. 64849, Monterrey, NL, Mexico
c
Laboratorio de Síntesis y Modificación de Nanoestructuras y Materiales Bidimensionales, Centro de Investigación en Materiales Avanzados S.C, Alianza Norte 202,
Parque PIIT Apodaca Nuevo León, C.P. 66628, Mexico

H I GH L IG H T S

• Sulfuric and nitric acid ratio controls the oxidation degree in graphite oxide.
• Less dangerous reactions in obtaining reduced graphene oxide were generated.
• Traces of graphitic nitrogen into the material structure were observed.
• A first stage for the direct synthesis of reduced graphene oxide was found.

A R T I C LE I N FO A B S T R A C T

Keywords: In this work, a first stage of synthesis to obtain reduced graphene oxide (rGO) using an efficient chemical
Reduced graphene oxide exfoliation method from graphite was studied. An ammonium hydroxide and a nitric-sulfuric acid mixture were
Graphite oxidation used for in situ oxidation and partial-reduction of graphite. Flakes with a thickness of 3 nm were observed by
Exfoliation using AFM, suggesting the presence of ten or less graphene layers. The average C/O atomic percentage ratio
Reduction
obtained was 4.27, which is similar to those results obtained by conventional reduction processes associated
with using hydrazine. In addition, a graphitic nitrogen functionalization was observed during the proposed
process. Besides that, the precursor of rGO suspension obtained remained stable for six months. Therefore, the
present study showed a less aggressive and dangerous chemistry route in order to rGO production than others
previously reported works.

1. Introduction energy in the band structure of the material [4,6–8]. This band gap
energy can be modulated according to the number and type of func-
Graphene oxide (GO) is defined as a graphene sheet with functional tional groups [9]. Boukhvalov and Katsnelson [6], theoretically showed
groups such as hydroxyl, epoxide, carbonyl and carboxyl, forming dif- the influence of the oxygen concentration on the band gap energy and
ferent hybrid orbitals (sp2 and sp3) that can modulate its physical and studying oxygen group concentrations between 50%, and 75% pre-
chemical properties [1–3]. This allows a wide range of applications like dicted variation in the band gap between 1.80 eV and 2.90 eV, re-
electronic devices, energy storage, sensors, photocatalytic system for spectively. Photocatalytic applications of GO and rGO have been re-
water splitting, hydrogen storage, electrodes in lithium batteries and ported [10,11]. One of them focused on the conversion of water to
biomedical applications, and its pseudo-capacitive behavior is a prop- hydrogen (H2) and oxygen (O2) from solar energy [11–13]. In this ap-
erty that has been used in supercapacitors [4,5]. plication Tan et al. [14] and Zhang et al. [11], improve the rGO pho-
When graphene is functionalized up to form GO, some sp2 hy- tocatalytic efficiency by adding TiO2 and Zn0.8Cd0.2S nanoparticles,
bridizations are changed to sp3, ones by the binding between the respectively, showing that rGO is an ideal material for the charge
functional groups and the pz electron orbitals, modifying the electron photo-generation on water decomposition processes”. Other photo-
cloud distribution around the carbon atoms and generating a band gap catalytic applications of GO and rGO can be found in Refs. [15,16]. But

∗
Corresponding author.
∗∗
Corresponding author.
E-mail address: [email protected] (A.G. García).

https://doi.org/10.1016/j.matchemphys.2018.07.019
Received 2 May 2018; Received in revised form 5 July 2018; Accepted 9 July 2018
Available online 12 July 2018
0254-0584/ © 2018 Elsevier B.V. All rights reserved.
A.F. Betancur et al. Materials Chemistry and Physics 218 (2018) 51–61

just like graphene, the efficiency and quality in large-scale production 2.2. Characterization
of GO are issues that still need to be improved for better performance in
real applications. Microscopic characterization was carried out by a field emission
In 1859, Brodie [17] obtained GO with an oxidative process by scanning electron microscope (FE-SEM). The model Nova Nano SEM
using graphite and potassium chlorate (KClO3) on a nitric acid (HNO3) 200 brand FEI and Microanalysis System Energy Dispersive X-ray
solution at 60 °C for 4 h. The resulting material was C2.19H0.80O1.00. (EDX), Mark Oxford INCA Model X-Sight were used. For X-ray photo-
Some decades later several authors contributed to improve the oxida- electron spectroscopy measurements (XPS), a Thermo Scientific Escalab
tion process using reagents such as potassium permanganate (KMnO4), 250Xi spectrometer with monochromatized Al Ka radiation (1486.6 eV)
sulfuric acid (H2SO4), HNO3 and sodium nitrate (NaNO3), therefore was used. An atomic force microscope AFM Asylum Research, model
reducing dangerous reactions and improving the efficiency of chemical MFP3D-SA, in noncontact mode or AC was used. Using rectangular
exfoliation [1–7]. Although the Hummers' method [18] is the preferred cantilever model AC240TS-R3, with 2 N/m at a scanning speed of
approach for producing GO, nevertheless dangerous reagents are re- 70 kHz the AFM measures were carried out to analyze the nanometric
quired in the synthesis process. Marcano et al. [19] removed the use of structures obtained during the exfoliation process.
NaNO3 and increased the amount of KMnO4, reducing the risk of ex- The Fourier transform infrared spectrophotometer (FTIR) used for
plosion during the reaction, but obtaining lower efficiencies than those this analysis was a SHIMADZU IR Affinity-1S. All Infrared measure-
obtained by the traditional Hummer's method, although they achieved ments were made using attenuated total reflection (ATR). Raman
GO with fewer irregularities and increased the concentration of func- measurements were carried out by using an inVia Renishaw confocal
tional groups such as hydroxyl and epoxy on the GO's surface. Raman spectrometer system. The Raman spectra were obtained with a
On the other hand, Dimiev and Tour [20] showed the importance of wavelength of 633 nm. Crystalline structure was determined by X-ray
graphite bisulfate in graphene sheets exfoliation. Chen [21] and Sor- diffraction (XRD) with a 1.54059 Å Cu Kα1 wavelength on a Panalytical
okina [22] also showed the importance of graphite bisulfate and the Empyrean diffractometer (PANalytical Inc.). The rGO weight ratio was
possibility of producing GO in the presence of any oxidant agent and analyzed by thermogravimetric analysis (TGA) and recorded using an
H2SO4. SDT Q 600 TA Instruments equipment in the range of 25°C–1190 °C in
Commonly the hydrazine is employed to reduce the graphene oxide nitrogen.
to obtain graphene [23] or reduced graphene oxide (rGO), which has a
physical and chemistry properties close to graphene [24,25]. But the 3. Results and discussions
hydrazine is a dangerous substance that has toxic effects on the kidneys,
lungs, nervous system and mucous membranes. Furthermore, it is po- 3.1. Scanning electron microscopy (SEM) measurements
tentially hazardous to human health and to the environment, both in
the short- and long-term, due its extreme corrosive potential and its SEM images and EDX measurements were taken to observe the
reactivity with moisture and other oxidants [26]. morphology and composition, respectively. Fig. 1 shows the surfaces
Due to all the above, in this work, a new improved graphite ex- obtained by the exfoliation process with using NH4OH. Fig. 1a and c
foliation rout has been studied for obtaining rGO. The proposed che- shows structures with a rough surface and low transparency which are
mical rout uses only nitric and sulfuric acid to begin the exfoliation of structural characteristics related to sheets compound by a few graphene
graphite. Subsequently, this process is finished by using a solution of layers [29]. Conversely, the sheets observed in Fig. 1b show little
NH4OH for continuing the exfoliation and partial reduction of material roughness and white zones, indicating a greater number of graphene
synthetized. Unlike previously reported methods, NaNO3 and KMnO4 layers; whereas in Fig. 1d is observed a structure with noticeable
are not used since NaNO3 generates very toxic gases (NOx) and ex- transparency, nonetheless, its oxygen concentration is slightly greater
plosive reactions with oxidizing agents like KMnO4, in this way, these than in the others and the carbon concentration is the lowest as well,
reactions are also avoided in this work. Likewise, hydrazine has been which could indicate an efficient reduction of graphene layers from
completely dismissed as a consequence of its environmental and health graphite.
effects [27]. In addition, analytical grade graphite was not used but a EDX analysis was performed in order to determine the concentra-
mineral one which contributed to have a less expensive synthesis. tions of carbon and oxygen during the synthesis process. This analysis
was done utilizing the scanning area and statistical count of each mi-
crograph (see Table 1 and Fig. 1). The average value obtained for the C/
2. Materials and methods O ratio was 4.27, which depict a semi-reduction due to a concentration
value in agreement with that C/O ratio of 5 reported by Park et al. [24],
2.1. Graphite exfoliation where hydrazine is used for the reduction process. On the other hand,
Zhou et al. [30], implemented ammonium borane (NH3BH3) to reduce
Mineral graphite was used without previous treatment, 95% H2SO4 the GO, obtaining a C/O ratio of 9.6 and improved the reduction pro-
and 68–70% HNO3 were obtained from Sigma-Aldrich. While 28% v/v cess compared with those results reported by Fan et al. [31], with a C/O
NH4OH was purchased from JT Baker. Initially, 0.4 g of graphite was ratio of 7.9. Therefore, the rout, developed in this work, generates an
added to a H2SO4:HNO3 concentrated solution (3:1 vol ratio). This alternative to obtain rGO with a low reduction degree, which is inter-
mixture was sonicated (40 KHz) for 90 min at constant temperature esting for approaches where band gap could be modulated according to
(60 °C) before starting the oxidation process. The solution was heated the oxidation degree. All images in Fig. 1 show few graphene layers,
with thermal oil until 70 °C to prevent contraction between graphene nonetheless, the process could be improved by increasing the exfolia-
layer due to loss of temperature [28]. This process improves the con- tion time.
tinuous action of oxidizing agents, inserting functional groups between Fig. 2 shows the result of exfoliation without the exothermic neu-
each graphene sheet. Later, the oxidation started with intense and tralization reaction. The structural and elemental concentration
constant stirred at 90 °C for 24 h. Afterwards, the mixture was cooled changes are evident. Due to the absence of this last reaction, the oxygen
and sonicated for 30 min at room temperature. Finally, an aliquot concentration is higher and consequently, the resulting average value of
(10 mL) of oxidized solution was added slowly in a separation funnel C/O ratios without using NH4OH is 1.05. Fig. 2a, b, 2c and 2d show the
containing 5 mL of NH4OH concentrated. The resulting mixture was need to apply more energy since the sheets are very large and thick
recirculated several times in order to homogenize the reaction. In the because of they are compound of many layers. Therefore, NH4OH is
last step, the ammonium hydroxide helps not only to exfoliate the used in order to reduce graphene layer and oxygen concentration.
graphene sheets but also to reduce the functional groups. The results obtained with the proposed method (see Table 1) reflect

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A.F. Betancur et al. Materials Chemistry and Physics 218 (2018) 51–61

Fig. 1. FE-SEM image of exfoliated graphite using NH4OH.

Fig. 2. FE-SEM image from exfoliated graphite without NH4OH.

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A.F. Betancur et al. Materials Chemistry and Physics 218 (2018) 51–61

Table 1
Carbon and oxygen concentrations from Figs. 1 and 2 (EDX measures).
Weight% Atomic% Ratio

C O C O C/O

Fig. 1 Fig. 2 Fig. 1 Fig. 2 Fig. 1 Fig. 2 Fig. 1 Fig. 2 Fig. 1 Fig. 2

a 77.19 47.71 22.81 52.29 81.85 54.86 18.15 45.14 4.5096 1.215
b 77.4 39.31 22.6 60.69 82.02 46.32 17.98 53.68 4.5617 0.863
c 76.36 46.58 23.64 53.42 81.14 53.74 18.86 46.26 4.3022 1.162
d 73.12 41.42 26.22 58.58 78.58 48.5 21.15 51.5 3.7154 0.942

Fig. 3. XPS measurements after chemical exfoliation and reduction. The concentration obtained were C1s = 68.21%at, O1s = 21.83 %at, N1s = 5.35 %at and
S2p = 4.63%at.

the action exerted by the NH4OH during the graphite exfoliation. An rings, corresponding to sp2 hybridization. This suggest the presence of a
acceptable separation of graphene layers was achieved in mineral reduced material [32]. In Fig. 3, other peaks are observed around
graphite, including a nitrogen functionalization over the graphene 285.3 eV and 286.1eV which could be assigned to the C-O and C=O,
structure (see section 3.2). respectively [33]. The binding energy of 286.9 eV correspond to O-
C=O [21,33,34] and the last peak at 288.6 eV is attributed to π-π
3.2. X-ray photoelectron spectroscopy (XPS) analysis transitions which indicate the restoration of sp2 hybridization [35]. The
value around to 285.96 eV is related to two types of bonds C-O from
In this study, the main values of binding energy show the presence hydroxyl and epoxy groups and C-N from graphitic and pyrrolic ni-
of nitrogen-carbon, oxygen-carbon and sulfur-oxygen bonds. The mea- trogen [36].
surements give a bond energy range corresponding to each element (N, Some authors reported a nitrogen functionalization formed into
S, O, C) and information about the kind of bond and functional groups graphene sheets. Susi et al. [37], made a XPS study about graphitic
which possibly correspond. carbon nanomaterials doped with heteroatoms, and showed specific
The C1s spectra of GO are shown in Fig. 3. The highest intensity of functional groups formed with nitrogen (graphitic nitrogen). They re-
binding energy is 284.3 eV and belongs to C=C/C-C in the aromatic ported that the energy value of graphitic N is 401.3 eV, for pyridinic N

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Fig. 4. a) and b) AFM images after chemical exfoliation. b) Thickness measurements along the cross section from b images showing several sheets, with the thinnest
sheet measuring 3 nm.

is 398.4 eV and pyrrolic N the bond energy is 400.1 eV. In the present impurities. This sheet has an area around to 9 μm2. The measurement of
work, the total nitrogen found was 5.35 at% respect to total C and the thickness was made over a region of the sheet containing some holes,
main functional group obtained was a graphitic N with bond energy of measured around to 3 nm. According to Botas et al. [27], the thickness
401.28 eV, but it was also found a pyrrolic N with 400.44 eV and oxi- range to obtain a GO monolayer is between 0.40 nm and 2.04 nm.
dized N around 402.02 eV. Whereas Dubin et al. [39], reported a thickness of 0.93 nm for one
In O1s spectra three different bonds are displayed. The main bond graphene oxide layer. In accordance with Stankovich et al. [23], a
found was at 531.29 eV and it corresponds to C=O bond. The complete exfoliation process is presented when the thickness is around
532.60 eV was from hydroxyl and epoxy groups [32], but there is a 1 nm, because of the presence of oxygen covalent bonds and displace-
possible contribution of H-O-S from H2SO4 [38]. This shows that the ment of sp3 hybridized carbon atoms slightly above and below the
reduction of functional groups using NH4OH due to the C-O bonds do original graphene plane. But if there is not a complete chemical ex-
not predominate over C=O bonds. Finally, the value of 535.01 eV foliation it could be consider the graphene thickness (graphite thickness
corresponds to the contribution of carboxylic group. 0.34 nm [40]) to establish the number of graphene layers inside the
For sulfur the bonds are displayed near to 167.5 eV and 169.5 eV. some sheets. Therefore, following the Sorokina, Botas and Dubin stu-
According to the work reported by Wahlqvist et al. [38], the binding dies, the obtained sheet in this work, with 3 nm, corresponds between
energy values reported in Fig. 3 S1p, correspond to sulfates from three and four graphene oxide layers or ten graphene layers.
(NH4)2SO4 and H2SO4, which do not belong to GO structure, but rather The shape of edges in the obtained material is correlated with
are reaction products. images in Fig. 2a, where are observed rounded corners. It is attributed
to not defined pattern (not armchair or zigzag cut) during oxidation
3.3. Study by atomic force microscopy (AFM) process where C-C bonds are broken in aleatory form.

In Fig. 4a, a big sheet is shown over a silicon substrate with some

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1581 cm−1 show the sp2 hybridization and this may indicate some re-
duction degree [19,42,45]. The deoxygenation, due to reduction pro-
cess, decreases the intensity of all functional groups, principally from
the hydroxyl groups [46].
The oxidative power of nitric acid is high enough to dislodge sheets
with fewer irregularities, as can be observed in SEM micrographs
(Section 3.1) and later, in the Raman analysis (Section 3.5). Due to the
strong reduction potential of HNO3 (E = 0.79 V), when it is mixed with
H2SO4, the mixing can be used for purification and functionalization of
carbon materials [47]. Marshall et al. [48] achieved the single wall
carbon nanotubes (SWCNT) functionalization with 3:1 vol ratio of
H2SO4 and HNO3 acids. The acid treatment generated carboxylic groups
(-COOH) on the nanotube walls which was quantified using dodecyla-
mine. The percentage of functional groups in 35 mg of SWCNT in-
creased from 1% to 7% during 7 h of process. This is an important fact
because it shows the surface modification by breaking carbon-carbon
bonds in the external carbon nanotubes (CNT's) wall. The edges are
necessary for the oxidizing agent attack and graphite bisulfate forma-
tion. Therefore, it is possible obtain GO using the same oxidizing agent
because graphite has more edges than CNT's.
The reduction potential of HNO3 (E = 0.79 V) is smaller than that
Fig. 5. FTIR spectrums were obtained after chemical exfoliation with different for KMnO4 (E = 1.5 V) [47]. Hence, KMnO4 contributes to the forma-
volume ratios of H2SO4 and HNO3. tion of HSO4 as a graphite intercalation component (HSO4-GIC) and
helps to separate the GO sheets normally with a significant number of
3.4. Infrared spectroscopy analysis defects. Nonetheless, it is important to highlight that this work seeks to
synthesize the larger and homogeneous sheets with few defects and
Fig. 5 shows the infrared spectra of exfoliated graphite to different using a weaker oxidizing agent than KMnO4. It can be observed in FTIR
volume ratio of sulfuric and nitric acid. The spectrum with 3:1 vol ratio results.
shows greater differences with regard to the graphite structure. In this As the H2SO4/HNO3 ratio was increased, an increasing in the in-
spectrum (Fig. 5, 3:1), different functional groups were identified: the tensity of the bands associated to the C-O, C=O and C-O-C functional
vibrational modes near to 3788 cm−1 and 1489 cm−1 might be as- groups was observed. This is an indicative of an increasing in the pre-
signed to N-H and C-N bonds, formed during the last step in the ex- sence of oxygen groups [33,49,50]. However, the FTIR intensities ob-
foliation process; since the use of NH4OH contributes to the formation tained are smaller than those reported by other authors using the
of graphitic nitrogen (see section 3.2.) [41]. The carboxyl groups classical Hummers' method [19,51]. This suggests that controlling the
(-COOH) are related with C=O and C-O bonds around 1750 cm−1 and H2SO4/HNO3 ratio allows a better control of the oxidation degree,
1350 cm−1, respectively, but the mode around 1350 cm−1 and limiting the oxygen groups concentration into the carbon structure.
3390 cm−1 could be a contribution of hydroxyl groups [35,42]. Other
vibration mode around 1204 cm−1 was observed, corresponding to
epoxide group (C-O-C) [43,44]. The aromatic bond (C=C) near to

Fig. 6. Normalized Raman spectra of graphite source, chemical exfoliation of graphite (a) chemically exfoliated and reduced graphite and (b) deconvolution of the G
and D bands corresponding to the (a) spectrum.

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Table 2 systems like this. Moreover, one way to observe the change of number
Spectral features of deconvolution made from spectra in Fig. 6 a). of layers is with the position of G band [55]. In the spectra shown in
Band Fig. 6 a Fig. 6, there is a clear change in the G band position before and after
exfoliation process. For graphite and the chemically exfoliated and re-
cm−1 Intensity duced graphite the G band components are located at 1578.09 cm−1
and 1604.91 cm−1 respectively. In this case, the position of G band
D 1360.5 13037.92
GDecon 1570.7 8147.788 increases as the number of layer decreases. The intensity ratios calcu-
D' 1607.8 11263.996 lated for complete process were ID/IG = 0.86 and I2D/IG = 0.802. It is
G Exp 1604.9 15577.82 important to take into account that the vibrational modes associated
with D band are influenced by several factors; therefore, the ratio ID/IG
would be an indication that there are several layers but not a specific
3.5. Raman spectroscopy analysis number of them. In this way, the 2D band is related to G band to es-
timate the number of layers. The results obtained in this work were
Fig. 6 shows the characteristic vibrational modes, where G (IG) is the compared with those results obtained by Lee et al. [54], in order to
mayor mode. The latter, it is a first order vibration mode and corre- calculate approximately the minimum layers. Lee provided ratio values
sponds to graphitization degree. D (ID) and 2D (I2D) modes are attrib- for one layer of I2D/IG = 2.4 and for three layers of I2D/IG = 1.2. Other
uted to the disorder degree and the double second-order resonance, authors such as Gluba et al. [56], reported the same relationship for
respectively. The work developed by Dimiev and Tour [52] showed graphite monolayer. The number of layer grows up with the reduction
different oxidation processes over graphite applying the Hummers' of the intensity ratio I2D/IG. The intensity ratio calculated in this work
method. This study revealed changes in the Raman vibration modes was I2D/IG = 0.802, therefore, according with Lee results; the number
that can give information about to exfoliation degree. This information of layers obtained in this work was four, approximately.
can be related to the number of layers and oxidation degree. Raman spectroscopy can provide criteria for a qualitative descrip-
As can be seen in Fig. 6, the increasing of the D band intensity is due tion of materials from synthesis process. Therefore, this could elucidate
to an increase in structural disorder caused by oxidizing agents that which is the direction of the chemical reaction describing the type of
break and detach the graphene sheets, adhering functional groups such carbon nanostructure obtained. One of these criteria is through a G
as hydroxyl, epoxy and carboxyl. These changes were studied by Shin band deconvolution (G band from experimental measurements, GEXP) in
et al. [47]. Shin and coworkers showed how the intensity ratio of G and two fundamental components GDecon and D' (See Table 2). According to
D bands (ID/IG) varies after exfoliation process in 0–4 days reporting the King et al. [57], there is a range between the difference of these bands
following ratios: 0, 0.09, 0.33, 0.46 and 1.05, respectively and the obtained from the deconvolution and the C/O ratio, which could help to
oxidation degree was established following these ratios. For each day of elucidate the type of structure. These ranges are: If GO is obtained, the
exfoliation, they measured the atomic percentage of carbon and difference between D′ and GDecon band must be less than zero (D ′-
oxygen, obtaining for the first day 98.42% C and 1.58% O, for the GDecon < 0) and the ratio of C/O < 10. If rGO is obtained, the range
second 89.92% C and 10.08% O, in the third 86.64% C and 13.36% O would be 0 < D ′- GDecon < 25 and 10 < C/O < 500. Therefore, the
and in the fourth day the atomic percentage was 79.06% C and 20.94% results in the present work (Fig. 6b), the synthesized material has a
O. In this work, the chemical exfoliation proposed was done in one day. value of D' - GDecon = 2.94, indicating the rGO obtaining, but the ratio
After that, the atomic percentage of C and O was 78.58% and 21.15% C/O = 4.27 obtained does not fit with this range. However, this cri-
respectively, with an ID/IG ratio of 0.86. This oxidation degree obtained terion is discussed, because some authors mentioned above establish
in just one day is close to the results obtained in Ref. [47] with four that the rGO has a relation of C/O > 5 depending of the reduction
days of exfoliation. This indicates an improvement in the process, re- process [24,30,31]. An increase of ID/IG ratio, leads to an increase in
ducing the exfoliation time and with an upper oxygen concentration. It the degree of exfoliation of graphite [47].
is important to establish the differences between both processes. In Ref.
[47] it is reported an exfoliation using a ratio between sulfuric acid and 3.6. X-ray diffraction (XRD)
nitric acid of 1.78 (v/v), respectively, and a stirred at 100 °C under a
nitrogen atmosphere for one, two, three and four days. In this work, the XRD measurements were performed. The graphite has two char-
process conditions are the follow: first the ratio of sulfuric and nitric acteristic planes (Fig. 7b). The first peak corresponds to a basal re-
acid is 3:1 (v/v), respectively. The mixture was sonicated for 90 min to flection plane (002) at 26.51° and the second plane corresponds to
70 °C and later stirred to a temperature between 80 °C and 90 °C for one plane (004) at 54.52° [58]. These planes are characteristic of graphite
day. Subsequent it was sonicated for 60 min and finally a neutralization structure and change when the graphite is subjected to milling [59] or
reaction was made using ammonium hydroxide. some oxidation process [60]. Both diffractograms show a contribution
Some authors use Raman spectroscopy as a tool for estimate the of some impurities around 12.5° and 24.9°, because of graphite is not a
number of graphene layers by using the G and 2D bands. Malard et al. pure source and has traces of aluminum silicate hydroxide.
[53], carried out a detailed study of Raman spectroscopy in graphene Fig. 7a shows the characteristic peaks, which are 26.62° and 43.27°,
and showed how the characteristic bands change with the number of and coming from (002) and (100) reflection planes, respectively. Kwon
layers, edges and irregularities. All these alter the phonon vibrations, et al. [61], shown similar results with characteristic peaks for reduced
modifying the intensity of the first and second order vibrational modes. graphene oxide obtained by thermal exfoliation method and hydrazine.
They reported a range of 0.05 < ID/IG < 0.3 for the intensity ratio On the other hand, the peaks observed in the present work about 7.27°
between the D and G bands for a monolayer of graphene. However, it is and 9.12° correspond to plane (001) from GO and are near to those
important to consider that D band intensity is mainly due to irregula- reported by other authors [32,35,62]. It is clear that the loss of graphite
rities and edges of graphene in areas with a constant number of layers. crystallinity due to significantly changes after the exfoliation process
In addition, this band provides a lot of information about determination result in low intensity peaks with broad shape, compared with Fig. 7b.
of the oxidation degree, instead of being used to determine the number These changes indicate amorphousness, particle reduction to nano-
of layers. Therefore, the work done by J. Lee et al. [54], helped to metric scale and the insertion of water and functional groups between
supplement this information using a second-order vibrational mode (2D layers of graphite changing the interplanar distance [63].
band). The peak close to 43.27° has two possible explanations. Initially, it
Although the technique reported by Malard et al. [53] is used for may indicate the presence of graphite intercalation compounds (HSO4-
graphene, it is a theoretical basis that could be applied in similar GIC) during formation of GO as suggested by Diemev [20], but it is

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Fig. 8. Thermogravimetric analysis of a) graphite and b) chemically exfoliated

and reduced graphite.

[24,33,39,69] in which the weight loss reported generally does not

exceed 40% up to 800 °C.

4. Suggested mechanism for rGO synthesis

According to the results, a possible mechanism for the synthesis of

rGO is proposed. It was assumed that the H2SO4/HNO3 mixture behaves
similarly as in Hummers method, causing the entering of sulfates into
the graphite structure up to form graphite intercalation compounds
(GIC) complexes, which help in the exfoliation process (Fig. 9). Ac-
Fig. 7. XRD spectra for chemical exfoliation (a) with NH4OH and (b) Graphite cording to Sorokina et al. [22], and depending on the oxidant nature,
source. concentration and redox potential of the oxidizing solution, the GIC
may form and attain different compositions. The GIC formed is mainly
close to the crystallographic plane (100) of GO according to Guerrero- bisulfate graphite (HSO4-Graphite), a key component to start the se-
Contreras [64]. This reflection plane corresponds to a turbostratic band paration and oxidation of graphene sheets present in graphite. The rate
of disordered carbon materials [59]. Therefore, the origin and broad of formation depends on the electrochemical potential and the sur-
shape of this angle could be due to the contribution of both phenomena. rounding medium, taking a time of 3–5 min [20].
Although the angle of 26.62° is normally given to plane (002) [35,50], According to Dimiev work it is supposed that the GIC were formed
Zang et al. [36] shown the formation of this characteristic peak during during step 2 (shown in Fig. 9). The sulfuric acid reaction with an
GO functionalization with amino groups, as can be seen from XPS oxidizing agent (HNO3) is fundamental to the formation of the inter-
analysis (see section 3.2). Similarly, Dubin et al. [39], reported the calation component (HSO4-Graphite) and subsequent transformation of
same peak for GO solvothermally reduced. This would confirm the re- pristine graphite oxide (PGO) (Fig. 9 step 1–3), acting in a similar way
ductive action of NH4OH and functionalization with graphitic nitrogen to KMnO4 in the Hummers method. This reaction needs an oxidizing
principally (see section 3.2), for which both works evidence the for- agent because the graphite bisulfate has a positive enthalpy formation
mation of two characteristic peaks around 26° and 43°. The previous (ΔH+). Therefore, it is necessary to add more energy in the synthesis
results shown by different authors can help to confirm the reduction process in order to break more efficiently the Van Der Waals forces that
process due to the peaks formed close the angles around to 9.12°, 26.62° are binding the graphene sheet. The energy can be provided by adding
and 43.27°, which are essential to identify a reduction of functional other oxidizing agents or increasing the temperature in the process
groups [35,62,65]. [52]. Thus, the energetic contribution in the process is also made too
with high temperatures close to 80 °C–90 °C.
The reduction stage used to minimize the functional groups (hy-
3.7. Thermogravimetric analysis (TGA) droxyl and epoxy groups) present after oxidation process (Fig. 9 step 4
to 5). During this process, ammonium hydroxide generates exothermic
In order to evaluate the thermal stability of the material thermo- neutralization reaction. This reaction increases the temperature around
gravimetric analysis was carried out. The measurements were carried 70 °C while reacting with the GIC compounds and contributing with the
out in a controlled nitrogen environment and heating rate of 1 °C/min. required amount of energy necessary to separate, reduce and functio-
Temperature was ranged from 25 °C to 1190 °C. A comparison between nalize the graphene sheets from graphite. After these four steps, water
the thermal behavior of the graphite source (curve a) and the obtained culminates the separation of each layer and removes some remaining
material (curve b) is shown in Fig. 8. As it is observed, the synthetized compounds (Fig. 9, step 5). The reduction process alters some proper-
material presented a good thermal stability over all the measured ties such as conductivity [7]. Therefore, reduced graphene oxide (rGO)
temperature range, losing only a total weight of 19%, which suggests has more applications than GO, due to the rGO has properties closer to
that a carbon reduced material was obtained [66–68]. This behavior is the graphene sheet. Some compounds used to reduced GO are ammonia
similar to that observed in rGO synthesized by different authors borane [30], hydrazine [24], sodium borohydride [70] among others

58
A.F. Betancur et al. Materials Chemistry and Physics 218 (2018) 51–61

Fig. 9. Reaction mechanism during the chemical exfoliation proposes. 1) graphite, 2) oxidation graphite start, GIC formation 3) Transition of graphite bisulfate to
POG, 4) the salts and functional groups formation begin the sheet detachment and functionalization of graphitic nitrogen (see 3.2 section, XPS results). The step 5
corresponds to reduction of functional groups.

[61]. Each of these processes seeks to increase the atomic ratio C/O (see and functionalize as well, obtaining a C/O ratio of 4.27 similar to that
section 3.1). According to different authors, this ratio varies between 7 obtained by using hydrazine. In addition, traces of N-C bonds were
and 10, indicating an oxidation degree [23,24,30,31]. measured, mainly from nitrogen graphitic. The material obtained had a
EDX results showed an average C/O ratio of 4.27 after of reaction thickness of 3 nm which corresponds to four graphene oxide layers or
with NH4OH (Table 1 Fig. 1) and C/O ratio without NH4OH is 1.05 ten graphene layers. In brief, the proposed method contributes to (1)
(Table 1 Fig. 2). This is important because some functional groups are reduce the toxic and dangerous waste products; (2) reduce the oxida-
being eliminated by amino groups released during the reaction. When tion time; (3) eliminate functional groups of GO; (4) simplify the ex-
there are high concentrations of sulfuric acid in the presence of nitric foliation process and finally (5) reduce the cost of the process by using
acid (ratio 3:1), the nitric acid ionizes as shown in the reaction common and economic reagents. Moreover, the material synthetized
HNO3 + 2H2SO4 ⇌ NO2+ + H3O+ + 2HSO4. Within the reaction, needs more energy to get up to rGO like as temperature increase and
these products between the graphite sheets, separate the sheets and addition of an additional oxidizing agent.
form an exchange components (GIC) described in stage 3 of the exposed
synthesis mechanism (Fig. 9). But when NH4OH is added, this forms Acknowledgments
mainly ammonium sulphate (NH3SO4) and nitronium ions (NO2+) react
easily with the π clouds present in the graphene sheets [71], but they Authors acknowledge financial support of this work by Colciencias,
are unstable and transitional compounds, since oxygen and Nitrogen Universidad Pontificia Bolivariana (UPB, Medellín-Colombia) and the
are very electronegative and the environment makes them react im- Centro de Investigación en Materiales Avanzados S.C. (CIMAV,
mediately with protonated water (H3O+) and H+ presents in the Monterrey-México). We thank to Nayely Pineda Aguilar, Oscar Eduardo
medium to form water and functional groups based on oxygen and Vega Becerra, Francisco E. Longoria Rodríguez, Luis Gerardo Silva
nitrogen such as graphitic nitrogen, which occur in higher concentra- Vidaurri and Alberto Toxqui Terán for the technical support from
tion (5.38% wt) according to the XPS analysis. But more experimental CIMAV and Iris Aguilar-Hernández for the technical support from
and theoretical studies are necessaries in order to clarify the details of ITESM. Authors thank the financial support obtained from the
the mechanisms involving in the processes. Departamento Administrativo de Ciencia, Tecnología e Innovación,
Colciencias, Colombia, through the call 617 for exchange of researchers
Colombia-México UPB-CIMAV, contract 684 UPB-Colciencias. Thanks
5. Conclusions to Bilateral project CONACyT - COLCIENCIAS number: 233535, for the
support given to the mobility of researchers and students involved in
A new possible rout to obtain rGO directly by chemical exfoliation the research project.
of mineral graphite with oxidizing agents like nitric and sulfuric acid
was studied. The oxidation process is less dangerous because the tra- References
ditional regents used on Hummer's method such as sodium nitrate
(NaNO3) and potassium permanganate (KMnO4) were eliminated. It [1] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater. (2007) 183–191
was evaluated the capability of NH4OH to eliminate functional groups https://doi.org/10.1038/nmat1849.

59
A.F. Betancur et al. Materials Chemistry and Physics 218 (2018) 51–61

[2] M. Batzill, The surface science of graphene: metal interfaces, CVD synthesis, na- vol. 5, (2011), pp. 191–198.
noribbons, chemical modifications, and defects, Surf. Sci. Rep. 67 (2012) 83–115, [32] S. Drewniak, R. Muzyka, A. Stolarczyk, T. Pustelny, M. Kotyczka-Morańska,
https://doi.org/10.1016/j.surfrep.2011.12.001. M. Setkiewicz, Studies of reduced graphene oxide and graphite oxide in the aspect
[3] D.R. Dreyer, The chemistry of graphene oxide, Graphene Oxide Reduct. Recipes, of their possible application in gas sensors, Sensors 16 (2016) 103, https://doi.org/
Spectrosc. Appl. (2015) 61–95, https://doi.org/10.1007/978-3-319-15500-5_3. 10.3390/s16010103.
[4] F. Li, X. Jiang, J. Zhao, S. Zhang, Graphene oxide: a promising nanomaterial for [33] P.G. Ren, D.X. Yan, X. Ji, T. Chen, Z.M. Li, Temperature dependence of graphene
energy and environmental applications, Nanomater. Energy 16 (2015) 488–515, oxide reduced by hydrazine hydrate, Nanotechnology 22 (2011), https://doi.org/
https://doi.org/10.1016/j.nanoen.2015.07.014. 10.1088/0957-4484/22/5/055705.
[5] E. Mitchell, J. Candler, F. De Souza, R.K. Gupta, B.K. Gupta, L.F. Dong, High per- [34] X. Zhou, J. Zheng, H. Wu, H. Yang, J. Zhang, S. Guo, Reducing graphene oxide via
formance supercapacitor based on multilayer of polyaniline and graphene oxide, hydroxylamine: a simple and efficient route to graphene, J. Phys. Chem. C 115
Synth. Met. 199 (2015) 214–218, https://doi.org/10.1016/j.synthmet.2014.11. (2011) 11957–11961, https://doi.org/10.1021/jp202575j.
028. [35] K. Muthoosamy, R. Geetha Bai, I.B. Abubakar, S.M. Sudheer, H.N. Lim, H.S. Loh,
[6] D.W. Boukhvalov, M.I. Katsnelson, Modeling of graphite oxide, J. Am. Chem. Soc. N.M. Huang, C.H. Chia, S. Manickam, Exceedingly biocompatible and thin-layered
130 (2008) 10697–10701, https://doi.org/10.1021/ja8021686. reduced graphene oxide nanosheets using an eco-friendly mushroom extract
[7] Y. Zhu, S. Murali, W. Cai, X. Li, J.W. Suk, J.R. Potts, R.S. Ruoff, Graphene and strategy, Int. J. Nanomed. 10 (2015) 1505–1519, https://doi.org/10.2147/IJN.
graphene oxide: synthesis, properties, and applications, Adv. Mater. 22 (2010) S75213.
3906–3924, https://doi.org/10.1002/adma.201001068. [36] C. Zhang, R. Hao, H. Liao, Y. Hou, Synthesis of amino-functionalized graphene as
[8] S. Tang, W. Wu, X. Xie, X. Li, J. Gu, Band gap opening of bilayer graphene by metal-free catalyst and exploration of the roles of various nitrogen states in oxygen
graphene oxide support doping, RSC Adv. 7 (2017) 9862–9871, https://doi.org/10. reduction reaction, Nanomater. Energy 2 (2013) 88–97, https://doi.org/10.1016/j.
1039/C7RA01134B. nanoen.2012.07.021.
[9] B. Kang, H. Liu, J.Y. Lee, Oxygen adsorption on single layer graphyne: a DFT study, [37] T. Susi, T. Pichler, P. Ayala, X-ray photoelectron spectroscopy of graphitic carbon
Phys. Chem. Chem. Phys. 16 (2014) 974–980, https://doi.org/10.1039/ nanomaterials doped with heteroatoms, Beilstein J. Nanotechnol. 6 (2015)
c3cp53237b. 177–192, https://doi.org/10.3762/bjnano.6.17.
[10] K. Krishnamoorthy, R. Mohan, S.J. Kim, Graphene oxide as a photocatalytic ma- [38] M. Wahlqvist, A. Shchukarev, XPS spectra and electronic structure of Group IA
terial, Appl. Phys. Lett. 98 (2011) 2013–2016, https://doi.org/10.1063/1.3599453. sulfates, J. Electron. Spectrosc. Relat. Phenom. 156–158 (2007) 310–314, https://
[11] J. Zhang, J. Yu, M. Jaroniec, J.R. Gong, Noble metal-free reduced graphene Oxide- doi.org/10.1016/j.elspec.2006.11.032.
Zn x Cd 1– x S Nanocomposite with enhanced solar photocatalytic H 2 -production [39] S. Dubin, S. Gilje, K. Wang, V.C. Tung, K. Cha, A.S. Hall, J. Farrar, R. Varshneya,
performance, Nano Lett. 12 (2012) 4584–4589, https://doi.org/10.1021/ Y. Yang, R.B. Kaner, A one-step, solvothermal reduction method for producing re-
nl301831h. duced graphene oxide dispersions in organic solvents, ACS Nano 4 (2010)
[12] W. Fan, Q. Lai, Q. Zhang, Y. Wang, Nanocomposites of TiO2 and reduced graphene 3845–3852, https://doi.org/10.1021/nn100511a.
oxide as efficient photocatalysts for hydrogen evolution, J. Phys. Chem. C 115 [40] W. Luo, W.H. Doh, Y.T. Law, F. Aweke, A. Ksiazek-sobieszek, A. Sobieszek,
(2011) 10694–10701, https://doi.org/10.1021/jp2008804. L. Salamacha, K. Skrzypiec, A. Machocki, S. Zafeiratos, Single-layer Graphene as an
[13] T.F. Yeh, J. Cihlář, C.Y. Chang, C. Cheng, H. Teng, Roles of graphene oxide in Effective Mediator of the Metal − Support Interaction, (2014).
photocatalytic water splitting, Mater. Today 16 (2013) 78–84, https://doi.org/10. [41] B. Ramezanzadeh, S. Niroumandrad, A. Ahmadi, M. Mahdavian,
1016/j.mattod.2013.03.006. M.H. Mohamadzadeh Moghadam, Enhancement of barrier and corrosion protection
[14] H.L. Tan, F. Denny, M. Hermawan, R.J. Wong, R. Amal, Y.H. Ng, Reduced graphene performance of an epoxy coating through wet transfer of amino functionalized
oxide is not a universal promoter for photocatalytic activities of TiO2, J. Mater. 3 graphene oxide, Corrosion Sci. 103 (2016) 283–304, https://doi.org/10.1016/j.
(2017) 51–57, https://doi.org/10.1016/j.jmat.2016.12.002. corsci.2015.11.033.
[15] G. Liao, S. Chen, X. Quan, H. Yu, H. Zhao, Graphene oxide modified g-C 3 N 4 hybrid [42] W. Gao, Graphene Oxide Reduction Recipes, Spectroscopy, and Applications,
with enhanced photocatalytic capability under visible light irradiation, J. Mater. Springer, Los Alamos, 2015, https://doi.org/10.1007/978-3-319-15500-5.
Chem. 22 (2012) 2721–2726, https://doi.org/10.1039/C1JM13490F. [43] N. Wu, X. She, D. Yang, X. Wu, F. Su, Y. Chen, Synthesis of Network Reduced
[16] M. Zhu, P. Chen, M. Liu, Graphene oxide enwrapped Ag/AgX efficient visible-light Graphene Oxide in Polystyrene Matrix by a Two-step Reduction Method for
plasmonic, ACS Nano (2011) 4529–4536, https://doi.org/10.1021/nn200088x. Superior Conductivity of the Composite, (2007), pp. 282–283, https://doi.org/10.
[17] B. Brodie, On the atomic weight of graphite, Philos. Trans. R. Soc. (1859) 249–259 1007/978-94-007-0693-4.
http://www.jstor.org/stable/108699 , Accessed date: 1 December 2014. [44] N. Kumar, S. Das, C. Bernhard, G.D. Varma, Effect of graphene oxide doping on
[18] J. William, S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem. superconducting properties of bulk MgB 2, Supercond. Sci. Technol. 26 (2013)
Soc. 80 (1958) 1339, https://doi.org/10.1021/ja01539a017. 095008, https://doi.org/10.1088/0953-2048/26/9/095008.
[19] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, [45] Z. Huang, S. Wang, J. Wang, Y. Yu, J. Wen, R. Li, Exfoliation-restacking synthesis of
L.B. Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, ACS Nano 4 coal-layered double hydroxide nanosheets/reduced graphene oxide composite for
(2010) 4806–4814, https://doi.org/10.1021/nn1006368. high performance supercapacitors, Electrochim. Acta 152 (2015) 117–125, https://
[20] A.M. Dimiev, J.M. Tour, Mechanism of graphene oxide formation, ACS Nano 8 doi.org/10.1016/j.electacta.2014.11.085.
(2014) 3060–3068. [46] A. Kaniyoor, R.I. Jafri, T. Arockiadoss, S. Ramaprabhu, Nanostructured Pt
[21] J. Chen, B. Yao, C. Li, G. Shi, An improved Hummers method for eco-friendly Decorated Graphene and Multi Walled Carbon Nanotube Based Room Temperature
synthesis of graphene oxide, Carbon 64 (2013) 225–229, https://doi.org/10.1016/ Hydrogen Gas Sensor, (2009), pp. 382–386, https://doi.org/10.1039/b9nr00015a.
j.carbon.2013.07.055. [47] Y.-R. Shin, S.-M. Jung, I.-Y. Jeon, J.-B. Baek, The oxidation mechanism of highly
[22] N.E. Sorokina, M.A. Khaskov, V.V. Avdeev, I.V. Nikol’skaya, Reaction of graphite ordered pyrolytic graphite in a nitric acid/sulfuric acid mixture, Carbon 52 (2013)
with sulfuric acid in the presence of KMnO4, Russ. J. Gen. Chem. 75 (2005) 493–498, https://doi.org/10.1016/j.carbon.2012.10.001.
162–168, https://doi.org/10.1007/s11176-005-0191-4. [48] M.W. Marshall, S. Popa-Nita, J.G. Shapter, Measurement of functionalised carbon
[23] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, nanotube carboxylic acid groups using a simple chemical process, Carbon 44 (2006)
S.T. Nguyen, R.S. Ruoff, Synthesis of graphene-based nanosheets via chemical re- 1137–1141, https://doi.org/10.1016/j.carbon.2005.11.010.
duction of exfoliated graphite oxide, Carbon 45 (2007) 1558–1565, https://doi. [49] S. Syama, R.S. Cherian, A.C. Poulose, T. Maekawa, D. Sakthikumar, P.V. Mohanan,
org/10.1016/j.carbon.2007.02.034. Synthesis and characterization of pegylated reduced graphene oxide : determination
[24] S. Park, J. An, J.R. Potts, A. Velamakanni, S. Murali, R.S. Ruoff, Hydrazine-reduc- of toxicity using bone marrow arrow mesenchymal stem cells, J. Appl. Chem. Sci.
tion of graphite- and graphene oxide, Carbon 49 (2011) 3019–3023, https://doi. Int. (2015) 1–11.
org/10.1016/j.carbon.2011.02.071. [50] H. Feng, R. Cheng, X. Zhao, X. Duan, J. Li, A low-temperature method to produce
[25] L. Qiu, H. Zhang, W. Wang, Y. Chen, R. Wang, Effects of hydrazine hydrate treat- highly reduced graphene oxide, Nat. Commun. 4 (2013) 1539, https://doi.org/10.
ment on the performance of reduced graphene oxide film as counter electrode in 1038/ncomms2555.
dye-sensitized solar cells, Appl. Surf. Sci. 319 (2014) 339–343, https://doi.org/10. [51] R. Muzyka, M. Kwoka, Ł. Smędowski, N. Dí, G. Gryglewicz, Oxidation of Graphite
1016/j.apsusc.2014.07.133. by Different Modified Hummers Methods vol. 32, (2017), pp. 1–5, https://doi.org/
[26] G. Choudhary, H. Ii, D. S, K. C, Toxicological Profile for Hydrazines, (1997), p. 224. 10.1016/S1872-5805(17)60102-1.
[27] C. Botas, P. Álvarez, C. Blanco, M.D. Gutiérrez, P. Ares, R. Zamani, J. Arbiol, [52] A.M. Dimiev, S.M. Bachilo, R. Saito, J.M. Tour, Reversible formation of ammonium
J.R. Morante, R. Menéndez, Tailored graphene materials by chemical reduction of persulfate/sulfuric acid graphite intercalation compounds and their peculiar Raman
graphene oxides of different atomic structure, RSC Adv. 2 (2012) 9643, https://doi. spectra, ACS Nano 6 (2012) 7842–7849, https://doi.org/10.1021/nn3020147.
org/10.1039/c2ra21447d. [53] L.M. Malard, M. a. Pimenta, G. Dresselhaus, M.S. Dresselhaus, Raman spectroscopy
[28] C. Zhang, W. Lv, X. Xie, D. Tang, C. Liu, Q.-H. Yang, Towards low temperature in graphene, Phys. Rep. 473 (2009) 51–87, https://doi.org/10.1016/j.physrep.
thermal exfoliation of graphite oxide for graphene production, Carbon 62 (2013) 2009.02.003.
11–24, https://doi.org/10.1016/j.carbon.2013.05.033. [54] J. Lee, S. Shim, B. Kim, H.S. Shin, Surface-enhanced Raman scattering of single- and
[29] A.V. Rozhkov, G. Giavaras, Y.P. Bliokh, V. Freilikher, F. Nori, Electronic properties few-layer graphene by the deposition of gold nanoparticles, Chemistry 17 (2011)
of mesoscopic graphene structures: charge confinement and control of spin and 2381–2387, https://doi.org/10.1002/chem.201002027.
charge transport, Phys. Rep. 503 (2011) 77–114, https://doi.org/10.1016/j. [55] A.C. Ferrari, Raman spectroscopy of graphene and graphite: disorder, electron-
physrep.2011.02.002. phonon coupling, doping and nonadiabatic effects, Solid State Commun. 143 (2007)
[30] Q. Zhuo, Y. Zhang, Q. Du, C. Yan, Facile reduction of graphene oxide at room 47–57, https://doi.org/10.1016/j.ssc.2007.03.052.
temperature by ammonia borane via salting out effect, J. Colloid Interface Sci. 457 [56] M. a. Gluba, D. Amkreutz, G.V. Troppenz, J. Rappich, N.H. Nickel, Embedded
(2015) 243–247, https://doi.org/10.1016/j.jcis.2015.07.029. graphene for large-area silicon-based devices, Appl. Phys. Lett. 103 (2013) 073102,
[31] Z. Fan, W. Kai, J. Yan, T. Wei, L. Zhi, J. Feng, Y. Ren, P. Song, F. Wei, Facile https://doi.org/10.1063/1.4818461.
Synthesis of Graphene Nanosheets via Fe Reduction of Exfoliated Graphite Oxide [57] A.A.K. King, B.R. Davies, N. Noorbehesht, P. Newman, T.L. Church, A.T. Harris,

60
A.F. Betancur et al. Materials Chemistry and Physics 218 (2018) 51–61

J.M. Razal, A.I. Minett, A new Raman metric for the characterisation of graphene Chem. Phys. 153 (2015) 209–220, https://doi.org/10.1016/j.matchemphys.2015.
oxide and its derivatives, Sci. Rep. 6 (2016) 1–6, https://doi.org/10.1038/ 01.005.
srep19491. [65] A. Shalaby, D. Nihtianova, P. Markov, A.D. Staneva, Structural analysis of reduced
[58] W. He, L. Zhu, H. Chen, H. Nan, W. Li, H. Liu, Y. Wang, Electrophoretic deposition graphene oxide by transmission electron microscopy, Bulg. Chem. Commun. 47
of graphene oxide as a corrosion inhibitor for sintered NdFeB, Appl. Surf. Sci. 279 (2015) 291–295.
(2013) 416–423, https://doi.org/10.1016/j.apsusc.2013.04.130. [66] X. Xu, T. Wu, F. Xia, Y. Li, C. Zhang, L. Zhang, M. Chen, X. Li, L. Zhang, Y. Liu,
[59] Z.Q. Li, C.J. Lu, Z.P. Xia, Y. Zhou, Z. Luo, X-ray diffraction patterns of graphite and J. Gao, Redox reaction between graphene oxide and in powder to prepare In2O3/
turbostratic carbon, Carbon 45 (2007) 1686–1695, https://doi.org/10.1016/j. reduced graphene oxide hybrids for supercapacitors, J. Power Sources 266 (2014)
carbon.2007.03.038. 282–290, https://doi.org/10.1016/j.jpowsour.2014.05.051.
[60] N.I. Kovtyukhova, Y. Wang, A. Berkdemir, R. Cruz-Silva, M. Terrones, V.H. Crespi, [67] K.S. Kumar, S. Pittala, S. Sanyadanam, P. Paik, A new single/few-layered graphene
T.E. Mallouk, Non-oxidative intercalation and exfoliation of graphite by Brønsted oxide with a high dielectric constant of 106: contribution of defects and functional
acids, Nat. Chem. 6 (2014) 957–963, https://doi.org/10.1038/nchem.2054. groups, RSC Adv. 5 (2015) 14768–14779, https://doi.org/10.1039/C4RA10800K.
[61] J. Kwon, B. Lee, Bisphenol a adsorption using reduced graphene oxide prepared by [68] V. Loryuenyong, K. Totepvimarn, P. Eimburanapravat, W. Boonchompoo, A. Buasri,
physical and chemical reduction methods, Chem. Eng. Res. Des. (2015), https://doi. Preparation and characterization of reduced graphene oxide sheets via water-based
org/10.1016/j.cherd.2015.09.007. exfoliation and reduction methods, Ann. Mater. Sci. Eng. 2013 (2013), https://doi.
[62] N.Y. Yuan, F.F. Ma, Y. Fan, Y.B. Liu, J.N. Ding, High conductive ethylene vinyl org/10.1155/2013/923403.
acetate composites filled with reduced graphene oxide and polyaniline, Compos. [69] T. Wu, X. Wang, H. Qiu, J. Gao, W. Wang, Y. Liu, Graphene oxide reduced and
Part A Appl. Sci. Manuf 43 (2012) 2183–2188, https://doi.org/10.1016/j. modified by soft nanoparticles and its catalysis of the Knoevenagel condensation, J.
compositesa.2012.06.003. Mater. Chem. 22 (2012) 4772, https://doi.org/10.1039/c2jm15311d.
[63] X. Qiao, S. Liao, C. You, R. Chen, Phosphorus and nitrogen dual doped and si- [70] G. Wei, J. Yu, M. Gu, X. Ai, X. Xu, T.B. Tang, Dielectric relaxation characteristics of
multaneously reduced graphene oxide with high surface area as efficient metal-free chemically reduced graphite oxide, Carbon 95 (2015) 374–379, https://doi.org/10.
electrocatalyst for oxygen reduction, Catalysts 5 (2015) 981–991, https://doi.org/ 1016/j.carbon.2015.08.031.
10.3390/catal5020981. [71] P.A. Quadros, N.M.C. Oliveira, C.M.S.G. Baptista, Benzene nitration: validation of
[64] J. Guerrero-Contreras, F. Caballero-Briones, Graphene oxide powders with different heterogeneous reaction models, Chem. Eng. Sci. 59 (2004) 5449–5454, https://doi.
oxidation degree, prepared by synthesis variations of the Hummers method, Mater. org/10.1016/j.ces.2004.07.107.

61