Research Article
ChemistrySelect doi.org/10.1002/slct.202400820
Green Chemistry Approach for One-Step Synthesis of
Iodinated Graphene Material for Supercapacitor
Applications
Alvin Kalicharan,[a] Jayaraman Pitchaimani,[b] C. Barath Kanna,[c] Vudata Rajesh,[d]
Mohan Rao Tamtam,*[e] Ravindranadh Koutavarapu,*[f] P. Baby Shakila,*[g] and
Pugalenthi Ramesh*[g]
Iodinated graphene is a promising 2D material with unique
physical and chemical characteristics. A new synthesis method
that combines iodine intercalation and surface reduction of
graphite sheets in a single step was developed. This method
uses NaIO4 and m-CPBA to efficiently incorporate iodine and
selectively remove oxygen from the graphene network at room
temperature. The presence of iodine moieties in the graphene
network was confirmed using various techniques such as XPS
photoelectron spectroscopy, HR-TEM, XRD, FT-IR, TGA, and
Raman spectroscopy. The high iodine content of the material
Introduction
Electrochemical supercapacitors have gained significant atten-
tion in recent decades owing to their unique properties such as
fast charging, stable cycling characteristics, flexibility, low
[a] A. Kalicharan
Department of Chemistry, Panimalar Engineering College, Chennai, Tamil
Nadu 600123, India
[b] J. Pitchaimani
Department of Chemistry, Sri Sai Ram Institute of Technology, West
Tambaram, Chennai, Tamil Nadu 600044, India
[c] C. Barath Kanna
Department of Electrical and Electronics Engineering, Sri Sairam Engineer-
ing College, West Tambaram, Chennai, Tamil Nadu 602109, India
[d] V. Rajesh
Department of Chemistry, V.R. Siddhartha Engineering College, Kanuru,
Vijayawada, Andhra Pradesh 520007, India
[e] M. R. Tamtam
Data Science Lab, Department of Information and Communication
Engineering, College of Mechanical and IT Engineering, Yeungnam
University, Gyeongsan 38541, Republic of Korea
E-mail: mohantamtam@yu.ac.kr
[f] R. Koutavarapu
Physics Division, Department of Basic Sciences and Humanities, GMR
Institute of Technology, Rajam, Andhra Pradesh 532127, India
E-mail: ravindranadh.k@gmrit.edu.in
[g] P. Baby Shakila, P. Ramesh
Department of Biochemistry, Department of Chemistry, Vivekanandha
College of Arts & Sciences for Women (A), Tirchengode, Namakkal, Tamil
Nadu 637205, India
;
E-mail: babyshakilaodc@gmail.com
drramesh2608@gmail.com
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202400820
ChemistrySelect 2024, 9, e202400820 (1 of 8)
www.chemistryselect.org
enhanced the d-spacing and ion mobility of the electrolyte,
thereby improving the storage capacity. In addition, the
potential of iodinated graphene as an electrode material was
investigated through EIS, CV, and GCD using 1 M H2SO4 solution
as the electrolyte. The iodinated graphene material exhibited
EDL capacitance and demonstrated an impressive specific
capacitance of 535.4 F g 1 at a high rate, with a current density
of 1 A g 1. Moreover, it exhibited exceptional stability over 5000
cycles. These halogenated graphene derivatives are attractive
options for use in supercapacitors.
weight, and environmental friendliness.[1] The electrochemical
supercapacitor process can be divided into two phases: electric
double-layer capacitors (EDLC) redox supercapacitors (PC), and
hybrid capacitors.[2] EDLCs rely on the accumulation of charges
that adhere to the electrode-electrolyte interface, whereas
pseudocapacitors rely on Faradaic processes. Two-dimensional
(2D) layered materials such as graphene have excellent electron
transport properties, fine wettability, cost-effectiveness, expan-
sive surface area, and resistance to chemicals and electro-
chemical processes, making them highly suitable for EDLCs.[3,4]
Graphene, in particular, has sparked widespread interest in
supercapacitor research owing to its 2D structure, which gives it
unique properties, such as outstanding electrical conductivity,
mechanical characteristics, and larger surface area than CNTs.
Graphene is a carbon-based material used in supercapacitor
applications owing to its distinct advantages. It offers excep-
tional suitability owing to its dual accessibility to the electrolyte
and consistent surface area, regardless of the pore size
distribution.[5,6]
Several types of graphene and GO derivatives, especially
those mixed with heteroatoms (such as B, P, O, N, and S), have
been thoroughly examined for various applications.[7–11] There is
a lot of debate that heteroatoms undergo more nucleophilic
reactions; this has been done to multifunctionalize the GO
interface. The chemical functionalization of graphene can also
be customized using halogen-functionalized graphene materi-
als, which are used in bandgap engineering of graphene
groups. Among these materials, fluorinated and brominated
graphenes have received considerable attention in a wide range
of fields and are members of the halogen family.[12] Although
this material exhibits a variety of unusual features, it cannot be
chemically modified further because of its comparatively strong
© 2024 Wiley-VCH GmbH
 Research Article
ChemistrySelect doi.org/10.1002/slct.202400820
C F and C Br bonds.[13] In this case, iodinated graphene (C I)
may be a fascinating material. This material can be employed as
both a flame retardant and potent forerunner for the iodination
of other chemicals. Iodinated GO and RGO materials can be
used in various applications such as sensors,[14] catalysts,[15] solar
cells,[16] and batteries.[17] In terms of supercapacitance, the
electrical conductivity of graphene can be increased using the
powerful p-type dopant iodine through a charge-transfer
process, which improves the capacitive performance of the
devices. Iodine functionalization improves the electrical con-
ductivity, which increases rGO utilization and yields superior
capacitive performance. This improved electrical conductivity
facilitates ion and electron transfer, leading to improved rate
performance.[18] Therefore, it is unexpected that few studies
have focused on the production of iodinated graphene
compounds. Furthermore, no substantial organized research
has been published.
Pumera et al. presented a scalable process to introduce
halogen (Cl, Br, and I) groups onto a graphene surface.[19] These
chemically bonded halogen atoms constitute the fundamental
building blocks of graphene nanostructures. Sofer et al. experi-
mented with various processes to convert thermally reduced
graphene and graphene oxide into chlorinated graphene
derivatives.[20] Brominated graphene derivatives can be pre-
pared in various ways, with excellent potential for the
bromination of graphite oxide derivatives as a starting point for
further chemical alterations or as reversible bromine storage
systems.[21] Chlorine-doped RGO has been described as a
reliable and effective electrode for supercapacitors in acidic
media.[22] In 1 M H2SO4 aqueous media, the specific capacitance
of the chlorinated RGO electrode material was 178 F g 1. Naji
et al. reported the incorporation of iodine into graphite during
a reduction reaction by hydrogen iodide.[23] The potential of the
iodinated reduced graphene oxide enhanced the band gap,
charge carrier, and charge density electrochemical properties. Li
et al. doped a graphite surface with iodine using HI via a
hydrothermal process.[24] These results demonstrate that the
iodine doping behavior in rGO may enhance the electro-
chemical performance of the graphene anode surface for SIBs.
Wadekar et al. reported iodine-functionalized reduced graphene
oxide (I@RGO) as an active oxygen reduction reaction (ORR)
electrocatalyst and an energy storage component for super-
capacitors. Additionally, the material displayed specific capaci-
tance of 242 F g 1 and energy density of 27.2 Wh kg 1 at a
current density of 1 A g 1.[25] Flexible RGO films and RGO
powders were produced by Kamila et al. using the HI reduction
technique, and their electrochemical energy storage potentials
in supercapacitors were examined. When graphene is doped
with iodine, the specific capacitance rises from 73 F g 1 to
122 F g 1. At a scan rate of 1 mVs 1, the RGO/P provides
233 F g 1 of specific capacitance.[26] High-temperature/pressure
reactions in an autoclave with HCl and HI reflux were used by
Sofer et al. to synthesize a high amount of iodine on the
graphite surface. This dramatically improved the thermal
stability and increased the combustion temperature,[27] com-
pared with graphite oxides that were not doped. Based on the
above studies, there are no direct chemical methods for the
ChemistrySelect 2024, 9, e202400820 (2 of 8)
synthesis of heteroatom-doped rGO and graphene derivatives.
Most of the reducing agents are produced in toxic environ-
ments. However, the incorporation of heteroatoms or the
removal of oxygen from the surface of graphite must cross over
the intermediate graphene oxide product. Our previous
research illustrated an uncomplicated one-pot approach to
introduce iodine and oxygen onto graphite surfaces, employing
cost-effective oxidizing agents such as NaIO4 and m-CPBA,
which are completely consumed and, the reaction does not
require any subsequent reducing agents to reduce i-GO into i-
RGO.[28] We prepared iodinated rGO with simultaneous iodine
intercalation and selective deletion of oxygen from the graphite
surface in a single-step process using a nonmetallic approach
with NaIO4 and m-CPBA. In this continuation, a large-size iodine
(IO4) ion easily replaced an SO42 ion and enhances d-spacing
between graphene layers. Although m-CPBA is a good oxidizing
agent, in the presence of concentrated H2SO4 it supported the
hydrolysis process under exothermic conditions with the
deletion of oxygen and the formation of a monolayer of
iodinated graphene. This method promotes metal-free and
non-toxic electron transfer on monolayer graphene surfaces. In
addition, based on the green chemistry approach, we did not
use any reducing agents separately for i-GO reduction to avoid
extra waste formation. Moreover, we performed the reaction in
a single step for i-reduced GO synthesis with more advanta-
geous waste, as we know that traditional methods follow
multiple steps to synthesize functionalized reduced GO.
Herein, we report an iodine-incorporated graphene material
in a one-pot synthetic methodology by using NaIO4 and m-
CPBA as oxidizing and iodinating agents at room temperature
for supercapacitor application (Figure 1). NaIO4 is effectively
supported in the iodination and oxidation processes, and the
effective deoxygenation of i-GO takes place to produce i-
graphene when m-CPBA is added to the mixture with H2SO4 via
an exothermic process.[29] The iodine functionality on the
graphene surface increases the sheet d-spacing, thereby
enhancing the ion mobility and bolstering the cyclic stability of
the graphene surface. GCD, EIS, and CV studies showed that the
i-graphene electrode material displayed a favorable capaci-
tance. These graphene materials with iodine functionalities
demonstrated EDL capacitance. The i-graphene electrode
Figure 1. Diagrammatic representation of simultaneous iodine, oxygen
addition, and reduction of oxygen on graphite surface.
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 Research Article
ChemistrySelect doi.org/10.1002/slct.202400820
material exhibited remarkable stability over 5000 cycles and a
remarkable specific capacitance at a high rate, reaching
535.4 F g 1 at a current density of 1 A g 1.
Materials: We obtained the following materials: Con. H2SO4
(98.08 %), HCl (35 %) and NaIO4 from Merck; graphite (500
mechs) and m-CPBA from Sigma-Aldrich. A chemical of
analytical grade was used to carry out the reactions.
Synthesis: The synthesis of iodine intercalated graphene (i-
Graphene) and iodinated graphene oxide (i-GO) is carried out
using a novel one-step methodology, which is shown in
Figure 1. At below 0 temperature, the mixture of graphite
powder (1 g) and con.H2SO4 (40 mL) was stirred for an addi-
tional 20 min after being ultrasonically homogenized for 20 min
(RT). Then NaIO4 (12 g) was gradually added, and continuously
stirred for one day (24 h) at RT. Stage two involved gradually
adding the m-CBPA to the mixture and allowing it stir for a
further 8 h at RT. The mixture was rinsed with distilled water to
keep the pH at a neutral level and obtain a pure product of
iodinated graphene oxide (i-GO). Separate analyses were
performed on the i-GO and i-RGO products. The little amount of
sample taken out from stage one for analysis and repeatedly
rinsed with water to obtain i-GO. Then, a small portion sample
was taken out from stage 2 and repeatedly rinsed with water to
analyze i-reduced graphene. The whole experiment was con-
ducted repeatedly to check the reproducibility and scalability.
Every time we got the same quality product and also we
increased the weight of the starting material to get more yield.
Which was also well achieved in the sense of scalability. From
the continuous test of the reaction, we suggest this method is
highly scalable and reproducible. Moreover the whole reaction
was carried out in cost-effective mannaer.
Results and Discussion
Powder XRD was used to examine the crystalline properties,
conduct structural analysis, and assess the intercalation d-
spacing of the i-GO and i-graphene materials. Figure 2 shows
the XRD patterns of the original graphite, i-GO, and i-graphene.
For graphite, a very strong peak was observed at 26.5° (d-
spacing = 0.34 nm). A new broad peak, which corresponds to
the diffraction peak of i-GO, developed at 2 = 11.4° after
Figure 2. XRD patterns of graphite, i-GO, and i-graphene.
ChemistrySelect 2024, 9, e202400820 (3 of 8)
chemical oxidation with NaIO4 completely reduced the strong
graphite peak. Additionally, the graphite interlayer distance,
initially 0.3 nm, expanded to 0.7 nm through the incorporation
of different hydrophilic O2 and newly introduced iodine-
containing functional groups. The introduction of the m-CPBA
agent induced a chemical reduction, causing d-spacing of the i-
graphene sheet to revert to 0.3 nm from 0.7 nm. This alteration
led to an 11.4-degree shift in the 2 theta angle, as the oxygen
moieties on the graphite surface basal plane were removed,
and the gap between the layers was adjusted. Which is also in
good agreement with the FT-IR results. The Debye-Scherrer
formula was used to estimate the crystallite sizes of i-graphene
and i-GO. i-GO and i-graphene have average crystallite sizes of
71 A° and 12 A°, respectively. It was discovered that the lattice
spacings are multi-layer and few layer, respectively.[30,31]
Futhermore, synthesized materials were analyzed by TEM
and HR-TEM to investigate the structural morphologies of i-
graphene and i-GO. The layered structures of i-GO and i-
graphene were clearly evident in the TEM images (Figure 3(a
and d), as well as the smooth surface with iodine ornamenta-
tion, which was extremely electron-transparent. The inclusion of
various defect types and functional moieties, characterized by
sp3 hybridized carbon, during the oxidation and reduction
processes had a notable impact on the structure of the sheet.
This resulted in the presence of numerous parallel lattice
fringes, leading to the formation of a few-layered structure in
both i-GO and i-graphene, as shown in Figure 3(c and f). In
Figure 3(b and e), the selected area electron diffraction (SAED)
patterns were observed. These patterns exhibit diffraction spots
and ring-like features, which indicate the crystalline nature of i-
GO and i-graphene, confirming the presence of few-layered
nanosheets.
The (002) diffraction plane assigned to the figure satisfies
the reciprocal relationship between the diameter of the SAED
rings and the Miller indices (h, k, and l planes) and corroborates
the Braggs’ plane derived from the XRD patterns.[32,33] SEM was
used to further analyze the surface structural characteristics of i-
graphene and i-GO materials. SEM also revealed the surface
ornamentation of graphene sheets, including flakes and dots
Figure 3. (a, d) TEM images of i-GO and i-graphene, (b, e) SAED pattern
image of i-GO and i-graphene, and (c, f) HR-TEM Images of i-GO and i-
graphene.
© 2024 Wiley-VCH GmbH
 Research Article
ChemistrySelect doi.org/10.1002/slct.202400820
like structure. These results are consistent with the HRTEM
results, and the surface morphology of i-graphene (Figure 4c
and d) is similar to that of i-GO (Figure 4a and b), to which it
corresponds.[34]
The typical thickness of the i-graphene and i-GO sheets
were calculated using AFM imaging. Figure 5 shows that i-
graphene sheets typically have a thickness between 0.9 and
Figure 4. SEM images of i-GO and i-graphene.
Figure 5. AFM images of i-GO and i-graphene.
Figure 6. XPS deconvoluted spectra of (a) i-GO and (b) the high resolution
I3d peaks of the iodine for i-GO and i-graphene.
ChemistrySelect 2024, 9, e202400820 (4 of 8)
1.1 nm, proving that a layer of i-graphene sheets has been
formed. The i-GO sheets average thickness is 1.1–1.4 nm as a
result of the addition of oxidation, with some thickness ranges
much higher than those of i-graphene material.[35]
XPS was used to determine elemental composition and
surface functionalities. The elemental composition mentioned
in the supplimentary section (Table S1). Figure 6(a) shows the
chemical constituents of the i-GO and i-graphene modified with
NaIO4 and m-CPBA. XPS analysis of these materials revealed
three distinct peaks at 284, 612, and 532 eV, corresponding to
the binding energies of carbon (C1s), iodine (3d), and oxygen
(O1s), respectively. The O1s peak intensity was reduced in the i-
graphene material because the majority of the connected
carbon networks were recovered following the reduction
reaction. Percentages of iodine and oxygen functionalities with
carbon above 8 % were introduced and validated. Using
deconvoluted XPS analysis, we verified that GO and i-graphene
contained iodine (3d) on various surfaces (Figure 6b). In both i-
graphene and i-GO, the 3d peaks (621 and 632 eV) represent
3d5/2 and 3d3/2, respectively (C I). This outcome is in line with
the studies by Sofer et al., in which an aqueous iodine solution
was used to analyze iodinated GO and graphene.[36] The direct
inclusion of elemental iodine (3d) species through C I bonds in
the graphene-layered network suggests an electrostatic con-
nection between carbon and iodine.
The strength of the C-sp2 bond ratio decreased with
increasing oxidation levels, as indicated by the XPS analysis of
the deconvoluted C1s spectrum of i-GO. This change is
characterized by the steady growth of a new peak, primarily
due to carbon bonding with electronegative (C O) atoms and
the addition of iodine (C I). In the high-resolution (HR) C1s
spectra of I-GO, five Gaussian peaks emerged at 285.4, 285.8,
286, 287.1, and 289.2 eV (Figure 7a), representing C C bonds,
secondary alcohols (C OH), epoxides (C O C), iodine (C I), and
terminal acids (O C=O), respectively. These peak values were
closely aligned with those reported in the literature. After
reduction, the intensity ratio of the oxygen band to that of the
carbon band increased (C C peak), but the reversible iodine
process remained unchanged. In contrast, the two-peak mode
in i-GO shifted to a single-peak mode in i-graphene. Figure 7(b)
illustrates the deconvolution of the XPS HR C1S spectra of
iodinated graphene into four peaks centered at 284.6 eV.
Following reduction, this band displayed a more pronounced
C C network, with peak positions at 285.4, 286.5, and 288.4 eV
Figure 7. XPS for deconvoluted C1s of i-GO and i-graphene.
© 2024 Wiley-VCH GmbH
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ChemistrySelect doi.org/10.1002/slct.202400820
indicating lower oxygen functionality compared to iodinated
graphene oxide.[37,38]
Raman spectroscopy is frequently used for assessing the
degree of disorder and defect content in graphitic materials.
Figure 8 displays i-graphene and i-GO Raman spectra. This study
measures the G and D peaks of i-GO at 1599 and 1345 cm 1,
respectively. The higher the G and D peaks indicate that the
graphene sheets were severely oxidized, leading to the
development of defects. After reduction, the i-GO G-band was
centered at 1568 cm 1, whereas the D-band was located at
1347 cm 1. It is clear that the reduced GO was successfully
functionalized when the D-band shifted. Moreover, the hydrol-
ysis of m-CPBA caused a significant decrease in the GO intensity
ratio of the D to G bands (ID/IG) to 1, indicating the conversion
of i-GO into i-graphene. The 1.00 value of i-GO, with an ID/IG of
0.87. According to the Raman spectra presented above, i-GO
was effectively deoxygenated when m-CPBA was used in the
hydrolysis process, which is in accordance with the findings of
Chen et al. The most important information for calculating the
layer count in graphene can be found in the Raman spectra of
the 2D band. Distinguishing between a single layer, bilayer, and
multiple layers of graphene is made easy by examining the
position and shape of the 2D band. Single-layer sheets
(graphene) display a sharp 2D peak below 2700 cm 1, while
bilayer sheets exhibit a broader and upshifted 2D peak at
approximately 2700 cm 1.[39,40] In the Raman spectra of i-
Graphene and i-GO, there are 2D peaks at around 2693 cm 1
and 2700 cm 1, respectively, clearly indicating that the region
under investigation consists of single-layer graphene.
FT-IR spectroscopy was used to confirm the degree of
reduction, oxygen functionality, and C I intercalation on the
graphite sheets surface. FT-IR spectra show the range of
functionalization found in i-Graphene and i-GO materials. The
FT-IR i-GO spectra after graphite chemical oxidation were
displayed in Figure S1 (see the supporting information), and
they contained numerous unique absorption peaks. The peaks
observed at 1012 and 1615 cm 1 correspond to the stretching
vibrations of the (O C O) epoxy and (C=C) bonds within the
sp2 aromatic network. Additionally, the peaks at 1729 and
3431 cm 1 represent the stretching vibrations of the secondary
alcohol ( OH) and carbonyl (C O) bonds, respectively. However,
a novel intercalation bond (C I) was discovered in the FT-IR
image both i-GO and i-Graphene materials at 751 and 758 cm 1,
Figure 8. Raman spectra of i-GO and i-graphene.
ChemistrySelect 2024, 9, e202400820 (5 of 8)
confirming the presence of iodine moieties on the graphite
layers. With the chemical reduction of i-GO, the oxygen func-
tional moieties’ peak intensities alter dramatically. The epoxy
peak intensity and 2° alcohol peaks is diminished in i-Graphene
material (1040 and 1725 cm 1). Moreover, identical peaks at
3435 and 1622 cm 1 are indicated for the stretching vibration
band of the COOH or traped water molecules and C=C peak
bands, respectively. The FT-IR data showed that while oxygen
functionalization was successfully eliminated during the reduc-
tion process, iodine functional moieties were successfully
synthesized on the surface of the graphite.[41,42]
Using TGA, the i-graphene and i-GO thermal stability were
determined. At 50 and 230 °C, the i-GO and i-TGA graphene
curves show a slight and steady weight decrease (Figure S2).
There will be a weight loss of 15 %–20 % during this time as a
result of eliminating volatile species, bound water molecules
and the presence of oxygen in functioning. According to
typically modified GO, the breakdown of oxygen functional
groups such epoxide, OH, and COOH caused rapid consid-
erable weight loss around 230 °C. Also, the significant weight
loss that results from the stable and functional moieties of the
iodine type that are seen at 250 °C is demonstrated by i-
graphene. Unfortunately, the sp3 hybridization carbon network
broke down, losing 30 % of its weight, and the i-Graphene
began to slowly deteriorate above 250 °C. The carbon network’s
iodine incorporated Graphene surface, in comparison to i-GO
material, is more resistant to high-temperature regions, accord-
ing to TGA research.[43,44]
The benefits of using iodinated graphene as a super-
capacitor electrode material were assessed through a range of
electrochemical tests conducted on the coatings applied to
carbon electrodes. These assessments included cyclic voltam-
metry (CV), GCD cycles, and electrochemical impedance spec-
troscopy (EIS). The electrochemical characteristics of iodinated
graphene electrodes were studied using CV. Figure 9(a) shows
Figure 9. Electrochemical analysis of electrode materials mode using a three-
electrode system in 1 M H2SO4. (a) CV diagram of i-graphene at 10 mVs 1, (b)
i-graphene’s CV spectra were measured at various scan rates, (c) i-graphene
electrode’s galvanostatic charge-discharge (GCD) at the current density rate-
dependent graphic of the individual capacitance values (1 A g 1), and (d)
specific capacitance at different scan rates.
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ChemistrySelect doi.org/10.1002/slct.202400820
the CV curve of i-graphene at a scan rate of 10 mV. Originally,
CV was performed in 1 M H2SO4 using a conventional 3-
electrode setup. Figure 9(b) displays the CV plots of the
graphene electrode that has been functionalized with iodine at
various scan rates between 10 and 100 mV 1. The electro-
chemical studies showed a potential window of 0.7–0.6 V.
During the scan, the CV plots of functionalized graphene were
rectangular and free of redox peaks. It was explicitly stated that
the formation of electrical double layers at the electrode-
electrolyte interface was the cause of the apparent super-
capacitor activity of the electrodes. The easy accessibility of the
iodine functional moieties on the graphene basal plane
between the electrode and electrolyte surface causes EDLC to
arise. However, a significant current response from i-graphene
showed that the material and the electrolyte solution interacted
well (a much larger CV areaIodine is formed during oxidation
process I-3d 3/2 and 5/2 are present on the surface of the
graphite), which results in high-rate capability at high current
densities. The interlayer spacing of the graphene sheets is
improved by adding the iodine functional group, which
promotes ion diffusion during the electrochemical reaction.
However, the ability of iodine to donate electrons may enable
electrons to move into the graphene lattice, thereby enhancing
the capacitance of functionalized graphene.[45,46] Further proof
of the synthesis of iodine functionalization on the graphene
basal plane was provided by XPS and FT-IR investigations.
The i-graphene material was assessed by examining its
specific capacitance and cyclic life using the GCD method. The
specific capacitance (Cs) was determined using the formula:
Cs=I×Δt/(Δv×m), where Δv represents the potential difference
during the sweep, Δt is the discharge duration, I is the
discharge current, and m is the mass of electroactive materials
coated on the electrode’s surface (in grams). The specific
capacitance is typically denoted as C (F g 1), and the GCD
experiments on i-graphene were conducted at a constant
current density of 1 A g 1 within a voltage range of 0.0–0.4 V. A
current density of 1 A g 1 is commonly employed to evaluate
the charge-discharge performance of electrode materials in
supercapacitor applications. The resulting charge-discharge
curve of i-graphene (Figure 9c) had a linear and symmetric
triangular morphology, suggesting capacitance characteristics.
For i-graphene, the projected capacitance-specific value was
535.4 F g 1. The capacitance value of 398.4 F g 1 is related to i-
GO.[53] According to the findings, iodination improved the
specific capacitance of graphene materials by one fold times
compared with i-GO electrode materiasl (Figure 9d). However,
the specific capacitance is enhanced by more than two-fold due
to the significant role played by iodine on the surface of
graphene derivatives.The increase in the specific capacitance as
a result of the electrochemical charge penetration reaction rate,
ion diffusion, and intercalation of iodine content into the
graphene layer surface polarization is due to the increased
interlayer d-spacing value caused by the addition of larger ions
with high iodine moieties, which may make it simpler for a
large number of ions to enter the interface between the
electrode and electrolyte for energy storage.[47,48] In addition, as
shown in Figure 10(a), the i-graphene EIS plots show the
ChemistrySelect 2024, 9, e202400820 (6 of 8)
Figure 10. (a) AC impedance Nyquist plot of materials made of graphene, (b)
at a scan rate of 5000 mV s 1. The capacitance retention of i-Graphene
materials was studied with respect to the cycle number.
behavior of the electrochemical double-layer capacitance. From
a frequency range of 1–100 kHz, all values were constant with
an amplitude of 0.005, a starting voltage of 0.4 V, and an open
circuit potential. The Nyquist plots of the i-graphene electrode
were used to analyze the EIS data. In the Nyquist plots of the
iodine-functionalized graphene, noticeable characteristics
emerged: a sloping line in the low-frequency range, signifying
desirable capacitance behavior, and a small semicircle in the
higher frequency range. These observations indicate that
charge transfer between the electrode and the electrolyte is
limited in functionalized graphene electrodes.[49–52]
At the electrolyte–electrode interface, frequency-dependent
ion diffusion is demonstrated by the Warburg resistance, which
is the slope of the curve at an angle of 45°. With a reduction in
the Warburg resistance, the ion diffusion path length decreased.
Purely capacitive behavior occurs in the low-frequency zone,
represented by a vertical line. The presence of extra function-
ality on the graphene sheet containing iodine considerably
increased the wettability of the ions in aqueous electrolytes on
the electrodes. i-graphene rate capacitors are superior because
of their low frequency. The cyclic stability of the charge/
discharge profile information is crucial for determining the
material performance and is applied to energy storage devices.
Cyclic voltammetry investigations were performed 5000 times
at 1 A g 1 at a current density and scan rate of 100 mV s1 to
study the i-graphene electrode material. As shown in Fig-
ure 10(b), the i-graphene electrode improved the capacitance
retention by over 96 %. After 10 repeated CV tests over a range
of current densities from 1 A g 1, the capacitive response
remained stable and the i-graphene electrode improved the
capacitance retention by over 96 %. This unequivocally proves
that iodine (I-3d 3/2 and 5/2) treatment enhances the cycling
stability of the i-graphene electrode material. Hence, the
utilization of i-graphene electrode material enhances electro-
chemical behaviour and makes it a potential candidate for
supercapacitor electrodes.
Table 1 highlights the superior electrochemical performance
of i-graphene compared to other functionalization chain
moieties. This is evident in specific capacitance, cyclic stability
and energy density.[55–60] The enhanced performance is attrib-
uted to i-graphene’s optimal hydrophilicity and controlled
surface functionalization in aqueous environments, governed
by iodine functional groups. These groups enhance water
© 2024 Wiley-VCH GmbH
 Research Article
ChemistrySelect doi.org/10.1002/slct.202400820

Table 1. i-Graphene nanosheets electrochemical performance is compared to that of other organic long-chain molecule functionalized graphene sheets
with analogous and functional moieties.
Materials Specific capacitance Stability Ref.
1
Sodium dodecylbenzene sulfonate 159 Fg 90 % after [54]
1
(SDBS) modified grapheme at 1 Ag 1000 cycles
Sodium 4-aminoazobenzene-40- 170 Fg 1 3000 cycles [55, 58]
1
sulfonate modified graphene at 4.5 Ag
(SAS G)
Aryl diazonium salt of SAS 210 Fg 1 3000 cycles [56, 59]
1
(ADS) modified graphene (ADS G) at 4.5 Ag
Poly(sodium 4-styrenesulfonate) functionalised graphene (PSSS-GR) 210 Fg 1 95 % after [57, 60]
at 5 Ag 1 1000 cycles
4-Benzenediazonium sulfonate functionalised grapheme 51.6 Fg 1 1000 cycles [58]
at 5 mVs 1
Poly(p-phenylenediamine)- 248 Fg 1 72 % after [59]
graphene at 2 Ag 1 1000 cycles
Reduced graphene oxide- 224 Fg 1 83 % after [60]
1
polypyrrole composite at 240 Ag 5000 cycles
(RGO–PPy)
1
i-Graphene material 535.4 F g 96 % after Present studies
1
at 5 mVs 5000 cycles

dispersibility via p-p interactions, making i-graphene ideal for Acknowledgements

use in physiological fluids, particularly for energy storage
applications requiring interaction with aqueous solutions. Dr. Ramesh Pugalenthi thanks Dr. Shaik Gouse Peera, Keimyung
University, Republic for Korea for technical discussions.

Conclusions
A new method was developed to produce graphene with
simultaneous iodine intercalation, oxygen addition, and selec-
tive reduction of oxygen using NaIO4 and m-CPBA for super-
capacitor applications. The process is non-metallic and eco-
friendly, and effective iodine intercalation along with selective
deletion of oxygen are the key components of this approach.
The product formation was confirmed by several analyses,
including XPS, HR-TEM, XRD, FT-IR, AFM, TGA, and Raman
spectroscopy. The greater iodine concentration is due to
improved d-spacing (2θ = 24.4° from 11.4°) and higher ions
mobility to the electrolyte electrode, resulting in enhanced
charge holding capacity of iodinated GO material. The i-
graphene produced from this process displayed an impressive
performance in galvanostatic charge and discharge cycles,
sustaining up to 5000 cycles at a current density of 1 A g 1, with
a robust cycling stability retention of 96 %. An investigation of i-
graphene revealed a specific capacitance of 535.4 F g 1 at a
scan rate of 5 mVs 1. Additionally, this straightforward proce-
dure provides an opportunity for the chemical functionalization
of iodine-intercalated graphene to produce unique materials.
High-performance energy storage systems can use electrode
materials made of i-graphene, which have a superior specific
capacitance.
Conflict of Interests
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
Keywords: Iodinated graphene · Green chemistry approach ·
Specific capacitance · Electrochemical · and Supercapacitors
[1] R. Kumar, E. Joanni, R. K. Singh, D. P. Singh, S. A. Moshkalev, Prog. Energy
Combust. Sci. 2018, 67, 115–157.
[2] R. Kumar, E. Joanni, R. Savu, M. S. Pereira, R. K. Singh, C. J. L.
Constantino, L. T. Kubota, A. Matsuda, S. A. Moshkalev, Energy 2019,
179, 676–684.
[3] a) R. Kumar, S. Sahoo, E. Joanni, R. K. Singh, W. K. Tan, K. K. Kar, A.
Matsuda, Prog. Energy Combust. Sci. 2019, 75, 100786; b) P. R.
Kharangarh, N. M. Ravindra, G. Singh, S. Umapathy, J. Energy Storage
2022, 55, 105388; c) P. R. Kharangarh, N. M. Ravindra, G. Singh, S.
Umapathy, Energy storage 2023, 5, e390.
[4] R. Kumar, M. M. Abdel-Galeil, K. Z. Ya, K. Fujita, A. Matsuda, Appl. Surf.
Sci. 2019, 481, 296–306.
[5] a) K. Thiagarajan, J. Theerthagiri, R. A. Senthil, P. Arunachalam, J.
Madhavan, M. A. Ghanem, J. Solid State Electrochem. 2018, 22, 527–536;
b) P. R. Kharangarh, N. M. Ravindra, R. Rawal, A. Singh, V. Gupta, J. Alloys
Compd. 2021, 876, 159990; c) P. R. Kharangarh, G. Singh, ECS J. Solid
State Sci. Technol. 2023, 12, 031006.

ChemistrySelect 2024, 9, e202400820 (7 of 8) © 2024 Wiley-VCH GmbH

 Research Article
ChemistrySelect doi.org/10.1002/slct.202400820
[6] S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas, A. Kleinhammes, Y.
Jia, Y. Wu, S. T. Nguyen, R. S. Ruoff, Carbon 2007, 45, 1558–1565.
[7] B. Song, C. Sizemore, L. Li, X. Huang, Z. Lin, K. C. M. Wonga, J. Mater.
Chem. A. 2015, 3, 21789–21796.
[8] P. Ramesh, S. Sambathkumar, R. Jagatheesan, S. A. Vasanth Kumar, Mat.
Lett. 2019, 256, 126639.
[9] U. Saha, R. Jaiswal, T. Hari Goswami, Electrochim. Acta. 2016, 196, 386–
404.
[10] J. Han, L. Zhang, S. Lee, O. Junghoon, K. S. Lee, J. R. Potts, J. Junyi, X.
Zhao, R. F. Ruoff, S. Park, ACS Nano 2013, 7, 19–26.
[11] Z. Luo, Q. Qi, K. Chen, L. Min Zou, X. Yuwen, Zhang, W. Huang, L. Wang,
Adv. Funct. Mater. 2016, 26, 2739–2744.
[12] L. G. Bulusheva, V. A. Tur, E. O. Fedorovskaya, I. P. Asanov, D. Pontiroli,
M. Ricco, A. V. Okotrub, Carbon 2014, 78, 137–146.
[13] R. Thiruppathi, B. Sidhureddy, W. Keeler, A. Chen, Electrochem. Commun.
2017, 76, 42–46.
[14] Z. Zou, J. Chen, Z. Shi, C. Yuan, G. Zhou, Q. Liu, H. Chen, Q. Zeng, T.
Liang, K. L. Tang, C. M. Li, ACS Appl. Nano Mater. 2021, 4, 3631–3638.
[15] M. Marinoiu, D. Ion-Ebrasu, A. Soare, M. Raceanu, Materials 2022, 15,
6174.
[16] Z. Fakharan, L. Naji, K. Madanipour, J. Colloid Interf. Sci. 2019, 540, 272–
284.
[17] M. S. Mirshekarloo, M. C. D. Cooray, P. Jovanović, C. D. Easton, F. Wu,
T. D. Gamot, M. J. Abedin, M. Rasit Yuce, M. Shaibani, M. Majumder,
Batteries & Supercaps. 2021, 4, 1–12.
[18] Z. Wang, X. Liu, J. Liu, Y. Zeng, J. Shi, Y. Tong, X. Lu, J. Power Sources
2019, 442, 227188.
[19] H. L. Poh, S. Petr, Z. K. Sofer, M. Pumera, Chem. Eur. J. 2013, 19, 2655–
2662.
[20] D. Bousa, J. Luxa, W. Mazanek, O. Jankovsky, D. Sedmidubsky, K.
Klımova, M. Pumerab, Z. Sofer, RSC Adv. 2016, 6, 66884.
[21] O. Jankovsky, P. Simek, K. Klimova, K. Sedmidubsky, S. Matejkova, M.
Pumerac, Z. Sofer, Nanoscale 2014, 6, 6065.
[22] K. Kakaei, M. Hamidi, S. Husseindoost, J. Colloid Interface Sci. 2016, 479,
121–126.
[23] Z. Fakharan, L. Naji, K. Madanipour, J. Colloid Interface Sci. 2019, 540,
272–284.
[24] J. Li, L. Xifei, D. Y. Xiong Hao, H. Kou, W. Liu, D. Li, Z. Niu, RSC Adv. 2017,
7, 55060.
[25] P. H. Wadekar, D. A. Pethsangave, R. V. Khose, S. Some, Energy Technol.
2021, 9, 2000750.
[26] S. Kamila, M. Kandasamy, B. Chakraborthy, B. K. Jena, New J. Chem.
2020, 44, 1418–1425.
[27] P. Simek, K. Klimova, D. Sedmidubsky, O. Jankovsky, M. Pumera, Z. Sofer,
Nanoscale 2015, 7, 261–270.
[28] Gupta, S. Bikash Kumar, S. K. Saha, J. Phys. Chem. C 2014, 118, 6972–
6979.
[29] P. Ramesh, A. Alvin Kalicharan, J. Pitchaimani, R. Koutavarapu, New J.
Chem. 2023, 47, 4609–4613.
[30] T. Tsoufis, G. Tuci, S. Caporali, D. Gournis, G. Giambastiani, Carbon 2013,
59, 100–108.
[31] J. R. Lomeda, C. D. Doyle, D. V. Kosynkin, D. F. Hwang, J. M. Tour, J. Am.
Chem. Soc. 2008, 130, 16201–16206.
[32] Z. Fakharan, L. Naji, K. Madanipour, J. Colloid Interface Sci. 2019, 540,
272–284.
[33] M. Marinoiu, Appl. Surf. Sci. 2017, 424, 93–100.
[34] Marinoiu, M. Raceanu, E. Carcadea, M. Varlam, I. Stefanescu, Arab. J.
Chem. 2019, 12, 868–880.
[35] P. Ramesh, B. Jebasingh, Mater. Chem. Phy. 2019, 222, 45–55.
ChemistrySelect 2024, 9, e202400820 (8 of 8)
[36] A. Navaee, Salimi, RSC Adv. 2015, 5, 59874–59880.
[37] N. Ashok Kumar, S. Gambarelli, F. Duclairoir, G. Bidan, L. Dubois, J. Mater.
Chem. A. 20131, 2789.
[38] M. Marinoiu, J. Chem. 2019, 5, 860–880.
[39] R. Kumar, H. Kim, S. Park, A. Srivastava, I. K. Oh, Carbon 2014, 79, 192–
202.
[40] R. Kumar, R. Matsuo, K. Kishida, M. M. Abdel-Galeil, Y. Suda, A. Matsuda,
Electrochim. Acta. 2019, 303, 246–256.
[41] J. Zhu, J. He, ACS Appl. Mater. Interfaces 2012, 4, 1770–1776.
[42] Y. Li, N. Zhao, C. Shi, E. Liu, C. He, J. Phys. Chem. C 2012, 116, 25226–
25232.
[43] P. Bandyopadhyay, T. Kuila, J. Balamurugan, T. T. Nguyen, N. H. Kim, J. H.
Lee, Chem. Eng. J. 2017, 308, 1174–1184.
[44] Song, J. Z. M. Wang, J. Mullavey, Y. Zhu, Z. Geng, D. Chen, Y. Ding, K.
Moon, M. Liu, C. Wong, Nano Energy 2017, 31, 183–193.
[45] a) Z. Lin, Y. Liu, Y. Yao, O. J. Hildreth, Z. Li, K. Moon, C. Wong, J. Phys.
Chem. C. 2011, 115, 7120–7125; b) Z. Xiong, T. Gu, X. Wang, Langmuir
2014, 30, 522–532.
[46] a) M. Jana, S. Saha, P. Samanta, N. C. Murmu, J. H. Lee, T. Kuila, Mater.
Chem. Phys. 2015, 151, 72–80; b) H. Tian, L. Wang, X. Qin, G. Shao, Ionics
2014, 20, 1055–1061.
[47] a) X. Cai, X. Shen, L. Ma, Z. Ji, L. Kong, RSC Adv. 2015, 5, 58777–58783;
b) J. Wang, Y. Xu, J. Zhu, P. Ren, J. Power Sources 2012, 208, 138–143.
[48] a) E. E. Miller, Y. Hua, F. H. Tezel, J. Energy Storage 2018, 20, 30–40; b) K.
Zhang, L. Mao, L. L. Zhang, H. S. O. Chan, X. S. Zhao, J. Wu, J. Mater.
Chem. 2011, 21, 7302–7307.
[49] a) J. Shi, Z. Zhao, J. Wu, Y. Yibo, Z. Peng, L. Baojun, Y. Liu, H. Kang, L.
Zhongyi, ACS Sustain. Chem. Eng. 2018, 6, 4729–4738; b) B. T. Mazhar,
S. M. Moataz, S. Ebrahim, M. E. Harb, J. Electron. Mater. 2016, 45, 820–
828.
[50] P. Bandyopadhyay, T. Kuila, J. Balamurugan, T. T. Nguyen, N. H. Kim, J. H.
Lee, Chem. Eng. J. 2017, 308, 1174–1184.
[51] H. Zhou, Y. Liu, M. Ren, H.-J. Zhai, Inorg. Chem. Front. 2022, 9, 1920–
1930.
[52] A. A. Kalicharan, V. Rajesh, J. Pitchaimani, A. Rajalakshmi, S. Kathiresan,
R. Koutavarapu, M. R. Tamtam, P. Ramesh, Mater. Chem. Phys. 2023, 310,
128485.
[53] P. Ramesh, J. Pitchaimani, S. Amalraj, R. Koutavarapu, Diam. Relat. Mater.
2022, 127, 109140.
[54] R. Kumar, H. Kim, S. Park, A. Srivastava, I. K. Oh, Carbon 2014, 79, 192–
202.
[55] Rajesh Kumar, R. Matsuo, K. Kishida, M. M. Abdel-Galeil, Y. Suda, A.
Matsuda, Electrochim. Acta. 2019, 303, 246–256.
[56] J. Zhu, J. He, ACS Appl. Mater. Interfaces 2012, 4, 1770–1776.
[57] Y. Li, N. Zhao, C. Shi, E. Liu, C. He, J. Phys. Chem. C. 2012, 116, 25226–
25232.
[58] W. J. Z. M. Song, J. Mullavey, Y. Zhu, Z. Geng, D. Chen, Y. Ding, K. Moon,
M. Liu, C. Wong, Nano Energy 2017, 31, 183–193.
[59] a) Z. Lin, Y. Liu, Y. Yao, O. J. Hildreth, Z. Li, K. Moon, C. Wong, J. Phys.
Chem. C 2011, 115, 7120–7125; b) Z. Xiong, T. Gu, X. Wang, Langmuir
2014, 30, 522–532.
[60] a) M. Jana, S. Saha, P. Samanta, N. C. Murmu, J. H. Lee, T. Kuila, Mater.
Chem. Phys. 2015, 151, 72–80; b) H. Tian, L. Wang, X. Qin, G. Shao, Ionics
2014, 20, 1055–1061.
Manuscript received: February 19, 2024
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