CJCHE-01502; No of Pages 10

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Chinese Journal of Chemical Engineering

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Review

Structure and synthesis of graphene oxide☆

a r t i c l e i n f o a b s t r a c t

Article history: Graphene oxide (GO) is one typical two-dimension structured and oxygenated planar molecular material.
Received 30 January 2019 Researchers across multiple disciplines have paid enormous attention to it due to the unique physiochemical prop-
Received in revised form 6 May 2019 erties. However, models used to describe the structure of GO are still in dispute and ongoing to update. And cur-
Accepted 16 May 2019
rently, synthesis methods for mass production are seemingly abundant but in fact, dominated by a few core
Available online xxxx
methodologies. To update with the state-of-art opinions and progresses, herein we present a mini critical review
Keywords:
regarding the synthesis of GO as well as its models and simulations of structure. Also, we discuss the perspectives.
Graphene oxide © 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.
Structure
Synthesis
Preparation

1. Introduction these defects of various kinds are brought into the naturally inert
graphene structure, further categorized into on-plane functionalization
Graphene oxide (GO) is the oxidized analogy of graphene, recog- defects and in-plane lattice defects (vacancy defects and hole defects)
nized as the only intermediate or precursor for obtaining the latter in which semi-randomly distribute in GO's σ-framework of the hexagonal
large scale, [1] since the English chemist, sir Brodie first reported about lattice [1,7]. Such a defect-rich structure gives birth to unique properties
the oxidation of graphite centuries ago [2]. About thirty years ago, the of GO and renders its availability and scalability for further applications
term graphene was officially claimed to define the single atom-thin in various forms, e.g., chemically-derived graphene-like materials, func-
carbon layer of graphite [3], which structurally comprises sp2 hybridized tionalized graphene-based polymer composites, sensors, photovoltaics,
carbon atoms arranged in a honeycomb lattice, rendering itself large membranes [14] and purification materials. On the structure of GO,
surface area and some promising properties in terms of mechanical, however, it remains ambiguous, and literature reports are still in argu-
electrical, and others [4,5]. Despite these excellent properties, purely ment (Fig. 1) [11,13,15–23]. Also, methods about the synthesis of GO
single-layer graphene achieves limited success in practical applications have been massively studied in the past few years. The effectiveness
due to the difficulties in the large-scale formation of specifically orga- and environmental benignity were core driven forces for the continuous
nized structures [6]. But the precursor GO has advanced much in both evolvement. Herein, we update the progress and make a short yet
academics and industries in the last decades because of its readiness critical review on model structures of GO as well as the synthesis.
by exfoliating bulk graphite oxide facilely prepared from the oxidation
of graphite [7,8]. This bottom-down chemical strategy features the 2. Graphene Oxide Structure and Theoretical Simulation
utmost flexibility and effectiveness thereby arousing the significant
interest in practical applications. 2.1. Models
GO is known as a non-stoichiometric chemical compound of carbon,
oxygen, and hydrogen in variable ratios which heavily relates to the In 1939, Hofmann and Rudolf [22] demonstrated a structural model
processing methodologies [2,9–11]. GO possesses abundant oxygen of GO (Fig. 1, the top-leftmost schematic) in which a lot of epoxy groups
functional groups that are introduced to the flat carbon grid during randomly distribute on the graphite layer, and then in 1946, Ruess [21]
chemical exfoliation, evidenced as oxygen epoxide groups (bridging updated this model by incorporation with hydroxyl entities and alter-
oxygen atoms), carbonyl (C_O), hydroxyl (\\OH), phenol, and even nation of the basal plane structure (sp2 hybridized model) with an sp3
organosulfate groups (impurity of Sulfur) [12,13]. In other words, hybridized carbon system. By contrast, in 1969, Scholz and Boehm
[19] proposed a less ordered structure with C_C double bonds and pe-
riodically cleaved C\\C bonds within the corrugated carbon layers and
☆ Supported by Beijing University of Technology (105000546317502, 105000514116002)
hydroxyl, carbonyl groups in different surroundings, free from ether
and Beijing Municipal Education Commission (KM201910005007) oxygen. Further, in 1994, Nakajima and Matsuo [18] proposed a stage
E-mail address: [email protected]. 2 graphite intercalation compound (GIC)-resembled lattice framework

https://doi.org/10.1016/j.cjche.2019.05.003
1004-9541/© 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.

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Fig. 1. Theoretical models for structures of graphite or graphene oxide.

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based on the fact that fluorination of graphite oxide gives the same X- 2.3. Functioning sites
ray diffraction pattern as that of stage 2-type graphite fluoride, (C2F). In
1998, Lerf et al. [17] characterized their GO by the 13C and 1H nuclear The structure of GO is often simplified to be a graphene sheet
magnetic resonance (NMR), and subsequently found the 60 ppm line bonded to oxygen in the form of carboxyl, hydroxyl or epoxy groups
better related to epoxide groups (1,2-ethers) other than 1,3 ethers, [28]. To understand the configuration and arrangement of hydroxyls
and the 130 ppm line to aromatic entities and conjugated double and oxygens on the GO layers, Lahaye et al. [29] studied graphite
bonds. The carbon atoms attached to OH groups slightly distorted oxide of different oxidation levels by DFT calculation. They found that
their tetrahedral structure, resulting in partial wrinkling of the layers. during the oxidation plenty of carbon atoms were available to support
Accordingly, they proposed a model featuring a nearly-flat carbon grid the formation of 1,2-ether oxygens which stably attached on the adja-
structure with randomly distributed aromatic regions with unoxidized cent carbon atoms of the carbon grid, other than 1,3-ethers because of
benzene rings and regions with aliphatic six-membered rings. This energetical instability, but at the opposite side of the carbon plane was
Lerf and Klinowski model (L–K model) has become one of the most ac- the hydroxyl molecules. The deformation of carbon grid around the
ceptable for moderately oxidized samples [15]. However, all these ear- hydroxyl bonds allows for the transverse wrinkling about 0.05 nm, yet
lier models could not well explain the origin of the planar acidity of the in-plane lattice axes retain the hexagonal features of graphene.
GO, which is now a well-understood chemical property for GO. After Thus, it suggested that a stable structure requires hydroxyl groups to
that, Szabó and coworkers in 2006 [16] revived but a little modified balance the tension on the carbon grid from the 1,2-ether oxygens.
the Scholz–Boehm model, etc. by again examining the results from ele- Tang and Zhang [30] investigated the evolution of epoxy and hydroxyl
mental analysis, transmission electron microscopy, X-ray diffraction, groups adsorbed in locations of various kinds on zigzag graphene
diffuse reflectance infrared Fourier transform spectroscopy, X-ray pho- nanoribbons and found that the adsorbed epoxy groups and both the
toelectron spectroscopy, and electron spin resonance besides NMR. epoxy and hydroxyl groups can be transformed to a carbonyl pair and
They then proposed a carboxylic acid-free model comprising two dis- a carbonyl–hydroxyl pair, respectively. Besides, the vacancy defects
tinct domains: trans-linked cyclohexyl species interspersed with ter- can enhance such adsorption and formation of oxygen-containing
tiary alcohols and 1,3-ethers, and a keto/quinoidal species corrugated groups on graphene from the point of the energy barrier change, that
network. manifests the extreme difficulty in ultimately reducing oxygen moieties
Interestingly, as to the phenomenon of GO in basic solution Roukre from the planar structure. Savazzi et al. [15] investigated the GO at low
et al. [23] found that GO decomposed into slightly oxygenated degrees of oxidation by combining classical molecular dynamics and all-
graphene part and strongly graphene-bound oxidative debris (OD) electron DFT simulations. With finding the 1,2-ether groups in the basal
upon suffering a base washing, and then suggested a simple OD-base plane of GO from identifying XPS C-1s photoelectron peaks, a modifica-
washed GO two-component model, which was much different from tion of the L–K model was then inclusive of ether groups. Recently,
those previously proposed, upgrading the way we used to understand Moreira et al. hypothesized the hydroxyl chains were targeted sites of
about GO. Besides, they also mentioned about the metastability of un- attack by hydroxide ions in the base medium and ultimately led to the
washed GO, which reminded us of the previous room-temperature cracking of GO sheets. As manifested by the theoretical calculation,
metastable film [24], while the internal mechanism of external they learned the bond breaking of the ketones at both sides of the
stimuli-responded structural instability was lack of sufficient investi- basal plane initiated this change at the very beginning.
gation. In 2013, Dimiev et al. [11] revisited the structure via acid titra- Oxygen functional groups are known uniformly but randomly
tion and ion exchange experiment in terms of acidity of GO and attached on the graphene plane. But the oxygen atoms were ever in ob-
proposed a novel dynamical structural mode (DSM), which describes servation arranged in a rectangular lattice, displaying a series of epoxy
the evolution of several carbon structures with attached water beyond groups present in strips previously. It suggests that such an arrange-
the static L–K model. More recently, Liu et al. [25] experimentally ob- ment of epoxy groups is energetically favorable according to DFT calcu-
served oxygen bonding and evidenced the C_O bonds on the edge lations [31,32]. However, this observation is inconsistent with another
and plane of GO, confirming parts of earlier proposed models, espe- research, in which GO was found on average to maintain the hexagonal
cially the L–K model. symmetry in order and have carbon–carbon bond length of an un-
Amongst these models from 1939 through 2018, the L–K model modified graphene sheet, indicating the oxygen atoms did not form pe-
has been the most widely used due to the excellent interpretability riodic structures [33].
over the majority of experimental observation, and easiness of further Moreover, Mkhoyan et al. [28] performed an ab initio DFT using a
adaption/modification, for example, with which as the starting basis plane wave pseudo-potential approach and confirmed that the partial
the Rourke–Wilson model [23], Dimie–Alemany–Tour model [11], amorphization of GO occurs as a result of the sp2 bonds of carbon
etc. were successively publicized and continually paved the way for- atoms of the graphene converted into the sp3 bonds during oxidation,
wards. Nonetheless, the unique two-dimensional geometry of GO has and corresponding carbon atoms moved from original sites to form
been widely accepted as the primary character, and this laid an essen- the off-plane sp3 bonds.
tial foundation for GO subsequently blooming in enormous researches,
especially after the Nobel Award honored the discovery of graphene in 2.4. Oxygen coverage
2010.
Intensive studies proposed the band gap opening of GO. Via a pro-
posed model of graphite, Boukhvalov and Katsnelson [34] investigated
2.2. Simulations the evolution of the electronic structure of graphite oxide with the
coverage change of oxygen-containing moieties, found graphite oxide
GO is considered with great versatility, as its properties are tunable becomes conducting at 25% coverage, being an insulator at more essen-
by changing the type and concentration of oxygen-containing func- tial coverage. And they also resolved the puzzle of the extreme value of
tional groups attached to its surface. In contrast to the tedious experi- the C:O ratio hardly above 16:1 after having optimized a variety of
mental observations, the Density functional theory (DFT) has been structures of graphite oxide. Lundie et al. adopted the extensive ab initio
intensively used for the prediction and investigation of the atomic struc- and hybrid DFT calculations to derive GO with optically active gap and
ture and corresponding properties based on a determination of mole- identified fully oxidized graphene (O:C = 1:1) to be an insulator with
cule electron density [26,27]. It features a relatively low cost as a a band gap of 6.50 eV [27,35]. However, Mattson et al. [36] experimen-
unique experiment-simulating computing tool. GO and its nearest rela- tally prepared highly ordered graphene monoxide (GMO) by annealing
tive graphite oxide are often targeted. multilayered G-O in vacuum and reported that such structure with a

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stoichiometric ratio of C:O = 1:1 has semi-conductance with a band gap thus, found that non-oxidizing Brønsted acids can reversibly intercalate
~0.9 eV, which is somewhat different from that by Lundie et al. graphite, such as phosphoric (85%), sulfuric (H2SO4-SO3 (20%),
Rosas et al. [37] reported the effect of the incorporation of hydroxyl dichloroacetic (Cl2CHCOOH ≥ 99%) and alkyl sulfonic acids (e.g.,
and carboxyl groups on the electronic properties of the GO (C55H17 C2H5SO3H ~95%, C3H7SO3H ≥ 99%, CH3SO3H ~99.5%). This work further
+ O+(OH)3 + COOH, band gap 0.42 eV) structure via the DFT calcula- expanded the knowledge about the graphite intercalation compound.
tion and to control the electronic properties of GO through a careful se- Moreover, Cortés Arriagada [47] found that the global and intramolecu-
lection of the chemical radicals adsorbed on its surface. Once upon lar local reactivity of the basal plane is improved mainly by hydroxyl
removing hydroxyl groups the gap energy decreases (0.404 eV), the re- groups, with the investigation of changes in the local and global elec-
lease of the carboxyl group results in a semimetal–semiconductor tran- tronic reactivity of oxidized graphene system. For charge-controlled in-
sition (1.14 eV). Huang et al. [38] hypothesized the oxidation of termolecular interactions, hydroxyl groups allow the physisorption of
graphene in O2 atmosphere or oxygen plasma, then further studied small molecules, while, active carbon atoms around the functional
the stability of reduced GO for oxygen density ranging from 6.25% to groups would allow enhancement of the consecutive chemisorption.
50% and found a series of stable oxygen configurations. The relaxation On the other hand, negatively-charged epoxide, carbonyl, and carboxyl
of lattice on the electronic properties was found to be negligible for groups allow an increase of intermolecular non-bonded and hydrogen
low O coverage and yet crucial for higher O coverage, respectively. Cor- bond interactions with positive centers.
responding bandgaps are found to be a non-monotonic function of oxy-
gen density, with minima at O/C = 11.1% (0.78 eV) and 25% (0.354 eV), 3. Synthesis and Progress
and a peak at 25% (1.135 eV). Lahaye et al. [29] and Chen et al. [39] both
theoretically discovered that a higher oxygen content induces a red- 3.1. Methods of solution-processed GO
shift to obtain a relatively larger band gap, while the latter explained
this by that more sp3 bonds between O and C atoms exist in a graphene Brodie reported about the changes of graphite which blended with
sheet with more relatively small sp2 carbon clusters. Similarly, Savazzi strong oxidants, and this work can be regarded as the earliest prepara-
et al. [15] also found high-concentration of epoxy groups can buckle tion of GO, although he termed the final material as “graphic acid”,
the layers and increase the band gap. Jiang et al. investigated the elec- which we know now as graphite oxide. So far, the chemistry of graphite
tronic structure, work function of catalyst-targeted GO, etc. by tuning oxide has advanced much with efforts of scientists worldwide, espe-
compositions of epoxy (\\O\\) and hydroxyl (\\OH) groups. About cially from the time graphite oxide is known capable of transformation
40%–50% (33%–67%) coverage and the \\OH:\\O\\ ratio of 2:1 (1:1) into graphene oxide/graphene as the easily-obtainable precursor.
in the structures lead to both reduction and oxidation reactions for Graphite oxide-derived GO becomes one of the most tangible outcomes
water splitting. More specifically, the GO with a composition with 50% of the graphene research in terms of scalable production and commer-
coverage and OH:O (1:1) ratio can work even better as a visible-light- cialization. Such top-down strategy endows the preparation with visible
driven photocatalyst [40]. flexibility and relatively low cost of input. Various methods (Table 1)
Besides, abundant DFT based research is underway in continuation adopting graphite including its expanded form as starting materials be-
to clarify characteristics of GO in different structural configurations. come prevailing in laboratories and industries.
For instance, after Mattson's work [36], researchers such as Zhang [41] Now the Hummers method of 1958 has been widely employed to
and Dabhi [42] delivered more and more theoretical insights through delaminate and oxidize graphite because of the improved convenience
theoretically studying GO models with various configurations, such as compared to those methods by Brodie and earlier followers. This
as ether-type GMO, epoxy GMO, zigzag GMO, armchair GMO, and way relies on a mixture of sulfuric acid and potassium permanganate
graphene dioxide. More recently, Guilhon et al. [43] developed a com- (Fig. 2, the first two steps), and the whole procedure comprises three
bined DFT calculation to discuss the GO in terms of those aspects stages: a period for the intercalation of graphite and a simultaneous/
above, consequently derived the favorability for the formation of hy- subsequent oxidization of the above-mentioned graphite intercalation
droxyl groups and epoxy groups concerning oxidation and accounted compounds (GICs); next, to obtain homogeneous GO solution (Fig. 2,
for the antiparallel orientation of hydroxyl groups. Advances of explora- the third step), graphite oxide then hydrolyzes and straightforward
tion towards physio-chemical properties of GO by DFT means may also exfoliates into single sheets via mechanical peeling, like sonication
refer to other review papers [26,30]. [62], swirling (by shearing stress) [63], or others. Noticeably, many
groups prefer using a some-time certain-strength ultra-sonication to
2.5. Interactions completely break up the stacked structure of graphite oxide into GO
sheets.
2.5.1. Inter-layers As shown in Table 1, Brodie [2] provided an oxidization mixture
Duong et al. [44] investigated a model of graphite oxide consisting of recipe of fuming HNO3 and KCIO3 in 1859 before the Hummers', but
a hexagonal in-plane structure of graphene with hydroxyl and epoxide the method was tedious and not benign. Then Staudenmaier [48] fur-
groups, different oxidation levels and water content. Through DFT ther adjusted the acid component via the addition of H2SO4, rendering
study, they found the graphitic AB stacking order of anhydrous graphite the process with fast completion in one single-vessel reaction and
oxide has nothing to do with the oxidation levels, while the AB stacking thereby improved the processing yield. However, it remained ample
order gets lost if water molecules enter the highly oxidized graphite space for further cutting off the processing time and reducing the out-
oxide interspacing. The hydrogen bonding interaction of layers posi- come of hazards, such as toxic gases. Years later, did Hummers, and
tively relates to the oxidation level. The calculated interlayer distance Offeman [10] express the attitude to the previous methods “described
of hydrated graphite oxide was 0.73 nm, coinciding with the experi- in the literature is time-consuming and hazardous”, so they altered
mental observations. And Skákalová et al. [45] showed that the inclusion the oxidants to a water-free mixture via replacing the HNO3, KClO3
of oxygen functional groups on equivalent facing GO layers turned out with KMnO4. The new process taking less than 2 h with a lower working
to dramatically increase the interlayer distances, which was slightly temperature turned out to be more productive and less hazardous than
smaller than the observed spacing in the fully oxidized sample if it did before. Towards large-scale and safe production of GO, there remained
not count the steric hindrance. to some extent unsatisfactory problems. Thus, variations were proposed
in succession and seem to reach a research summit appearing in these
2.5.2. Inter-objectives years (2013–2018).
Kovtyukhova et al. [46] reported that polarized graphene layers Again, the Hummers method stresses on the three-stage reaction
could appear in a dipolar interaction with guest molecules or ions and [49]: low-temperature (below 5 °C) intercalation, mid-temperature

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Table 1
Method for preparation of GO

Methods Carbon source Oxidants Reaction time for Temperature/°C Features

Brodie, 1859 [2] Graphite KClO3, HNO3 3–4 days 60 Earliest method
Staudenmaier, 1898 [48] Graphite KClO3, HNO3, H2SO4 96 h RT Improved efficiency
Hummers, 1958 [10] Graphite, ~44 μm KMnO4, NaNO3, H2SO4 b2 h b20–35-98 Water-free, less than 2 h processing
Fu, 2005 [49] Graphite KMnO4, NaNO3, H2SO4 b2 h 35 Validated NaNO3 unnecessary
Shen, 2009 [50] Graphite colloidal, ~10 μm Benzoyl peroxide(BPO) 10 min 110 Fast and non-acid
Su, 2009 [51] Sonicated graphite, b3000 μm KMnO4, H2SO4 4h RT Large-size GO
Marcano, 2010&2018 [9] Graphite, ~150 μm H2SO4, H3PO4, KMnO4 12 h 50 Bi-component acids, high yield
Sun, 2013 [52] Expanded graphite KMnO4, H2SO4 1.5 h RT-90 Size-confined high yield, safe
Eigler, 2013 [53] Graphite, ~300 μm KMnO4, NaNO3, H2SO4 16 h 10 High-quality GO
Chen, 2015 [54] Graphite, 3-20 μm KMnO4, H2SO4 b1 h b20–40-95 High-yield
Panwar, 2015 [55] Graphite H2SO4, H3PO4, KMnO4, HNO3 3h 50 Tri-component acids, high yield
Peng, 2015 [56] Graphite, N10 μm K2FeO4, H2SO4 1h RT High-yield, less pollution
Rosillo-Lopez, 2016 [57] Defective arc-discharge carbon HNO3 20 h RT Nano-sized GO
Yu, 2016 [58] Graphite, ~44 μm K2FeO4, KMnO4 H2SO4, H3BO3 5h b5-35-95 Less manganite impurity, less acid,
high yield
Dimiev, 2016 [59] Graphite (NH4)2S2O8, 98%H2SO4, fuming H2SO4 3~4 h RT Lightly oxidized, 25 nm thick,~100%
conversion
Pei, 2018 [60] Graphite foil H2SO4 b5 min RT Electrochemistry support; high
efficiency and high yield
Ranjan, 2018 [61] Graphite H2SO4, H3PO4, KMnO4 N24 h bRT-35-95 Cool the exothermal reaction to keep
safe

RT: abbreviation of room temperature.

Fig. 2. Schematic diagram of GO preparation via the Hummers–Offeman method [10].

(~35 °C) oxidizing of the GIC and high-temperature (98 °C) hydrolysis prosperity of GO applications. However, novel methods with less acid
of consequences. Fu et al. [49] investigated the details of each stage are even scarcely reported.
and compared the results of changes of the parameters concerning, Sun and Fugetsu [52] conceived a simple principle as shown in Fig. 3.
e.g., the mass ratios amongst graphite, H2SO4 and KMnO4, and the They hypothesized that graphite in varying sizes and textures carried
ways to add water. They concluded the NaNO3 did not play an impor- out the oxidations consuming different times: under an identical condi-
tant role in adequate oxidization of graphite and suggested the cancel- tion, the intercalation of large graphite is longer than that of the small
ation of the use of NaNO3. To the best of our knowledge, this probably one, the tightly-structured graphite is likewise beyond the loosely-
is the earliest research to clarify the redundancy of NaNO3 in the Hum- structured graphite (Fig. 3A). With the implication, they selected com-
mers method. These changes not only simplify the process and modity expanded graphite of different sizes. They observed the mixture
the composition of discharged water but also alleviate the evolution underwent a fast and distinctly volumetric expansion along with
of toxic gasses, e.g., NO2/N2O4. Notably, these findings were also re- continuous magnetic stirring and formed a pale-gray foam-like slurry
declared or replicated in other respective researches by the Tour in the end (Fig. 3B) [52]. The addition of water, therefore, became secure
group (2010) [9], Fugetsu group (2013) [52], Shi group (2013) [64] and straightforward without fearing the splashing of acid. Regarding the
and others [51,55,58,59,61]. volumetric expansion as the visible indicator that can reflect the end of
One other point we highlight is the widely accepted ingredient, the a reaction and an improved security measure, they proposed one
concentric H2SO4. It features readiness due to the relatively high boiling modified Hummers method with expanded graphite. Not only did
point, non-volatility, and low cost. Therefore, it was retained in a majority the demand for acid (10 ml vs. 13 ml per gram of graphite before) reduce
of modified Hummers method [9,51,53,55,56,58,61], except those but also a yield of nearly 100% with the graphite of a suitable size
changed either the oxidization phase [50] or the raw material [57]. The (D50 ~ 15 μm) became available in contrast to that with a larger one
amount of acid per gram graphite consumed is so largely (N10ml 95– (D50 ~50 μm). Coincidently, Chen et al. [54] found that the flake graphite
98% purity H2SO4 per gram of graphite) that we have to take seriously with sizes in the range of 3–20 μm is converted entirely into GO without
the recycling of acid and the avoidance of accidental leakage into the en- additional centrifugation, yet with a routine mass configuration.
vironment. In other words, the post-treatment for the GO purification The size confinement will differentiate current strategies, in which
should have deserved more attention. the total acid might decrease even more than one fifth or one fourth
Considering the disposing, the overall cost per gram GO obtained for smaller graphite (b20 μm); for the large-sized graphite, a trade-off
remains as high as that of the skyscraper. It undoubtedly hinders the between the acid and oxidants needs more investigations.

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Fig. 3. (A) Difference in intercalation time for graphite with different lateral sizes or vertical textures, adapted from the Sun paper [52]; (B) photos related to the preparation procedure of
GO from expanded graphite ~15 μm following the Sun–Fugetsu modified Hummers method: (a) mixing, (b) the form-like slurry after a full expansion ends, (c) a light-brown GO “cake”
after high-temperature hydrolysis, (d) a stock solution of GO after purification.

For the latter, there have been a few advances. The mechanisms reported in a modified NaNO3-free method by Sun and Fugetsu [52],
were evolved by either extending the time of intercalation/oxidation re- demonstrating great effectiveness except for a longer time versus the
action or changing the oxidants. Huang et al. [65] introduced one-pot original Hummers method.
chemical oxidation method by only stirring large graphite (~500 μm) Ultrasound is also capable of reducing both the vertical and lat-
in a mixture of acids and potassium permanganate at room temperature eral size of graphite, so several modifications included the pre-
for 72 h, achieving large-area GO sheets with nearly 100% conversion. sonication or synchronous sonication over the graphite [57,67].
Similarly, Eigler et al. [53] prolonged the low-temperature oxidation of Rosillo-Lopez and Salzmann [57] pre-sonicated arc-discharge car-
graphite (~ 300 μm) over 16 h and then stepwise fed diluted sulfuric bon source and then oxidized them in half-concentrated nitric
acid and water for further hydrolysis. Noticeably, the entire process acid to successfully obtain the nano GO. Yang et al. [67] proposed
was at a temperature below 10 °C. A new form of GO as prepared their method by taking advantage of the synergistic effect between
consisted of a hexagonal intact σ-framework of C-atoms, which easily intercalation and sonication, resulting in a substantial decrease in
reduced to graphene that is no longer dominated by defects. demand for time and acid as compared to that of the Hummers
In contrast to the variation on time, Peng et al. reported a K2FeO4- method. Likewise, pre-oxidization of graphite is also beneficial for
based modified Hummers method (Fig. 4A), replacing KMnO4 with synthesis. It enlarges the interlayer spacing, in other words, de-
K2FeO4 due to the higher oxidation potential [56]. Such iron-based crease the vertical size of graphite. It then alleviates the resistance
oxidization realized a green production of GO in 1 h and enabled the for molecule/ion intercalation into interlayers. Having this strategy,
recycling of sulfuric acid and elimination of the emission of heavy Kovtyukhova et al. [68] found incompletely oxidized graphite-core/
metals and toxic gas, as forwarded from the paper. This work ignited graphite oxide-shell particles always existed. In 1999, they tried a
the ferric acid-based applications in modifying methods targeting high pre-oxidation with a tri-component mixture H2SO4–K2S2O8–P2O5
greenness and conversion efficiency. However, due to the instability of over graphite followed by the Hummers method, which succeeded
iron when dissolving in acidic aqueous the process as mentioned in complete oxidation of graphite. So far, this methodology remains
above did not go well with the repeatability [66]. Even though the diffi- inspiring for subsequent research. All the above techniques fell into
culty exists, the improvement of iron-based methods did not hang up. such a liquid-phase chemical method. And some of them have been
Yu et al. [58] used K2FeO4 to replace KMnO4 (Fig. 4B) partly and at the used for moderate-scale production of commercial GO despite high
same time reduced the acid amount to the same extent as previously time cost and potential environmental risk.

Fig. 4. Iron-based modified methods for the preparation of GO. (A). Synthesis of GO with introducing the oxidant of K2FeO4 following the Peng–Gao method [56]; (B). synthesis with
involving the K2FeO4-KMnO4 bi-component oxidant following the Yu–Zhang modified method [58].

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We also noticed some other remarkable progress had been made: oxidant is of great importance, e.g., KMnO4 [74] or HNO3. The intercala-
(1) By electrochemical solution exfoliation. In detail, Pei et al. [60] tion of H2SO4 into graphite can be accomplished by chemical oxidation
employed a lower-voltage (1.6 V) power to drive sulfate radical into in the presence of an oxidant in addition to electrochemical oxidation,
graphite foil to generate intercalated GICs in 98% sulfuric acid and a but both of them occur with the same reaction mechanism, confirmed
higher voltage (DC 5 V) to oxide the obtained GICs into graphite by measuring the potential of the carbon electrode by Inagaki, Iwashita,
oxide. This method was found based on a mechanism of water electro- and Kouno [72]. They further demonstrated, the relation between the
lytic oxidation towards graphite. Although featuring fast and high yield, onset potential for stage transformation of GIC and the upper limit of
somewhat greener that sole liquid-phase chemical oxidation, this saturated potential governs the intercalation reaction; the oxidation of
method still suffers from the critical use of strong high and concentrated graphite by acids leads to the accumulation of surface potential, that
acids. And for industrial scale, a set of specific apparatus is necessary is oxidant molecules get reduced by the electron extracted from the car-
since it cannot work without electric power. (2) By one single-step ex- bon host (e.g., Mn7+ → Mn3+,NO− −
3 → NO2 ), and if the potential goes be-
foliation. Shen et al. [50] discovered at high-temperature (~110 °C) mol- yond a threshold then the intercalation starts [72,79–81].
ten organic oxidant benzoyl peroxide can quickly intercalate and Besides, the structural properties of graphite strongly influence the
oxidize graphite to form GICs and then through sonication and wash, intercalation reaction [79]. The degree of graphitization and the crystal-
GICs exfoliate into GO sheets; Dimiev et al. [59] developed a water- lite size along c-axis can affect the formation of stage-1 GIC structure
free tri-component acidic system to fast splitting graphite. The expan- and, thus, was experimentally found to be 0.2 and 20–30 nm as the
sion of graphite took place, and the mixture turned out to become a criteria values, respectively [79,82]. Meanwhile, nanotexture affects
greenish-yellow foam. What they reported was graphene, however, the oxidation rate during the intercalation, too; as a consequence, it
on which were still oxygen-containing functionalities. The devotion of necessitates the high-percentage exposure of the edge surface of
these methods aspires the community of continuous innovation [69, graphite in a reaction medium [82,83].
70], but the security risk remains to hinder the way to production on a Accompanied by oxidizing the side-edge exposed carbon, some oxi-
large scale. dants are capable of directly etching outer-layer surface carbon and thus
We find the modern synthesis much depends on the intercalation form micro-passages/structural defects parallel to c-axis. Shin et al. [84]
chemistry of graphite in terms of the size, the time, and the kinds of examined highly ordered pyrolytic graphite treated in a 100 °C H2SO4/
oxidants. Even though less suffering from explosion risk, and environ- HNO3 mixture for different times and found that acid directly pene-
mental pollution along with the efforts from chemists, all these methods trated from the outer to inner graphitic layers, resulting in nitration
remain inherent limitations associated with acid recycle and post water and sulfonation. Such kind of structural variation conversely promotes
treatment. However, we keep ourselves with high confidence that these the reactions. To some extent, this opinion agrees to that of a previous
issues can be step-by-step addressed by, for example, using relatively work by Rodríguez et al. [73], who illustrated that the oxidation rate of
safe yet highly efficient oxidizing intercalation agents, applying electro- graphite negatively correlates with the size of graphite layers and the
chemical oxidation or other smarter ways. Besides, the expanded structural perfectness of carbon arrangement. For more intercalation-
graphite as starting materials could be another way for the turning- mechanistic research about graphite by other acids or chemicals, a re-
around, due to commercial availability, pre-oxidized feature and its cent review delivered by Xu et al. [85] is suggested although the main
potential to further decrease the dose of oxidants, focus is on the rechargeable metal-ion batteries application with GIC.

3.2. Intercalation of graphite precursors 3.3. Exfoliation of graphite to GO

Synthesis of GO mainly follows two preparative routes: treating The way to GO production remains the graphite oxide route [86] as it
graphite in a mixture of acid with an oxidizing agent or electrochemically was a hundred years ago. Flaky graphite is the typical raw material and
treating graphite in contact with an acid solution. Both these processes turns into semi-tightly stacked graphite oxide via intercalation along
comprise three common steps [71–73]. First, the fast formation of with oxidation. Subsequently comes the mono-sheet exfoliation,
stage-1 graphite intercalation compound (GIC) from graphite once which is often a special process, such as sonication, stirring/shaking,
attached in acidic oxidizing medium, namely, graphite bisulfate homogenization, etc.
(Scheme 1); next, the conversion of low-stage GIC into oxidized graphite
within a relatively long period; and the last step is that the above 3.3.1. In-lab prerequisite: sonication
graphite converts into single/fewer-layered GO after exposure to water. If the sonication (directionless force) were absent, abundant
Intercalation and oxidization with the oxidant KMnO4 [74] are ac- research relative to GO would have gone nowhere. As discussed above
cessible to implementation, and the reaction occurs by Scheme 1: it has become one of the most straightforward measures for graphite
Undoubtedly, full intercalation is a prerequisite and plays a crucial exfoliation [7,64,86–88]. Sonication featuring magnetoelectrically-
role in exfoliating the stacked structure of graphite into single layers. induced high-frequency soundwaves (N20 kHz) in the liquid medium,
Strong Brønsted acids, such as H2SO4, HNO3, and HCIO3, have mani- produces the cavitation to quickly split apart graphite oxide into single
fested to form staged graphite intercalation compounds [73,75,76]. No- yet small sheets and shorten the time usage significantly. Applying a
tably, due to effectiveness and high availability, sulfuric acid has become mild sonication (low power input, short time) can avoid over-
for long one of the most-frequently used intercalants for the graphite cracking of graphite during the processing [86,89]. Zhao et al. succeeded
lattice expansion and has gained much attention from thousands of in preparing GO sheets with the area up to 40000 m2 with such sonica-
literatures [2,9,10,48,49,51–53,55,56,59–61,77]. tion as well as mild oxidation and additional centrifugation [89].
On the one hand, the concentration of acid matters. An anodic
electro-oxidation report suggested the level of acid inversely affects 3.3.2. Towards scalability: shaking/stirring/homogenization/vortex turbu-
consequent stage index of GIC [78], that means to achieve GO/GIC at lence/micro-fluidization
lower stage indexes requires a higher level of acid. It is consistent with In comparison to the sonication, shaking, stirring, or others likewise
the current situation in which various syntheses still have high desire can deliver less destructive energy. Especially for the shaking and stir-
for extremely concentrated acids. On the other, at least one additive ring, they have become textbook-fashioned measures in conducting

Scheme 1. Intercalation and oxidization with the oxidant KMnO4.

Please cite this article as: L. Sun, Structure and synthesis of graphene oxide, Chinese Journal of Chemical Engineering, https://doi.org/10.1016/j.
cjche.2019.05.003
8 L. Sun / Chinese Journal of Chemical Engineering xxx (xxxx) xxx

the preparation towards large sheets of GO because of the great poten- research of this field. On the other, such learning certainly extends the
tial in a wide span of applications [86]. In this aspect, a review published course to precisely transferable operation conditions. Take the supple-
recently has demonstrated a detailed discussion, specific to the produc- mentary use of sonication as an example. Yuan et al. [96] re-examine
tion of large-sized GO [87]. Some reports mentioned mono-layer dis- the synthesis progress, particularly identifying the oxidation as a
persed moderately-sized GO could be obtained straightforwardly with three-step reaction, and consequently introduced ultrasonic treatment
only stirring, although subject to that dimension of raw graphite [52, over such the rate-limiting procedure, gaining higher efficiency, while
90]. In the meantime, it has stepped much farther for the production it was three years before Yang et al. [67] had already reported a similar
of GO beyond the lab, since such engineered exfoliation has already methodology yet with expanded graphite as the resource. Such a time
been practically available to satisfy the long-lasting mass-loading oper- gap reflects from the side that accelerating the recognition towards
ation condition. For example, homogenization can well slip graphite basis knowledge of GO is still an essential direction for mass production.
oxide in the in-plane direction, forming the GO layers with relatively
large sizes [91]. Besides, graphite precursors can also be sheared into 3.6. Technical factors
single-layer GO by concentric cylinders-based Taylor vortex flow [63]
or micro-fluidized turbulence flow [92], and the former declared to ex- Selecting and controlling of size dimensions inclusive of lateral size
foliate large-area single- or few-layer GO with high yields (N90%). and vertical thickness of raw graphite are still the most influential tech-
nical factors. GO is the derivative of graphite suffering from intercalation
3.3.3. One more: ball milling and oxidation. And the size differences of natural graphite have demon-
Differently, the ball milling depends on the impact and frictional strated in no small extent to influence the final GO products in terms of
forces resulting from the relative motion between the ball and the sizes, structures, yields, or even relative applications [52,97]; even fur-
graphite precursors. It is a reproducible and green approach to large- ther for one-pot synthesis of GO, the resulted sheets may appear with
scale and low-cost of GO. However, a large proportion of ball-milling a multimodal distribution of size, and a subsequent size fractionation
based research is graphene-making related. Only a few works are turns out as a consequence [39,98–103]. Thus, the variation of
concerning about GO. procedure-dependent sizes from batch to batch is still a strongly sup-
Fu et al. [93] showed the ball milling of graphite oxide prepared by pressive factor for mass scalability, not to mention the lengthy but
the modified Hummers method using water as the medium. Along tedious post-treatments [64] and the room-temperature structural
with the graphite oxide being thoroughly exfoliated to GO sheets after metastability [24] of GO.
being ball-milled, the resultant GO sheets were found with less
oxygen-containing functional groups such as carbonyl and epoxy groups
on the surface which got effectively removed through the mechano- 4. Prospective
chemical process. It is definitely not desirable for specifically GO-
oriented preparation. Remarkably, Dash et al. [94] adopted an in-house From the static to a dynamic model, with theoretical speculation to
designed horizontal dual-drive planetary ball milling system to directly experimental observation, the time dependence has been taken into ac-
delaminate graded graphite into GO with eliminating any addition of sol- count for intrinsic property investigation of GO. Fascinating measures
vents, catalysts and harsh chemicals. As compared, the 16-hour milling and characterization are in continuity on the way to development.
was selected as the optimized condition for GO preparation concerning Therefore, it is expected that complete characters of the GO shall be-
per the degree of oxidation, time and energy consumption. Since this come fully unraveled and universally acceptable, consequently benefi-
work did not mention much about the yield of single layers GO, there cial for understanding and guiding in-depth applications.
might exist a further space to modification. Research about the synthesis of GO now is at such a turning plateau
where the Hummers method (concentrated sulfuric acid) dominates as
3.4. Key factors influencing the mass synthesis of GO the mainstream strategy. Greener and more effective breakthroughs are
much desirable, calling more contributions from more intelligence with
To date, the high price of commercially highly-pure, fully-exfoliated, multi-discipline field background. Moreover, real synthesis of GO has
single-layered GO hints the cost of production is still the tiger in the to tackle the problems to the uniformity of sizes and properties. It is un-
road, not to mention to incorporate with downstream industries and realistic for downstream industries to embrace GO products from up-
serve the daily human life. Excepting from the essential factor of unde- stream entities having varying performances.
veloped marketing demand, we'd better frankly face the underlying dif-
ficulties of GO production, that hinders the in-depth development. References
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