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The green reduction of graphene oxide

Cite this: RSC Adv., 2016, 6, 27807
M. T. H. Aunkor,a I. M. Mahbubul,*b R. Saidurb and H. S. C. Metselaar*a

Graphene is an ultra-thin material, which has received broad interest in many areas of science and
technology because of its unique physical, chemical, mechanical and thermal properties. Synthesis of
high quality graphene in an inexpensive and eco-friendly manner is a big challenge. Among various
Published on 08 March 2016. Downloaded on 10/30/2018 2:49:04 AM.

Received 3rd February 2016
Accepted 5th March 2016
DOI: 10.1039/c6ra03189g
www.rsc.org/advances
methods, chemical synthesis is considered the best because it is easy, scalable, facile, and inexpensive.
Different kinds of chemical reducers have been used to produce graphene sheets. However, some
chemicals are toxic, corrosive, and hazardous. For this reason, researchers have been using different
environmentally friendly substances (termed green reducers) to produce functional graphene sheets.
This paper presents an overview and discussion of the green reduction of graphene oxide (GO) to
graphene. It also reviews the characterization of GO and its oxide reduction through the analysis of
different spectroscopic and microscopic techniques such as Raman spectroscopy, Fourier transform
infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron
microscopy, scanning electron microscopy, and atomic force microscopy.

shielding application,34 water purication,35 absorption of

1. Introduction
Graphene promises to be the most exciting material of the
decade. It is a plane sheet of sp2 hybridized carbon atoms tightly
conned into a honeycomb lattice. In 2004, the rst discovery of
graphene using a scotch tape peeling method brought
a dramatic revolution, especially in the world of materials
science.1 Recently, this single sheet of carbon has attracted huge
interest among the scientic community owing to the two
dimensional structure.2 It is proved that an ideal graphene
sheet is highly ordered and shows several extraordinary
behaviors including outstanding surface areas (2630 m2 g
1),
high Young's modulus (1.0 TPa), high thermal conductivity
(5000 W m
1 K
1) and strong chemical durability and high
electron mobility (2.5  105 cm2 V
1 s
1).3 It also exhibits
single-molecule gas detection sensitivity,4 quantum conne-
ment in nano scale ribbon,5 long range ballistic transport at
room temperature6 and high optical transmittance (97.7%).7,8
These unique characteristics of graphene opened a new way for
its wide range of application at different branches of technology
such as: lithium-ion batteries,9,10 catalyst engineering,11–15
chemically derived sensor,16–18 biosensor,19,20 anti-bacterial
activities,21 exible thin lm transistor,22 delivery of drugs,23,24
solar cells,18,25,26 photovoltaic devices,27 imaging,28 p–n junction
materials,29 super capacitor,30 touch panel,31–33 electromagnetic
a
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya,
50603 Kuala Lumpur, Malaysia. E-mail: h.metselaar@um.edu.my; Fax: +603 7967
5317; Tel: +603 7967 4451
b
Center of Research Excellence in Renewable Energy (CoRE-RE), Research Institute,
King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, 31261, Saudi
Arabia. E-mail: mahbub_ipe@yahoo.com
different non aqueous liquid e.g., oils, alkenes, aromatic
compounds, dyes, organic solvents, and ionic solutions.36–41
Large quantities of graphene materials are required to full
the huge demand of the aforementioned applications. Produc-
tion of the best quality graphene in an inexpensive manner and
on the desired scale is a big challenge of the time. There are
a number of approaches have been designed to synthesis gra-
phene from pristine graphite such as: epitaxial growth,42–44
vacuum thermal annealing,45,46 non-catalytic synthesis,13 scotch
tape method,47 micromechanical cleavage,48 chemical vapour
deposition (CVD),49,50 thermal exfoliation,51 carbon nanotubes
cutting,52 liquid phase exfoliation,53,54 direct ultrasound soni-
cation52 and reduction of graphene oxide.55 There are also some
unconventional and hazardous methods of graphene produc-
tion i.e. the chemical based detonation,56 arc discharging57 and
carbon nano tube unzipping.58 Epitaxial growth is able to
produce good quality multilayer graphene but it cannot isolate
conductive single or bilayer that are suitable for device appli-
cations.48 A remarkable limitation of mechanical cleavage is
repeated peeling during layer isolation and it is difficult to
maintain the number of separated layers produced by this
method.59 On the other hand, thermal exfoliation results in
high production costs.48 In case of CVD, it is not easy to achieve
layer separation without material damaging and successful
exfoliation from the substrate has been a stumbling block. In
contrast, graphene oxide (GO) reduction is considered a prom-
ising approach for the mass production of graphene. The
product obtained by this method is commonly termed as
reduced graphene oxide (RGO) or graphene nano sheet (GNS).
However, GO acts as a precursor to synthesis RGO or GNS. It
is produced from graphite akes by oxidative reaction, which

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heavily decorates the sheets with different oxygen moieties. The
presence of abundant amounts of oxygen functional groups
over the carbon basal plane not only makes GO electrically
insulating but also provokes thermal instability.54,60 Therefore,
reduction of oxygen molecules is the only key to resettle the p
lattice. It helps to produce thermally stable graphene and regain
electronic conductivity. Several reduction approaches of GO e.g.,
the electrochemical reduction,13,61–70 thermal reduction,71,72
photocatalytic reduction,73,74 and chemical reduction have been
reported in recent time. Electrochemical reduction is unable to
heal the defects and vacancies inherited from the precursor GO.
Secondly, the oxygen content should be as low as possible in the
GO precursor for exfoliation to single layer GO sheets. But the
low oxygen content in GO may depress the interaction between
oxygen functionalities. It could produce stable species like in-
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plane ether or out-of-plane carbonyl groups which are rela-
tively difficult to remove by the electrochemical reduction
method.75 Meanwhile, thermal deoxygenation is expensive. It is
also a complicated phenomenon because of the thermal-energy
induced multistep removal process of intercalated H2O and
oxide groups of –OH (hydroxyl groups), –COOH (carboxyl
groups) and pO (epoxy groups).76 Photocatalytic reduction
requires active performance of light sensitive materials under
continuous ultraviolet radiation.73,74 Hence, in comparison with
the aforementioned reduction approaches, the chemical
reduction is considered as the easiest way to produce ultrathin
graphene sheet with large lateral dimension and area.77 In
addition, this method is relatively fast, economic, facile, and
suitable for subsequent processing and chemical modications.
Scientists have applied different types of reducing agents to
convert GO to graphene. Hydrazine, sodium borohydride,
hydroquinone, etc. are toxic reducers. As alternatives, different
kinds of organic acids, biochemical substances, amino acids,
bacteria, fungus, plant extract, cellulosic compounds or metal
powders have been applied to prepare graphene sheets from the
GO. These reducing agents are termed “green reducers”. Since
they are free from corrosion, carcinogenicity, and toxicity. There
are few review papers available about the chemical or other
reduction of GO.75,78 However, there is no compilation giving an
overview of the green reduction of GO to graphene. Therefore,
in this review, we summarize the reduction of GO using
different environmentally friendly reducing agents in recent
time. Herein, we also briey discussed the selection of pristine
graphite, synthesis of GO precursor and the exfoliation of GO.
The results of different characterization techniques such as
Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelec-
tron spectroscopy (XPS), Fourier transform infrared spectros-
copy (FTIR), transmission electron microscopy (TEM), scanning
electron microscopy (SEM), and atomic force microscopy (AFM)
have also been summarized in this study. Obviously, this review
will show a guideline to the researchers interested in the green
synthesis of graphene.
2. Synthesis of graphene nano sheets
This is a two step procedure. The rst step is the production of
GO precursor from graphite and the following step is the
27808 | RSC Adv., 2016, 6, 27807–27828
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reduction of oxygen from the GO sheets. In order to synthesise
GO the selection of graphite is also important. Brief descrip-
tions of the processes are presented in the following
subsections.
2.1. Selection of parent graphite
Parent graphite is the source for GO production, which is
exfoliated and later reduced to synthesise functional graphene
sheets. It is experimentally investigated79 that the GO produced
from natural graphite (NGrO) performs better than the
synthetic graphite (SGrO) when exfoliating in aqueous solution.
The probable reason is that NGrO possesses a larger crystalline
structure. It also contains a large number of sp3 carbon to
carbon bonds (NGrO z 12.8% and SGrO z 4.9%) and C–OH
bonds (NGrO z 36.2% and SGrO z 1.8%). In contrast, GO
produced from synthetic graphite (SGrO) possesses higher
degree of carboxylic groups (NGrO z 4.4% and SGrO z 10.7%)
and ring shaped epoxy groups (C–O–C) (NGrO z 14.3% and
SGrO z 39.4%). This presence of large amounts of C–OH
groups in the inward direction of the basal plane leads to easy
exfoliation of NGrO. According to the same study the exfoliation
yield of NGrO is nearly double that of SrGO.79 The size of
graphite ake also plays important role in the oxidation of
graphite. McAllister et al.80 observed that the small sized akes
(45 mm) are quickly oxidized and intercalated with
a maximum reliability, while large sized akes (400 mm) take
more time to oxidize and it regularly fails to intercalate
completely. It is noteworthy that the reduction of the size of
starting akes allows faster and more reliable oxidation without
a signicant difference in the nal size of the GO sheets.80
Different types of graphite powder can be used as a starting
material such as natural aky graphite, articial graphite, kish
graphite and highly oriented pyrolytic graphite (HOPG) (please
refer to Table 1 from the cited article).81 This selection of
starting graphite is an important factor to pre-determine the
number of layer in functional graphene produced upon the
reduction of GO.82 Table 1 discusses the possible layer number
of functional graphene obtained from different types of parent
graphite. Signicantly, graphite with low crystallinity and small
lateral size is suitable to produce high quality single layer gra-
phene with good electron conductivity  1  103 S cm
1. On
the other hand, the highly oriented pyrolytic graphite (HOPG)
is appropriate to produce thick or multiple layer graphene
(>10 sheets).
Table 1 The relationship between parent graphite and number of
layers in graphene
Types of parent Number of layers
graphite in graphene Possibility Reference
Articial graphite Single layer
Flake graphite Single and double layer
Kish graphite Double and triple layer 80% 82
Natural akes Few layers (4–10)
Highly-oriented Thick graphene (>10)
pyrolytic graphite
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2.2. Synthesis of graphene oxide from graphite akes the suspension. The rate of addition was managed carefully to
83 keep the suspension temperature below 20  C. Aer that the ice
The Hummers method (HM) and the modied Hummers
bath was removed and the solution was warmed at 35  3  C for
method (MHM)84 are the commonly used method of graphene
30 minutes. As the oxidation progressed, the mixture gradually
oxide synthesis. In Hummers method the oxidation of graphite
thickened. At the end of 20 minutes the mixture became pasty
is conducted with the assistance of sodium nitrate (NaNO3),
with the release of small amounts of gas. The colour of the paste
potassium permanganate (KMnO4) and sulphuric acid (H2SO4).
was brownish gray. At the end of 30 minutes, 4.6 liters of water
Hydrogen peroxide (H2O2) is added to terminate the reaction
and remove residual permanganate and manganese dioxide was gradually added and stirred into the paste to dilute it. The
producing a bright-yellow colour suspension. This colour dilute suspension was brown in color. During this addition of
water a large exothermal heat was generated to 98  C which is
ensures the successful conversion of GO from pristine graphite.
maintained for more 15 minutes through exothermal heating.
Here, H2SO4 helps to create acidic reaction condition.85 And
The suspension was further diluted by pouring 14 liter of warm
KMnO4 acts as a strong oxidizing agent specially in the acidic
water and treated with 3% H2O2. Aer treating with peroxide,
media.86 With the aid of this KMnO4, a complete intercalation of
the suspension took brownish yellow color appearance. Later
graphite with concentrated H2SO4 can be occurred. It develops
the suspension was ltered resulting a yellow-brown lter cake.
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graphite bisulfate in which each mono-layer of graphene is

sandwiched by the layer of bisulphate ions.87,88 This successful The lter cake was washed 3 times and the obtaining residue
intercalation conrms the efficacious penetration of KMnO4 was dispersed in 32 liter of water to yield 0.5% solids. The dry
form of the product was obtained by centrifugation followed by
into graphene layers for the oxidation of graphite.
vacuum dehydration at 40  C.
The modied Hummers method is either one step method
2.2.2. The two step modied Hummers' method. The
or two step method. The one step modied Hummers method is
graphite ake (20 g) was added to a mixture of concentrated
developed by Chen et al.89 It is also called as “Improved
H2SO4 (30 mL), K2S2O8 (10 g) and P2O5 (10 g). Aer the admix-
Hummers” method where the graphite was oxidized without
ture a dark blue color suspension was produced with large
using NaNO3. In two step modied Hummers method the
graphite powder is initially oxidized by H2SO4, K2S2O8 and P2O5. exothermal heat. The resultant suspension allowed to cool at
Then the pre-oxidized graphite was subjected to oxidation by ambient temperature over a period of 6 h. Distilled water was
carefully added to the mixture to dilute it. Several ltration and
Hummers method. Marcano and co-workers90 developed a new
washing was carried out until the pH of the rinse water became
method which they called “Improved synthesis” of GO that can
neutral. The product was dried in the room temperature for
be seen in Fig. 1. They used KMnO4 in a 9 : 1 weight ratio with
overnight. Thus the pre-oxidized graphite was prepared which is
H2SO4 and H3PO4 mixture. In addition to, Xu et al.91 developed
later subjected to oxidation by the Hummers' method. The pre-
another method by reducing KMnO4/graphite ratio from 3 : 1 to
oxidized graphite powder (20 g) was put into cold concentrated
1 : 1. This approach is termed “mild oxidation”. A brief experi-
mental procedure of all the aforementioned methods has been H2SO4 (460 mL). KMnO4 (60 g) was slowly added while agitating
discussed below. In Table 2 a comparative study of all these and cooling the solution, during which the temperature of the
solution was not allowed to exceed 20  C. Then the mixture was
methods has also been discussed.
stirred at 35  C for 2 h with the addition distilled water (920
2.2.1. The original Hummers' method. The GO was syn-
mL). Upon 15 min, the reaction was terminated by pouring
thesised by stirring 100 g of graphite ake and 50 g of NaNO3
a large amount of distilled water (2.8 L) and a 30% H2O2 solu-
into 2.3 liters of H2SO4. The ingredients were mixed in 15 liter
tion (50 mL), aer which the color of the mixture was turned
battery jar and cooled to 0  C in an ice bath. During the
into bright yellow. Aer that, the mixture was ltered and
conduction of vigorous agitation 300 g of KMnO4 was added to
washed with a 1 : 10 HCl solution (5 L) to discard metal ions.

Fig. 1 Representation of GO synthesis by different methods with the production of under-oxidized hydrophobic carbon material.90

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Table 2 A comparative study of GO synthesis

Method of oxidation Advantages Disadvantages

HM  One step method  Higher degrees of defect due to harsh oxidation

 High efficiency  Production of higher under-oxidized
hydrophobic carbon materials
 High yielding  Generation of toxic gases (NO2, N2O4, ClO2)
 Free from the emission of acid fog  Production of residual Na+ and NO3
ions which are
difficult to remove from the waste water

Two step modied HM  High yielding  Two step method

 Penetration of more oxygen functional  Time consuming
groups throughout the sheets  Formation of higher defects or disorders

One step modied  Short oxidation period N/A

HM/improved HM  Simple procedure
 High yielding
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 Low cost
 Free from the production of toxic
gases and residual Na+ and NO3
ions
 Production of very low under-oxidized
hydrophobic carbon materials

Improved synthesis  One step method  Lengthy oxidation period

 High yield  Requires twice as much KMnO4 and 5.2 times as
much H2SO4 as those applied by Hummers method
 Fewer defects  Introduction of H3PO4 as an additional oxidising
 Free from the production of toxic gases agent in the reaction system
 Production of lower under-oxidized
hydrophobic carbon materials

Mild oxidation  One step method  Low yield

 Good water solubility  Production of higher unoxidized
 Large p-conjugated structure graphite in the form of aggregate
 Less lattice disorder
 Act as a low defect precursor to prepare highly
conductive graphene upon chemical reduction

2.2.3. The improved Hummers' method/one step modied
Hummers' method. The graphite ake (3 g) was added to
a mixture of concentrated H2SO4 (70 mL) under the agitation in
an ice bath. Under vigorous stirring, KMnO4 (9 g) was slowly
added to keep the suspension temperature lower than 20  C.
Successively, the reaction mixture was shied to a 40  C oil bath
and vigorously stirred for about 30 minutes. Aer that, 150 mL
distilled water was poured and the solution was stirred for more
15 min at 95  C. The reaction was terminated by pouring
additional water (500 mL) and a 30% H2O2 solution (15 mL),
aer which the colour of the suspension was turned into yellow
from brown. The mixture was then ltered and washed with
a 1 : 10 HCl solution (200 mL) to discard metal ions.
2.2.4. The method of “improved synthesis” of GO. A 9 : 1
mixture of concentrated H2SO4/H3PO4 (360 : 40 mL) was poured
into a mixture of graphite powder (3 g, 1 wt equiv.) and KMnO4
(18 g, 6 wt equiv.), producing a mild exotherm to 35–40  C. Then
the reaction mixture was warmed to 50  C and stirred for 12 h.
The mixture was cooled to room temperature and poured onto ice
(400 mL) with 30% H2O2 (3 mL). For work-up, the mixture was
sied through a metal U.S. Standard testing sieve (W.S. Tyler, 300
mm) and then ltered through polyester ber (Carpenter Co.) The
ltrate was centrifuged at 4000 rpm for 4 h and the supernatant
was removed. The remaining solid material was then washed in
succession with 200 mL of water, 200 mL of 30% HCl and 200 mL
of ethanol (2). For each wash, the mixture was sied through
the U.S. standard testing sieve and then ltered through polyester
ber. Later the ltrate was centrifuged at 4000 rpm for 4 h and the
supernatant was decanted away. The remaining material was
removed by multiple-washing and the resulting suspension was
ltered over a polytetrauoroethylene membrane with a 0.45 mm
pore size. The solid yield on the lter was vacuum-dried at room
temperature for overnight to extract 5.8 g of GO.
2.2.5. The method of “mild oxidation”. Graphite (0.5 g, 1 wt
equiv.) and KMnO4 (0.5 g, 1 wt equiv.) were successively mixed with
concentrated sulphuric acid (15 mL) under stirring at room
temperature. Then the reaction mixture was transferred to a 50  C
water bath for about 3 h. Then the mixture was poured into 150 mL
water and the solution was agitated for another 15 min. The
oxidation was terminated by the addition of 10 mL H2O2 (30%).
The mixture was then ltered and washed with 1 : 10 HCl aqueous
solution (50 mL) to discard metal ions followed by washing with
water to remove the acid. The resulting solid was dispersed in 150
mL water by ultrasonication for 1 h to make an aqueous disper-
sion. The obtained dispersion was then centrifuged at 3000 rpm
for 30 min to get a black-brown supernatant. The sediments at the

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bottom were again dispersed in 50 mL water by ultrasonication for 2.3. Exfoliation of graphene oxide
1 h and the dispersion was treated by centrifugation as above. The
The oxidation reaction helps to penetrate oxygen functionalities
two parts of supernatants were mixed to get the aqueous disper-
on both sides of the sheets. It widens the inter sheet distance
sion of mildly oxidised GO. The yield of as-synthesised GO was
and disbands the tightly packed sp2 hybridized atoms of
calculated to be about 20% (the weight of mildly oxidized graphene
carbon.98,99 Botas et al.100 pointed out a probable mechanism for
divided by the weight of graphite powder).
the invasion of oxygen into the graphite akes. They claimed
The physical properties of GO including electron conduc-
that in the case of graphites with smaller crystal size (optical
tivity, surface charge, transparency, band gap energy etc. can be texture composed of mosaics) the invasion of oxygen occurs
determined by the type and quantity of oxygen functionalities predominantly at the boundaries of the sheets, yielding small
over the GO sheets. The lateral size of GO is affected by the
size GO sheets. In contrast, the more ordered graphites (optical
degree of oxidation, oxygen moieties and defect sites. It can be
texture composed of ow domains) are predominantly attacked
increased by a high degree oxidation which can rupture the GO
in the basal plane where the epoxy groups are developed. It
sheets during the exfoliation step.92 Lerf et al.93 proposed a new
yields large size GO sheets. This study also revealed that GO
structural model of GO. They demonstrated that the hydroxyl
derived from lower crystalline graphite contains a large number
and epoxy groups are the major or dominant oxygen function-
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of carboxyl and hydroxyl groups and GO obtained from higher

alities of GO. These groups are located at the basal plane of the crystalline graphite contains abundant epoxy groups. As a result
sheets. In contrast, the other oxygen moieties such as the of the above mechanism, the material becomes hydrophilic
carboxyl and carbonyl groups are typically found at the edge of
facilitating the separation of individual GO sheet using soni-
the sheets.94 The quality of graphene oxide is evaluated by the
cation99 or magnetic stirring.95,101 This phenomenon is called
carbon and oxygen (C/O) atomic ratio and the average size of the
exfoliation of GO. Water is the widely used solvent to disperse
GO sheets. The increment of oxidation temperature decreases
GO. Samulski et al.102 claimed, Water soluble graphene is
the C/O atomic ratio and the size of the sheets. It is attributed to
similar to single graphene sheets peeled from pyrolytic graphite
the formation of more functional groups and defect sites due to
(0.9 nm thick). Besides water the dispersion of GO is also
the extensive oxidation.95 This relationship can be represented possible in several organic solvents such as: N-methyl pyrroli-
as follows in Fig. 2. dine (NMP), ethylene glycol and N,N-dimethyl formamide
The thickness of GO is another important parameter to
(DMF).96 It has been observed that graphite could utilize the
evaluate the successful production of GO. Typically it is
surface energy of NMP to exfoliate and produce single layer GO
increased aer oxidation owing to the attachment of covalently
sheets.54,103 But solvents are expensive and their high boiling
bonded oxygen. It is briey discussed in the AFM section of the
point limited their applications. Lotya et al.53 demonstrated that
study. A list of C/O atomic ratio and thickness of GO produced
graphene exfoliation is possible in a surfactant–water solution
by different procedure has been tabulated in Table 3.
(sodium dodecyl benzene sulfonate). The major benet of

Fig. 2 The relationship of oxidation temperature with C/O atomic ratio and average size of the sheets.

Table 3 Summary of C/O atomic ratio and thickness of GO samples

Size of graphite Time of Temperature of Ratio of Thickness

Method of GO synthesis akes oxidation oxidation C/O of GO (nm) Reference

Hummer method <1 mm 2 hours 98  C 2.30 1.0–1.4 96

Hummer method 30 mm 4 hours 35  C 2.33 0.9–2.3 97
Hummer method 30 mm 2 hours 60  C 2.28 1.0 97
Hummer method 30 mm 2 hours 45  C 2.25 1.0 97
Two step MHMa 74 mm 8.5 hours Pre-oxi: 80  C 1.18 0.80 95
Oxi: 35  C
Two step MHMa 74 mm 8.5 hours Pre-oxi: 80  C 1.24 0.89 95
Oxi: 27  C
Two step MHMa 74 mm 8.5 hours Pre-oxi: 80  C 1.26 0.82 95
Oxi: 20  C
One step MHM 325 mesh 1 hour 40  C 2.36 0.80 89
Improved synthesis 150 mm Over night 50  C N/A 1.1 90
Mild oxidation 325 mesh 3 hours 50  C 3.1 0.90 91
a
Modied Hummer method.

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Table 4 A list of different green reducing agents used in graphene oxide reductiona

Concentration of
Reducing agents of GO GO in aqueous solutions (mg mL
1) Temperature of reduction Time of reduction Ref.

Aluminum powder 1 RT 30 min 109

Aqueous phyto extracts 0.5 RT 5–8 h 130
Baking soda 0.1 90  C 3h 131
Benzylamine 0.5 90  C 90 min 123
Benzyl alcohol 8 100  C 5 days 132
Beta carotene 2 95  C 24 h 133
Caffeic acid 0.1 95  C 113
Carrot root 0.5 RT 48 h 134
Casein 1 90  C 7h 116
Cinnamon 1.6 N/A 45 min 135
Clove extract 1.6 100  C 30 min 136
Coconut water 0.66 100  C 12, 24, 36 h 137
Curcumin N/A 85  C 2h 138
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E. coli 5 37  C 48 h 139
Enhanced green uorescent protein 1 90  C 1h 140
Formic acid 2.5 100  C 18 h 141
G. biloba 0.5 30  C 12 h and 24 h 142
Grape juice 0.6 95  C 1 h, 3 h and 6 h 143
Gallic acid 4 RT and 95  C 24 h and 7 h 115
Green tea polyphenol 1 80  C 8h 128
Green tea polyphenol + iron 0.1 40, 60, 80  C 10 min 144
Glucosamine 0.496 90  C 7h 52
Glycine 0.25 95  C 24 h 145
H. sabdariffa 0.4 N/A 1h 146
Humanin 1 40  C 1h 147
Iron powder 0.5 RT 30 min 114
L-Ascorbic acid 0.1 23  C N/A 148
L-Cysteine 0.5 26  2  C 12–72 h 124
L-Glutathione 0.1 50  C 6h 149
L-Lysine 1 90  C 9h 150
L-Valine 0.1 90  C Several hours 118
Low temperature aluminum 4 100–200  C 3h 151
Melatonin 0.1 40, 60, 80  C 3h 152
Metallic zinc 0.5 RT 6h 119
Metal salts 0.1 RT 1h 153
Manganese powder 0.5 RT Till black sedimentation 154
Nascent hydrogen 1.0 RT 30 min, 20 min, 6 h 155
Natural cellulose + ionic liquid 0.8 80  C 12 h 156
Oligothiophene 0.48 RT 6h 126
Oxalic acid 2.5 75  C 18 h 157
P. glutinosa 5 98  C 24 h 158
PDDA 3 90  C 5h 159
Polyphenol 1 80  C 8h 128
Pomegranate juice 0.4 N/A 12 h, 18 h, 24 h 160
Potassium hydroxide 0.5–1 50–90  C Few minutes 122
Pyrrole 0.5 95  C 12 h 161
Rose water 7 95  C 5h 162
Reducing sugar 0.1 95  C 1h 117
Spinach 1.6 N/A 30 min 163
Shewanella sp. 300 RT 48 h 164
Sodium acetate trihydrate 1 95  C 24 h 165
Sodium carbonate 2 80  C 4h 110
Sodium hydroxide 0.5–1 50–90  C Few minutes 122
Supercritical alcohols 125 400  C 2h 127
T. chebula 1 90  C 24 h 166
Tea solution 0.5 90  C N/M 167
Thiourea dioxide (TUD) 1 90  C Several hours 125
Tin powder 1 RT 0.5–3 h 112
Tannin N/A N/A Several hours 168
Vitamin C 0.1 95  C 0.5–4 h 120
Vitamin C + amino acid 0.1 80  C 24 h 129
Yeast 0.5 35–40  C 72 h 169

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Table 4 (Contd. )

Concentration of
Reducing agents of GO GO in aqueous solutions (mg mL
1) Temperature of reduction Time of reduction Ref.

Zn powder + ultrasonication N/A RT Till black sedimentation 170

Zn powder + acid 1 RT 30 min 171
a
RT ¼ room temperature.

surfactant is the prevention of sheet aggregation. In another
study, Green and Hersam53 used sodium cholate to simulta-
neously extract single graphene sheets from the bulk graphite
with the help of a density gradient centrifuge machine at
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repulsion. Bosch et al.121 clearly illustrated the effects of different
pH values on the GO sheets. According to their ndings, acidic
pH is responsible for a higher concentration of defects with sheet
aggregation and size reduction. An acidic pH may turn the sheet

different buoyant density. like structure of graphene into other nano forms of graphite such
Both ultrasonication102 and magnetic stirring101 can be used as fullerene, nanoonion or multi-walled carbon nano tubes. This
in graphene exfoliation. However, excessive sonication can investigation suggests that the alkaline pH is more suitable to
reduce the sheet quality. Chhowalla et al.104 found that GO produce high quality or less defective graphene.122 Aer reduc-
dispersed in DMF solution could laterally degrade aer 10 hours tion the brownish yellow colour solution of GO turns into black.
of sonication. Over sonication may increase the number of sheet Graphene sheets are extracted from the black slurry by ltra-
to sheet junctions which limits electron mobility.104 These types tion113,119,123 or centrifugation.118 Aer centrifugation, the product
of sheets are not suitable for device applications. A higher should be washed and recentrifuged several times with deion-
amount of oxygen functionalities (epoxy and hydroxyl) can ised water, alcohol or 5% ammonia to remove all the unwanted
generate areas of weakness mainly consisting of cracks and fault materials (unreduced graphene, excess reducers, and reaction
lines. This defective zone leads to sheet breaking when ultra-
sonicated for a longer duration. It follows the mechanism of
cooperative unzipping proposed by Li et al.105 In addition,
erosion of ultrasound tip is an unavoidable outcome of pro-
longed ultrasonication.106 Furthermore, a recent investigation by
Qi et al.107 showed that the rst hour of sonication is the critical
point. Because the exfoliation and sheet break up mainly occur
in the very rst hour, while later sonication facilitates sheet
restacking. This suggests that when GO sheets are degraded in
size, they would trend to intercalate or restack together. There-
fore in order to address poor quality or hole defects of graphene
higher sonication time should be avoided.108 It is better to Fig. 3 The green reduction of graphene oxide using L-valine.118
continue until the whole solution becomes clear with no visible
particulate matter and brilliant yellow in colour.99

2.4. The green reduction of graphene oxide

In a typical reduction, dispersed GO suspension and environ-
mentally friendly reducing agents are mixed together to produce
reaction solution rst. Secondly, the reaction solution is kept
under controlled temperature for different duration. In most of
the previous studies, the reaction temperature and the concen-
tration of GO have been observed 80–95  C and 0.5–1 mg mL
1,
respectively. In Table 4, the concentration of GO, temperature
and time of GO reduction for different studies has been dis-
cussed. The adjustment of pH is an important parameter for the
reaction solution. Because the reduction is possible in both
acidic109 or alkaline environment.110,111 Notably, HCl,109,112–114
NH4OH115–118 and dilute NaOH52,119 are used to regulate the pH of
the solution. According to Merino et al.120 alkaline condition is
able to reduce the time of reduction. It can deoxygenate GO
sheets without using any further reducer.110 It strongly stimulates
the colloidal durability of GO with the help of electrostatic Fig. 4 A schematic representation of green reduction of graphene oxide.

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by-products). Aer completing the washing procedure, the pH of double resonance Raman scattering with two-phonon emission.
the product should be neutral (pH ¼ 7).124,125 It can be used to see whether the RGO is single layer or
But in case of ltration, aer each ltering the lter cake multiple.174 Generally, the Lorentzian peak for the 2D band of
should be dissolved in deionised water and resonicated for 10
minutes prior to next ltering.125 In different studies, 0.45 mm
poly ether sulfonate paper,126 poly vinylidene uoride lter,127
0.22 mm nylon membrane128,129 or 0.20 mm Whatman paper have
been used to drain out the waste solution. Finally, the solid and
black RGO sediment can be dried inside a vacuum oven at 50–100
 109,124
C. Xiao et al.115 also dried the graphene at room tempera-
ture but it took 2 days. Thus the functional graphene sheets are
obtained as nal product. A pictorial image of green reduction of
GO using L-valine is shown in Fig. 3. Moreover, the quality of the
functional graphene highly dependents on the following factors:
(i) the properties of pristine graphite, (ii) method of oxidation,
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and (iii) nal deoxygenation procedure of GO to graphene. A ow

chart of green reduction of GO is shown in Fig. 4.

3. Characterization techniques to
Fig. 5 Raman spectra of graphite, GO and RGO (here SRGO ¼ baking
evaluate GO and RGO soda reduced graphene oxide).131

GO and RGO expose unique set of spectroscopic and micro-

scopic characteristics that differentiate them. The coming Table 5 ID/IG ratio of GO and RGO after different chemical reduction
reactionsa
section will discuss the commonly used spectroscopic and
microscopic techniques to evaluate GO and RGO. Reducing agents GO RGO Reference

Aluminium powder 0.96 1.81 109

3.1. Raman spectroscopy characterization
Amino acid (L-cysteine) 0.94 1.17 124
Raman spectroscopy is a most important tool to characterise Baking soda 1.47* 1.37* 131
graphene and other carbon related materials such as carbon Benzyl alcohol N/A 1.20 132
E. coli 1.37* 0.97* 139
nano tube,172 graphene oxide,64 and graphite.173 Its main
Gallic acid 1.74 1.86 115
purpose is to study the electronic and compositional charac- Carrot root 0.80 1.09 134
teristics of graphene. The spectrum of Raman displays two Glucose amine 1.43 1.50 52
bands: the D band and the G band together with a weak 2D Glycine 0.98 1.09 145
band.174 The D band is associated with the breathing mode of K Humanin 1.4 2.3 147
Iron powder 0.96 1.02 114
point phonons of A1g symmetry. It mainly indicates the surface
Lithium aluminium 0.96 1.30 191
disorder and defects of graphene.175 And the G band is the result hydride
of rst order scattering of E2g phonon from sp2 carbon. It Hydrazine hydrate 0.96 1.21 191
expresses the graphitic composition of the materials.176 In Metallic zinc 1.19 1.40 119
pristine graphite, a sharp and intense G band observes at 1575 Manganese dioxide 1.44 1.68 194
Nascent hydrogen 1.01 1.36, 1.65, 1.88 155
cm
1. It is related to the lattice structure of graphite. It also
Natural cellulose 1.32 1.53 156
displays a weak D band at approximately 1355 cm
1 caused by Non aromatic amino acid 0.95 1.02, 1.05, 1.11 118
the graphite edges.177 Aer the oxidation reaction the synthe- Oligothiophene* 1.19* 1.02* 126
sized graphene oxide exhibits characteristic D band G band at Oxalic acid 1.2 1.3 157
around 1350 and 1580 cm
1, respectively.174 In GO the G band is Pyrrole* 1.3* 0.1* 161
Sodium acetate trihydrate 0.87 0.96 165
broaden and blue shied to higher wave number compared to
Sodium hydrosulphite 0.73 1 195
the pristine graphite.177 On the other hand, the D band of the Sodium carbonate 0.81 1.04 110
Raman spectrum of GO becomes prominent. It ensures the Solvothermal 0.86 1 190
degradation of the in-plane sp2 domains in GO due to the Sulfur coating compounds N/A 0.95–1.22 196
extensive oxidation.99 While GO is being reduced, both of the D Supercritical alcohols 1.11 1.30 127
Tanin 0.97 1.18 168
band and G band is blue shied to lower wave number.178 It
Thiourea dioxide 0.83 >1 125
reveals the construction of new structure through reduction Tin powder 0.94 $1.30 112
reaction. Structurally, the D band and G band of RGO are Vitamin C + amino acid 1.56 1.75 129
sharper and more intense in comparison with those of GO.177,179 Vitamin C/L-ascorbic acid 0.95 1.2 120
Additionally, the weak 2D band of the Raman spectrum of RGO Yeast 0.80 1.44 169
Zinc powder + acid 0.89 1.61 171
centres within the range of 2700 cm
1. It is ascribed to the
second-order of the zone-boundary phonons generated by the a
*the decrease of ID/IG ratio from GO to RGO.

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single layer graphene is observed at 2679 cm
1. This peak is
broadened and shied to a higher wave number if multilayer
graphene is formed.130 For example, Akhavan found this band at
2699 cm
1 for the bilayer graphene.180 In Fig. 5 the Raman
spectroscopy of graphite, GO and RGO has been given.
The intensity ratio of band D and G ((ID/IG)) is used to
investigate the degree of disorders in graphene. This ratio is
unique to differentiate RGO from GO. Because it is either
increase or decrease in RGO (Table 5). The value of both of the
band is required to calculate this ratio through the Tuinstra–
Koenig relation.173 Aer reduction two different types of regime
can arise in RGO: the high defect density regime and the low
defect density regime.59,181,182 In high defect density regime, the
ratio starts to fall with the increment of defect density. This is
ascribed to the larger amount of sp2 amorphous texture of
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sign of crystal defects, which are of two types. The rst one is the
edge defect, which does not cause structural rapture. It plays the
main role to the increment of ID/IG ratio in RGO. And the second
one is the basal defect responsible for structural disruption.145
Moreover, the ID/IG ratio of high temperature reduction is
greater than that of room temperature, which indicates a lower
degree of disorder at room temperature.119 But room tempera-
ture reduction is unable to increase the average size of the
graphene domains.115
The Knights empirical equation is used to calculate the size
of the sp2 carbon domains (designated as La) using the ID/IG
ratio of the samples.192
La ¼ 4.35(ID/IG)
1 (1)

carbon. In this case the ID/IG ratio is proportional to the square
of the size of nanocrystalline graphitic domains.183
On the other hand, in the low defect density regime the ID/IG
ratio starts to increase. Here defect density is assorted with the
generation of higher elastic scattering. This regime is regarded
as nanocrystalline graphite.184–187 The reason of this increment
is the degradation of overall size of sp2 domains.188,189 In this
case the intensity ID/IG ratio is inversely proportional to the size
of sp2 domains.190 Notably, in RGO the new graphitic domains
are more numerous than those of GO.191 In order to explain this
phenomenon Stankovich et al.99 pointed out that the reduction
of GO increases the number of aromatic domains of smaller
average size in graphene, which could lead to an increase of the
ID/IG ratio. Additionally, the increase of ID/IG ratio is a proven
In an investigation, Khai et al.193 calculated the size of sp2
domains to be approximately 5 and 4 nm for GO and RGO,
respectively. This achievement suggests that the chemical
reduction can cause nucleation of sp2 domains in the sp3
matrix. As a result, the density of small sized sp2 nuclei
increases and the average size of sp2 domains decreases.
3.2. Fourier transforms infrared spectroscopy
characterization
In graphene research, it is important to study what types of
oxygen functional groups are attached to the basal plane. FTIR
is the technique to identify the bonding conguration of
various sorts of oxygen. It is also a complementary tool to
Raman spectroscopy. The FTIR spectrum of pristine graphite

Table 6 FTIR characterization of GO in different studiesa

Peak positions of oxygen functionalities for GO samples

C]O stretching Epoxy C–O Alkoxy C–O O–H stretching O–H deformation Agents of GO reduction Ref.

1746 1220 1053 3420 1395 Amino acid (L-cysteine) 124

1720 1204 1049 3400 N/M Aquatic phyto extract 130
1706 1219 1052 3395 1386 Baking soda 131
1728 1223 1051 N/M 1395 Carrot root 134
1720 1224 1048 3424 N/M Gallic acid 115
1727 1224 1065 3424 N/M Glycine 145
N/M 1250 1120 N/M N/M Glucose amine 52
1720 1220 1030 3400 1400 Humanin 147
1726 1226 1052 3395 1410 L-Ascorbic acid 148
1730 1064 1123 3430 1410 Metallic zinc 119
1730 1220 1050 N/A N/A Natural cellulose 156
1730 1224, 985 N/M N/A 1417 Oligothiophene 126
1740 N/M N/M N/A N/A Polyphenol 128
1739 N/M 1600 3403 1395 Reducing sugar 117
1730 1037 N/A 3420 1395 Sodium acetate trihydrate 165
1730 1222 1050 3387 N/A Sodium carbonate 110
1730 1220 1050 3380 N/A Super critical alcohol 127
1718 1050 N/A 3200 1380 Thiureadioxide 125
1725 1224 1054 3421 1398 Tin powder 198
1700 1600 N/A 3650 N/A Urea ammonium nitrate 199
1720 1220, 980 N/A 3000–3500 1300–1350 Vitamin C 120
1732 1231 1051 3408 1394 Yeast 169
a
N/A ¼ not available.

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exhibits no characteristic peak for the discernible functional
groups.197 It only displays two peaks at approximately 1610 and
450 cm
1 attributed to the skeletal vibrations from graphite
domains (the sp2 aromatic C]C) and the vibration of adsor-
bed water molecules (the O–H stretching), respectively.52 Aer
treating with oxidizing agents, the oxygenated graphene sheet
could display a series of different absorption bands or char-
acteristics peaks ranging from 900 to 3500 cm
1. These
includes carboxyl peaks (1700–1750 cm
1) mainly present at
the edges of the sheet, alkoxy stretching vibrations (1040–
1170 cm
1), O–H stretching vibrations (3300–3500 cm
1), O–H
deformation peaks (1300–1400 cm
1) and the stretching
vibration of epoxy C–O groups (1000–1280 cm
1). Notably, the
aromatic C]C peak could be seen between the range of 1600–
1650 cm
1. This peak is resulted from the sp2 domains of the
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disappeared carboxyl acid and hydroxyl peaks aer the sol-
vothermal treatment of GO. This is attributed to the mild
reduction procedure. Herein, Fig. 6 shows the FTIR spectra of
GO and RGO and Table 6 shows the FTIR characterization of
different GO samples.
3.3. X-ray photoelectron spectroscopy characterisation
It is very difficult to reduce hundred percent of the oxygen
molecules from the sheets of GO.90,97,109,200 That is why
elemental analysis is crucial to characterize the newly syn-
thesised graphene. XPS is commonly used to determine the
relative amounts of carbon, oxygen, and other functional
groups present in graphene.201 The XPS spectrum of GO and
RGO exhibit two major peaks (C1s and O1s) at the wide

unoxidized graphite125,165 and this vibration generated from
the unoxidized region is termed skeletal vibration.102,126
However, in different GO samples, the above characteristic
peaks are found in slightly different positions (Table 6). This
may be the consequence of different reaction system and
conditions.
While GO is being reduced by the chemical reducers, the
abovementioned characteristic peaks are gradually weaker
over the course of the reaction and some of them vanish
completely. This indicates the successful removal of oxygen
from the sheets. The spectra of RGO displays a sharp C]C
band within the range of 1600 cm
1.124,165 Additionally, It
displays two new peaks in the region of 2922 and 2853 cm
1
attributed to the presence of –CH2 and –CH stretching vibra-
tions. It is also explained as the adsorption of reducing agent
by the sheet surface.126,134,169 These observations conrm that
the atomic frame of sp2 carbon has formed in RGO. In
a previous study, the alkoxy and epoxy vibration peaks
remained undistorted in RGO although their position has been
changed. This is ascribed to the partial reduction of GO.134 In
another study, the absorption peaks of alkoxy and carboxyl
groups are found to be weaker at higher temperature reduced
graphene oxide (HT-RGO) than those of room temperature
reduced graphene oxide (RT-RGO). This investigation suggests
that higher degree of reduction is related to higher tempera-
ture (90–95  C).115 Khai et al.193 also found in completely
regions.109 The characteristic C1s peak is the result of sp2
carbon–carbon bonding and the O1s peak is associated with
different sp3 carbon–oxygen bonding. The relative intensity of
these two peaks varies with sample to sample, depending on
the conditions of the reaction system.91 Both of the O1s and
C1s spectra can be used to calculate the ratio of peak intensity
between O1s and C1s i.e. the C/O atomic ratio. This ratio can
be used to determine the oxygen moieties present in the
carbon skeleton of graphene.202 Table 7 discusses the C/O
atomic ratio of RGO produced using different reducing
agents.
Typically, in the wide region the C1s and O1s peak of GO and
RGO can be observed at 530 eV and 284 eV (Fig. 7a). In order
to conduct the quantitative analysis, both of the C1s and O1s
spectra are needed to be separated into their individual
components. This is performed by tting the total spectrum
into a linear superposition for all elements. Gaussian–Lor-
entzian peak shape method is used to t the C1s and O1s curve
aer performing the Shirley background correction.112,202 This
separation helps to determine the fractions of every single
element present in the sheet. The soware XPSPEAK41 is an
Table 7 C/O atomic ratio of RGO at different studies
Reaction C/O atomic
Reducing agents time ratio References

Aluminium powder 30 min 18.6 109

Caffeic acid 24 h 7.15 113
Carrot root 72 h 11.9 134
Glycine 24 h 11.14 145
Gallic acid 6h 5.82 115
Hibiscus sabdariffa 1h 3.1 146
Hydroxyl amine 1h 9.7 208
Iron powder 6h 7.9 114
L-Ascorbic acid 48 h 5.7 148
Metallic zinc 7h 3.76 119
Oligothiophene 6h 6.12 126
Pyrrole 2h 7.7 161
Sodium citrate 3h 5.6 209
Sodium carbonate 4h 8.15 110
Tea solution Several hours 3.1 167
Yeast 72 h 5.9 169
Fig. 6 FTIR spectra of GO and RGO (here, SRGO ¼ baking soda Zn powder + acid 30 min 8.2 171
reduced graphene oxide).131

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Fig. 7 XPS pattern of graphene: (a) wide region (GO + RGO), (b) C1s region of GO, (c) C1s region of RGO109 and (d) O1s region of GO.202
useful tool for background subtraction, curve tting, and peak
separation.119,203
The high resolution C1s signal of GO and RGO represents
ve different elemental peaks: C–C z (BE ¼ 284.6 eV), C–OH
z (BE ¼ 285.6 eV), C–(epoxy group) z (BE ¼ 286.8 eV), C]O
z (BE ¼ 288.2 eV) and O–C]O z (BE ¼ 289.4 eV), as seen in
Fig. 7b and c; although the accurate position of these peaks as
well as their exact binding energy (BE) is difficult to
specify.202,204–206 On the other hand, the O1s spectrum of GO
displays several individual component peaks which represent
C]O groups z (BE ¼ 531.20 eV), C–O groups z (BE ¼ 533
eV), O–C]O groups z (BE ¼ 534.4–535.6 eV), respectively, as
seen in Fig. 7d. All of this information allows to determine the
fraction of epoxy, hydroxyl or carboxyl groups present in the
basal plane.202,205 The information obtained by the analysis of
O1s spectrum can complement the information obtained by
the analysis of C1s spectrum. Because the photoelectron
kinetic energies of O1s are lower than those of the C1s, the
O1s sampling depth is smaller, and therefore the O1s spectra
are slightly more surface specic.202
Aer the reduction of GO the intensity of the peak related to
the C]O, C–O and O–C]O groups decreases to a much lower
value (Fig. 7c and d). This phenomenon suggests that most of
the oxygen functional groups have been disappeared aer the
reduction of GO.66 Secondly, the pick intensity of the sp2 carbon
to carbon bonding considerably increases in the C1s spectrum
of RGO. This result suggests the restoration of new sp2 network
of graphene.66,207 Besides these two peaks some additional
peaks might be observed in the spectra of RGO such as sodium
peak,124 nitrogen peak,123 iron peak,114 sulphur peak,126 tin
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peak,112 phosphate peak.169 These are probably the residual
components of the reaction mixture caused by other side reac-
tions. These components clearly show the involvement of the
reducing agent in the reaction.145
The elemental analysis on the basis of C1s spectrum indi-
cated that GO contained approximately 69.63 at% carbon and
30.37 at% oxygen in the C–C/C]C and C–O bonds.146 Upon
reduction the atomic percentage of carbon is increased in
RGO. According to several studies the better range of carbon
percentage is found to be 90–95%.109,134,198 Meanwhile, the C/O
atomic ratio of GO is around 2.3, as mentioned in Table 3.
Aer the reduction of GO the C/O atomic ratio is also
increased in RGO, as discussed in Table 7. Temperature is an
important factor to control the graphene C/O atomic ratio.
Yang et al.119 and Zhang et al.122 demonstrated that the gra-
phene produced by the room temperature reduction contains
large amount of residual oxygen than that of higher temper-
ature. Reduction time is another important factor. It is
established that the increment of reduction time is propor-
tional to the removal of oxygen groups from the plane of
graphene.113,123,203
3.4. X-ray diffraction characterization
The inter sheet gap is the most signicant parameter to access
the structural information of graphene. XRD is the technique
which deals with the layer to layer space and crystalline
structure of graphene. In this study, we highlighted the
interlayer distance of GO before and aer reduction. The XRD
spectra of primitive graphite revels more intense and sharp
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peak in comparison to GO and RGO.124 Typically, this graphitic

peak is found at 2q z 26 corresponding to a d-spacing of 0.34
nm.90 Aer oxidation, this sharp and strong graphitic peak
becomes invisible and a new peak observes in the range of 2q
z 9–11 .210,211 It has been reported that the value of d-spacing
is found within the range of 8–9 Å upon different method of
oxidation such as: Hummer method (8 Å), modied Hummer
method (9.5 Å), and improved synthesis (9 Å).90 This result
strongly indicates that the d-spacing of GO is directly
increased by oxidation due to the penetration of epoxy,
hydroxyl, and carboxyl groups on both side of the sheets.212,213
From this result, it can be said that the inter layer spacing of
graphene material is proportional to the degree of oxidation.
Aer treating with the green reducing agents the XRD peak of
GO vanishes and a broad, prominent and new pick can be seen
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near 2q z 26 . It is related to the opening of epoxy rings and

removal of other oxygen moieties. This result conrms the
successful restoration of new graphitic network in RGO. Table
8 shows the interlayer distance of GO and RGO aer different
reduction reactions (Fig. 8).
3.5. Microscopy characterization
Microscopy is essential to study morphology of graphene. The
TEM, SEM and AFM are commonly used in this purpose. A brief
of the above techniques are discussed below:
3.5.1. Transmission electron microscopy. TEM acts on the
basis of diffraction patterns emitted by the samples.215,216 To
generate this diffraction pattern the highly energetic electrons
beams are transmitted through the sheet. The scattered elec-
trons are captured and processed by an electromagnetic lens to
display an image. The low magnication TEM image is quite
Fig. 8 XRD spectra of (a) GO, (b–d) aquatic phytoextract reduced
graphene oxides and (e) graphite.130
useful in sheet visualization, but they are unable to provide
complete information about the internal atomic structure of the
sheets. For the structural characterization, the selected area
electron diffraction (SAED) patterns are oen obtained from the
individual sheets.
The two dimensional (2D) GO and RGO nano sheets show
transparent, corrugated or wrinkled structure under the
TEM.148,217 It is also explained as ultrathin silk veil morphology

Table 8 Interlayer distance of different GO and RGO samplesa

Reducing agents GO (2q) d-Spacing of GO (nm) RGO (2q) d-Spacing of RGO (nm) Ref.

Aluminium powder 10.3 0.80 nm 23.4 0.375 nm 109

L-Cysteine 11.3 0.78 nm 26.2 0.370 nm 124
Phytoextract 9.75 0.906 nm 25 0.360 nm 130
Calcium carbonate N/A N/A 26.3 N/A 214
Caffeic acid 10.02 0.880 nm 24.79 0.359 nm 113
Carrot root 11.2 0.79 nm 23.96 N/A 134
Gallic acid 9.8 0.90 nm 26 N/A 115
Glucose amine 11.2 0.79 nm N/M N/A 52
Glycine 11.05 0.7997 nm 23.9 0.3718 nm 145
Iron powder 10.3 N/A 24.3 N/A 114
Metallic zinc 11.6 0.779 nm 24 0.368 nm 119
Cellulose 11.9 0.74 nm 22.5 N/A 156
Oxalic acid 11.9 0.743 nm 21.9 0.405 nm 157
PDDA 11.4 0.78 nm 20 N/A 159
Pyrrole 10.1 0.87 nm 20.1 N/A 161
Sodium acetate 11.2 0.790 nm 25.4 0.350 nm 165
Supercritical alcohol 11.76 0.752 nm 23–25 0.358–0.381 nm 127
Tannin 9.7 0.90 nm 26.3 0.340 nm 168
Tin powder 11 N/A 26.6 N/A 112
Tea solution 9.6 0.92 nm 24.6 0.340 nm 167
Yeast 11.32 0.7816 nm 23.5 N/A 169
a
N/A – not available.

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Fig. 9 TEM image of GO and RGO at lower magnification (a and b)
over a TEM grid with lacey carbon support.131 HR-TEM image (c) of
RGO is showing the formation of single layer graphene.214
218
with fold and scroll on its edges. It is attributed to the
intrinsic nature of graphene.169,219 Yu et al.219 claimed that the
corrugation can be present not only at the edge but also in the
middle of the nanosheets. It is responsible for the sheets to
look folded and coiled.119,124,134,219 Notably, high resolution
transmission electron microscopy (HR-TEM) is able to show
the number of layers at different locations of the sheets.134,145
With this technique, the measured lattice spacing of single
layer graphene is 0.345 nm.214 Some TEM and HR-TEM images
of RGO are portrayed in Fig. 9.
The structure of GO is different from RGO particularly in the
SAED analysis. This illustrates the crystalline structure or
hexagonal symmetry of the graphene layer. Aer chemical
reduction, strong and well-dened diffraction spots are
observed in the polycrystalline ring of SAED (Fig. 10b). This
result clearly conrms the destruction of inter layer coherence
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Fig. 10 SAED pattern of (a) GO and (b) RGO displaying six fold
symmetry.118
and random orientation of oxygen free sheets.127,145,148,151,159,169,220
The SAED patterns of GO and RGO are depicted in Fig. 10.
3.5.2. Scanning electron microscopy. The SEM is
commonly used to study the surface morphology of graphene,
GO and graphite. Generally, graphite sheets appears to be
heaped up in thick cakes.221 It also exhibits aky appearance
for the strong sp2 carbon to carbon bonding in the plane.131
In contrast, the GO nanosheets show wavy wrinkled appear-
ance under the SEM where the surface are hairy and coarse,
and the edges of the sheets are blurry.221 At higher concen-
tration the surface of the GO displays so carpet like
morphology which may be the attachment of residual water
molecules, carboxyl and hydroxyl groups with the sheets.147 In
RGO the nanosheets display thin and wrinkled texture. It is
caused by the stacking of individual sheets by various self-
assembly techniques. This is attributed to the intrinsic prop-
erties of graphene.75 However, the average lateral size of giant
GO sheets have been reported to be 18.5 mm with a relatively
wide size distribution ranging from one to several micro-
metres.222 Gurunathan et al.147 also used the SEM image to
count the average lateral size of GO and RGO. They found the
average lateral size of GO and RGO sheets are 8 and 10 mm,
respectively, although a wide range of sizes (between 2 and 20
mm) were analysed in the study. The SEM images of graphite,
GO and RGO are portrayed in Fig. 11.
3.6. Atomic force microscopy
AFM is a promising technique to measure the atomic steps
present on a surface. It is used to determine the morphology
and texture of the graphene materials. It also helps to determine
the exact Z-height and number of layers in the specimen. The
well-known van der Waals thickness of a pristine graphene
sheet is 0.34 nm and it is atomically at. Aer oxidation the
graphene oxide sheets are expected to be thicker due to the
presence of covalently bound oxygen on either side of the
sheets.99 The typical thickness of single layer GO sheets is 0.8
nm which is 0.44 nm thicker than that of pristine graphene.180
In the case of bi-layer graphene oxide, the thickness was found
to be 1.7 nm.134
Upon the reduction of GO the smaller thickness of RGO
sheets is a clear proof of oxygen elimination from the gra-
phene oxide.122,145,148,165,194 A AFM image of GO and RGO is
depicted in Fig. 12. But in several studies the thickness of
RGO was found to be higher than that of GO. It is attributed to
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Fig. 11 SEM image of (a) graphite, (b) GO131 and (c) RGO.214
either the binding of capping agents with the sheets or
restacking of sheets in the absence of stabilizer mole-
cules.134,168 For example, Akhavan et al.144 observed an
increased thickness of graphene caused by the attachment of
oxidized green tea polyphenols (GTPs) on both sides of the
RGO. Some of the similar types of results have been reported
in Table 9. Therefore, it is reasonable to conclude that the
stabilizer or capping reagent play an important role to
increase the thickness of graphene sheet, although most of
the oxygen-containing functional groups are vanished aer
the reduction.117 Notably, the stabilization mechanisms
between the reducer and the graphene layer are proposed to
be p–p interactions or hydrogen bonding.128,138 Here, the
capped molecules supply steric hindrance to stabilize the
graphene sheets.128,168 Beside thickness analysis AFM has also
been applied to analyse the lateral dimension of GO and RGO.
27820 | RSC Adv., 2016, 6, 27807–27828
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Review
Fig. 12 AFM image of (a) GO and (b) RGO.134
In one of our previous work Mehrali and co-workers measured
the average lateral dimension of GO and RGO around 3.88 
0.99 mm and 2.37  0.65 mm.178 This nding also pointed out
that the RGO sheets are laterally smaller than the GO sheet.
4. Conclusion and suggestions
The chemical reduction of GO is found to be very promising
technique to produce large scale functional graphene. The use
of eco-friendly reducing agents to synthesis graphene achieves
a great interest of the scientic community, evidenced by the
continuous increment of research publications on the topic. In
this review, the authors described some of the recent achieve-
ments in the green reduction of GO. It is considered as one of
the most versatile method. These types of reagents are seemed
to be an alternate of hydrazine or other poisonous reducing
agents. They are also safe to handle and the reaction coproduces
are biocompatible. But green reducing agents are not out of
limitations. Sometimes one agent cannot fully deoxygenate the
GO alone, but it needs the aid of a supporting reducing agent or
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Review RSC Advances

Table 9 A comparative study of the thickness of GO and RGO

Thickness of Number of Thickness of Number of Attachment of molecules on

Reducing agents GO (nm) layers RGO (nm) layers both side of the RGO sheets References

Alkaline conditions 1.2 Single 0.881 Single N/A 122

Caffeic acid 1.116 Single 0.846 Single N/A 113
Calcium carbonate + N/A N/A 2.5 4–10 N/A 214
magnesium
Carrot root 1.7 Bilayer 2.5 Restacked N/A 134
Curcumin 0.8 Single 1.5 Single Curcumin molecules 138
E. coli 1 Single N/A N/A N/A 223
Gallic acid 1.0 Single 1.0 and 1.4 Single N/A 115
Green tea polyphenol 1.19 Single 1.39 N/A Oxidized tea polyphenol (TP) 128
Green tea polyphenol + iron 1.2 Single Average 1.8, considered Single Oxidized greentea polyphenol (GTP) 144
one layer as 0.80 nm
Humanin N/A N/A Between 1 and 3 N/A N/A 147
Iron powder 1 Single 1–5 Multiple N/A 114
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L-Ascorbic acid 1.2 Single N/A N/A N/A 148

L-Cysteine 1 Single 0.8 Single 124
L-Glutathione N/A N/A 8 N/A Capping agent 149
L-Valine 1 Single 1 Single N/A 118
Melatonin 0.9 Single 1.8 (considered Single N/A 152
one layer as 0.80 nm)
Metallic zinc 1.22 N/A 0.93 Single N/A 119
Metal salts 1.50 N/A 0.86 Single N/A 153
Natural cellulose + ionic liquids 1 Single 1.9 N/A Cellulose chains 156
Pomegranate juice N/A N/A 0.67 Single N/A 160
Pyrrole 1.3 Single 2.7 N/A Stabilizer molecules 161
Reducing sugar 0.97 Single 1.1 Single Capping agent 117
Sodium acetate trihydrate 0.97 Single 0.79 Single N/A 165
Tannin 1.1 Single 1.5 Single Tannic acid (TA) 168
Tea solution 1 Single Average 2 N/A Tea polyphenol (TP) 167
Vitamin C 1 Single 1 Single N/A 120
Vitamin C + amino acid N/A N/A Average 2 N/A L-Tryptophan 129
Yeast 0.8 Single 1.2 Bilayer NADPH 169
Zn powder 1 Single 0.55 Single N/A 170
Zn powder + acid 1.2 Single N/A N/A N/A 171

surface modier. There is also a big possibility for the attach-
ment of addition functional groups or capping agents with the
sheets supplied by the reducers. This phenomenon can hamper
the electron conductivity of the sheets. Notably, The irreversible
aggregation, lower electron conductivity, increased thickness,
substrate specicity, chance of product contamination e.g.
mixing of metallic impurities when reduced with metal
powders, limited solubility, several downstream processing e.g.
repeated centrifugation or ltration to remove all the reaction
by-products and maintenance of complex or light sensitive
reaction system e.g. bacterial reduction of GO can be considered
as the limitations of the approaches. These drawbacks limited
their application to the laboratory and they are not yet
encouraged in the industrial batch production of graphene. To
overcome all the drawbacks is a challenging task for the
researchers in the eld.
The replacement of the toxic and harsh chemical agents with
mild reagents will be a big achievement of this study. More
studies can help to understand the exact reduction mechanism
of GO using most of the reported green reducing agents.
Theoretical calculations, modeling the interaction between GO
and reducing molecules could offer some solutions.
Acknowledgements
“The authors are thankful to University of Malaya for nancial
support under the High Impact Research MoE Grant: UM.C/
625/1/HIR/MoE/ENG/40 (D000040-16001) from the Ministry of
Education Malaysia.”
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