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Bio-inspired unprecedented synthesis of reduced

graphene oxide: a catalytic probe for electro-/
Cite this: New J. Chem., 2018,
42, 2067 chemical reduction of nitro groups in an aqueous
medium†
Suhasini Mahata,a Anjumala Sahu,a Prashant Shukla,b Ankita Rai, b

Manorama Singh a and Vijai K. Rai *a

Received 2nd December 2017,
Accepted 23rd December 2017
DOI: 10.1039/c7nj04732k
rsc.li/njc
The first green reduction of graphene oxide (GO) using cashew leaf extract as biorenewable reducing
agents containing water soluble tannins and gallic acid is reported herein. The synthesized rGO has
been well characterized by TEM, SEM, XRD, FTIR, Raman, UV-vis spectroscopy, and cyclic voltammetry.
A catalytic probe for electro-/chemical reduction of a nitro group into an amino group in an aqueous
medium was also performed successfully.

The graphene community has shown significant promise in In view of filling the remarkable gap in the literature and in
various potential applications due to its remarkable features.1–4 continuation of our ongoing efforts to develop a synthetically
Single-layer graphene is hundred times more chemically reactive useful green process,29 especially for graphene fabrication,30 we
than multilayer graphene. The large scale production of superior are first to exploit the leaf extract of Anacardium occidentale Linn
graphene sheets via an easy, cost effective, and green processing (Cashew) to produce single layer graphene sheets (Scheme 1).
route is the principal approach on which the applications of In the present study, the driving force to use cashew leaf extract
graphene depend.5–9 To date, a number of approaches, such as for the production of rGO is based on the constitution, such as
chemical vapour deposition (CVD),10 electronic arc discharge,11 quercetin, glycosides, condensed tannins, and phenolic acids,31 and
epitaxial growth on electrically insulating surfaces i.e. SiC,12 ability of this extract to reduce various metallic nanoparticles.32a–d
micromechanical-13/thermal exfoliation,14 direct sonication,15 The leaf extract of cashew contains polyphenols, such as
microwave assisted,16 photocatalytic,17 and chemical oxidation– catechin and quercetin, which readily get oxidized to the
reduction method,18–21 have been reported for the synthesis of corresponding quinone moiety. Presumably, the EWGs of quercetin
single layer graphene sheets. Furthermore, in literature, several and catechin rings make the O–H bonds much more acidic, which
bioreducing agents, such as vitamins,22 amino acids,23 micro- readily get dissociated and act as an excellent nucleophile. This
organisms,24 proteins, peptides,25 hormones,26 and plant O-nucleophile attacks on the electrophilic carbon of epoxide in
extracts,27,28 have been reported for the reduction of GO to
rGO. Among these, plant extracts have attracted significant
interest due to their huge bio-availability and low cost for bio-
reduction of GO. However, most of the reported methods suffer
from one or more disadvantages such as expensive reagents,
hazardous chemicals,19–21 low yield, longer reaction time,22–26
high consumption of extract, higher reaction temperature,27,28
and poor structure of graphene. Therefore, the synthetic
community still has a great challenge to develop a non-toxic,
economical, and green method using bio-renewable reducing
agents for the reduction of GO to produce high quality graphene
sheets.

a
Department of Chemistry, Guru Ghasidas Vishwavidyalaya,
Bilaspur (C.G.)-495009, India. E-mail: vijaikrai@hotmail.com; Tel: +91-7587178627
b
School of Physical Sciences, Jawaharlal Nehru University, New Delhi, 110027, India
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c7nj04732k Scheme 1 Schematic of the synthesis of reduced graphene oxide.

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GO, causing epoxide opening to relieve the ring strain through

an SN2 mechanism, followed by dehydration.
Similarly, this polyphenol moiety reacts with the reactive
hydroxyl and carbonyl groups in GO by nucleophilic attack
along with release of a water molecule and successfully produce
reduced graphene oxide. The plausible mechanism for the
reduction of GO to rGO is shown in Scheme 2.33
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GO has been synthesized by the oxidation of graphite flake

using the modified Hummers method.34 The reduction of GO
using cashew leaf extract was performed at 68 1C for 3 h under
heating conditions. This proposed method is better as compared
to those reported in other studies28a–f in terms of amount,
processing time of reduction, and temperature (Table 1). At the
outset, the dispersibility of CLRG 1, 2, 3, and 4 was investigated
along with GO and chemically reduced graphene (CRG). A black
homogenous colour was observed after immediate dispersion of
CLRG 1–4 (0.1 mg mL 1) in water. In the preliminary experiment,
the effect of temperature and reaction time on dispersion was
Scheme 2 Plausible mechanism for the reduction of GO with cashew leaf
extract.
Fig. 1 Images of water dispersibility of GO and various CLRG4s under
different reduction conditions as compared to that of chemically reduced
graphene oxide (CRG; prepared with NaBH4).
optimized. The images of all GO reduced by the cashew leaf
extract (40 mL) at different reaction temperatures and times as
compared to dispersed GO and CRG are shown in Fig. 1. The
CLRG 4 prepared at 45 1C and 58 1C could not reduce GO
(Table 2, entries 1 and 2), whereas those prepared at higher
temperatures showed short-term stability and precipitated
out (Table 2, entry 4). Interestingly, the CLRG 4 prepared
at 68 1C resulted in satisfactory dispersion with negligible
sediment settlement only in 3 h (Table 2, entry 3), with
relatively long-term stability even after 1 week. Presumably,
this may be due to the removal of polar oxygen-containing
groups and re-establishment of p–p interaction between
adjacent layers.

Table 1 Comparative study of the plant extracts utilized in the reduction of GO

Green reducing agents
Wild carrot root extract
Drained water from soaked
mung beans (Phaseolus aureus L.) beans into 100 mL DI water
P. pectinatus plant
Salvadora persica L. root
(Miswak) extract
Cherry leaf, Magnolia leaf,
Persimmon leaf, Ginko leaf,
Maple leaf, Plantanus leaf
Oak apple (fruit)
Green tea powder solution
Carrot root extract
Rose water
C. esculenta leaf, M. ferrea
L leaf, Citrus sinensis peel
Cashew nut leaf
Extract preparation process GO reduction process Condition Ref.
5 g sliced carrot 5 g sliced carrot + 200 mL GO suspension 48 h stirring at 28a
(0.5 mg mL 1) RT + 24 h reflux
at 100 1C
Drained water of 10 g soaked mung 100 mg GO in 100 mL DI water + 100 mL 24 h RT (30  2) 1C 28b
drained water
500 g plant powder in 80 mL DI water 80 mL plant extract 24 h at 90 1C 28c
Refluxed 1.3 kg soaked root in 3 L for 200 mg GO in 40 mL of DI water. 10 mL, 24 h at 98 1C 28d
4 h, Filtered and dried at 50 1C 20 mL, and 50 mL of root extract
(100 mg mL 1)
Boiled 5 g dried crushed leaf in Refluxed 20 mL plant extract in 100 mL 12 h at 95 1C 28e
100 mL sterile DI water for 5 min. GO (0.5 mg mL 1) in oil bath
Decanted and stored at 4 1C
— 400 wt% relative to GO 10 h at 80 1C 28f
Boiled 2 g tea powder in 100 mL DI Refluxed 50 mg GO in 100 mL tea powder 2 h at 90 1C 27a
water at 100 1C for 20 min; filtered off extract
to get extract
Boiled 20 g carrot in 100 mL at 100 1C 20 mL of 1 mg mL 1 GO suspension in 2 h at 90 1C 27b
for 50 min and filtered. DI water + 200 mL 1 M NaOH + 100 mL
carrot extract
10 mL rose water 10 mL rose water (12%) + 10 mL GO 5 h at 95 1C 27c
suspension (7 mg mL 1)
Stirred a certain amount in 50 mL DI Refluxed 60 mg GO in 120 mL DI water + 8–10 h at 100 1C 27d
water at 50 1C for 20 min 10 mL of aqueous phyto-extract
Heated 5 g cashew nut dried leaves 10 mg GO in 10 mL of DI water 3 h at 68 1C Present
powder in 100 mL for 30 min at 50 1C work
10 mL, 20 mL, 30 mL and 40 mL of leaf
extract (1 mg mL 1)

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Table 2 Optimization of the reaction conditions for the reduction of GO
a which indicates the best reduction of GO using cashew leaf
Entry Sample GO (mg) Vol. (mL) Temp. (1C)
1 CLRG 4 10 40 45
2 CLRG 4 10 40 58
3 CLRG 4 10 40 68
4 CLRG 4 10 40 75
a
10 mg GO was taken in DI water (1 mg mL 1).
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Next, to ensure the reduction and extent of reduction of GO
for 3 h at 68 1C using different volumes of cashew leaf extracts
as a mild reducing agent, the following experiments were
carried out, and we adopted optical measurements to find
out the color change occurring before and after the reduction
of GO directly. Herein, we dispersed 10 mg of graphene oxide in
deionized water (1 mg mL 1) and prepared four different
samples of leaf extract-reduced graphene oxide (CLRGs): CLRG
1: prepared using 10 mL cashew leaf extract; CLRG 2: prepared
using 20 mL leaf extract; CLRG 3: prepared using 30 mL leaf
extract; and CLRG 4: prepared using 40 mL leaf extract. The
UV-vis spectra were obtained for the reduction procedure using
a UV-vis spectrophotometer (Fig. 2A). GO shows a characteristic
absorbance peak at 234 nm, which is attributed to the p - p*
transition of the graphitic C–C bond, and a very weak shoulder
absorbance peak at 304 nm for the n - p* transition of CQO
bonds. Furthermore, we progressively examined CLRG 1, CLRG
2, and CLRG 3, respectively. No dramatical change in the peak
position was noticed in the case of CLRG 1 and CLRG 2, but in
the case of CLRG 3, a gradually red shift was observed from
234 nm to 276 nm, which appeared as a distinct peak for the
re-establishment of electronic conjugation in graphene nanosheets.
Amongst these, the best reduction was achieved by CLRG 4 as
the characteristic peak shifted towards 283 nm. Herein, we have
compared the results with those of other chemically reduced19,20
or green reduced23,24 GO reported in previous studies and
Fig. 2 (A) UV-vis spectra of GO, CRG, and CLRG (10–40 mL). (B) XRD
pattern of GO and CLRGs. Inset: XRD pattern for CLRG 4. (C) FTIR spectra
of GO, CLRG 4, and pure cashew leaf extract (CL Ext.) before reduction.
(D) Raman spectra of CLRG 1–4.
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investigated that the absorption peak shows a higher red shift,
Time (h)
extract as a bio-renewable reducing agent.
5 The reduction was observed by UV-visible spectra with
5
3 different concentrations of cashew leaf extract. The UV-visible
5 spectra show that maximum reduction is achieved with 40 mL
cashew leaf extract at 68 1C for 3 h. The prepared CLRG 1–4
have been characterized using Raman spectrometry, Fourier
transform infrared (FTIR) spectrometry, X-ray diffraction (XRD)
analysis, scanning electron microscopy (SEM), and transmission
electron microscopy (TEM). The bio-reduction of GO was con-
firmed by the XRD pattern (Fig. 2B). For graphite powder, a
sharp peak at 26.511 (002) was observed corresponding to the
interlayer spacing of 3.56 Å. After the chemical oxidation of
graphite and exfoliation, the 26.511 peak disappeared, and a
broad diffraction peak (002) appeared, which was centred at
10.441 with the corresponding interlayer spacing of 8.46 Å.
During reduction, the sharp peak at 10.441 of GO was decreased,
and a new broad peak appeared at 26.551, 26.511, and 26.361 for
the basal plane (002) with the interlayer spacings of 3.35 Å,
3.28 Å, and 3.37 Å for CLRG 1, CLRG 2, and CLRG 3, respectively,
which was much similar to the 2 theta value for graphite. In
addition to this, CLRG 4 shows better reduction with the XRD
peak at 2y = 23.561 (d-spacing 3.77 Å) than other CLRGs. The
d-spacing was decreased due to the removal of maximum
oxygen-containing groups in GO.
In the FTIR spectra (Fig. 2C), an intense and broad peak at
3413.34 cm 1 for O–H str. vibrations, a strong band at 1717.72 cm 1
for the {CQO group of –COOH present at the edge of GO, and
a peak at 1621.94 cm 1, a resonance peak assigned to the str.
and bend vibrations of –OH groups of water molecules adsorbed
on GO, were observed. The peaks at 1326.36 cm 1 and
1245.66 cm 1 denote the C–OH group and epoxy (C–O) groups
and that at 1064.06 cm 1 denote C–O (alkoxy) str. vibration,
respectively. After the bio-reduction of graphene oxide, the peaks
belonging to the COO– groups, –OH groups of water molecules,
and epoxy groups completely disappeared, the intensity of hydroxyl
functional groups significantly decreased, and a new intense peak
arose at 1569.08 cm 1 attributed to the restoration of electronic
configuration in the graphene sheets. FTIR analysis of pure cashew
leaf extract (CL Ext.) was conducted to ensure the presence of
different varieties of secondary metabolites viz., tannins, alkaloids,
flavonoids, phenolic compounds (quercetin, catechin, tetramer of
proanthocyanidin, gallic acids, anacardic acids etc.). Broad and
intense peaks at 3474 cm 1 (hydroxyl functional groups),
1634.38 cm 1 (amide I-band of proteins), and 2074.72 cm 1
(C–H str. of hydrocarbon chain) symbolize the presence of electron
rich groups, proteins, polyphenols etc., which play an important role
as bio-reducing agent as well as stabilizing agents.
Raman spectroscopy is a very popular and dominant non-
destructive technique that estimates the electronic band structure
of graphite and graphene-based materials. Raman spectra of CLRG
4 were obtained and compared with those of other batches of
CLRG 1, 2, and 3 (Fig. 2D). The Raman spectrum of defect-free
graphene shows a G band, a 2D band, and a sharp D-band,
which measure the disorders and appear due to the A1g mode of
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Table 3 Comparison of the measured Raman parameters of CLRG 1–4 supported by an amorphous diffraction pattern (inset, Fig. 3c).
1 1 1 On the other hand, a transparent and folded layer (Fig. 3d)
CLRGs D band (cm ) G (cm ) 2D (cm ) ID/IG
indicates the formation of single-layered reduced graphene
CLRG 1 1308.82 1603.27 2671 0.84 oxide with a re-established crystalline state (inset, Fig. 3d).
CLRG 2 1303.33 1597.78 2673 0.86
CLRG 3 1308.35 1597.83 2691 0.91 As a probe, the electrocatalytic application of synthesized
CLRG 4 1313.82 1596.04 2682 1.01 CLRG 4 was also investigated using CLRG 4-modified GC
electrode for electrochemical reduction of nitromethane in an
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symmetry. The G-band arises at 1575 cm 1 for the E2g mode of
sp2 carbons in both rings and chains, whereas the D-band at
1350 cm 1. After the bio-reduction of GO, the G-band in CLRG 4
was shifted from 1575 to 1596 cm 1, and a slightly narrower
peak was found, whereas the shift in the D-band was observed
from 1350 to 1313 cm 1. The intensity ratio of CLRG 1, 2, 3, and
4 was calculated, and it was found that the ID/IG ratio increased
significantly with an increase in the volume of leaf extract used
than the intensity ratio in GO (Table 3). This observation confirms
the removal of oxygen functionalities and the restoration of the sp2
network during reduction and finally indicates the degree of
disorders such as defects, ripples, and edges. A weak peak at
2671–2691 cm 1 for the 2D band, originating from the two
phonon double resonance process, suggests the formation of
few layered graphene.35 This 2D band is related to the band
structure of graphene layer peak and indicates the complete
reduction of GO to rGO using cashew leaf extract (2D is almost
absent in GO).
The SEM image (Fig. 3a) of CLRG 4 shows a flake-like sheet
and is obtained at 30 keV. The EDX spectra (Fig. 3b) of CLRG
4 show 87.98% of carbon and a trace amount of unreduced
oxygen. According to the EDX analysis, the carbon to oxygen
ratio in graphene after reduction is about 7.3, indicating that
only 12% oxygen is left for reduction. The HR-TEM image of GO
(Fig. 3c) consists of aggregated disordered layers, which are
aqueous medium at 0.89 V (vs. Ag/AgCl). In this regard,
electrochemical experiments were performed on the prepared
CLRG 4-modified GC electrode. Cyclic voltammograms (CV) of
reduced GO were obtained in water with KCl as a working
solution at the scan rates of 5, 10, 20, 50, 100, 200, 300, and
400 mV s 1 (vs. Ag/AgCl) (Fig. 4A). The CV was obtained in the
potential range from 1.0 to 1.0 V (vs. Ag/AgCl), which indicated
that the active electron transported successfully on the immobilized
CLRG 4 film on GCE. The cathodic and anodic current increased
with the increasing scan rates from 5 to 400 mV s 1. The observed
CVs are distorted rectangular in shape with no significant redox
couples, and the current increases with the increase in scan rates
progressively. At lower scan rates, the ionic moieties and scan rates
are in equilibrium, resulting in distorted CV curves.
However, at high scan rates, the CV curves are completely
distorted from the rectangular shape possibly due to the speedy
movement of ions in the solution. On the other hand, the
establishment of symmetric adsorption is a very slow process,
which is governed by the diffusion film width at the electrode–
electrolyte interface. This observation is in better agreement
with the CV behavior of CLRG 4.
The differential pulse voltammogram (DPV) was obtained in
water with KCl for the electro-reduction of nitromethane with
four different concentrations utilized: 0.05 mM (curve b),
0.1 mM (curve c), 0.15 mM (curve d), and 0.2 mM (curve e).
Moreover, a control experiment on GO-modified GCE for the
reduction of nitromethane was performed (curve a) (Fig. 4B).
The stock solution of nitromethane was prepared by direct
dilution with required amount of water. Nitromethane undergoes
green reduction to methylamine, and the reduction current (ic)
increases with the increasing concentration of nitromethane.
Further, the biological reduced GO-modified GCE could be an
attractive and excellent platform for sensing purposes.

Fig. 3 (a) SEM image of CLRG4, (b) EDX image of CLRG4; HR-TEM image
of (c) GO and (d) CLRG4 (inset: SAED pattern).
Fig. 4 (A) CV of CLRG 4-modified GCE at the scan rate 5, 10, 20, 50, 100,
200, 300, and 400 mV s 1 in water with KCl; (B) curves a–e; (a) DPV of
electro-reduction study of nitromethane on CLRG4/GCE in the presence
of 0.05 mM, (b) 0.1 mM, (c) 0.15 mM, (d) 0.2 mM, and (e) through
differential pulse voltammetry at 10 mV s 1 in water with KCl.

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Scheme 3 Reduction of nitrobenzene using CLRG 4.
The catalytic activity of cashew leaf-reduced graphene oxide
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(CLRG 4) has been investigated for the reduction of nitro-
benzene using hydrazine hydrate as a reducing agent, and
aniline, which is a widely useful intermediate and substrate
for chemical industry, has been successfully produced.
Carbocatalysts play an important role as adsorbents and
electrical conductors; thus, both oxidants and reductants are
adsorbed on the material surface, and electrons can flow
through it to precede the reaction. Graphene oxide contains
an ample number of reactive oxygen-containing groups such as
hydroxyl, epoxide, carboxylate, and carbonyl groups, which also
influence the reduction process. Due to these literature reports,
we decided to utilize graphene-based materials for the reduction
of nitrobenzene to aniline (Scheme 3).
In our optimization experiments, various catalysts viz. graphitic
oxide, Fe3O4–GO–DMAP, GO, rGO etc. were screened (Table 4) and
prepared by the reported methods: GO,34 graphitic oxide,38a
Fe3O4–GO–DMAP,30a and rGO.38b Initially, we performed a blank
test (0.5 mL nitrobenzene and 0.4 mL hydrazine hydrate were
refluxed at 70 1C in 1 mL DI water), and no product formation was
indicated by TLC even after 8 h refluxing. This clearly indicates
that hydrazine hydrate alone is unable to reduce nitrobenzene.
This is because of the mismatch of electronic requirements for the
reduction of nitrobenzene as the process follows the six-electron
process (Scheme 4), whereas hydrazine is a two-electron reducing
agent.36 Among various catalysts screened for the reduction of
nitrobenzene to aniline, CLRG 4 was found to be the best in terms
of yield and conversion rate (Table 4). Thus, CLRG 4 successfully
reduced nitrobenzene into aniline in 94% yield only in 4 h. The
reason for the higher catalytic efficiency of CLRG 4 than that of the
chemically reduced GO is presumably the presence of several
defects and unsaturated carbon atoms at its edge in the prepared
CLRG 4 as well as its single layered structure37 (Fig. 3d).
Table 4 Screening of the catalyst for the reduction of nitrobenzene in an
aqueous medium
Entry Catalyst Timea (h) Yieldb,c (%)
1 None 8 —
2 Carbon black 8 13
3 Activated carbon 4 38
4 Natural graphite 6 8
5 Graphitic oxide 4 20
6 Fe3O4–GO–DMAP 4 25
7 Graphene oxide 4 82
8 RGOd 4 85
9 CLRG 4e 3 94
Reaction condition: 0.5 mL (4.8 mmol) nitrobenzene, 0.4 mL hydrazine
hydrate, 1 mL DI water, refluxing at 70 1C, 5 mg catalyst.a Stirring time for
completion of the reaction at room temperature. b Yield of isolated and
purified product. c Characterized by IR, 1H NMR, and 13C NMR spectral
data. d Chemically reduced graphene oxide (RGO). e Cashew leaf extract-
reduced graphene oxide (CLRG 4, 5 mg).
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Scheme 4 Plausible mechanism for the reduction of nitrobenzene.
The reduction of the nitro into amine group was confirmed
by comparing the FTIR spectra of nitrobenzene and the prepared
aniline (Fig. S1, ESI†). In the IR spectrum of aniline, two sharp
bands at 3426.81 cm 1 and 3360.45 cm 1 were obtained due to
N–H str. vibrations (asymmetric and symmetric) along with a
weak band at 3219.99 cm 1 for the N–H str. vibration (N–H


N
hydrogen bonds). Absorptions at 3027.64 cm 1 and 1615.15 cm 1
were obtained forQC–H str. and CQC str. Vibration, respectively,
in aromatic nuclei. The C–N primary aromatic amines showed the
characteristic bands at 1301 cm 1 and 1278 cm 1. On the other
hand, nitrobenzene showed two strong bands at 1531.92 cm 1 and
1366.98 cm 1 for the NQO str. vibrations.
The characteristic NQO str. at 1531.92 and 1366.98 are now
completely removed, and a significant peak at 1278.42 cm 1
appears for the C–N str. in primary aromatic amines.
The formation of aniline was further confirmed by 1H NMR
(Fig. S2, ESI†) and 13C NMR (Fig. S3, ESI†) spectroscopy. A singlet at
d 4.14 is attributed to two hydrogens of the –NH2 group. Moreover,
three sets of equivalent proton appeared at the low field, indicating
that they were more deshielded due to being directly linked to the
benzene ring. The 2H doublet at d 6.68, 1H triplet at d 6.75 ppm,
and 2H double doublet at 7.15 were found in the 1H NMR spectrum.
The 13C NMR spectra of aniline showed four peaks at d 146.47,
129.34, 119.60, and 115.1 for aromatic sp2 hybridized carbons.
In summary, we have demonstrated a simple, cost effective
synthesis of rGO using cashew leaf extract as a bio-renewable
catalyst. The envisaged method has significant advantages of
restoring the electronic conjugation in graphene sheet along
with the removal of oxygen-containing functionalities of GO.
This green method provides a large-scale production of high
quality polycrystalline graphene sheets and has potential appli-
cation in electrochemistry as well. Moreover, the prepared rGO
efficiently catalyses the electro-/chemical transformation of
nitro to amino group; this indicates that it’s a valuable method
to cater the need of industries and academia.
Preparation of cashew leaf extract
The preparation of aqueous cashew leaf extract was as follows:
5 g powder of dried cashew leaves was dispersed in 100 mL
distilled water, and the solution was gradually heated for 30 min
up to 50 1C. A pale yellow colour solution was obtained, cooled
down, and filtered. The prepared filtrate was called cashew leaf
extract, and its pH was measured to be 6.0.
Synthesis of rGO using cashew leaf
extract
For the reduction of GO, 10 mg of GO was dispersed in 10 mL
distilled water and stirred for 30 min to make a homogeneous
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suspension. Then, 40 mL of the prepared cashew leaf extract
(1 mg mL 1) was added to this and stirred vigorously for 3 h by
increasing the reaction temperature up to 68 1C. Initially, the
brownish colour solution started turning black gradually, and
finally, after 3 h, a dark black colour solution was obtained. The
reaction solution was cooled down to room temperature and
washed 5 times with a mixture of distilled water and ethanol.
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After centrifuging it at 3500 rpm, a black solid mass was
obtained and dried in vacuum. It is named as a cashew leaf
extract-reduced graphene oxide (CLRG) (Scheme 1).
General method for the reduction
of nitrobenzene
Initially, 5 mg CLRG 4 was dispersed in 1 mL DI water for 30 min
in a 50 mL round bottom flask. Then, 0.5 mL nitrobenzene and
0.4 mL hydrazine hydrate were added. The whole reaction mixture
was refluxed for 4 h. After the completion of the reaction as
indicated by TLC, 20 mL of distilled water was added, and the
product was extracted with ethyl acetate (3  5 mL). The combined
organic layer was then dried over anhydrous Na2SO4, concentrated,
and evaporated under vacuum to afford the crude product.
Electrochemical measurements were performed using CHI610E
series (CHI, USA). Electrochemical studies were performed using a
three-electrode system consisting of modified GCE as the working
electrode, an Ag/AgCl reference electrode, and platinum wire as the
counter electrode. All measurements were conducted in 4 mL of
water. The whole assembly was purged with nitrogen gas for 10 min
before experiments.
Spectral data of PhNH2
Pale yellow liquid (95%), IR (KBr) nmax 3463, 3389, 3221, 1601,
1521, 1478, 1310, 1245 cm 1. 1H NMR (CDCl3/TMS) d: 7.15 (dd,
2Harom, J = 7.2, 0.8 Hz) 6.75 (t, 1Harom, J = 7.6 Hz), 6.68 (d, 2H arom,
J = 7.2, 0.8 Hz), 4.14 (s, 2H, N–H). 13C NMR (CDCl3/TMS) d: 115.2,
118.6, 129.3, 146.4. EIMS (m/z): 93 (M+). Anal. calcd for C6H7N:
C, 77.38; H, 7.58; N, 15.04. Found: C, 77.54; H, 7.41; N, 14.88.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We sincerely thank the SERB (No. SR/FT/CS-99/2010), DST, for
partial financial support, AIRF, Jawaharlal Nehru University,
New Delhi, for providing TEM, Raman, and XRD spectra, and
Gandhigram rural institute, Tamilnadu, for SEM characterizations.
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