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Safer modified Hummers’ method for the synthesis of graphene oxide

with high quality and high yield.
To cite this article before publication: Guillermo Santamaría-Juárez et al 2019 Mater. Res. Express in press https://doi.org/10.1088/2053-
1591/ab4cbf

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Page 1 of 10 AUTHOR SUBMITTED MANUSCRIPT - MRX-115834.R2

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Safer modified Hummers’ method for
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7 the synthesis of graphene oxide with
8

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high quality and high yield.
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12 Guillermo Santamaría-Juárez 1, Estela Gómez-Barojas1*, Enrique Quiroga-González2**, Enrique Sánchez-Mora2,
13 Mildred Quintana-Ruiz3 and J. Deisy Santamaría-Juárez4

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14 1 Benemérita Universidad Autónoma de Puebla (CIDS, IC-BUAP). PO Box 196, 72000 Puebla, México.
15 2 Institute of Physics, BUAP. PO Box J-48, 72570 Puebla, México.
16 3 Institute of Physics, UASLP. 78290 San Luis Potosí, México.
17 4 Faculty of Chemical Engineering, BUAP. 72570 Puebla, México.
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19 E-mail: *egomez@ifuap.buap.mx, **equiroga@ieee.org.
20

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21 Received xxxxxx
22 Accepted for publication xxxxxx
Published xxxxxx
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Abstract
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We report on an improved method for the synthesis of graphene oxide based on the modified Hummers’ method
proposed by Marcano et al. Different steps of the process were optimized. First, the concentration of the reactants and the
reaction conditions were optimized to improve the efficiency of the oxidation process of graphite. The Raman spectrum of
30 the GO shows the typical D and G typical of graphite oxide materials. The contribution of the area under the band D to the
31 total area is 98 %, confirming that almost the whole graphene was oxidized (high oxidation yield). Furthermore, the
32 quantification of the C 1s XPS spectrum of our GO nanosheets indicates that about 77 wt % of oxygen in the form of
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33 oxygenated groups is bonded to the carbon nanosheets. Second, the reaction time was minimized to 12 h, without
34 compromising the quality (as confirmed by micrography). Third, the production of toxic gases has been reduced. Fourth, a
35
thermal treatment was introduced instead of the vacuum drying procedure traditionally used, greatly diminishing the overall
36
graphite oxide processing time that includes: the reactant preparation, graphite oxidation process, rinsing and dispersion
37
38 procedures, and drying (the drying time went from 12 h to 2 h). Reducing the total time by a half, compared to other
39 methods, is an important finding considering scaling for industrial production.
40
41 Keywords: Graphene oxide; Hummers’ method; graphite.
42
43 surface area, transparency [5], thermal conductivity [6] and
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1. Introduction
44 During the last decade, graphene, a monolayer one-
good interface contact with adsorbents [7-9], etc.
45 As with any new material that is intended for large-
atom-thick planar sheet of sp 2 hybridized carbon atoms
46 scale applications for example in the areas: analog
densely packed in a honeycomb crystal lattice [1], has
47 electronics and photonics/optoelectronics [10,11], the
gained considerable interest because of its possible
48 development, and optimization of methods that allow the
potential use as multifunctional material and wide range of
49 mass production and processing of graphene sheets is a top
applications in different kind of devices [2,3] . In this
50 priority. At present, the only route that affords graphene-
51 regard, although the originally reported approach to the
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based sheets in considerable quantities relies on the

52 preparation of graphene (i.e. micromechanical cleavage of
chemical conversion of graphite into graphite oxide.
53 bulk graphite) leads to high-quality 2D crystals and is
Graphite oxide often called graphitic acid or graphitic
54 suitable for fundamental studies, it suffers from extremely
oxide is a polycyclic aromatic hydrocarbon oxide
55 low productivity and is therefore inadequate for large-scale
interrupted by epoxides, alcohols, ketone carbonyls, and
56 use [4]. However, graphene has emerged as a material with
carboxylic groups [12-14].
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57 high potential due to its remarkable properties such as high

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3 According to Hontoria et al. [15, 16] this disruption
4 of the lattice is reflected in an increase of interlayer space
5 from 0.335 nm for graphite to more than 0.65 nm for
6 graphite oxide layers. The oxygen functional groups
7 convert the graphite oxide into a hydrophilic character;
8
then; graphite oxide can be exfoliated in many polar
in Hummers’ method acted as a chemical ‘‘scissor’’ and a
chemical ‘‘drill’’ in graphene planes to facilitate the
penetration of the oxidant solution. However, the risk of
explosion caused by HNO3 was still present; this is why
this acid was substituted by KMnO 4 [33]. Thus, a complete
oxidation of graphite could be achieved using a mixture of

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9
solvents and dispersed particularly well in water [17-19]. KMnO4/H2SO4 forming a graphite bisulfate product in
10
The graphite oxidation processes via strong oxidants which every single-layer of graphene is sandwiched by the
11
produce graphite oxide nanosheets with different oxygen- layers of bisulfate ions [34,35]. The complete intercalation
12
containing functional groups and defects [14]. Brodie et al. of bisulfate ions ensures the effective infiltration of the
13

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14 [20-22] first demonstrated the synthesis of graphite oxide KMnO4 solution among the graphene layers for their
15 in 1859 by adding a portion of potassium chlorate (KClO 3) surface oxidation.
16 to slurry of graphite in fuming nitric (HNO 3) acid. The The objective of this work is to optimize the steps of
17 product they obtained was insoluble in acids and saline the graphite oxidation process such as: (1) reactants ratio
18 solutions, but it was soluble in pure water and in alkalis; in following the Marcano et al. [30] and Yeon-Ran et al. [32]
19 comparison to other graphite oxides, this product was more methods, (2) experimental conditions: reaction time and
20 difficult to purify. They found that this product contained: environmental parameters as temperature, pressure and

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21 the elements of sulfuric acid (H 2SO4) combined with stirring, in order to improve the efficiency of the oxidation
22 oxygen, hydrogen and a large amount of carbon. In 1898, process and reduce toxic gases reaction sub-products and
23 Staudenmaier improved Brodie’s method by replacing (3) final product purification as rising and drying
24 about two-thirds of fuming nitric acid (HNO 3) by procedures. This optimization will allow increasing the
25 concentrated H2SO4 enhancing the acidity in the mixture amount of hydrophilic graphite oxide in less processing
26 and added KClO3 to oxidize the graphite in nitric acid, time. Moreover, different microscopic and spectroscopic
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minimizing in this way the risk of explosion [23-25]. It
was until 1909, that Charpy developed a method using the
an techniques were used to analyze the shape, quality and
oxidation degree of the synthesized graphite oxide sheets.
potassium permanganate (KMnO 4) as the oxidant agent to
30 oxidize the graphite in H 2SO4 at room temperature [26,27]. 2. Materials and Methods
31 The most important and widely used method for the
32 2.1 Synthesis of Graphite oxide.
synthesis of graphite oxide is the one developed by
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33 Hummers and Offeman in 1958 (Hummers’ method)
34 [28,29]. This method includes all former developments but
We started the synthesis of graphite oxide by using
35 with key improvements. It consists of carrying out a
graphite powder (Bay carbon, spectroscope powders, Bay
36 City, Michigan 48706, ~100 μm) and followed mainly
reaction of graphite powder with KMnO 4 and NaNO3 in
37 concentrated H 2SO4. They used H2SO4 to disperse graphite
Marcano et al. [30] method because it produces graphene
38 oxide sheets of good quality and does not use NaNO 3 as
and a mixture of KMnO 4 and NaNO3 as oxidant agent; the
39 the oxidant to avoid the residual Na + and NO3- ions.
temperature was kept below 45 °C and the reaction time
40 Hummers et al. [25, 36] and Nekahi et al. [26, 37] used
was just a few minutes long. Basically, the reaction took
41 KMnO4 as the oxidant agent to oxidize graphite and
place in an acid solution and the addition of hydrogen
42 Drewniak et al. [27,38] used H2SO4 acid to improve the
peroxide (H2O2) made easier to remove the metal salts.
43
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oxidation efficiency of KMnO4. We have improved further

44 In general, all methods mentioned above produce
the oxidation efficiency of KMnO4 by adding H3PO4 to
45 explosive exothermic reactions and generate toxic gases
increase the acidity of the medium. Thus, we added a
46 such as NO 2, N2O4, and ClO 2 during the reaction; besides,
mixture of graphite and KMnO 4 powders (3:18 g; 3:6 wt
47 residual Na+ and NO 3 ions are difficult to be removed
%) into an H2SO4/H3PO4 solution (360:40 ml; 9:1 v/v %).
48 during the procedures of rinsing and purifying the graphite
One of the sub-products of the KMnO 4 and H2SO4 reaction
49 oxide. It was in 2010 that Marcano et al. [30,31] improved
is Mn2O7 which detonates at temperatures above 55 °C
50 the Hummers’ method by excluding NaNO 3, increasing the
[22, 35]; thus to prevent an explosion we cooled down
51 KMnO4 oxidants, and performing the reaction in a mixture
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both mixtures before mixing them. Consequently, only a

52 of H2SO4/H3PO4 in volume proportion 9:1. This
slightly exothermal reaction took place at 35-40 °C and the
53 modification was successful in increasing the reaction
solution turned purple-brown color. Next, the mixture was
54 yield and reducing the toxic gases production. Later on, in
heated at 50 °C with continuous stirring for 12 h. At this
55 2013 Yeon-Ran Shin et al. [32] returned to the idea of the
point the mixture turned dark brown indicating that the
56 first reports for producing graphite oxide, by observing
graphite oxidation reaction already took place. During this
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57 that the optimized ratios of the H 2SO4/HNO3 mixture used

58 thermal process the mixture undergoes remarkable
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3 changes: gases are given off from the interior of the unsaturated aliphatic double bonds over aromatic double
4 substance, which swells up the system in a most singular bonds, which may have important implications for the
5 manner separating the carbonaceous sheets and reducing structure of graphite and reaction pathway(s) occurring
6 them to the minutest state of division which have the during the oxidation. [33,44].
7 appearance and the structure of lamellar graphite [16,20],
8
larger surface areas of the carbonaceous sheets are in KMnO4  3H 2 SO4  K   MnO3  H 3O   3HSO4

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9 (1)
contact with the KMnO4 increasing their oxidation state.
10  MnO3  MnO4  Mn 2 O7
The chemical reaction that takes place during the
11
thermal process is shown in eq. (1). The oxidation of
12 Based on these experimental results we infer that 12 h
graphite by potassium permanganate (KMnO4) is usually a
13 of the oxidation process is the appropriate time in which an

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14 multi–stage process. The reaction of KMnO4 with sulfuric
acid (H2SO4) produces diamanganese heptoxide (Mn2O7) efficient graphite oxidation reaction takes place. We
15
being this the active species to oxidize graphite. The Mn2O7 highlight that 12 h of the graphite oxidation process is 73%
16
is far more reactive than its monometallic tetraoxide (MnO4-) shorter than 72 h used by Chandra et al. [39] and 50%
17
counterpart and it is known that Mn2O7 detonates when shorter than 24 h used by Nekahi et al. [37]. Reaction
18
heated to temperatures greater than 55 °C or when placed in times shorter than 12 h produce inefficient graphite
19
oxidation processes [28,38,40,45]. For comparison, in
20 contact with organic compounds [41-43]. The reduction in

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21 the permanganate ions (MnO4-) to an oxidation manganate Table 1 we list the reaction conditions, reactants and
22 state has been reported in alkaline pH aqueous systems and it reaction times used in the different modified versions of
23 is considered to be responsible for an alkane oxidation the Hummers’ method.
24 reaction decrease [33]. The oxidizing power of the
25 permanganate anions decreased remarkably in the order of
26 (MnO4)-˃(MnO4)2-˃(MnO4)3- [42]. Tromel and Russ
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29
demonstrated the ability of Mn2O7 to selectively oxidize
an
Table 1 Reaction conditions for the oxidation of graphite.
Reactants
30 Method Graphite NaNO3 KMnO4 Na2Cr2O7 H2SO4 H3PO4 Reaction Ref
31 (g) (ml) (g) (g) (ml) (ml)
32
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Chandra et al. 1 ---- --- 4 15 ---- 72 [39]
33
34 Nekahi et al. 1 15 3 ---- 20 ---- 24 [37]
35 Drewniak et al 1 3g 3 ---- 30 --- 2 [38]
36 Hummers et al. 1 0.5 g 3 ---- 22.5 ---- 0.5 [28]
37 Marcano et al. 3 ---- 18 ---- 360 40 16 [30]
38
39
This work 3 ---- 18 ---- 360 40 12
40
41
As can be seen from the Table 1, we avoided the use temperature, afterwards 400 ml of DI water in ice form
42
of NaNO 3 to minimize the evolution of toxic gases, and was added to decrease its viscosity and avoid overheating
43
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reduced the processing time used by Marcano et al. [30]. [46,47]. Later on, 9 ml of H 2O2 (H2O2/DI water, 30% v/v)
44
According to the literature, Hummers et al. [36], Hummers was added to the mixture to make easier the removal of
45
46 and Offeman [28], Nekahi et al. [37] and Drewniak et al. metal salts such as permanganate and manganese residuals
47 [38] used H2SO4 to disperse graphite, and a mixture of from the mixture, now this solution turned to a bright
48 KMnO4 and NaNO3 as oxidant agents. All these methods yellow color. The solution was centrifuged at 1500 rpm for
49 produce explosive exothermic reactions and generate toxic one hour and the supernatant decanted away. The
50 gases such as NO2 and N2O4 besides, residual Na + and - remainder was repeatedly rinsed in continuous succession
51 NO3 ions are difficult to be removed during the procedures with: 1) 200 ml of DI water, 2) 200 ml of HCl at 30% v/v
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52 of rinsing and purifying the graphite oxide. Since we did and 3) 200 ml of ethanol to remove the byproducts (e.g.,
53 not use NaNO 3 as oxidant agent, the reaction produces no potassium-containing compounds) that can cause an acute
54 toxic gases such as the ones mention above. The reaction explosion [36,48]; after each rinsing step, the solution was
55 between H2SO4 and KMnO4 as oxidant agent is a centrifuged at 4000 rpm for 2 h and the supernatant
56 dissociation given by Eq. (1).Continuing with the rinsing decanted away. Then, the remainder obtained after the
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57 procedure, the mixture was let cool down to room rinsing procedure was coagulated with 40 ml of ether.
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3 Later on, the resulting suspension was filtered through a
4 PTFE membrane with 0.45 μm pore size.
5 The solid material obtained on the filter was vacuum-
6 dried for overnight at room temperature. To remove left
7 over water from graphite oxide, we carried out a thermal
8
treatment at 60 °C under nitrogen flux for 2 h. The
beam of X-ray, Al Kα (1486.6 eV). The primary beam energy
of 12 kV and primary current of 6 mA were used, operating
at pass energy of 0.2 eV. The pressure in the analysis
chamber was 2x10-9 Torr. XPS gives quantitative information
about chemical groups and the chemical shift in XPS is a
measure of the valence charge on the atom of interest.

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9
temperature of 60 °C was chosen because in the range
10
from 30 °C to 150 °C no chemical reactions take place, but 3. Results
11
only an evaporation of the solvents contained on the
12 3.1 Morphological and structural characterization.
graphene sheets is carried out; therefore, only a mass loss
13

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14 is observed as indicated by the thermograms of GO
performed by Michael J. McAllister et al in 2007 [49] and The surface morphology and crystallinity of
15 synthesized graphite oxide was analyzed by means of an
16 Cheng-Meng Chen et al in 2012 [50]. Besides, at 60 °C the
evaporation is relatively slow, preventing any structural HRTEM and selected area electron diffraction (SAED).
17 Figure 1 a,b shows TEM micrographs of graphite oxide
18 damage. The nitrogen flux prevents any reflux, decreasing
the time for the drying process. The final product in previously dispersed in DI water by sonication and set on a
19
Carbon/Nickel holder for characterization. Figure 1a shows a
20 powder form weighted 6.8 g. By considering a graphite

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representative TEM micrograph of a GO sheet, it shows and
21 initial weight of 3 g, it is estimated that about 80 % of
22 carbon is linked to oxygen in different ways, including - average size of ~2±0.2 µm. It can be observed that the
23 OH groups. morphology of GO is sheet-like; the sheets look translucent,
24 It is already known that chemically both graphite well defined with some wrinkles on the surface and with no
25 oxide and graphene oxide (GO) have similar or identical folding on the edges. In these micrographs, dark and light
26 structures. Both possess stacked structures with chemical zones and some imperfections like dark points on the surface
27
28
29
functionality on their basal planes and at their edges [33].
The only difference between them is the number of stacked
an can be observed. They are related to the existence of carbon
atoms with sp3 hybridization that constitute the hydroxyl or
epoxy groups in the GO sheet.
layers; GO possesses a monolayer or just a few stacked
30 layers, while graphite oxide contains a greater number of
31 stacked layers [33,51]. Taking into account that the
32 formation of oxygenated functional groups in graphite
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33 oxide makes them easier to exfoliate it into monolayers of
34 GO, we dispersed 1 mg of graphite oxide powder in 100
35 ml DI water by sonication for 10 min to obtain GO
36 nanosheets. Then, the prepared samples were analyzed by
37 microscopic and spectroscopic techniques.
38
39
40 2.2 Characterization techniques.
41
42 The surface morphology of the GO samples was
43 analyzed using a high-resolution transmission electron
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44 microscope (HRTEM) JEOL JEM-2100F operated at 200 kV

45 acceleration voltage. The FTIR spectrum (400-2000 cm-1)
46 was measured by means of a Spectrum One Perkin Elmer
47 system with an ATR accessory and at 8 nm/s scan velocity.
48 Raman spectra were recorded with a Raman Scientific XRD,
49 Thermo SCIENTIFIC system with a He-Ne laser (λ =632.8 Figure 1. Observations of GO sheets in a TEM
50 nm) as the excitation source and 10 mW of power. The microscope: (a) and (b) TEM micrograph, (c) HRTEM, with
51
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entrance and exit slits aperture was 50 µm. Also, an optic the inset presenting the SAED pattern of this area, and (d)
52 microscope is coupled to this system. 10X magnification was FFT of the SAED pattern.
53 used to select the region of interest. X-ray Photoelectron
54 Spectroscopy (XPS) system K-Alpha+ Thermo Scientific, Figure 1c shows an HRTEM image of the GO
55 with a Constant Analyzer Energy (CAE), was used to nanolayer and in the inset its corresponding SAED pattern.
56 investigate the state of elements present in the graphite oxide. In the SAED pattern clear diffraction spots are observed; by
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57 XPS spectra were obtained by irradiating the sample with the applying the Fast Fourier Transform (FFT) to the SAED
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3 pattern, the Moiré pattern with the hexagonal lattice structure 3.2 FTIR spectroscopy.
4 formed by carbon atoms is revealed as shown in Fig. 1d; for
5 a better visualization a magnification of the lattice is shown Figure 3 shows an FTIR transmission spectrum
6 in the inset. recorded with ATR accessory from GO in the range from
7
4000 to 700 cm-1. In this spectrum different peaks appear that
8

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9 are assigned to vibrational modes of functional oxygen-
10 containing groups; for a better visualization see points (A),
11 (B) and (C) on the inset of this figure. Additionally, C=C
12 vibrations of graphene and C-O vibrations of GO are also
13 present, as expected.

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14
15
16
17
18

Intensity (Arb. Unit)

19 3407
(B) 1734
20 (A)

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1430
21 1625
C=C OH
22 stretching bending
23
1225
24
(C)
25
26 1055
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29
Figure 2. (a) A TEM micrograph of the surface
morphology of a GO sheet. EDS compositional maps: (b)
carbon, (c) oxygen and (d) an overlay of carbon and oxygen
an C-O
stretching

maps. 4000 3500 3000 2500 2000 1500 1000

30 Wavenumnber (cm )
-1

31 Furthermore, the GO nanolayer was analyzed by

32 Figure 3. FTIR-ATR transmission spectrum of GO.
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Energy Dispersive Spectroscopy (EDS). Figure 2a shows
33 the GO nanosheet set on the Carbon/Nickel holder. The
34 bands in this figure correspond to the grid that holds the
35
sample. EDS mapping images are shown: in b) carbon in red,
36
c) oxygen in blue and d) the overlay of the two maps; in this
37
image we observe the distribution of the Carbon and Oxygen
38
chemical elements constituting the GO nanosheets.
39
40 Table 2. GO vibrational modes assignments reported in the literature and measured.
41 Reported Peak Measured Peak Vibration
Functional Group Ref.
42 Position (cm-1) Position (cm-1) Mode
43
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3410 3407 Water (-OH) stretching [52]

44 1734 1734 Carboxylates or Ketone (C=O) stretching [53,54]
45 1629 1625 Bonding C=C stretching [55]
46 1420 1430 *Alcohols (-OH) bending [56,57]
47 1227 1225 Epoxide (C-O-C) or Phenols (C-
stretching [57,58]
48 O-H)
49 1055 1055 Bonding C-O stretching [57,58]
50 *Shoulder of bending OH
51
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52
53 In Table 2 the measured peaks positions, the reported and carboxylic (-COOH) groups. It is worthwhile to mention
54 ones, and their assignments according to the literature are that the FTIR spectrum of GO recorded after one year is very
55 listed. There is a good concordance between the two groups. similar to the one recorded from fresh GO, this means that
56 We infer then, that the GO nanosheets are covered by GO is stable with respect to aging.
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57 functional groups such as hydroxyl (-OH), epoxy (C-O-C)

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3 phonons with opposite wave vectors, no defects are required
4 for their activation, and are thus always present.
5 The band L2+D’ is the product of overtones of the D2
6 3.3 Raman spectroscopy.
band and the interactions of optical longitudinal and acoustic
7 vibrations [63]. The peak D1 is intense, wide, and it belongs
8 Raman spectroscopy is commonly used to investigate
to carbonaceous materials with disordered structure,

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9 the microstructure and perfectness of carbon-based materials.
attributed to in-plane defects like heteroatoms (O, H, N for
10 The main Raman parameters to be evaluated are the peak
instance) or structural defects. Its peak position depends on
11 position, Full Width at Half Maximum (FWHM), intensity
wavelength of the incident laser [64]. The integral of D1 is
12 ratio of the bands peaks, and the total areas under the Raman
small when the aromatic planes are ordered and this band
13 curves. Figure 4 shows the Raman spectrum of GO in the

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14 range (750–3100 cm-1). This spectrum can be divided into gets more intense and wide when there exist some defects in
15 two regions: the first order effect region (750–2500 cm-1) and graphite [65]. The D3 band is attributed to a disordered
16 the second order effect region (2500–3100 cm-1) [59]. carbonaceous material containing out of plane defects like
17 tetrahedral carbon atoms, organic molecules, and functional
18 groups, and it is absent in samples having undergone thermal
19 treatments at a temperature higher than 450 ˚C [65]. The D2
20 band (also named Dˊ) at about 1635 cm-1 is due to the non-

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21 homogeneity or deformation of the material [66].
22 In the second order range the 2D band appears, which is
23 wide and of low intensity and it is composed of S1 and S2
24 sub-bands. The S1 band at 1350 cm-1 is considered by
25 Stephanie et al. as an overtone of D1 [61]. The S2 band at
26 2900 cm-1 appears only on graphitic materials as a
27
28
29
an consequence of C-H bonding [64]. This band has also been
interpreted as the combination of the D and G bands [67].
The D and G bands of GO differ from those of graphite
30 in three aspects: 1) a significant increase in the D/G intensity
31 ratio (ID/IG) associated to a disruption of the lattice
32 Figure 4. Raman spectrum of GO. symmetry; 2) broadening of both the D and G bands
dM
33 associated with the introduction of hydroxyl and epoxy
34 In the first order range, there appears the D band (the groups and 3) shifts of the D and G bands towards higher
35 symmetry A1g mode) at 1350 cm-1. It corresponds to a defect- wavenumbers are related to an increase of isolated carbon
36 induced vibration mode or to vibrations caused by double bonds in GO [15]. This is why it is difficult to use the
37 imperfections due to the attachment of functional groups to ratio ID/IG as an indicative of pureness or graphitic level of
38 the graphitic carbon basal plane [59], such as the hydroxyl GO. Instead, Beyssac et al. [64] have proposed other figures
39 and epoxide groups. Other origins of this band have been of merit calculated as the ratio of areas under the bands, in
40 attributed to a symmetry loss due to the finite size of graphite order to estimate the carbonaceous material (CM) degree of
41 crystals [60], to stretching vibrations of carbon bonds with a organization. They defined the ratio of areas R2 =
42 sp3 hybridization [60] or to breathing modes of the aromatic D1/(D1+G+D2). The authors excluded D2 from R2 because
43
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rings with free bonds in the plane terminations [61]. The G the D2 band corresponds to poorly ordered carbons and to
44 band (the E2g mode of the sp2 carbon atoms) at 1580 cm-1 is
45 out-plane defects like tetrahedral carbons that, as Beny-
due to first order scattering E2g mode of graphene [61,62], Bassez et al. [65] suggest, are released early during the
46 that is, to vibrations inside the aromatic layers of the graphite
47 graphitization process at high temperatures as happens in
structure, see Figure 4. mineral graphite. It is worthy of mention that the figure of
48
The D band in Figure 4 has been fitted by a sum of two merit was proposed for mineral graphite, where the most
49
Gaussian bands centered at 1233 cm-1 (L2+D’) and 1350
50 representative D band is D1, thus, in that case, R2 gets the
cm-1 (D1) and the G band by a sum of three Gaussian bands form, R2’ = D1/(D1+G). For poorly organized CM, R2’ is
51
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centered at 1521 cm-1 (D3), 1580 cm-1 (G) and 1632 cm-1 greater than 0.5, while in CM well organized R2’ smaller
52
(D2). Double resonance can also happen as an intravalley
53 than 0.5. It is important to take into account that he spectra
54 process that is, connecting two points belonging to the same measured at the surface exhibit a higher contribution of the
55 cone around K (or Kʹ). This gives the so-called Dʹ peak. The defect bands (D1 and D2) [66,67]. For the GO produced in
56 2D peak is the D-peak overtone, and the 2Dʹ peak is the Dʹ this work, the bands D1, D2, and D3 appear due to the low-
overtone. Because the 2D and 2Dʹ peaks originate from a
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57 temperature synthesis process and it is better to consider the

58 process where momentum conservation is satisfied by two
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3 areas ratio R’=(D1+D2+D3)/(D1+D2+D3+G) i.e. the ratio of (and deformations) produced by the oxidation of the carbon
4 modes from defects (non-graphitic modes) to the total sheets give rise to the D band. However, certain graphitic
5 modes. From data in Table 3, it was possible to calculate R’, level is still present inferred by the presence of the G band
6 which gives a value of 0.98. Such a high value may indicate indicating that GO is not just in the form of monolayers.
7 that almost the whole graphene was oxidized. The sp1 bonds
8

pt
9 Table 3. Intensity and areas of the main and secondary Raman bands.
10 Theoretical Experimental
FWHM Intensity Area (Arb.
11 Band position position
-1 -1 (nm) (Arb. units) units)
12 (cm ) (cm )
13 L2+D’ 1230 1233 263 402 132337

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14 D1 1350 1348 241 1347 380698
15 D3 1578 1580 159 754 55466
16 G 1580 1579 123 766 11092
D2 1635 1632 210 143 37573
17
S1 2700 2701 183 65 14863
18
S2 2900 2898 100 62 7813
19
20

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21 Figure 5. XPS spectra of GO: (a) C 1s and (b) O 1s.
3.4 XPS
22 The C 1s in the XPS spectrum shows 5 components
23 The chemical state of the GO was analyzed by XPS. assigned to binding energies of: C=C (284.8 eV, FWHM=1.5
24 Figure 5 shows the two most prominent bands of GO: a) eV), C-C (285.4 eV, FWHM=2.29 eV), C-O (287.1 eV,
25 spectrum of the C 1s (FWHM=4.77 eV) and b) the O 1s FWHM=2.12 eV), C=O (287.7 eV, FWHM=1.92 eV) and
26
27
28
29
spectrum (FWHM=2.04 eV).

a)
285.4
C 1s
an O=C-OH (289.2 eV, FWHM=2.3 eV) [33,42,68,69]. The
presence of these groups suggests a considerable degree of
oxidation of the GO nanosheet [47]. This last assumption is
C-C confirmed by the position of the O 1s band, which is in the
30
Intensity (Arb. U.)

range of carbon-oxygen bonds.

31 287.7
287.1
C-O
32 C=O The quantification of the XPS spectrum of our graphene
dM
284.8
33 C=C nanosheets is: 56.2 wt % of C and 42.9 wt % of O, and the
34 elements N and S wt % values correspond to trace impurities
289.2
35 O=C-O-H in the nanosheets. These C and O percentages mean that
36 about 77 wt % of oxygen in the form of oxygenated groups is
37 bonded to the carbon nanosheets; thus, the process has a high
38 oxidation yield. In Table 4 the elemental composition of the
39 291.2 289.8 288.4 287.0 285.6 284.2 282.8 here produced GO is compared with the composition of the
Binding Energy (eV)
40 GO prepared by other chemical methods, reported in [40]. It
41 is important to mention that the data of the reference was
42 obtained from CHNOS elemental analysis.
43
pte

44 Table 4. Elemental composition of Graphite oxide obtained

45 by different Hummers’ modified methods [40].
46 Elemental analysis (wt %)
47 Sample
48 C N S O
49 Chandra et al. 75.97 0.10 2.53 21.40
50 Nekahi et al. 59.17 0.10 0.10 40.63
51
ce

Drewniak et al. 57.19 0.10 0.30 42.41

52 Hummers et al. 65.71 0.10 0.61 33.58
53 This work 56.2 0.20 0.70 42.90
54 In the oxidation route of Chandra, the treatment
55 with sodium dichromate provided the lowest oxygen content
56 (21.40 wt %) even with very long reaction time (72 h). The
Ac

57 Hummers’ method gave 33.58 wt % of O in 0.5 h of reaction

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1
2
3 time. The Nekahi et al. and Drewniak et al graphite oxidation [2] ChaoXie,Yi Wang, Zhi-Xiang, Zhang Di, Wang Lin and
4 methods provided about the same oxygen weight percentage, BaoLuo. Graphene/Semiconductor Hybrid Heterostructures for
5 being the sample of Drewniak et al the one with the highest Optoelectronic Device Applications. Nano Today 2018, 19,
6 O content (42.41 wt %). We obtained a slightly higher O
41-83.
7 [3] Anirban Maitra, Amit Kumar Das, Ranadip Bera, Sumanta
percentage (42.9 wt %), see Table 4. In conclusion, our GO Kumar Karan, Sarbaranjan Paria, Suman Kumar Si, Bhanu
8 Bhusan Khatua. An Approach To Fabricate PDMS
presents the highest degree of oxidation. Moreover, a

pt
9 Encapsulated All-Solid-State Advanced Asymmetric
highlight of our process is that we excluded the use of the
10 Supercapacitor Device with Vertically Aligned Hierarchical
NaNO3 reactant, minimizing the production of toxic gases.
11 Zn–Fe–Co Ternary Oxide Nanowire and Nitrogen Doped
12 Graphene Nanosheet for High Power Device Applications.
13 4. Conclusions ACS Appl. Mater. Interfaces 2017, 9, 5947-5958.

cri
[4] Li Peng, Zhen Xu, Zheng Liu, Yangyang Wei, Haiyan Sun,
14 Increasing the amount of KMnO4, excluding the NaNO3 Zheng Li, Xiaoli Zhao and Chao Gao. An iron-based green
15 and adding a mixture of H2SO4/H3PO4 in proportion 9:1, the approach to 1-h production of single-layer graphene oxide.
16 efficiency of the oxidation process of the graphite has been Nature Communications 2015, 6, 5716.
17 improved compared with the method that uses KMnO4, [5] Yue Qi, Bing Deng, Xiao Guo, Shulin Chen, Jing Gao, Tianran
18 NaNO3, and H2SO4 for preparing GO. With the present Li, Zhipeng Dou, Haina Ci, Jingyu Sun Zhaolong Chen, Ruoyu
19 method, no toxic gases are generated, and it results in a
Wang, Lingzhi Cui, Xudong Chen. Switching Vertical to
Horizontal Graphene Growth Using Faraday Cage‐Assisted
20 higher amount of hydrophilic oxidized graphene material. By

us
PECVD Approach for High‐Performance Transparent Heating
21 carrying out a thermal treatment in an oven at low Device. Advanced Materials 2018, 30, 1704839
22 temperature and under nitrogen flux, the drying procedure [6] Tao Ma, Huai‐Ling Gao, Huai‐Ping Cong, Hong‐Bin Yao,
23 Liang Wu, Zi‐You Yu, Si‐Ming Chen and Shu‐Hong Yu. A
time has been greatly reduced and graphite oxide has not
24 Bioinspired Interface Design for Improving the Strength and
been reduced. TEM micrographs indicated that the GO
25 Electrical Conductivity of Graphene‐Based Fibers. Advanced
sheets are translucent and wrinkled. SAED patterns reveal Materials 2018, 30, 15, 1706435
26
27
28
29
the hexagonal lattice structure of carbon atoms. EDS
mappings show the distribution of Carbon and Oxygen in the
GO nanosheets. By FTIR characterization it was possible to
an [7] Shi‐Yu Lu, Meng Jin, Yan Zhang, Yu‐Bing Niu, Jie‐Chang Gao
and Chang Ming Li. Chemically Exfoliating Biomass into a
Graphene‐like Porous Active Carbon with Rational Pore
Structure, Good Conductivity, and Large Surface Area for
30 identify the functional oxygen-containing groups. Raman
High‐Performance Supercapacitors. Advanced Energy
31 spectra of the synthesized GO showed the D and G Raman Materials 2017, 8, 11, 1702545
32 bands typical of graphite oxide materials. The deconvolution [8] George Z., Kyzas, Eleni A. Deliyanni, Dimitrios N. Bikiaris and
dM
33 of these bands revealed the secondary Raman bands: D1, D2 Athanasios C. Mitropoulos. Graphene composites as dye
and D3 which indicate the disordered structure of adsorbents: Review. Chemical Engineering Research and
34 Design 2018, 129, 75-88.
35 carbonaceous materials, most probably due to the oxidation
[9] Gamze Ersan, Onur G.Apul, Francois Perreault, Tanju Karanfil.
36 of graphite. This inference is confirmed by the presence of Adsorption of organic contaminants by graphene nanosheets:
37 the 2D band. The proportions of the areas under the curves of A review. Water Research 2017, 126, 385-398.
38 the G and D bands indicate that the GO nanosheets are [10] Antonio Gaetano Ricciardulli, Sheng Yang, Gert‐Jan A. H.
39 almost completely oxidized. The deconvolution of the C 1s Wetzelaer, Xinliang Feng and Paul W. M. Blom. Hybrid Silver
Nanowire and Graphene‐Based Solution‐Processed
40 XPS spectrum reveals the 3 different carbon bonds in GO,
Transparent Electrode for Organic Optoelectronics. Advanced
41 suggesting a considerable oxidation degree of the GO Functional Materials 2018, 28, 14, 1706010.
42 nanosheets. The main conclusion of this work based on the [11] Feng-Xia Liang, Yang Gao, Chao Xie, Xiao-Wei Tong,
43
pte

characterization results shown above is that the optimization Zhong-Jun Li and Lin-Bao Luo. Recent advances in the
44 of the graphite oxidation process performed in this work fabrication of graphene–ZnO heterojunctions for
45 produces GO nanosheets of good quality in a high yield. optoelectronic device applications. J. Mater. Chem. C 2019, 6,
3815-3833.
46
[12] Zhaoqing Yang, Xiangping Hao, Shougang Chen, Zhenqing
47 Acknowledgements Ma, Wenhui Wang , Caiyu Wang, Longfei Yue, Haiyun Sun,
48 Qian Shao, Vignesh Murugadoss and Zhanhu Guo. Long-term
49 This work has been partially supported by CONACYT antibacterial stable reduced graphene oxide nanocomposites
50 through a graduate student scholarship and by SEP- IFUAP- loaded with cuprous oxide nanoparticles. Journal of Colloid
51 “Low Dimensional Structures” research group (CA-315).
ce

and Interface Science 2019, 533, 13-23.

52 [13] Qingsong Mei, Bianhua Liu, Guangmei Han, Renyong Liu,
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