The 5 th International Conference on Advanced Materials and Nanotechnology Hanoi, 2022

Facile synthesis of Graphite carbon nitride (g-C3N4) via the

polymerization method

Nguyen Quang Truong1 , Nguyen Thi Tuyet Mai2 , Nguyen Tuyet Nga 1, Pham Van Thang 1, Le Manh Cuong3,
Nguyen Cong Tu1 , Luu Thi Lan Anh1*
1 School of Engineering Physics, Hanoi University of Science and Technology, Hanoi, Vietnam
2 School of Chemical Engineering, Hanoi University of Science and Technology, Hanoi, Vietnam
3 Faculty Building Material, Hanoi University of Civil Engineering, Hanoi, Vietnam

*Corresponding author: anh.luuthilan@hust.edu.vn

Abstract: Graphite carbon nitride (g-C3 N4 ) is becoming increasingly important due to the theoretical predictions of its
unusual properties and promising applications. C3 N4 is a potential candidate, adding carbon applications in the field of
materials. Here study, g-C3 N4 was synthesized via a reported polymerization method. The effects of urea and thiourea
precursors on g-C3 N4 formation and properties were investigated. The structure of g-C3 N4 was analyzed using XRD and
FTIR methods. The analytical results showed that the two precursors used both f orm g- C3 N4 . The crystallinity is better
for the thiourea precursor.
Keywords: Graphite carbon nitride (C 3 N4 ), polymerization, urea, thiourea

at 550o C with a heating rate of 5o C/min for 2h. The

I. INTRODUCTION
The graphite carbon nitride (g-C3 N4 ) is the most
stable allotrope of carbon nitride (C3 N4 ). The g-
C3 N4 has been widely used in various application
fields such as photocatalysts, sensors, solar cells
and catalysts [1]–[4] and it has been the subject of
many studies in recent years. Currently, g-C3 N 4 is
often synthesized by pyrolysis of carbon and
nitrogenous precursors such as urea [5], [6],
melamine [7], [8], thiourea [9], dicyandiamide [10],
[11], and cyanamides [11]. The properties of g-
C3 N4 depend on synthesized conditions such as
temperature and holding time, heating rate,
precursor and synthesized method. Therefore,
testing, investigating, and optimizing the
technological conditions for manufacturing g-C3N4
is essential. In this study, we fabricated g-C3 N4 by
simultaneous pyrolysis of urea and thiourea and then
studied the influence of urea and thiourea precursors
on the formation and properties of g-C3N4.
II. EXPERIMENTAL
Synthesis of the g-C3 N 4 nanostructure
The chemicals used were Merck's pure urea and
thiourea.
The g-C3 N 4 was synthesized via a simple
polymerization method from urea and thiourea
precursors in the air. Weigh 10g of a mixture of
urea and thiourea into a porcelain cup with different
ratios of urea-thiourea (U-T) is 1-0, 3-1, 1-1, 1-3,
and 0-1, respectively. The mixture was then heated
obtained product has a pale yellow colour.
Synthetic samples are denoted as U, 3UT, UT,
U3T, and T respectively, corresponding to the mass
ratio of urea and thiourea of 1-0, 3-1, 1-1, 1-3 and 0-1.
Characterization
The crystal structure and phase purity were
obtained by using X’pert Pro (PANalytical) MPD
with CuK-α1 radiation (= 1.54056 Å) at a scanning
rate of 0.03o /2s in the 2θ range from 10o to 50o . The
crystal analysis was performed by HighScore Plus
software using the ICDD database. FTIR spectra
were analyzed using FT/IR-4600typeA (JASCO)
with wavenumber from 400 cm-1 to 4000 cm-1 . The
morphology of the materials was characterized by
scanning electron microscopy (SEM) by Hitachi
TM 4000 plus. The Zeta potential was measured by
the Zetasizer 500. The Diffusion reflectance and
Absorbance spectra of samples were measured in
JASCO V-750 using 60 mm Integrating Sphere
ISV-922 with the scan rate of 200 nm/min and UV-
Vis bandwidth of 0.50 nm.
III. RESULTS AND DISCUSSION
The crystal structure of the g-C3 N4 was examined
by X-ray diffraction (XRD) analysis. The XRD
patterns of samples were shown in Fig.1. Figure 1
shows that, at a heating temperature of 550 o C, all
the samples obtained with two peaks at 27.4o are
assigned to reflect the (002) crystal plane formed
by the inter-layer ordered stacking of aromatic
nitrocarbon-conjugated 3s-triazine ring,

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The 5 th International Conference on Advanced Materials and Nanotechnology Hanoi, 2022

corresponding to an interplanar spacing of 0.322 No Samples Average crystal sizes d

nm, while the peak is around 13.4o , with a (nm)
corresponding d= 0.658 nm of the plane assigned to 1 U 15.1
the in-plane structural superposition. This value is 2 3UT 17.7
smaller than the size of a tri-s-triazine unit (about 3 UT 18.9
0.713 nm). These two peaks are attributed to the 4 U3T 19.1
(002) and (100) planes for the graphite structure 5 T 19.6
class of g-C3 N4 [12], respectively. Likewise, no From Table 1, we notice that the average crystal
residue peaks were detected. size of the samples gradually increased from 15.1
nm to 19.6 nm. This shows that when increasing the
amount of thiourea, the particle size also increases.

Figure 1. XRD patterns of g-C3 N4 samples

The process of synthesizing g-C3 N4 from urea and Figure 2. High resolution XRD patterns of g-C3 N4 samples
thiourea according to the reaction equation [13]:

(NH 2 )2 CO g-C3 N4 + H2 O + CO 2
(NH 2 )2 CS g-C3 N 4 + H 2 S + CS2

When gradually increasing the thiourea amount,

there is a larger peak shift to the 2θ angle,
specifically for samples using urea precursors it is
27.4o , for samples using thiourea precursors it is
27.5o (Fig.2). This indicates that the stacking
distance is the overlap between adjacent faces
becomes smaller because there is an occurrence of
S in the samples [12], [14]. At the same time, when
increasing the amount of thiourea, the intensity of
(100) is higher.
Figure 3. FTIR spectra of g-C3 N4 samples
The average size of the crystal is determined
according to the Scherrer equation: FTIR spectra were detailed to investigate the g-
𝐾𝜆
D= (1) C3 N 4 molecular structures.
𝛽.𝐶𝑂𝑆𝜃
Fig.3 performed FTIR spectra of the g-C3N4
Where D is the average crystal size, K= 0.9, λ =
samples. The FTIR spectra of all samples are
1.54065 Å is the diffraction wavelength, β is the
similar. Similar characteristic bands of g-C3N4
half-width value of the maximum diffraction line
have been reported. The bands in the range of
height (FWHM), θ is the diffraction angle at the
3400~3000 cm-1 and 1700~1000 cm-1 were
surface position diffraction (002).
assigned to the stretching modes of - NH and C–
The results are presented in Table 1 below.
N, C=N. The two peaks located at about 806
Table 1. Average crystal sizes of g-C3 N4 samples and 884 cm-1 originated from the breathing

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modes of triazine units, indicating that the The optical bandgap was extrapolated via the
molecular structure of the prepared g-C3N4 Kubelka-Munk method, in which the relationship
consists of triazine units [15]–[18]. between incident photon energy hν and the
Fig.4 shows a scanning electron microscopy Kubelka-Munk function F(R) follows [19]:
(SEM) image of the as-obtained g-C3N4
samples. The bulk structure was composed of [(𝐹(𝑅). ℎ𝜈] = 𝐵(ℎ𝜈 − 𝐸𝑔 )𝑛 (2)
thick, micron-sized particles, which were where F(R) is the Kubelka-Munk function
unevenly distributed over the entire area of the determined from diffuse reflectance R via the
sample. Most of the particles had multiple
formula F(R) = (1-R)2 /2R; hν is the incident photon
stacked layers and rough surfaces. There was energy; and n = 2 for indirectly allowed
not much difference in surface morphology
recombination with nanocomposites.
between samples.
Fig.4f shows the EDS of the g-C3 N4 sample used
thiourea as precursors. The C, N and S elements
were detected in the sample, proving the very
small amount of sulfur present in the sample.

Figure 4. SEM images and EDS of the g-C3 N4 sample: (a) T,

(b) U3T, (c) UT, (d) 3UT, (be) U, and (f) the EDS of the g-
C3N4 sample used thiourea as precursors

Fig.5a presents the diffuse reflectance spectrum of

the samples. It is easy to see that when the ratio of
thiourea to urea is increased, there is a shift in the
absorption margin to the long wavelength.
Absorption peaks around 300 - 400 nm characterize
the π - π* transition in the conjugated ring system,
including heterocyclic aromatics. The near 500 nm
features are due to the n - π* transition involving
free pairs on the boundary N atoms of the triazine
ring and the increased intensity for the S presented,
respectively.
Figure 5. (a) UV-vis reflectance spectra and (b) (F(R)hν)1/2
vs. (hν) plot of the g-C3 N4 samples

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The optical bandgap of the samples was extracted
from the plot of (F(R)×hν)1/2 versus (hν) (Fig.5b).
The extracted optical bandgap of samples U, 3UT,
UT, U3T and T was 2.95 eV, 2.94 eV, 2.88 eV, 2.76
eV, and 2.73 eV respectively. The narrowing of the
optical bandgap when the content of thiourea
increasing might be due to different reasons such as
the presence of oxygen vacancies, and the interfacial
interactions between g-C3N4 and H 2S or CS2.
CONCLUSION
IV.
The g-C3 N 4 was synthesized by
polymerization method from urea and thiourea.
Results for the two precursors both obtained g-
C3 N 4 . When increasing the content of thiourea,
the average crystal size of the samples gradually
increased from 15.1 nm to 19.6 nm. The optical
bandgap of samples U, 3UT, UT, U3T and T was
2.95 eV, 2.94 eV, 2.88 eV, 2.76 eV, and 2.73 eV
respectively.
ACKNOWLEDGEMENT
The current work was financially supported by
the Vietnam National Foundation for Science and
Technology Development (NAFOSTED) under
grant number 103.02-2020.39.
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