J Mater Sci: Mater Electron (2025) 36:319
The significance of the synthesis method
for graphite‑like carbon: effects of acidifying agents
on properties and carbon monoxide sensitivity
Hassan Azimi‑Juybari1 and Mohammad‑Mehdi Bagheri Mohagheghi1,*
1
School of Physics, Damghan University, [Link]: 36716‑45667, Damghan, Iran
Received: 21 September 2024 ABSTRACT
Accepted: 31 January 2025 This study aimed to synthesize graphite-like activated carbon with different mor-
Published online: phologies using the solvothermal method and to evaluate the effects of different
14 February 2025 acidifying agents on the structure, morphology, porosity, CO gas sensitivity, and
optical properties. Graphite-like activated carbon was synthesized using the sol-
© The Author(s), under vothermal method in an autoclave at 160 °C with four acidic agents: hydrochloric
exclusive licence to Springer acid (HCl), phosphoric acid (H3PO4), sulfuric acid (H2SO4) and nitric acid (HNO3).
Science+Business Media, LLC, The activated carbon was produced using carbon black powder obtained from the
part of Springer Nature, 2025
carbonization process and the combustion of almond skin waste at 600 °C. The
properties of the synthesized activated carbon were analyzed by XRD, FESEM,
BET, UV–Vis spectrophotometry, and FTIR spectroscopy. The XRD analysis
revealed that the AC-HNO3 sample had the most graphite-like structure, with
a d002 value of 3.67 Å and an Lc value of 10.02 Å. The 002 peak appeared near
2θ = 23°, and the 10L peak was observed as a broad peak near 2θ = 43°. The FESEM
images showed that the carbon black sample had no pores, while the AC-HNO3
sample had the highest porosity and the most uniform pore size, with pore sizes
around 950 nm. The BET analysis also confirmed the largest specific surface area
of the AC-HNO3 sample with a surface area ( SBET ) = 340 m2/g, which correlates
with the superior light absorption capabilities compared to 67 m2/g for carbon
black. The absorption spectrum demonstrated enhanced light absorption for all
synthesized activated carbons compared to carbon black, with the AC-HNO3
sample exhibiting the highest optical absorption coefficient (α) in the order of 106.
Optical band gap calculations showed a reduction in the energy gap (Eg) from
3.83 eV for carbon black to 3.28 eV for the AC-HNO3 sample through activation
with different acidic solvents using the solvothermal method. The FTIR spectros-
copy detected several functional groups in all samples, including OH, CH2, C=C,
and CH aromatic, across all samples. According to the carbon monoxide (CO) gas
sensing characterization, the AC-HNO3 sample exhibited the highest sensitiv-
ity at S = 9.3%, while carbon black showed the lowest sensitivity at 2.1%. These
results indicated that the AC-HNO3 sample, with its high porosity, large specific
Address correspondence to E-mail: bmohagheghi@[Link]
[Link]
Vol.:(0123456789)
319 Page 2 of 15 J Mater Sci: Mater Electron (2025) 36:319
surface area, and superior gas sensitivity, could have been effectively utilized in
industrial applications such as water treatment, air filtration, and gas sensing.
1 Introduction of conducting further research in this area. Here are
some studies conducted by other researchers. Al Baro-
Activated carbon (AC), a type of porous black carbon roh et al. used coffee bean waste (CBW) as a carbon
material, is produced from carbon-rich substances source to produce porous carbon [11]. They carbon-
through carbonization and activation. Interestingly, ized the CBW at three different temperatures (500 °C,
this group of materials cannot be characterized by 600 °C and 700 °C) and found that 500 °C was the most
a structural formula or chemical analysis. The car- effective. After carbonization, they activated the car-
bonaceous materials can achieve a porous structure bonized CBW using a solvothermal method in a KOH
through either a chemical or physical activation and NH4OH vapor environment at 200 °C, with solvo-
method [1–5]. The chemical activation method is often thermal volumes varying at 30%, 40%, and 50%. Scan-
more cost-effective than physical activation because it ning electron micrographs revealed increased porosity
requires lower activation temperatures, faster process- and variations in the structural pores. Microporous
ing times, and higher carbon efficiency [2]. In contrast, carbon spheres were prepared and characterized using
physical activation mainly proceeds via the non-selec- a microwave-assisted solvothermal reactor with resor-
tive removal of carbon [3]. Various reactions that take cinol and formaldehyde as carbon sources [12]. Their
place within the carbon particles during chemical acti- results show that micropores below 0.4 nm are cru-
vation selectively remove non-graphitic parts [3]. Each cial for efficient carbon dioxide adsorption, with the
method has its advantages and is selected based on the synthesized carbon spheres achieving CO2 adsorption
specific requirements of the production process [2–4]. of nearly 7 mmol/g CO2 at 1 bar and 0 °C. Anchang
The production of AC has attracted consider- Li et al. prepared porous carbon for supercapacitors
able interest due to its diverse properties, including using a solvothermal reaction between p-phenylene-
the adsorption of many organic and inorganic com- diamine and dichloromethane [13]. The pores in these
pounds, environmental compatibility, filtration of materials provide diffusion pathways and spaces for
contaminants, thermal stability, and electrical and KOH to penetrate the precursor, leading to the direct
mechanical characteristics [6]. These properties make formation of porous carbon materials during the car-
it highly versatile, enabling its use in a wide range of bonization and activation process. Zhang et al. present
applications such as water purification, air filtration, a novel self-sacrificial salt templating method to con-
and medical treatments [1]. Different morphologies trol the nanoporous structure of porous carbon mono-
are influenced by the activation agent, whether acidic, liths synthesized via the solvothermal method [14].
organic, or alkaline solutions. Studies show that the The method allows for ambient drying and results
preparation of various carbon structures, such as lay- in microporous carbon monoliths with significantly
ered structures (graphite-graphene) and fully porous increased surface areas. In the solvothermal method
structures with high effective surface area, is related for the synthesis of porous carbon, organic materials
to these factors [3, 4, 7]. were typically used as both the carbon source and sol-
The solvothermal method has gained significant vent, with less frequent use of biomass materials. In
attention as a promising technique for the synthesis addition, this process tended to be time-consuming
of carbon materials, particularly activated carbon, due [7, 8, 15].
to its efficiency and versatility [7–9]. The ability of this In this study, almond skin was used as an inex-
method to precisely regulate pore size has led to its pensive carbon source for the synthesis of graphite-
widespread use in the synthesis of porous carbon, a like activated carbon, and inorganic substances were
topic that has attracted considerable interest in recent used as acidifying solvents. The effect of four acidotic
years [10]. Despite its potential, there are currently agents including hydrochloric acid (HCl), phosphoric
few studies reporting the production of AC using this acid (H3PO4), sulfuric acid (H2SO4), and nitric acid
method. This underscores the necessity of additional (HNO3) was investigated on the structural, morpho-
research in this field. This highlights the importance logical, porosity, and optical properties of activated
J Mater Sci: Mater Electron (2025) 36:319 Page 3 of 15 319
carbons prepared by the solvothermal method. The structural and optical properties of activated carbon.
properties of the samples were examined using Activated carbon was synthesized using the solvother-
X-ray diffraction (XRD), scanning electron micros- mal method in an autoclave at T = 160 °C with carbon
copy (SEM), Brunauer–Emmett–Teller (BET), UV–Vis black powder obtained from carbonization. Four dif-
spectrophotometry, and Fourier-transform infrared ferent acids, namely phosphoric acid (H3PO4), hydro-
spectroscopy (FTIR). A comprehensive analysis of the chloric acid (HCl), sulfuric acid (H2SO4), and nitric
internal structure of the graphite-like activated car- acid (HNO3) were used as solvents. The different acids
bon samples was conducted, considering changes in were diluted with deionized water so that the molarity
their structural parameters using XRD analysis and of all acids was 1 mol/L, and these diluted acids were
overlapping methods, including less-developed crys- used for the synthesis of the samples. The pH of the
talline carbon (LDCC) and more-developed crystalline acids was as follows: HCl (pH = 2.1), H3PO4 (pH = 1.7),
carbon (MDCC). In addition, the CO gas sensitivity of H2SO4 (pH = 1.6), and HNO3 (pH = 2.2). 10 g of car-
the samples to carbon monoxide gas was measured. bon black powder was mixed with 50 ml of each acid
The innovative aspects of synthesizing graphite-like solution. The mixtures were stirred for 2 h at room
activated carbon from almond skin are manifold. The temperature using a magnetic stirrer and then allowed
study emphasizes the use of almond skin as an eco- to rest for 24 h. After this resting period, each mix-
friendly and economical carbon source, supporting ture was transferred into a stainless-steel autoclave,
the environmental goals of waste valorization. This and the lid was tightly sealed. The autoclave was
research extends previous research by highlighting heated to T = 160 °C and maintained at this tempera-
the distinctive structural properties of carbon materi- ture for 6 h. After the heating process was completed,
als derived from almond skin, which can exhibit gra- the autoclave was allowed to cool naturally to room
phene-like features [16]. The study employs the solvo- temperature. The resulting powders were washed sev-
thermal method for controlled synthesis, optimizing eral times with ethanol and distilled water to remove
the structural and morphological characteristics of impurities, then filtered. Finally, the powders were
the activated carbon. Additionally, the investigation dried at T = 90 °C for 24 h in an oven. This process
includes a comparative analysis of four different aci- resulted in four different samples of activated carbon,
dotic agents on the properties of the activated carbon, labeled according to the acids used: AC-H3PO4 (phos-
a relatively unexplored area. phoric acid), AC-HCl (hydrochloric acid), AC-H2SO4
(sulfuric acid), and AC-HNO3 (nitric acid). The flow-
chart and Schematic representation of the activated
2 Materials and methods carbon synthesis steps are illustrated in Figs. 1 and 2.
2.1 Raw materials 2.3 Characterization method and apparatus
Carbon black, produced through the carbonization X-ray diffraction analysis was performed on activated
process and the burning of almond skin waste at carbon to determine the degree of crystalline or amor-
T = 600 °C, was used as the precursor material. The phous nature of the AC. The structural properties
purity of the carbon black was approximately 93% as of the samples were analyzed with a D8 Advanced
determined by the elemental analysis using EDAX. Bruker X-ray diffractometer using Cu Kα X-ray in the
Four different acids were used as solvents for the 2θ = 5° − 75°. The surface morphology of the synthe-
solvothermal method: hydrochloric acid (HCl, 37%), sized products was studied using a TESCAN MIRA3
phosphoric acid (H3PO4, 85%), sulfuric acid (H2SO4, field emission scanning electron microscope (FESEM).
98%), and nitric acid (HNO3, 65%). All solvents were The specific surface area of the prepared activated
sourced from Merck company. carbons was determined with a surface area analyzer
(BELSORP MINI X analyzer) using the BET method.
2.2 S
ynthesis of activated carbon using acidic The optical measurements were carried out with a
agents UNICO Double Beam UV–Vis spectrophotometer
in the range of 200–1100 nm. The functional groups
This experiment aimed to investigate the effect of dif- of the samples were examined with a PerkinElmer
ferent solvents in the solvothermal method on the Fourier-transform infrared spectroscopy (FTIR), in a
319 Page 4 of 15 J Mater Sci: Mater Electron (2025) 36:319
wavenumber range from k = 400 to 4000 cm−1. The CO
gas sensing properties of carbon black and activated
carbon samples were evaluated for the detection of
carbon monoxide. In a controlled environment, the
prepared samples were exposed to carbon monoxide
(CO) gas, and the resistance of the films was measured
over time to monitor their response.
3 Results and discussion
3.1 S
tructural analysis of the graphite‑like
activated carbon using XRD
Figure 3 shows the XRD patterns of the five samples,
including carbon black (CB) and four activated car-
bons synthesized with different solvents, including
phosphoric acid (H3PO4), hydrochloric acid (HCl),
sulfuric acid (H2SO4), and nitric acid (HNO3). These
patterns exhibit a very high baseline and wide peak
width. Notably, the (002) peak, which corresponds to
crystalline graphite, is typically observed at an angle
of 2θ = 26.56° [17, 18]. However, in our prepared
samples, the (002) peak appears at 2θ = 23° [19–21],
indicating differences in micro-crystallites compared
to graphite. In addition, the obvious changes of the
Fig. 1 Flowchart of the activated carbon synthesis steps using (002) peak show that the structure of the carbon black
solvothermal method
was affected by the activation process with different
solvents. In particular, the left part of the (002) peak
Fig. 2 Schematic represen-
tation of the solvothermal
process of Activated Carbons
synthesis
J Mater Sci: Mater Electron (2025) 36:319 Page 5 of 15 319
of the calculations, and the variations of the crystalline
and amorphous fractions for all samples, are shown in
Fig. 4. It can be seen that the activation process, when
performed with different acidic agents, affects both the
crystalline and amorphous carbon fractions. Specifi-
cally, it leads to an increase in the crystalline fraction
and a decrease in the amorphous fraction. Notably,
the AC-HNO3 sample appears to increase the crystal-
line carbon fraction most effectively in the form of a
graphite-like structure.
The structural parameters, including planar spac-
ing (d002) and crystallite size (Lc), were determined
by deconvoluting the asymmetric (002) peak into two
distinct bands. For the calculation of d002 and Lc, the
background was first removed from the analysis of the
Fig. 3 The XRD patterns of: a CB, b AC-H3PO4, c AC-HCl, d (002) peak. After background removal, all (002) peaks
AC-H2SO4, and e AC-HNO3 showed a certain degree of asymmetry.
According to X-ray diffraction theory, an asym-
shows increasing effects, leading to changes in the metric peak suggests the presence of defects in the
asymmetry. The (10L) peak appears as a broad peak, corresponding specimen [17]. The crystalline portion
with the mixed 100 and 101 peaks contributing to the of the samples prepared in this study, contributing
(10L) peak not clearly separated [17]. This indicates to the formation of the (002) peak, is assumed to be a
incomplete stacking of the carbon atom layers in the mixed combination of crystalline regions with varying
structure, and confirms that all samples are mainly degrees of defects. These regions are categorized as
composed of turbo-stratic structures [17, 22]. Conse- less-developed crystalline carbon (LDCC) and more-
quently, the micro-crystallites in the samples are more developed crystalline carbon (MDCC) regions [17, 23,
distinct from those found in graphite. 24]. As shown in Fig. 5, the (002) peak was smoothed
The internal structure of the carbonized materials after background removal and then deconvoluted into
was investigated by the researchers using XRD analy- the LDCC and MDCC fractions by Gaussian fitting.
sis. Their observations revealed a mixed structure con- In addition, the (10L) peak at 43° was analyzed. The
taining both crystalline and amorphous carbon [17, background was first removed in the range of 35–60°.
23]. Specifically, the researchers proposed that amor- Subsequently, the 2θ and the full width at half maxi-
phous carbon does not significantly affect the intensity mum (FWHM) of the peak were determined [17]. The
of the (002) peak in the XRD pattern; it appears in the 2θ and FWHM were measured for each peak, and the
background [17, 23, 24]. Accordingly, a quantitative respective interplanar distances were calculated using
analysis was conducted on the prepared carbon black the Bragg equation [17]:
and activated carbon samples. The crystalline and 2d sin 𝜃 = n𝜆, (1)
amorphous carbon fractions in the samples were cal-
culated based on the maximum intensity of the (002) where n is positive integer and λ is X-ray wavelength.
peak in the original XRD diffractogram before back- Also, the crystallite sizes Lc and La were calculated
ground subtraction. using the Scherrer equation [17]:
( )
K𝜆
Crystalline carbon fraction (%) = Icrystalline ∕Itotal × 100 L= (2)
𝛽 cos 𝜃
( )
Amorphous carbon fraction (%) = Iamorphous ∕ Itotal × 100,
In the above equation, K is a constant, λ is the
wavelength of the X-ray target source used (1.5406 Å,
where Icrystalline and Iamorphous are the diffraction inten-
Cu-Kα1), and β is the FWHM in radians. The interlayer
sities that correspond to the crystalline and amor-
spacing values, Lc and La, were calculated based on
phous portions, respectively [17, 23, 24]. The details
319 Page 6 of 15 J Mater Sci: Mater Electron (2025) 36:319
(a) Carbon black Graghite like peak 2500 (d) Activated carbon: Graphite like peak
1800 002 H2SO4 002
2000
Intensity (cps)
Intensity (cps)
1200 1500
Crystalline 63% Crystalline 67%
1000
600
Amorphous 37% 500 Amorphous 33%
0 0
5 10 15 20 25 30 35 5 10 15 20 25 30 35
o
2 ( )
2 (o)
2000
(e) Activated carbon: Graphite like peak
2500 (b) Activated carbon: Graphite like peak
HNO3 002
H3PO4 002
2000
1500
Intensity (cps)
Intensity (cps)
1500
1000
Crystalline 66% Crystalline 68%
1000
500
500 Amorphous 32%
Amorphous 34%
0 0
5 10 15 20 25 30 35 5 10 15 20 25 30 35
o
o
2 ( ) 2 ( )
2500 (c) Activated carbon: Graphite like peak
HCl
002
2000
Intensity (cps)
1500
1000 Crystalline 66%
500 Amorphous 34%
0
5 10 15 20 25 30 35
o
2 ( )
Fig. 4 a–e Methods of calculation and f variation of crystalline and amorphous fractions for all samples for graphite-like (002) peak
J Mater Sci: Mater Electron (2025) 36:319 Page 7 of 15 319
Fig. 5 Graphite (002) peak deconvolution for carbon black and activated carbons samples
319 Page 8 of 15 J Mater Sci: Mater Electron (2025) 36:319
the (002) and 1oL peaks, respectively. A summary of
interlayer spacing, along with Lc and La values for the
samples, can be found in Table 1. Based on the XRD
results and the data in Table 1, we can compare the
structure of the synthesized activated carbon samples
to that of ideal graphite. For ideal graphite, the value
of d002 for MDCC is 3.354 Å [17]. The closer the d002
value of a sample is to this value, the closer the struc-
ture of the sample is to that of ideal graphite. Review-
ing the d002 values for MDCC in Table 1, it can be seen
that the sample AC-HNO3 has the closest value to
3.354 Å, with a d002 value of 3.67 Å. Therefore, the acti-
vated carbon synthesized using nitric acid is the clos-
est to the structure of graphite among the samples. The
Lc value, which represents the size of the crystals along
the c-axis, is a key indicator of the organization and
continuity of the graphene layers in a carbon material.
A higher Lc value indicates a more graphite-like struc-
ture. A look at the Lc values for MDCC reveals that the
AC-HNO3 sample, with an Lc value of 10.02 Å, has the
most structured and continuous graphene layer, indi-
cating that the activated carbon synthesized with nitric
acid is very similar to graphite. Considering both the
d002 and Lc values, the activated carbon synthesized
with nitric acid is the most optimal of the samples. It
has the d002 value closest to that of ideal graphite and
the largest Lc value among all the samples, indicat-
ing a more graphite-like structure. Therefore, nitric
acid is the most effective solvent for the preparation
of activated carbon with a graphite-like structure in
the solvothermal method.
Fig. 6 The SEM images of carbon black and activated carbons
3.2 Morphological characterization samples
Figure 6 shows the SEM images of all synthesized
samples, which provide a detailed view of the micro- that the application of hydrochloric acid in the acti-
structure of each sample. As can be seen in Fig. 6a, vation process greatly changes the sample’s surface,
the CB sample has an almost uniform surface, with causing the sample to break into smaller pieces.
no grooves or pores [25]. In contrast, Fig. 6b illustrates Notably, there are clear gaps between these pieces.
Table 1 Structural parameters of samples obtained from XRD
Sample (002) peak by LDCC model (002) peak by MDCC model (10 L) peak
o o o o
2θ ( ) β( ) d002 (Å) Lc (Å) 2θ ( ) β( ) d002 (Å) Lc (Å) 2θ (o) β ( o) d10L (Å) La (Å)
CB 16.40 14.99 5.40 5.30 22.88 9.14 3.88 8.77 43.19 7.79 2.09 22.42
AC-H3PO4 17.00 14.74 5.21 5.39 23.24 8.82 3.82 9.10 43.18 7.91 2.09 22.08
AC-HCl 18.33 14.37 4.84 5.54 23.36 8.28 3.80 9.69 43.15 8.14 2.09 21.46
AC-H2SO4 13.35 10.86 6.63 7.28 23.72 8.19 3.75 9.80 43.16 8.19 2.09 21.33
AC-HNO3 13.78 10.17 6.42 7.78 24.20 8.01 3.67 10.02 43.27 8.41 2.09 20.78
J Mater Sci: Mater Electron (2025) 36:319 Page 9 of 15 319
Figure 6c shows that the activation of carbon black
with phosphoric acid does indeed cause significant
changes in the surface morphology of the material.
The previously smooth and pore-free surface of the
carbon black changes and corrosion and crevices form.
This is probably due to the corrosive effect of phos-
phoric acid, which can corrode the carbon surface and
cause these characteristics. In addition to the corrosion
and crevices, the activation process also leads to poros-
ity of the carbon black [26]. As depicted in Fig. 6d, the
SEM images of the AC-H2SO4 sample reveal a signifi-
cant number of pores on its surface. However, it is
important to note that these pores are not uniform in
terms of both size and shape. Interestingly, the AC-
H2SO4 sample has a higher number of pores compared
to the AC-H3PO4 sample. Therefore, the activation Fig. 7 Distribution chart of pore diameters for AC-H2SO4 and
process with sulfuric acid is more effective than phos- AC-HNO3 samples
phoric acid in creating porosity in carbon materials.
Figure 6e shows that the AC-HNO3 sample is char- ( )
1 1 C−1 P
acterized by a considerable number of pores that are ( )= +
(3)
P0 Vm C Vm C P0
relatively uniform in both size and shape. These pores Va P
−1
are larger compared to those found in samples treated
with phosphoric acid and sulfuric acid. In addition, By plotting (P
1
0 −1
) against P
P0
for each sample, a
Va
these pores penetrate deeper, indicating a more pro- P
straight line is obtained. The slope of this line is VC−1C
nounced porosity in the AC-HNO3 sample. Since the m
two samples prepared with sulfuric acid and nitric and the y-intercept is V 1 C . From these, the monolayer
acid had comparable morphology and a higher pore
m
volume ( Vm ) and the constant C are calculated. SBET
count than the other samples, the MiraTC software of calculated using the following equation [27]:
the TESCAN MIRA3 FESEM was used to allow a more
comprehensive and quantitative comparison of these SBET =
Vm Ns
, (4)
two samples. The size of all pores in both samples was V
determined using this method. Figure 7 presents the where N is the Avogadro number, s Adsorption cross
histograms of the pore sizes for these two samples. As section area and V the molar volume of the adsorb-
observed, the most abundant pore sizes are approxi- ate gas. The BET isotherm curve for carbon black and
mately 950 nm for the AC-HNO3 sample and 250 nm activated carbons samples, measured at a temperature
for the AC-H2SO4 sample. of 77 Kelvin, is shown in Fig. 8. Table 2 provides the
SBET values for CB and activated carbons samples. CB
3.3 The specific surface area by BET analysis has the smallest surface area available for adsorption
of all samples with a specific surface area of 67 m2g⁻1.
The BET theory is a fundamental idea that explains The AC-H3PO4 sample has a specific surface area of
the physical adsorption of gas molecules on a solid 92 m2g⁻1, which is larger than that of CB, indicating an
surface. This theory is the basis of an important ana- increase in surface area due to the activation process
lytical method for measuring the specific surface area with H3PO4. The AC-HCl sample displays a specific
(SBET) of materials. The BET isotherm technique, which surface area of 113 m2g⁻1, exceeding both CB and AC-
is based on the concept of multilayer adsorption, was H3PO4. This indicates that the surface area has been
applied to the carbon samples. The corresponding BET enhanced through the activation with HCl. The AC-
surface area was calculated from the isotherm using a H2SO4 sample has a significantly larger specific sur-
specific formula. The respective BET surface area was face area of 223 m2g⁻1 compared to the previous sam-
calculated from the isotherm using the following equa- ples, which shows that activation the activation with
tion [27]:
319 Page 10 of 15 J Mater Sci: Mater Electron (2025) 36:319
2.0
1.5
Absorbance
1.0
CB
AC-HCL
0.5 AC-H3PO4
AC-H2SO4
AC-HNO3
0.0
200 400 600 800 1000
(nm)
Fig. 8 BET isotherm plot for carbon black and activated carbons Fig. 9 Optical absorbance (A) spectra of carbon black and acti-
samples vated carbons samples
Table 2 SBET values of Carbon black (CB) and Activated carbon activated carbon, which increases the specific sur-
(AC) samples face area. This increase in surface area provides more
Sample CB AC-H3PO4 AC-HCl AC-H2SO4 AC-HNO3 opportunities for light to interact with the material,
improving its light absorption capacity.
SBET 67 92 113 223 340 Among the samples, the AC-HNO3 sample exhib-
(m2g−1)
its the highest light absorption, which is due to its
higher porosity compared to the other samples.
After the AC-HNO3 sample, the samples, in order of
2SO4 is particularly effective in increasing the surface
H decreasing absorbance are: AC-H2SO4, AC-HCL, AC-
area. The AC-HNO3 sample has the largest specific H3PO4, and finally, carbon black. These observations
surface area of 340 m2g⁻1. The activation process with are consistent with the BET results. As for porosity,
HNO3 therefore generates the largest surface area of the order of the samples matches the order observed
all the samples examined. These results indicate that in the absorbance spectrum. The AC-HNO3 sample
the use of different activating agents can significantly exhibited the highest porosity, followed by samples
influence the surface area of the samples, with HNO3 AC-H2SO4, AC-HCL, and AC-H3PO4 samples. Fig-
activation producing the largest surface area. ures 10 and 11 show the variations of the absorp-
tion coefficient (α) and the extinction coefficient (k)
3.4 Optical properties as a function of the wavelength (λ), respectively. As
observed, the optical absorption for the acidic agents
Figure 9 shows the optical absorption spectrum of of HNO3 and H2SO4 is the highest, ranging between
carbon black and activated carbon, synthesized by 105 and 106. The extinction coefficient for HNO3 acid
the solvothermal method using various of acidic sol- is also higher than for the others, which is due to its
vents: Hydrochloric acid, phosphoric acid, sulfuric larger surface area. This is due to their high absorp-
acid, and nitric acid. Figure 9 clearly shows that the tion. These materials are good candidates for solar
activation of carbon black with various solvents and energy and energy saving applications and sodium-
the solvothermal method enhances its absorption lithium battery electrodes due to their porosity and
capacity. All synthesized activated carbons show high ionic conductivity.
improved light absorption compared to carbon black. The optical band gap (Eg) of the CB and ACs sam-
This improvement is attributed to the increase in the ples is obtained using the Tauc’s relation, as shown
number of holes and pore size on the surface of the below [28]:
J Mater Sci: Mater Electron (2025) 36:319 Page 11 of 15 319
Fig. 10 Optical absorption coefficient (α) of carbon black and Fig. 12 The band gap (Eg) graph of carbon black and activated
activated carbons samples carbons samples
Table 3 Eg values of Carbon black and Activated carbons sam-
ples with various acidic agents
Sample CB AC-H3PO4 AC-HCl AC-H2SO4 AC-HNO3
Eg (eV) 3.83 3.77 3.71 3.47 3.28
presented in Table 3. From Table 3 and Fig. 12, it can
be seen that the activation of carbon black with dif-
ferent acidic solvents by the solvothermal method
reduces the E g from 3.83 eV for carbon black to
3.28 eV for the AC-HNO3 sample. These values of
the energy gap are in agreement with those reported
by other researchers in the field of carbon materials
[29]. The reduction of Eg from carbon black to acti-
Fig. 11 The extinction coefficient (k) plot versus wavelength (λ) vated carbon is attributed to the degree of graphiti-
for carbon black and activated carbons samples zation of the samples. Graphitization, the process of
converting carbon materials into graphite (a highly
( ) ordered crystalline form of carbon), can reduce the
(𝛼h𝜐)n = B h𝜐 − Eg (5) band gap. During graphitization, the carbon atoms
in the material rearrange themselves into a regular
In which, n is a constant that depends on the hexagonal lattice, forming layers of stacked gra-
nature of the transition ( n = 2 for direct allowed tran- phene sheets. In graphite, the band gap is minimal
sition and n = 21 for an indirect allowed transition), h𝜐 due to its highly ordered electronic structure. Con-
is the photon energy of radiation and B is constant. sequently, when carbon materials are graphitized,
The direct allowed band gap of the samples was cal- their band gap decreases, allowing for efficient light
culated using this relationship, which is represented absorption and improved electrical conductivity [30].
by plotting (𝛼h𝜐)2 versus h𝜐 . The Eg was determined As carbon materials undergo graphitization, their
by extrapolating the linear portion of this graph to atomic arrangement transitions from an amorphous
the point of intersection with the horizontal axis, state, where atoms are randomly distributed, to a
as shown in Fig. 12. The calculated E g values are more ordered crystalline structure. This transforma-
tion significantly enhances electron delocalization,
319 Page 12 of 15 J Mater Sci: Mater Electron (2025) 36:319
as the ordered arrangement facilitates better overlap
between the p-orbitals of adjacent carbon atoms. The
development of a graphitic structure creates a con-
tinuous network of π-bonds, which are formed by
the sideways overlap of p-orbitals. This continuous
π-bonding network allows electrons to move more
freely throughout the lattice, like to a sea of free elec-
trons. This enhanced electron mobility reduces the
energy required for electrons to be excited from the
valence band to the conduction band, resulting in a
decreased band gap.
The AC-HNO3 sample exhibits the highest degree
of graphitization, followed by the AC-H2SO4, AC-HCl,
AC-H3PO4, and finally, the CB samples. This order is
consistent with the trend observed in the band gap
values. It shows that the sample prepared with nitric
acid has the lowest energy gap, while carbon black Fig. 14 The FTIR spectra of carbon black and activated carbons
has the highest energy gap. The plot of the band gap samples
and porosity as a function of the different acids can be
seen in Fig. 13. This graph shows that the energy gap reveal the presence of several functional groups in all
decreases with increasing porosity, which is due to the five samples. These functional groups can be recog-
quantum confinement effect. Due to the effect of the nized by their characteristic absorption bands in the
acidic agent nitric acid, which increases the porosity FTIR spectrum. The broad absorption band observed
compared to other samples, the energy gap decreases, at around k = 3400 cm−1 in the IR spectrum of all sam-
which is also the reason for the formation of graphite- ples, can be attributed to the OH stretching of the
like layers. hydroxyl groups present in the materials [31]. There
are two distinct peaks at k = 2920 and 2851 c m −1,
3.5 FTIR analysis which are assigned as the CH2 stretching of methyl
groups [31, 32]. A significant peak, observed at
FTIR spectroscopy is used to characterize the sur- k = 1630 c m −1 , is ascribed to the C=C stretching
face functional groups of the CB and ACs samples. vibration present in the material [27]. Finally, a
The results of this FTIR analysis, depicted in Fig. 14, peak observed in the IR spectrum at k = 1083 cm−1 is
assigned to aromaticCH [27]. The shifts in the signals
of the CH₂, C=C, and CH aromatic bands, as well as
the changes in the peaks of the OH functional groups
during the synthesis of graphite-like carbon using
different acids, reflect the influence the type of acid
on the molecular interactions. The observed shifts
and peak behavior can be attributed to the different
degree of protonation and the electron-withdrawing
effects of the acids used. The activation process leads
to a shift of the C=C band peak to a higher wave-
number, indicating increased bond strength or modi-
fications in hybridization due to acid interactions.
Conversely, the peak of the C–H band peak shifts to
a lower wavenumber during activation, indicating a
weakening of the C–H bond, presumably due to pro-
tonation effects caused by the acids used. The CH2
Fig. 13 The plot of band gap and porosity versus different acidic band shows only a minimal shift during activation,
agents
J Mater Sci: Mater Electron (2025) 36:319 Page 13 of 15 319
suggesting that hydroxyl groups are less affected by
the acidic environment compared to other functional
groups. The sharpness of the O–H peak varies with
the type of acid, with hydrochloric acid producing
the sharpest peak.
3.6 CO gas sensing properties
The gas sensing properties of carbon black (CB) and
activated carbon (AC) samples were investigated for
carbon monoxide (CO). To perform the sensor test, the
prepared samples were exposed to the target gases in
a controlled environment. The resistance of the pow-
der was measured over time to monitor the response
of the sensor to the presence of the carbon monoxide
gas. The performance parameter, often referred to as Fig. 15 Gas (CO) sensitivity of carbon black and activated car-
sensitivity (S), is calculated by comparing the electrical bons samples
resistance of the sensor in the presence of the target
gas to its resistance in a gas-free environment. This is
a measure of how much the resistance (S) of the sensor
changes in response to the target gas. S is expressed by
the following equation:
R − R0
S(% ) = × 100, (6)
R0
where R is the electrical resistance of the sensor in the in improving the gas sensor properties of the samples.
presence of the target gas and R0 is initial electrical After the gas is turned off, the sensitivity of the sensor
resistance in a gas-free environment. begins to decrease gradually, indicating that the sensor
The time dependence of the sensitivity of the sen- recovers in the absence of carbon monoxide gas. This
sor for carbon monoxide gas is shown in Fig. 15. It means that the sensor returns to its initial state when the
can be seen that the sensitivity gradually increases carbon monoxide molecules are desorbed from the sen-
after the introduction of the gas, indicating that the sor material. However, the absorption and desorption
sensors respond to the presence of carbon monoxide curves are not symmetrical, and the slope of desorption
gas. The AC-HNO3 sample has the highest sensitivity is lower than that of absorption. This asymmetry indi-
with S = 9.3%, followed by the AC-H2SO4 sample with cates that the process of desorption (the release of gas
S = 6.8%. The AC-HCl and AC-H3PO4 samples have a molecules from the sensor) is slower than the process
moderate sensitivity of 4.3 and 3.4%, respectively, while of absorption (the uptake of gas molecules by the sen-
the carbon black sample has the lowest sensitivity of sor). One possible reason for this could be the presence
2.1%. The higher sensitivity of AC-HNO3 and AC-H2SO4 of residual gases from carbon monoxide, which impair
can be attributed to the significantly larger surface area the recovery of the sensor. Residual gases can interfere
of the samples and the presence of functional groups with the desorption process, and make it slower and less
that enhance the interactions with carbon monoxide efficient. In addition, the strong interaction between the
gas. A larger specific surface area provides more active carbon monoxide molecules and the active sites on the
sites for the adsorption of carbon monoxide molecules, sensor material can also contribute to this asymmetry.
resulting in higher sensitivity. When carbon monoxide During absorption, the gas molecules quickly occupy
gas is introduced, these sites can rapidly adsorb the gas the available active sites, leading to a rapid increase in
molecules, resulting in a significant change in the resist- sensitivity. Conversely, during desorption, these mol-
ance of the sensor. These results show that the activation ecules are released more slowly from the active sites,
process and the type of acid used play a decisive role leading to a gradual decrease in sensitivity.
319 Page 14 of 15 J Mater Sci: Mater Electron (2025) 36:319
4 Conclusions M. Bagheri-Mohagheghi. The first draft of the manu-
script was written by H. Azimi Juybari and all authors
In this study, activated carbon was successfully syn- commented on previous versions of the manuscript.
thesized using the solvothermal method at lower All authors read and approved the final manuscript.
temperatures and in less time than in other studies,
suggesting a promising route for more efficient pro-
duction. The main results and their implications are Funding
summarized below:
The authors declare that no funds, grants, or other
• The choice of solvent was found to significantly support were received during the preparation of this
affect the properties of the synthesized activated manuscript.
carbons, including morphology, porosity, pore size
uniformity, specific surface area, light absorption
capacity, and energy gap. Data availability
• Among the four solvents tested—hydrochloric acid,
phosphoric acid, sulfuric acid and nitric acid— The datasets generated during and/or analyzed during
nitric acid proved to be the most effective solvent. the current study are available from the corresponding
• Nitric acid produced activated carbon with a graph- author upon reasonable request.
ite-like structure (d002 value of 3.67 Å, Lc value of
10.02 Å), the highest porosity and most uniform
pore size (~ 950 nm), the largest specific surface Declarations
area (SBET = 340 m2/g), excellent light absorption
(optical absorption coefficient in the order of 10⁶), Conflict of interest The authors declare no conflict
and the lowest energy gap (Eg) of 3.28 eV. of interest.
• The gas sensing properties of the samples revealed
Ethical approval Not applicable.
their ability to detect carbon monoxide (CO), with
the AC-HNO₃ sample exhibiting the highest sen-
sitivity (S = 9.3%). This heightened sensitivity was
attributed to the significantly increased surface area
References
and the presence of functional groups that enhance
the interactions with the carbon monoxide gas.
1. R. Ganjoo, S. Sharma, A. Kumar, and M. M. A. Daouda,
• Innovative aspects: The potential for more efficient
in Activated Carbon (2023).
production of activated carbon using the solvother- 2. Z. Heidarinejad, M.H. Dehghani, M. Heidari, G. Javedan,
mal method was demonstrated. The influence of I. Ali, M. Sillanpää, Environ. Chem. Lett. (2020). [Link]
different solvents on the structural and functional doi.org/10.1007/s10311-019-00955-0
properties of activated carbon was examined, pro- 3. I. Yang, M. Jung, M.S. Kim, D. Choi, J.C. Jung, J. Mater.
viding valuable information for optimizing these Chem. A Mater. 9, 9815–9825 (2021)
materials for specific applications such as water 4. V.M. Vashchynskyi, I.V. Semkiv, A.I. Kashuba, R.Y.
purification, air filtration, and gas sensors. Future Petrus, Himia Fizika Ta Tehnologia Poverhni 13, 349–357
studies could investigate the use of other solvents (2022)
or their combinations to further improve the prop- 5. D. Wang, L. Yan, Y. Zhang, R. Ma, B. Zhang, N. Guo,
erties of activated carbon. L. Wang, L. Ai, D. Jia, M. Xu, J. Energy Storage (2024).
[Link]
6. M.M. Alam, M.A. Hossain, M.D. Hossain, M.A.H. Johir,
J. Hossen, M.S. Rahman, J.L. Zhou, A.T.M.K. Hasan, A.K.
Author contributions Karmakar, M.B. Ahmed, Processes (2020). [Link]
10.3390/pr8020203
All authors contributed to the study’s conception and
7. L. Wu, P. Wang, X. Chen, J. Zhang, H. Luo, Carbon Lett.
design. Material preparation, data collection, and
32, 849–862 (2022)
analysis were performed by H. Azimi Juybari and M.
J Mater Sci: Mater Electron (2025) 36:319 Page 15 of 15 319
8. H. Wang, S. Xu, W. Dong, D. Sun, S. Zhang, Z. Han, F. 23. D.-S. Kang, S.-M. Lee, S.-H. Lee, J.-S. Roh, Carbon Lett.
Huang, Chem.—A Eur J (2022). [Link] 27, 108 (2018)
chem.202200124 24. S.H. Lee, D.S. Kang, S.M. Lee, J.S. Roh, Carbon Lett. 26,
9. Y. Huo, S. Xiu, L.-Y. Meng, B. Quan, Chem. Eng. J. 451, 11–17 (2018)
138572 (2023) 25. A.P.S. Chauhan, K. Chawla, J. Mol. Liq. 221, 292–297
10. C. Wang, J. Huang, J. Li, L. Cao, Q. Xi, S. Chen, J. Elec- (2016)
troanal. Chem. (2020). [Link] 26. C. Dai, J. Wan, J. Yang, S. Qu, T. Jin, F. Ma, J. Shao, Appl.
2020.113924 Surf. Sci. 444, 105–177 (2018)
11. L.A. Al Baroroh, D. Fitria, M.I. Amal, A.S. Wismogroho, 27. A. Galarneau, D. Mehlhorn, F. Guenneau, B. Coasne, F.
W.B. Widayatno, J. Phys. Conf. Ser. 985, 12031 (2018) Villemot, D. Minoux, C. Aquino, J.P. Dath, Langmuir
12. P. Staciwa, D. Sibera, I. Pełech, U. Narkiewicz, W. (2018). [Link]
Łojkowski, S. Dąbrowska, R. Cormia, Micropor. Mesopor. 28. Dipti, P. Phogat, Shreya, D. Kumari, S. Singh, Phys. Scr.
Mater. (2021). [Link] (2023). [Link]
110829 29. I. Velo-Gala, J.J. López-Peñalver, M. Sánchez-Polo, J.
13. A. Li, J. Wang, K. Zhang, W. Fu, L. Cheng, M. Zhang, Z. Rivera-Utrilla, Appl. Catal. B (2013). [Link]
Shen, ChemElectroChem (2022). [Link] 1016/j.apcatb.2013.06.003
celc.202200190 30. S. Pagliara, G. Galimberti, S. Mor, M. Montagnese, G.
14. Z. Zhang, J. Feng, Y. Jiang, P. Liu, Q. Zhang, R. Wei, X. Ferrini, M.S. Grandi, P. Galinetto, F. Parmigiani, J. Am.
Chen, J. Feng, Nanomaterials (2018). [Link] Chem. Soc. 133, 6318–6322 (2011)
3390/nano8040255 31. R.I. Sugatri, Y.C. Wirasadewa, K.E. Saputro, E.Y. Mus-
15. L. Wang, T. Wang, R. Hao, Y. Wang, Chemosphere (2023). lih, R. Ikono, M. Nasir, Microsyst. Technol. 24, 749–755
[Link] (2018)
16. R. Appiah-Ntiamoah, M.E. Guye, M.D. Dabaro, H. Kim, 32. R. Ali, Z. Aslam, R.A. Shawabkeh, A. Asghar, I.A. Hus-
Small (2024). [Link] sein, Turk. J. Chem. 44, 279–295 (2020)
17. S.M. Lee, S.H. Lee, J.S. Roh, Crystals (Basel) (2021).
[Link] Publisher’s Note Springer Nature remains neutral with
18. T. Qiu, J.G. Yang, X.J. Bai, Y.L. Wang, RSC Adv. 9, regard to jurisdictional claims in published maps and
12737–12746 (2019) institutional affiliations.
19. C. A. Riyanto, M. S. Ampri, and Y. Martono, EKSAKTA:
Springer Nature or its licensor (e.g. a society or other partner)
J. Sci. Data Anal. (2020).
holds exclusive rights to this article under a publishing
20. N.M. Keppetipola, M. Dissanayake, P. Dissanayake, B.
agreement with the author(s) or other rightsholder(s);
Karunarathne, M.A. Dourges, D. Talaga, L. Servant, C.
author self-archiving of the accepted manuscript version of
Olivier, T. Toupance, S. Uchida, K. Tennakone, G.R.A.
this article is solely governed by the terms of such publishing
Kumara, L. Cojocaru, RSC Adv. (2021). [Link]
agreement and applicable law.
10.1039/D0RA09182K
21. P. Puech, A. Dabrowska, N. Ratel-Ramond, G.L. Vignoles,
M. Monthioux, Carbon 147, 602–611 (2019)
22. D.M. Stefanescu, T. Tokarski, G. Alonso, M. Górny, R.
Suárez, Metall. Mater. Trans. B: Process Metall. Mater.
Proc. Sci. 54, 2283–2290 (2023)