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Two-dimensional carbon nitride (C3N) nanosheets as promising materials for

H2S and NH3 elimination: A computational approach

Article · October 2019

DOI: 10.1016/j.physe.2019.113794

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 Physica E 117 (2020) 113794

Contents lists available at ScienceDirect

Physica E: Low-dimensional Systems and Nanostructures

journal homepage: http://www.elsevier.com/locate/physe

Two-dimensional carbon nitride (C3N) nanosheets as promising materials

for H2S and NH3 elimination: A computational approach
Omar Faye a, *, Ubong Eduok a, Jerzy A. Szpunar a, Aboubaker C. Beye b
a
Department of Mechanical Engineering, College of Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, S7N 5A9, Saskatchewan, Canada
b
Department of Condensed Matter Physics, University Cheikh Anta Diop of Dakar, Senegal

A R T I C L E I N F O A B S T R A C T

Keywords: Motivated by the increased emission of pollutant in the atmosphere, we explore the promise of pristine and
Two-dimension carbon nitride (C3N) defect carbon nitride (C3N) monolayers for H2S and NH3 capture by means of van der Waals corrected density
Partial dissociation functional theory (DFT) calculation. Our results reveal that the adsorption energies (Eb) of pristine C3N towards
Hydrogen sulfide (H2S)
H2S and NH3 are 0.610 eV and 0.444 eV, respectively. However, a spontaneous partial dissociation of H2S is
Ammonia (NH3)
Adsorption
observed in case of single C and N vacancy in C3N monolayer with minimum Eb values of 1.90 and 1.577 eV,
respectively. Furthermore, by using transition states (TS) calculation, we predicted a complete dissociation path
of H2S by ab-initio molecular dynamics simulation at 1000 K. Results show complete dissociation of H2S
molecule on C3N–C system. In addition, the trend of our results has demonstrated that O2 and H2O contami­
nations in our sample could barrier H2S adsorption. However, we also observed a physisorption phenomenon in
the case of the interaction between NH3 and C3N. In addition, the binding energy of NH3 at C and N vacancies
resulted in Eb values of 0.45 and 0.30 eV, respectively. This proves that the mono vacancy defect is highly se­
lective toward H2S gas than NH3. This study reveals a future for Two-Dimensional C3N nanosheets as H2S sensor.

1. Introduction
With the extensive use of fossil fuels during the last several decades,
air pollution has become a pressing problem to the environment due to
the consequences of toxic gas emissions. Among these pollutants,
hydrogen sulfide (H2S) and ammonia (NH3) are of particular interest
due to the fact that both gases are emitted from different sources like
processing and refining of fossil fuel, paper manufacturing, sewage and
wastewater treatment plants, composting works, and livestock farms [1,
2]. H2S and NH3 are irritating smelly gases with very low odor thresh­
olds of 1.1 ppb for H2S and 37 ppb for NH3. In particular, H2S is corro­
sive, extremely toxic gas, and a source of the acid rain upon oxidation to
sulfur oxide and subsequent reaction with atmospheric water [3].
Moreover, H2S can paralyze the sense of smell when rapidly absorbed by
the blood and could also lead to poor oxygen uptake at the cellular level
at a concentration of 30 ppm. Therefore, to reduce the detrimental ef­
fects of these gases, new environmental regulations have been enacted
to control H2S and NH3 gas emissions to the atmosphere. In 1988, the
Clean Air Act was the only legislation to regulate air pollution.
Furthermore, this act was consolidated along with the Ocean Dumping
Control Act, into the Canadian Environmental Protection Act (1999).
However, finding an efficient way to eliminate H2S and NH3 from
chemical industries: natural gas processing and utilization, hydro­
desulphurization of crude oil, and coal, also in livestock farms waste­
water treatment plants, is a key issue. The Claus process is a common
technique for H2S gas desulfurization and recovery of elemental sulfur
[4]. Nevertheless, its main problem is the recovery of elemental sulfur
from sulfur-containing gas which involves two reaction stages mainly as
described in Equations (1) and (2).
3
H2 S þ O2 →SO2 þ H2 O (1)
2
SO2 þ 2H2 S→2H2 O þ 3S (2)
Equation (1) is an endothermic process where the decomposition of
H2S into SO2 and H2O occurs in the temperature range of 1000–1200 � C.
However, in Equation (2), SO2 and H2S are transformed into elemental
sulfur and H2O, despite that 3–5% of the H2S is left in the tail gas [5]. On
the other hand, decomposition of NH3 is an endothermic process with
54.6 kJ/mol [6] and the decomposition process is given by equation (3).

* Corresponding author.,
E-mail addresses: omf071@mail.usask.ca, omsofaye@yahoo.fr (O. Faye).

https://doi.org/10.1016/j.physe.2019.113794
Received 22 August 2019; Received in revised form 3 October 2019; Accepted 18 October 2019
Available online 25 October 2019
1386-9477/© 2019 Elsevier B.V. All rights reserved.
O. Faye et al.
Fig. 1. Optimized structures of pristine C3N along with their spin density of state, where the symbols A, B, C and D denote CC ring, CN ring, single carbon defect and
single nitrogen defect respectively. The blue and gray balls are nitrogen and carbon respectively. (For interpretation of the references to colour in this figure legend,
the reader is referred to the Web version of this article.)
1 3
NH3 → N2 þ H2
2 2
The main issue surrounding this decomposition reaction is that the
recombinative N2 desorption is the rate-limiting step. Therefore, to
bridge this void different purifications processes such as cryogenic
distillation, membrane separation, absorption and adsorption have been
proposed [4–7]. Among these purification processes, adsorption method
has been successful in toxic gas removal [8,9] because of its unique high
efficiency and low cost. Different sorbents, such as carbon nanotubes
[10–12], polymers [8], activated carbons [8,13], carbon fiber [14,15],
metal-organic frameworks [16,17] and graphene [18–20] have received
great attention for toxic gas removal. However, these pristine materials
show a weak interaction with those pollutants. In addition, the
metal-functionalized versions of these materials are also susceptible to
sulfur poisoning [4]. Therefore, to overcome these drawbacks, intense
researches have been devoted on a new two-dimensional material,
carbon nitride (C3N), which is structurally similar to graphene and has
demonstrated immense prospects for many future applications [21,22].
Moreover, C3N can be synthesized by direct pyrolysis of hex­
aaminobenzene trihydrochloride single crystals [23,24] or by the
polymerization of 2,3-diaminophenazinehas [25]. Like graphene C3N is
a monolayer that has a 2D honeycomb lattice with the homogeneous
distribution of N and C atoms [25]. Furthermore, Yang et al. [25] stated
that C3N sheet is more stable than graphene at room temperature due to
the fact that it was found to be stable up to 1100 � C in argon atmosphere
and up to 550 � C in air. In addition, it has an excellent stiffness
(364.33 N m 1), high storage capacity (1071.56 mA h g 1), high
mobility charge carrier (180–200 cm2 V 1s 1 and good electronic con­
ductivity (band gap of 0.39 eV) [26,27]. Based on its physical, chemical
and mechanical properties, C3N has potential application in energy
application [26]. In addition, in our previous work, we have predicted
that two-sided Sc/Ti doped C3N has a high capacity of 9 wt% of
hydrogen storage [28]. Furthermore, recent results have shown that C3N
is a promising candidate for gas sensor [29–31], [32]. Ma et al. [33]
reported that the repair processes of C and N single vacancies by CO or
NO molecules are both thermodynamically and kinetically favorable.
Moreover, Cui et al. [34] stated that C3N monolayer is preferable for
Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794
NO2 and SO2 molecules with suitable adsorption strength and apparent
(3)
charge transfers. Despite its physical and chemical properties and its
efficiency for toxic gas removal reported in the literature, a detailed
theoretical study on the interactions between pristine and defected C3N
towards H2S and NH3 molecules has not been addressed. To bridge this
gap, we report here a detailed DFT investigation on the adsorption
mechanism of H2S and NH3 with pristine and defected C3N monolayers.
2. Computational details
We performed a first-principles calculation by using spin unrestricted
plane-wave density functional theory with the self-consistent field
method as implemented in the Dmol3 [35,36] module. The generalized
gradient approximation (GGA) using Perdew Burke and Ernzerhof (PBE)
[37] was used to approximate the exchange-correlation effects on
electron electron interaction. The semicore pseudopotentials were used
to represent the core electrons as a single effective potential [38]. The
double numerical plus polarization (DNP) used as a basis set included
the vdW interaction (DFT-D) as proposed by Grimme [39], which adds a
contribution of Rε 6 in the DFT total energy for each pair of atoms sepa­
rated by a distance R. We used a 2 � 2 supercell of C3N that consists of
24C and 8 N. The Brillouin zone integration was performed through the
Monkhorst Pack scheme [40] with kpoint mesh of 10 � 10 � 1. To find
the optimal size for the vacuum space, the convergence test with respect
to the box dimension in the z direction was performed and 20 Å was
found sufficient as a vacuum space. To calculate the chemical potential
of carbon and nitrogen we use a cubic cell with a lattice parameter
(ac ¼ 25 Å). The optimized lattice of the supercell was a ¼ b ¼ 9.716 Å
where a and are lattice constants. The energy minimization was done
with the convergence tolerance energy of 10 5 Ha. The atomic positions
were relaxed such that the force acting on each atom was less than 0.002
Ha/Å.
2
O. Faye et al. Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794

Fig. 2. Represent the intensity of the mono-vacancy formation energy. The

blue pick stands for the nitrogen vacancy while the red one for the carbon
vacancy. (For interpretation of the references to colour in this figure legend, the
reader is referred to the Web version of this article.) Fig. 3. Density of state of pristine C3N (red line), single carbon defect (Cde­
fectC3N (black line)) and single nitrogen defect (NdefectC3N (blue line)). (For
interpretation of the references to colour in this figure legend, the reader is
3. Results and discussions
referred to the Web version of this article.)

3.1. Electronic structure of pristine and defect carbon nitride (C3N)

Probing the electronic properties of bulk C3N is an important step
that allows us to figure out how the presence of foreign molecules could
affect its structure. Our calculations predicted that the lattice parameter
of bulk C3N is a ¼ b ¼ 4:858 � A, which is similar to the experimental
value a ¼ b ¼ 4.78 Å previously reported by Javeed et al. [24] and those
earlier from other literature sources [41,42]. The calculated bond
lengths of C–C and C–N are 1.400 and 1.397 Å, respectively, which
agrees very well with the results reported by Guo el al [26,41,43]. The
energy gap Eg of C3N is found to be 0.45 eV, which suggests its semi­
conducting nature and the value is close to what is reported in the
literature [25,30]. Magnetic calculations have revealed that pristine C3N
is nonmagnetic. Since, C3N is a honeycomb structure consists of two
types of hexagonal rings which are the CC rings with six carbon atoms
and the NC rings with two nitrogen and four carbon atoms as showed
Fig. 1 with the symbol A and B respectively.
Therefore, based on the symmetry of C3N monolayer, two single
defects can be created as displayed in Fig. 1, where the symbol C and D
indicate the optimized structure of mono-vacancy defects in C3N. The
defect formation energies that is the energy needed for the creation of
one single vacancy are determined from the formula:
Ef C ¼ EðC3 NÞdefected þ μðCÞ EðC3 NÞ
� �
Ef ¼ EðC3 NÞdefected þ μ N EðC3 NÞ
N
structure of pristine C3N and mono-vacancy C3N complexes were
investigated as showed in Fig. 3. Moreover, the introduction of va­
cancies on C3N decreased the intensities of the picks decreased of Cde­
fect and Ndefect compared to pristine C3N as illustrated in Fig. 3. This
phenomenon explains that the introduction of vacancy defect on C3N
system decreases the electrons mobility. To understand the changes in
density of state of C3N in C and N defects, the atomic charges of these
three different structures were analysed through Mulliken charge anal­
ysis. Charge analyses reveal averages of 0.410 |e| for N atoms and
þ0.137|e| for C atoms of pristine C3N compared to 0.072 |e| for the C
atom within the viscinity of the Ndefect while the N atoms bear an
average charge of 0.388 |e|. However, in the Cdefect the C atoms of the
vacancy bear an average charge of 0.060 |e| while the N atom gain an
average charge of 0.386|e|. The trend in charge distribution explains
the decrease in electron mobility from pristine C3N to mono-vacancy
defect structures (Cdefect and Ndefect).
3.2. Adsorption of H2S on pristine and defected C3N
To investigate the interaction of H2S molecule with pristine and
defected C3N sheet, we explore the different orientations of the H2S
(4) molecule at all the available binding sites of pristine and defected C3N.
The strength of this interaction is measured by evaluated the value of the
(5) binding energy (Eb) which is calculated by using the following relation:

where E (C3N) defected and E (C3N) are total energies of defected and Table 1
The binding energy (Eb), the corresponding energy gap (Eg) and the minimum
pristine C3N monolayers, respectively. Here μðCÞ and μðNÞ are the
distance between C3N plane and the closest atom of H2S of each orientation
chemical potentials of C and N atoms which are calculated using a cubic
(d_C3N-A).
cell of dimension (ac ¼ 25 Å), respectively. By using equations (4) and
Adsorption site H2S orientations Eb ðeVÞ Eg (eV)
(5), the formation energies of C and N defects are calculated to be 6.8 dC3N A ðAÞ
�

and 6.82 eV, respectively as illustrated in Fig. 2. CC ring PL 0.570 2.534 0.462
Introduction of vacancy defects caused a significant change in the PU 0.485 2.714 0.476
structural properties of C3N, especially in the vicinity of the vacancy PD 0.568 2.626 0.462
with C–C and C–N bond lengths elongated to 1.45 and 1.42 Å, respec­ V 0.499 2.550 0.473
IV 0.568 2.654 0.465
tively. Slight structural distortion breaks the symmetry of C3N mono­
layer as a result of local bonding rearrangement. A slight change has also Adsorption H2S orientations
been observed in the structure of C3N monolayer away the defected site. CN ring PL 0.587 2.506 0.467
Magnetic calculations have suggested that the mono-vacancy induced PU 0.488 2.650 0.471
PD 0.581 2.516 0.469
C3N monolayers are nonmagnetic as displayed in Fig. 1 where there is a
V 0.485 2.793 0.473
total overlap between the spin up and down. Furthermore, the electronic IV 0.585 2.560 0.470

3
O. Faye et al. Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794

Table 2 atoms, the most preferable orientation of H2S is also the plane one with
Adsorption energy (Eb) along with the distance between C3N–C sheet and the Eb, d_C3N-A and Eg values of 0.587, 2.506 Å and 0.467 eV, respectively.
sulfur atom (d_C3N–C–S) and the band gap energy (Eg). The Eb values for other orientations lie in the window of
Adsorption site H2S orientation Eb (eV) d_C3N-C-S (Å) Eg (eV) 0.488–0.585 eV, and the corresponding d_C3N-A distances are between
2.516 Å to 2.793 Å. The Eg values are found to be within
Cdefect PL 1.922 3.504 0.068
PU 2.843 1.759 0.399
0.469 eV–0.473 eV. We also notice that all these interactions happen in
PD 2.843 1.759 0.397 the gas phase for both adsorption site (CC an CN rings), which agree with
V 1.900 3.507 0.054 the one reported by Wang et al. [44] which can be described by the
IV 2.843 1.759 0.395 following reaction:
Adsorption site H2S orientations Eb (eV) d_C3N-C-S (Å) Eg (eV)
H2S(g) þ C3N(s) → H2S(g) þC3N(s) (7)
Ndefect PL 1.577 3.528 0.367
PU 1.581 3.489 0.378 To understand the interaction mechanism between H2S molecule and
PD 1.576 3.620 0.372 C3N system, we study the charge transfer mechanism. To do so, we have
V 1.583 3.472 0.372 employed Mulliken charge analysis. We found that the N atoms are more
IV 1.579 3.463 0.369
electronegative with an average charge of 0.345 |e| while the average
charge on the C atom is þ0.234 |e| for the NC ring. The charge distri­
Eb ¼ ðEðC3 N@H2 SÞ EðC3 NÞ EðH2 SÞÞ (6) bution of H2S molecule changes by approaching to the C3N plane where
the H atoms bear a charge of þ0.0 2|e| while the S atom possesses a
Here, the first, second and third terms represent the total energies of charge of 0.11 |e|. The weak interaction can be explained by the
pristine/defected C3N loaded with H2S, pristine/defected C3N and the competition between the inhomogeneous charge distribution of C3N
H2S molecule, respectively. H2S molecule can take five different orien­ complex. For H2S adsorption on the CC ring the average charge on the C
tations (planar (PL), perpendicular-up (PU), perpendicular-down (PD), and S atoms are þ0.23 and þ 0.12 e, respectively. These charges are in
V-form (V) and inverse-V (IV)) over CC ring and CN ring of C3N good agreement with Cui et al. [34]. Furthermore, we describe the
monolayer and these five orientations are given in the Supporting In­ adsorption mechanism of H2S on defected C3N monolayers. For this
formation (see Fig. S1). Using Equation (6), we also determine the most purpose, we created a mono-vacancy by removing one C or N atom from
favorable orientation of H2S on CC and CN rings. The calculated binding C3N monolayer and the structure is optimized as shown in Fig. 1 (C, D).
energy (Eb), the corresponding energy gap (Eg) and the minimum dis­ Adsorption of H2S in N and C vacancy-induced C3N (C3N–N and C3N–C)
tance between C3N plane and the closest atom of H2S of each orientation reveals a spontaneous dissociation of H2S is shown in the Supporting
(d_C3N-A) are summarized in Table 1. Information (see Figs. 4 and S5) compared with the earlier results re­
To give a better view for the reader, the initial and final (optimized) ported in the literature [45–48] The corresponding Eb, d_C3N-A and Eg
structures of the interaction between C3N system and the five orienta­ values are given in Table 2.
tions o H2S are given in the Supporting Information (see Figs. S2 and S3). The results in Table 2 show that inverse V, perpendicular–up and
Based on the calculated values in Table 1, we concluded that the plane down orientations of H2S have Eb, values of 1.900,2.843 and 2.843 eV,
orientation is the most favorable one with Eb, d_C3N-A and Eg values of respectively, which leads to the dissociation of H2S as depicted in
0.570 eV, 2.534 Å and 0.462 eV, respectively. The Eb values of other (Fig. S5). The equilibrium distance between C3N–C monolayer and the
orientations like inverse-V, V, perpendicular-up and perpendicular–­ H2S (d_C3N–C–S) for inverse V (perpendicular–up and down shape) and
down are found to be in the range [0.463–0.568 eV] and their corre­ planar (V shape) of H2S are 1.759 and 3.504 Å, respectively. A partial
sponding band gaps in the energy window are 0.462 eV–0.476 eV. dissociation of H2S without any energy barrier is also observed in case of
Moreover, the minimum d_C3N-A between C3N sheet and the closest atom N vacancy-induced C3N monolayer (C3N–N) for all the five orientations
of H2S of each orientation varies from 2.534 Å to 2.714 Å in the case of of H2S molecule and the Eb values lie in the range of 1.576 eV–1.583 eV
CC adsorption site. However, for the NC ring with two N and four C

Fig. 4. MD simulation at T ¼ 1000 K of H2S planar and inverse-V on C3N–C and planar H2S on C3N–N systems along with the reactant and product of the simulation.
The black curve represents H2S planar, the red curve stands for H2S inverse –V on C3N–C and the blue curve for H2S planar orientation on C3N–N complex. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

4
O. Faye et al. Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794

Fig. 5. Represents the two possible paths of the second hydrogen transfer from SH radical to the same carbon atom path (1) or on the nitrogen atom path (2).

and the corresponding d_C3N–N–S (Eg) vary between 3.463 (0.367) to
3.620 Å (0.378 eV). Furthermore, to understand the interaction mech­
anism, we explore Mulliken charge analysis which shows that C and N
atoms in vacancy-induced C3N carry charges of 0.55 and þ 0.23e
respectively. The strong interaction between H2S and C3N–C can be
explained by the attractive coulomb interaction between positive H
atom and negative charge of C atom of C3N–N and C3N–C which results
in a partial spontaneous dissociation of H2S which is shown in the
Supporting Information (see Figs. S4 and S5).
The H2S can partially dissociate in two ways on C3N–N depending on
its orientation and one way on C3N–C as depicted on (Fig. S4) and
(Fig. S5) compared to the results reported earlier by Khodadadi in

Fig. 6. The optimized structure of the adsorption of H2S in the presence of H2O and O2 on C3N–C and C3N–N complexes where red atom stands for O atom, gray atom
represents carbon atom C, the blue atom stands for N atom, the yellow atom stands for sulfur and the white ball for H atom. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

5
O. Faye et al. Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794

Fig. 7. Represents the optimized structure of the coadsorption of H2S, H2O and O2 on C3N–C and C3N–N complexes where red atom stands for O atom, gray atom
represents carbon atom C, the blue atom stands for N atom, the yellow atom stands for sulfur and the white ball for H atom. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

Ref. [49]. To check the thermal stabilities of H2S adsorbed defected C3N
monolayers, we have performed ab initio molecular dynamic simulation
(AIMD) for the most dominant orientation of H2S on C3N–C and C3N–N
complexes. For this purpose, we have employed the Nose Thermostat
algorithm at 1000 K for 6 ps on H2S dissociation on C3N–C and C3N–N
for different orientations. The simulation results are plotted in Fig. 4.
We also observe a complete dissociation of H2S on C3N–C while SH
radical remains physiosorbed on C3N–N as described by these following
reaction processes:
T¼1000K
C3 N C þ H2 SðgÞ → C3 N CH2 þ SðsÞ
T¼1000K
C3 N N þ H2 SðgÞ → C3 N NH þ SHðgÞ
Furthermore, a transition state calculations (TS) connecting two
stable structures through a minimum energy path has been examined
based on the complete linear synchronous transit (LST) and quadratic
synchronous transit (QST) method to determine the energy requires for
the second H atom transfer from SH radical to C3N–C system. The re­
action (Ereaction) and the activation energy (EðaÞ ) are defined by the
following equations:
Ereaction ¼ EðPÞ EðRÞ
EðaÞ ¼ EðTSÞ EðRÞ
where E(p) is the energy of the product of each reaction, E(R) is the
corresponding energy of reactant in each step, and E(TS) is the energy of
the transition state in each elementary reaction. The potential energy
diagram that links these two states is depicted in Fig. 5.
Using equations (10) and (11), we noticed that the second H atom
transfer from SH radical to C3N–C complex is an exothermic process
with Ereaction and Ea values of 0:293 and 0:035 eV respectively; for path
1 as compared to 0531 and 0.180 eV for the path 2. Based on the
activation energies, we can state that the H atom transfer from SH to the
nearest N atom of the defect is more favorable than the transfer of H
(8)
from SH radical to the nearest C atom of the defected C3N. These results
show that defective carbon nitride is an efficient sorbent to capture H2S
(9)
compare to the results reported earlier by Yousefian et al. [50].
In practical applications, oxygen (O2) and water (H2O) interfere
strongly with systems under investigation, as reported in our previous
work [51] during H2 storage. This has necessitated the further verifi­
cation of their potential influences on our system as we study in this last
section, the selectivity of the mono-vacancy C and N defect in the
presence of oxygen (O2) and water (H2O) molecules. To evaluate the
strength of the interaction between the C and N defect with O2 and H2O
in the presence of H2S, we use the following equations:
(10)
EbO2 ¼ EO2 þ EC3N X EC3N XþO2 (12)
(11)
EbH2 O ¼ EH2 O þ EC3N X EC3N XþH2O (13)

6
O. Faye et al. Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794

Fig. 8. Potential energy diagram showing the energies of the chemical species and transition state (TS) involved in the migration of H on C3N–C system.

EadsþH2S ¼ EH2S þ EC3N XþY EC3N XþH2 SþY (14) Table 3

Binding energy (Eb), the minimum distance between C3N plane and the closest
In equation (12),EbO2 is the energy of an isolated O2 molecule, EC3N X
atom of NH3 for each orientation (d_C3N–B) and the corresponding energy gap
the energy of the mono-vacancy (X ¼ C and N), EC3N XþO2 is the total
(Eg).
energy of the oxygen bind to the mono-vacancy (X ¼ C and N). Equation
(13) represents the adsorption energy of H2O in the mono-vacancy Adsorption site NH3 orientations Eb ðeVÞ d C3N B ðAÞ
� Eg (eV)

(X ¼ C an N) where EH2 O stands for the energy of an isolated H2O CC ring PL 0.448 2.678 0.446
molecule and EC3N XþH2O is the total energy of H2O in the mono-vacancy PD 0.387 2.362 0.446
(X ¼ C and N). Finally, equation (14) defines the binding energy of H2S Adsorption site NH3 orientations
in the presence of O2 and H2O in the mono-vacancy (X ¼ C and N). The
CN ring PL 0.332 2.673 0.427
relaxed structures are presented in Fig. 6.
PD 0.330 2.734 0.430
By using equation (12), we found that the adsorption energy of an O2
molecule on C3N–C was EbO2 ¼ 0.462 eV compared to the 0.677 eV for
O2 on C3N–N. In addition, using equation (13), we determine the EadsþH2S ðH2O=O2Þ ¼ 1.082 eV for C3N–N compared to 2.920 eV for C3N–C
adsorption energy of a H2O molecule on C3N–C is EbH2O ¼ 0.715eV case.
compared to 0.596 eV for H2O on C3N–N complex. Moreover, we eval­ Finally, a transition state (TS) calculation was used to determine the
uated the binding energy of H2S in the presence of an O2 molecules. The energy required for a complete dissociation of H2S in the coadsorption
calculated adsorption energy of H2S in the presence of O2 is Eads þ H2S/ with H2O and O2 molecules in C3N–C system. The potential energy di­
O2 ¼ 0.673 eV on C3N–C compared to 0.602 eV for C3N–N. In addition, agram that connects these two states is depicted in Fig. 8. Using equation
the binding energy of H2S in the presence of H2O in the vacancy defect as (10), we find that the reaction process is exothermic with an enthalpy o
also explored by means of equation (14). Our results show that the reaction EH ¼ 0.227 eV compared to 0.293 eV in the case of mono-
adsorption energy of H2S in the presence of water are Eads þ H2S/ vacancy Cdefect (C3N–C) system and 0.106 eV is the energy required
H2O ¼ 0.802 eV for C3N–N complex compared to 1.862 eV for C3N–C. to overcome the barrier compared to 0.035 eV or C3N–C compared to
Furthermore, to be more realistic, we investigate the strength of the 1.183 eV reported by Bo et al. [52]. These results show that the presence
simultaneous adsorption of H2S in the presence of both O2 and H2O with of O2 and H2O contaminations can be a barrier to the reactivity of the
C3N–C and C3N–N complexes. The strength of these interaction is mono-vacancy C3N toward H2S adsorption. Therefore, one can solve this
measured using the following equation: issue by pressurizing the sample at the vacuum level before any
adsorption test.
EadsþH2S ðH2O=O2Þ ¼ EH2 S þ EC3N XþH2 OþO2 EC3N XþH2 SþO2 þH2 O (15)

where EadsþH2S ðH2O=O2Þ is the adsorption energy of H2S in the presence of

3.3. Adsorption of NH3 on pristine and defect C3N
both H2O and O2 molecule, EC3N XþH2 OþO2 is the total energy of the
coadsorption of H2O and O2 in the mono-vacancy defect and
In this section, we investigate the interaction of NH3 molecule with
EC3N XþH2 SþO2 þH2 O the total energy of H2S in the presence of both H2O
pristine C3N, C3N–C and C3N–N monolayers. Like H2S binding, the NH3
and O2 molecules. The corresponding optimized structures of the
molecule was introduced to both CC- and the CN-ring on C3N mono­
interaction are portrayed in Fig. 7. Using equation (15), we find that the
layer. The optimized structures of the interaction between NH3 and C3N
strength of the binding energy in the presence of H2O and O2 is
and the two different orientations of NH3 are given in the Supporting

7
O. Faye et al.
Table 4
Binding energy (Eb) the closest distance between C3N sheet with the nearest
atom of NH3 molecule (d_C3N–B) and the energy gap denoted by Eg.
Adsorption sites NH3 orientations Eb ðeVÞ dC3N B (Å) Eg ðeVÞ
Cdefect PL 0.608 2.224 0.054
PD 0.573 2.312 0.043
Adsorption sites NH3 orientations
Ndefect PL 0.535 2.345 0.092
PD 0.533 2.265 0.087
Information (Figs. S6 and S7) and Eb, d_C3N-B and Eg values are sum­
marized in Table 3.
Our results show that the most favorable orientation of NH3 is its
planar one with Eb value of 0.448 eV as compared to 0.387 eV for the
perpendicular orientation in the CC-ring. The d_C3N–B (Eg) values are
2.678 Å (0.446 eV) for the planar orientation as compared to 2.362 Å
(0.446 eV) in the case of the perpendicular shape for the CC-ring.
However, in the CN-ring the planar orientation is the most preferable
with Eb ¼ 0.332 eV, d_C3N-B ¼ 2.673 Å and Eg ¼ 0.427 eV as compared to
0.330 eV, d_C3N-B ¼ 2.730 Å and Eg ¼ 0.430 eV for the perpendicular
one. The reaction process is described by the following reaction for the
both adsorption sites.
NH3(g) þ C3N(s) → NH3(g) þC3N(s) (17)
Mulliken charge analysis reveals that C and N atoms have an average
charge of þ0.2 and 0.345 e, respectively. These results revealed that a
weak interaction between pristine C3N and NH3 which is in agreement
with Cui et al. [34]. Furthermore, the interaction between NH3 and
mono-vacancy C (C3N–C) and N defect (C3N–N) was investigated in this
last section. The Eb, d_C3N–B and Eg values of NH3 adsorption on
vacancy-induced C3N are given in Table 4.
The initial and optimized structures are given in the Supporting In­
formation (Fig. S8). We noticed an enhancement in the interaction of
NH3 and C3N–C, with Eb values jumps to 0.608 eV for the planar
orientation and 0.573 eV for the perpendicular orientation. The d_C3N-B
(Eg) values for the planar and perpendicular orientations are 2.312
(0.054) and 2.224 Å (0.043 eV), respectively and the reaction that takes
place in the adsorption sites is:
NH3(g) þ C3N-X(s) → NH3(g) þ C3N-X(s) (18)
However, in the C3N–N complex we observed a slight increase of the
binding energy which goes from Eb, d_C3N-B and Eg values are 0.535
(0.533 eV), 2.345 (2.65 Å) and 0.092 (0.087 eV), respectively for the
planar (perpendicular) orientations of NH3. These results showed that
mono-vacancy C and N defect enhanced the interaction of NH3 with
C3N–C and C3N–N systems.
4. Conclusions
Motivated by the search of clean working conditions while also
avoiding environmental pollution, we performed first-principles calcu­
lations based on density functional theory (DFT) to study the interaction
between H2S and NH3 with pristine and defect C3N crystal. Our results
showed that the interactions between H2S and NH3 molecules with
pristine C3N are weak in the gas phase. Furthermore, the adsorption of
H2S and NH3 were enhanced by the presence of single carbon or nitrogen
vacancy on C3N. The results predicted a partial dissociation of H2S
molecule on single C or N vacancy with a minimum binding energy
Eb ¼ 1.900 eV for C3N–C compared to Eb ¼ 1.577 eV for C3N–N.
Furthermore, by means of TS calculation, our results revealed a com­
plete dissociation of H2S in C3N–C system as SH physiosorbed on C3N–N.
We also performed a MD simulation at 1000 K to prove this complete
dissociation process. However, the single C or N defect enhanced the
interaction between NH3 with single C and N vacancies with a binding
8
Physica E: Low-dimensional Systems and Nanostructures 117 (2020) 113794
energy varying from 0.234 eV for pristine C3N to 0.67 eV for defect C3N
complex. Our results predicted that single C defect may potentially help
to improve the adsorption capacity of C3N toward H2S and NH3 gases.
However, our results also show that the presence of O2 and H2O con­
taminations can be a barrier to the reactivity of the mono-vacancy C3N
toward H2S adsorption. Therefore, to avoid those contaminants, it is
recommended to pressurize the sample at the vacuum level before any
adsorption test for practical purposes. Experimental studies are required
in order to bring this founding in practical live.
Notes
The authors declare no competing financial interest.
Acknowledgments
This work was supported by the National Engineering Research
Council of Canada and the Canada Research Chair program.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.physe.2019.113794.
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