Accepted Manuscript

Effect of Hydrogen Peroxide on Properties of Graphene Oxide in Hummers Method

Myung Jin Yoo, Ho Bum Park

PII: S0008-6223(18)30923-0

DOI: 10.1016/j.carbon.2018.10.009

Reference: CARBON 13527

To appear in: Carbon

Received Date: 07 June 2018

Accepted Date: 04 October 2018

Please cite this article as: Myung Jin Yoo, Ho Bum Park, Effect of Hydrogen Peroxide on Properties
of Graphene Oxide in Hummers Method, Carbon (2018), doi: 10.1016/j.carbon.2018.10.009

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 ACCEPTED MANUSCRIPT
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1 Effect of Hydrogen Peroxide on Properties of Graphene Oxide in Hummers Method

2

3 Myung Jin Yoo and Ho Bum Park*

4 Department of Energy Engineering, Hanyang University, Seoul 04763, Republic of Korea
5

6 Abstract
7 Among the several methods to prepare graphene oxide (GO) from graphite by oxidation, Hummers
8 method has been the most widely used. Since Hummers method was first introduced about 60 years ago,
9 many researches have tried to reveal the effect of each reagent on the final properties of GO. In all
10 Hummers methods including the modified ones, sulfuric acid and potassium permanganate are used for
11 oxidizing graphite and exfoliating oxidized graphite, and water and hydrogen peroxide are used for
12 removing the residual manganese ions. However, the effects of hydrogen peroxide have been sometimes
13 ignored during synthesis since hydrogen peroxide has been understood as simply reducing the residual
14 manganese ions such as permanganate and manganese dioxide. For this reason, the quantity of hydrogen
15 peroxide used for Hummers method varies. Here we demonstrate that the quantity of hydrogen peroxide
16 added in the final stage strongly affects the final properties of GO. Experimental evidence is introduced
17 revealing that chemical decomposition of GO with slight reduction accompanies the addition of hydrogen
18 peroxide. The possible degradation mechanism by hydrogen peroxide in Hummers method is proposed
19 in the last part of this study.
20

21 1. Introduction
22 The synthesis of graphene oxide (GO) has a long history as it was first synthesized by Brodie in
23 1859. Brodie proposed GO synthesis by adding potassium chlorate (KClO3) to a slurry of graphite in
24 fuming nitric acid (HNO3) [1]. In 1898, Staudenmaier modified Brodie’s method by using multiple
25 additions of KClO3 during the reaction, instead of a single addition, and concentrated sulfuric acid (H2SO4)
26 to increase acidity in the reaction. Staudenmaier reported a C/O ratio of about 2 in a single-vessel reaction,
27 which is a similar degree of oxidation as compared with Brodie’s multiple oxidation method [2]. Finally,
28 in 1958, nearly 100 years after the first GO synthesis was proposed by Brodie, Hummers and Offeman
29 proposed a new GO synthesis method using a mixture of potassium permanganate (KMnO4) and
30 concentrated sulfuric acid (H2SO4), which is now the most commonly adopted method, also known as

* Corresponding author. Tel: +82-2-2220-2338. E-mail: badtzhb@hanyang.ac.kr (Ho Bum Park)

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1 Hummers method [3]. Since then, many modified versions have been developed, but their experimental
2 procedures are not much different from the original Hummers method in that they still use the
3 KMnO4/H2SO4 mixture for oxidation, and the addition of hydrogen peroxide for terminating the reaction
4 [4-8].
5 Efforts to develop modified approaches for GO preparation are ongoing. The main purpose of such
6 efforts is to control the GO properties depending on the specific requirements of various applications.
7 Thus, understanding the oxidation mechanism of GO is very important, but as yet not fully elucidated like
8 many controversial structure models of GO [9-13].
9 Nevertheless, many studies have tried to discover the oxidation mechanism by utilizing modern
10 technologies [14-18]. In 2014, Dimiev and Tour found three distinct independent steps of oxidation of
11 graphite: the conversion of graphite into a stage-1 graphite intercalation compound (GIC), the conversion
12 of stage-1 GIC into oxidized graphite (PGO), and finally the conversion of PGO into conventional GO
13 after exposure to water. They proposed that these three steps are each distinct and independent [14]. In
14 2015, Kang et al. elucidated in detail the oxidation step after the addition of water by various techniques.
15 They prepared several GO samples to verify the oxidation by water addition by controlling reaction time
16 and temperature. These samples were characterized by several methods, and they found the graphitic C=C
17 double bonds in GO decreased after water addition, while the number of carbonyl, lactol, carboxyl, and
18 hydroxyl groups increased. They also proposed two possible reaction routes based on conventional
19 organic chemistry: the oxidative cleavage of the C=C double bond by permanganate and the acid-
20 catalyzed hydrolysis of 1,2-epoxy [15]. Most recently, in 2018, Li et al. determined the reaction rate
21 constant and the kinetic parameters of the oxidation of graphite by investigating the influence of sulfuric
22 acid concentration, oxidizing agent, and reaction temperature. They obtained the reaction rate constant
23 and kinetic parameter by the one-half-order kinetic model based on their experimental results [18].
24 These efforts to reveal the oxidation mechanism of Hummers method allow us to control GO
25 properties depending on the purpose of various applications. However, most of the previous studies have
26 focused only on the oxidation mechanisms. Every modified version of Hummers method uses hydrogen
27 peroxide to eliminate the residual permanganate and manganese dioxide to colorless manganese sulfate
28 [3], but it has been proposed recently that hydrogen peroxide causes a large number of π-conjugated
29 carbon radicals in a GO by the reaction of hydroxyl radicals from the hydrogen peroxide to the double
30 bonds of the disrupted π-conjugated plane of a GO [19]. This implies that excessive hydrogen peroxide
31 would possibly affect the chemical structure of GO due to the large number of the radical generation, but
32 many groups have used the hydrogen peroxide without careful consideration of its effects. Hydrogen
33 peroxide (H2O2) is a nonplanar molecule with twisted C2 molecular symmetry. Hydrogen peroxide is

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1 usually used as a strong oxidant and is widely used in bleaching, detergents, disinfectant, propellant in
2 rocketry, etc. due to the highly reactive properties of its unstable peroxide bond [20-22]. The reactions
3 between nanocarbons and hydrogen peroxide have also been studied recently. The direct degradation of
4 graphene by hydrogen peroxide was reported in 2014 [23]. Moreover, a hydrogen peroxide reduction
5 mechanism by GO has also been proposed [24] and proven by experiment [25]. However, the effect of
6 hydrogen peroxide in Hummers method has been neglected so far, and hydrogen peroxide has been used
7 arbitrarily because its role was believed to be only an eliminating agent of purple permanganate ions.
8 However, the present study found evidence that GO properties can be strongly affected by the addition of
9 hydrogen peroxide in Hummers method. Thus, we introduce experimental results to elucidate the effects
10 of hydrogen peroxide on GO properties as synthesized by Hummers method.
11

12 2. Experimental
13 2.1 Materials
14 Graphite powder (99.99%, SP-1) was purchased from Bay Carbon Inc. (Bay City, MI). Sulfuric
15 acid (98.08%), hydrochloric acid (35%), and acetone (99.5%) were purchased from Dae Jung Chemical
16 (Gyeonggi-do, South Korea), and potassium permanganate (99.3%) was purchased from Junsei Chemical
17 (Tokyo, Japan). Hydrogen peroxide (30%) was purchased from Sigma Aldrich (St. Louis, MO). The glass
18 fiber filter and Anodisc (47mm, 0.1μm) were purchased from WHATMAN (Maidstone, UK). The
19 custom ordered double-jacket glass reactor was made by Unsah Lab (Seoul, South Korea).
20

21 2.2 GO preparation
22 GO samples were synthesized using Hummers method [3]. 10 g of graphite was mixed in 230 mL
23 of H2SO4, and stirred by mechanical stirrer (speed: 180 rpm) at 5 oC. After 1h, 30 g of KMnO4 was added,
24 and the temperature was increased to 40 oC. After 3 h, 460 mL of deionized water was added slowly by
25 dropping funnel to avoid a rapid temperature increase, and the temperature was gradually increased to 90
26 oC after water addition. It took about 40 min to reach 90 oC, and the mixture was stirred for another 30
27 min after the temperature reached 90 oC followed by a 230 mL water addition. All five samples were
28 prepared exactly the same as described above, except different amounts of H2O2 were added (0mL, 10mL,
29 20mL, 30mL, and 40mL, denoted as G0, G10, G20, G30, and G40, respectively). H2O2 was also added
30 using a dropping funnel, and after an additional 15 min of stirring, the mixtures were filtered by glass fiber
31 filter. The products were dispersed again in 3 L of 10 wt.% HCl solution by mechanical stirring. The
32 dispersion procedure in the acid facilitated the filtration process by the aggregation of graphite oxide
33 particles. The solutions were filtered with glass fiber filter again, and this procedure was repeated five

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1 times to remove residual salts. For more thorough purification, after five filtrations with HCl solution, the
2 products were filtered in 3 L acetone an additional five times. The final products were dried overnight in
3 vacuum oven at 40 oC.
4

5 2.3 GO characterization
6 The zeta potentials were measured with Zetasizer Nano ZS (Malvern Instrument, Malvern, UK).
7 The transmission electron microscope (TEM) images were taken by JEM-F200 (JEOL, Tokyo, Japan).
8 Flash2000 (Thermo Fisher Scientific, IL) was used for the elemental analyzer (EA). Fourier transform
9 infrared (FT-IR) spectra were measured by NICOLET IS50 (Thermo Fisher Scientific, IL) in the range
10 3800–900 cm-1. The X-ray photoelectron spectroscopy (XPS) spectra were measured with Thermo
11 ScientificTM K-AlphaTM XPS system (Thermo Fisher Scientific, IL). The Raman spectra were measured
12 with MonoRa750i (Dong Woo Optron, Gyeonggi-do, South Korea) in the range 1000–1800 cm-1. The
13 X-ray diffraction (XRD) patterns were measured by SmartLab (Rigaku, Tokyo, Japan). The UV/Vis
14 absorbance spectra were measured by SPECORD 200 (Analytic Jena AG, Jena, Germany) in the
15 wavelength range of 200–500 nm.
16

17 2.4 Degradation of GO in H2SO4/H2O2 mixture

18 Two GO solutions were prepared by the following method: 20 mg of GO was dispersed in 20 mL
19 of deionized water and sonicated in a bath for 1h. 20mL of H2SO4/H2O2 mixtures (3:1 and 10:1 by volume)
20 were prepared by stirring, and cooled down to room temperature. The H2SO4/H2O2 mixtures were
21 dropped slowly by dropping funnel into each GO solution, denoted as GSH3 and GSH10, respectively.
22 Both GSH3 and GSH10 were stirred for 1h, and filtered by Anodisc (47mm, 0.1 μm). The filtered GSH3
23 and GSH10 were re-dispersed in 40 mL of water, and deposited onto TEM grids (Ted Pella, 300 mesh).
24 The GO samples were analyzed by TEM analyses.
25

26 3. Results and discussion

27 3.1 GO Preparation
28 The literature ratios of graphite, H2SO4, KMnO4 and H2O2 for GO synthesis using Hummers
29 method (including modified Hummers method) are summarized in Table 1. Note that the amount of H2O2
30 used in the literature varies significantly, while the ratios of graphite: H2SO4: KMnO4 are maintained
31 almost the same as in the original Hummers method (~ 1: 23: 3). One reason for the disparity is because
32 the specific H2O2 amount used in the original Hummers method was not specified, whereas the amounts
33 of graphite, H2SO4 and KMnO4 were given in the original manuscript. Also, the action of H2O2 has been

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1 assumed as nothing more than reducing the residual KMnO4 to colorless manganese sulfate, making the
2 mixture appear brighter. Besides, in the original Hummers method, diluted H2O2 (3%) was used, but
3 almost every subsequent research group used 30% H2O2 without considering its effect. Thus, we prepared
4 different GO samples with different amounts of H2O2 to compare their properties.
5

6 Table 1. Chemicals and their compositions used for Hummers method in the literature.

Graphite H2SO4 KMnO4 H2O2 Graphite:H2SO4:

Ref.
(g) (mL) (g) (mL/%) KMnO4:H2O2

100 2300 300 - /3 1: 23: 3: - [3]

3 69 9 3/30 1: 23: 3: 1 [4]
3 70 9 15/30 1: 23: 3: 5 [6]
0.3 12 1.5 2/30 1: 40: 5: 6.7 [26]
5 375 22.5 15/30 1: 75: 4.5: 3 [27]
1 23 3 10/35 1: 23: 3: 10 [28]
3 70 9 20/30 1: 23: 3: 6.7 [29]
10 230 30 30/30 1: 23: 3: 3 [30]
10 230 30 100/- 1: 23: 3: 10 [31]
5 125 17 7/30 1: 25: 3.4: 1.4 [32]
10 230 30 0-40/30 1 : 23 : 3 : 0-4 This work
7

8 Photo images of G10 and G30 preparation procedures are shown in Figure 1. We will not discuss
9 the detailed oxidation mechanisms of the KMnO4/H2SO4 mixture and the effect of water addition because
10 they fall outside the scope in this work and many other research groups have devoted effort to those ends
11 as mentioned in the introduction. In this work we will focus on the post procedures after the addition of
12 water, which have been regarded as less important. As shown in Figure 1, the color of both mixtures
13 stayed the same as before the addition of H2O2, and every step in all five samples was kept strictly identical.
14 However, when different amounts of H2O2 were added, the colors changed. The fifth image in Figure 1
15 shows the color change immediately after the addition of H2O2. The right hand mixture, with more H2O2
16 (30 mL), appears slightly brighter than the left hand mixture, with less hydrogen peroxide (10 mL). H2O2
17 is known to reduce the residual purple permanganate to colorless soluble manganese sulfate, making the
18 suspension turn to bright yellow [3]. A reaction of H2O2 with permanganate is given as follows:
19

20 5H2O2 + 2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 8H2O + 5O2 (1)

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1 Thus, brighter color means more residual permanganate ions are reduced, and vice versa. However,
2 after 15 min, the suspension with more hydrogen peroxide became darker than the suspension with less
3 H2O2, which means a significant change occurred due to the addition of H2O2. We prepared three other
4 samples (G0, G20, and G40) by the same manner and analyzed their different properties.
5

6
7 Figure 1. Experimental procedure of GO synthesis used in this study, and color variations of G10 and
8 G30 after the addition of H2O2.
9

10 3.2 GO characterization
11 Photo images of final GO samples after purification and drying are shown in Figure 2a. The colors
12 became gradually darker with increasing amounts of H2O2 added. The gradual color differences were also
13 observed in water solutions held to the same concentration (0.1 wt.%), as shown in Figure 2b. Color
14 variance of GO can change depending on the sp2/sp3 ratio [33], which implies the GO samples with
15 different amounts of H2O2 added have different chemical compositions. For more information about
16 quantitative properties, we measured the exact C/O ratio of each GO sample by elemental analyzer (EA),
17 and the results are presented in Table 2. The C/O ratios were found to gradually increase, which implies
18 that chemical changes including partial reductions are involved due to the different amounts of H2O2
19 added. Although EA analyses confirmed the elemental differences of GO in quantity, the C/O ratio does
20 not provide chemical structure information on the various GO samples.

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1
2 Figure 2. (a) Photo images of final products of GO samples and (b) Photo images of 0.1 wt.% GO
3 solutions in water.
4

5 Table 2. C/O ratio of GO samples prepared in this study.

Sample G0 G10 G20 G30 G40
C (wt.%) 53.04±0.19 55.45±0.12 55.26±0.28 55.31±0.61 55.41±0.53
O (wt.%) 47.95±0.34 46.41±0.16 45.37±0.07 45.08±0.02 43.76±0.22
C/O ratio 1.47±0.01 1.59±0.00 1.62±0.01 1.64±0.02 1.69±0.02
6

7 Thus, we measured the Fourier transform infrared (FT-IR) spectra to analyze the chemical
8 structures in detail, which are shown in Figure 3. All GO samples had the characteristics of oxygen-
9 containing functional groups typical for GO, but we also found gradual changes with the increasing
10 quantity of hydrogen peroxide added. The distinctive peaks are marked by lines, except obscure peaks, to
11 compare the differences in oxygen-containing functional groups between the various GO samples. We
12 found four peaks which gradually diminished with increasing volume of hydrogen peroxide added, at

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1 1690cm-1, 1412cm-1, 1222cm-1, and 970cm-1, which correspond to C=O stretching vibrations in
2 conjugated carboxylic acid, O–H bending vibrations in carboxylic acid, C–O–C stretching vibrations, and
3 axial C-O stretching vibrations, respectively [17, 34-37]. The FT-IR spectra indicate that the carboxylic
4 acid groups and the ether groups are first decomposed by the hydrogen peroxide [38].
5 Two diminishing peaks resulting from carboxylic acid groups clearly indicate the partial
6 detachment of the carboxylic groups from the GO sheets. On the other hand, the reason for the diminished
7 peak at 1222cm-1 which corresponds to ether groups cannot necessarily be interpreted as a complete
8 removal of ether groups. The conversion of an ether group into a hydroxyl group is a well-known reaction,
9 which is caused by the room-temperature metastability of GO. The reaction mechanism was proposed in
10 a previous study to elucidate the metastable properties of GO. In 2012, Kim et al. found the degradation
11 of GO in ambient environment, and proposed the degradation mechanism. They suggested that GO can
12 be degraded by losing ether groups and gaining hydroxyl groups instead, and that the transition is limited
13 by the available hydrogen in GO [39]. In this regard, we tried to figure out the conversion of the ether
14 groups in detail as well as confirm the existence of the carboxylic groups by XPS analyses.

15
16 Figure 3. FT-IR spectra of GO samples prepared in this study.

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2 The X-ray photoelectron spectroscopy (XPS) spectra of the GO samples are represented in Figure
3 4. The baselines were subtracted by the standard Shirley approach, and the curve fittings of C1s spectra
4 were decomposed using Gaussian–Lorentzian curves [40, 41], which are represented in Figure 4.
5 Generally, an XPS spectrum of GO is divided into two intense peaks, at ~285eV and ~287eV, which
6 originate from C–C (including C=C) and C-O respectively [37, 40-42]. We can compare the C–O/C–C
7 bonding ratios by normalizing the peaks with respect to the C–C peak at ~285eV. Figure 4a represents
8 the normalized XPS C1s spectra, and it clearly shows that the C–O/C–C bonding ratios decrease with
9 increased H2O2 addition. Figures 4b-f show the Gaussian–Lorentzian curves of each GO sample, which
10 provide quantitative information about each bonding. Note that both the relative amounts of the ether
11 groups and the hydroxyl groups gradually decreased as the hydrogen peroxide addition amount increased.
12 This indicates that the ether groups were removed from the GO sheets, rather than being converted into
13 hydroxyl groups. In addition, the relative amount of the carboxylic groups (magenta lines) gradually
14 decreased, whereas the relative amount of ketone groups (orange lines) remained relatively constant as
15 confirmed by FT-IR analyses for reasons to be discussed in the last part of this paper.

16
17 Figure 4. C1s XPS spectra of GO samples. (a) Normalized C1s XPS spectra with respect to the C-C
18 peak. (b) G0, (c) G10, (d) G20, (e) G30 and (f) G40.
19

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1 Raman spectroscopy is a useful tool to investigate the chemical and physical properties of
2 nanocarbons, especially for characterizing the presence of various defects [43]. GO has two intense peaks
3 in its Raman spectrum, at 1350cm-1 and 1590cm-1, which are known as D and G peaks, respectively. The
4 D peak comes from breathing modes of A1g symmetry in sp2 systems due to the defect sites of GO, which
5 are generally produced by the oxidation process. The G peak is generated from E2g symmetry vibrations
6 in the plane, and is observed in all sp2 hybridized nanocarbons [43, 44]. In general, the degree of defect of
7 a carbon material can be determined by the intensity ratio of D and G peaks, which is also known as the
8 D/G ratio. The Raman spectra of GO samples are represented in Figure 5. Note that the D/G ratio of G0
9 shows a distinct difference as compared with the D/G ratios of G10 to G40. The D/G ratio of G0 is about
10 0.864, while the D/G ratios of G10 to G40 are between 0.950 and 0.997, which also indicates that GO
11 samples with H2O2 addition were slightly reduced. In general, an increased D/G ratio is usually reported
12 upon reduction of GO [38]. The reasons for the increasing D/G ratio of a reduced GO are still quite
13 controversial, but it has been proven by experiment that the D/G ratio is not always proportional to the
14 degree of defects [43]. At some defect quantity, the intensity begins to decrease as the defects increase
15 thereafter, which is known as stage 2 defect status. A previous study about Raman spectra from few-
16 layered graphene with increasing disorder found that the intensity of the D peak begins to decrease when
17 the mean distance between two defects (denoted as Ld) is less than 4 nm, and GO is known to follow the
18 stage 2 defect status, which means a higher D/G ratio indicates fewer oxygen groups [43-45]. However,
19 there is one thing that we should also note about the limitation of Raman characterization of GO as a
20 recent study has pointed out the metastable chemistry and fluorescence effect of GO, which causes
21 uncertainties to prove a structural integrity of GO by Raman characterization [46]. Thus, the Raman
22 characterization of GO should be interpreted as an extension of other characterization methods.
23 The XRD patterns in Figure 6 and the interlayer spacing calculated by Bragg’s law (denoted as d-
24 spacing) in Table 3 also support the evidence that GO samples were partially reduced by H2O2 additions.
25 The deviation of the X-ray diffraction scattering of GO can be attributed to three factors: first, the carbon
26 atom interactions become different depending on the oxidation degree. The different interlayer
27 connectivity force between carbon atoms causes the deviation of the diffraction positions as a result of the
28 different thermal vibrations [47]. Second, the decreased d-spacing due to the reduced quantity of oxygen
29 functional groups allows the vibrations across the horizontal-axis to be more violent than the vibrations
30 along the vertical-axis, which makes for deviation of the diffraction positions [47, 48]. Third, physically
31 adsorbed water can affect the d-spacing of GO. The water contents of our GO samples are listed in Table
32 3, and we found that the water contents were not much different, which means that the physically adsorbed

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1 water effect can be ignored. Thus, shifts in the XRD patterns indicate that the degree of oxidation of the
2 GO samples became different due to the addition of H2O2, which is consistent with the previous results.

3 Figure 5. Raman spectrum and ID/IG ratio of GO samples prepared in this study.

4
5 Figure 6. XRD patterns of GO samples prepared in this study.

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1 Table 3. 2θ, d-spacing values and water contents of GO samples prepared in this study.
Sample G0 G10 G20 G30 G40
2θ (degree) 11.29 11.45 11.48 11.71 11.86
d-spacing (Å) 7.83 7.72 7.70 7.55 7.45
Water content (%) 5.73 6.14 6.71 5.36 5.68
2

3 As used in our previous study, UV/Vis absorbance spectra provide useful information about the
4 chemical structure as well as the dispersion property of GO [49]. A maximum absorbance in the UV/Vis
5 absorption spectrum of GO usually occurs between 230–235nm depending on the degree of conjugation
6 of GO, which is dominated by the π–π* transition [50-52]. The broad shoulders between 280-310nm are
7 attributed to the n- π* transition of C=O bonds [38, 51, 53]. An absorbance of GO is determined by the
8 sp2 conjugated carbons in plane and conjugated chromophores within carbon planes. The π–π* transition,
9 which results in the absorption near 230 nm, occurs at longer wavelength when GO is more conjugated,
10 which is referred to as the bathochromic shift. In this regard, the bathochromic shifts of GO samples
11 shown in Figure 7a indicate the same order of overall oxidation as in previous data. The different degrees
12 of oxidation lead inevitably to the different absorptivities of GOs (Figure 7b).
13

14
15 Figure 7. (a) Bathochromic shifts of GO samples in UV absorbances and (b) absorpitivities of GO
16 samples by UV absorbances.
17

18 Zeta potential, which is defined as an electric potential difference between a dispersion medium and
19 stationary electric double layer of fluid close to a dispersed particle, explains the dispersion stability of
20 colloid particles. Negative zeta potential of GO induced by its oxygen functional groups allows the stable

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1 dispersion of GO in water by the repulsive forces between GO sheets, which means that a zeta potential
2 provides the status of the dispersion properties of a GO solution. We measured the zeta potential of each
3 GO sample in diluted water solution under weakly acidic conditions to analyze the dispersion properties
4 of each samples. In general, the zeta potential of GO is dependent on pH, and the zeta potential is known
5 to increase rapidly in acidic conditions, especially when GO is reduced [54]. The G0 and G10 samples
6 maintained nearly -50 mV at pH 6, but the zeta potentials began to increase from G20, which provides
7 evidence that GO samples were degraded by the addition of H2O2, eventually losing their oxygen
8 functional groups (Figure 8). These results also imply that the dispersion properties of GOs prepared by
9 Hummers method can be different depending on the amount of H2O2 added.
10

11
12 Figure 8. Zeta potentials of GO samples (0.003 wt.% in water, pH 6).
13

14 3.3 Proposal of GO degradation mechanism by H2O2

15 The results of the various analyses indicate that chemical changes were involved in the H2O2
16 addition, but the degradation mechanism remained as a question. Thus, we tried to figure out the GO
17 degradation mechanism by H2O2 addition. Among the possible side reactions, H2SO4/H2O2 reaction can
18 produce potent free radical oxygen. The mixture is also well known as Piranha solution, and is widely

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1 used especially as the cleaning agent in semi-conductor industries to clean photoresist residue from silicon
2 wafers. The reaction mechanism of H2SO4/H2O2 is known as the following formula:
3

4 H2SO4 + H2O2 → H3O+ + HSO4- + O∙ (2)

5

6 The free oxygen radical is a highly reactive and extremely powerful oxidizer, which is able to dissociate
7 all kinds of elemental carbon bonds. The reaction is known to be highly violent, so most organic
8 compounds are easily decomposed to carbon dioxide in a few minutes with no visible materials remaining
9 [55]. However, the H2SO4/H2O2 ratios in GO synthesis are not as high as Piranha solution (3:1) and some
10 of the H2O2 is used to convert KMnO4 into K2SO4 and MnSO4, so the effects may seem to be insignificant.
11 We thus tried to treat GO with a H2SO4/H2O2 mixture without KMnO4 to confirm their effects more
12 clearly. The transmission electron microscopy (TEM) images of GSH3 and GSH10 including G0, G10,
13 G20, G30 and G40 are represented in Figure 9.
14

15
16 Figure 9. TEM images of GO samples. (a) GSH3, (b) GSH10, (c) G0, (d) G10, (e) G20, (f) G30, and
17 (g) G40.
18

19 Note that the GSH3 (Figure 9a) and the GSH10 (Figure 9b) samples have distinctive destructed
20 structures, while the G0, G10, G20, G30 and G40 samples show no great difference. The TEM analyses
21 indicate that GO can be affected by the free oxygen radicals produced by H2SO4/H2O2 reaction, but the
22 effects were diminished enough to make it hard to distinguish by physical appearance due to the
23 consumption of H2O2 used in converting KMnO4 into K2SO4 and MnSO4. In addition, we can interpret
24 the reason for the decreasing amount of carboxylic acid groups while other groups remained relatively

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1 constant. According to the most widely accepted GO model (Lerf-Klinowski model), carboxylic groups
2 exist mostly at the edges of GO [9], and a recent study also found that the reaction kinetics of GO synthesis
3 begin from edges and transfer to center [18], which means that the carboxylic acid groups on the edges
4 are first decomposed by the oxygen radical attack. Overall, it is quite clear that H2O2 causes substantial
5 changes in GO, but we asked a question about the residual amount of potassium permanganate that had
6 not been converted into manganese sulfate by H2O2. Thus, we analyzed the potassium and the manganese
7 atomic content by energy dispersive spectrometer (EDS) analysis. The results are represented in Figure
8 10, and no potassium or manganese atoms were detected either in G0 or G40, only carbon and oxygen.
9 This means that all residual ions, whether potassium permanganate or manganese sulfate, were excluded
10 during the purification process by filtration. Thus, H2O2 is not necessary when less defective and highly
11 oxidized GO is desired.

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2 Figure 10. EDS analyses of G0 (a) and G40 (b) to compare residual potassium permanganate.
3

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2 4. Conclusion
3 The role of hydrogen peroxide and its effects on GO were investigated in this study. Here we tried
4 to find experimental evidence that H2O2, which has been used as a terminating agent for residual
5 potassium permanganate, directly influences the various properties of GO, leading to substantial changes.
6 Moreover, we proved that all residual unreacted ions can be eliminated by filtration without any H2O2
7 addition for less defective GO. This finding can be extended to every GO synthesis protocol that has been
8 developed based on Hummers method, which will lead to further enhancement of GO properties by
9 eliminating one process, H2O2 addition. In the same way, we may also consider using H2O2 to achieve
10 specific effects in GO synthesis. GO has been widely studied by itself due to its unique physical and
11 chemical properties, but GO is also known as a precursor for the solution-based bulk production of
12 graphene. Thus, it will be a valuable study to figure out the H2O2 effects on a reduced GO in the future.
13

14 Acknowledgements
15 This work was supported by the Korea CCS R&D Center (KCRC) grant funded by Ministry of Science,
16 ICT, & Future Planning from the Korean government (grant #2016910057).
17

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