Applied Surface Science Advances 11 (2022) 100301

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Applied Surface Science Advances

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Nitrogen doping effects on the physical and chemical properties of bilayer

graphdiyne: A density functional theory approach
Nguyet N.T. Pham
Faculty of Chemistry, University of Science, Vietnam National University Ho Chi Minh City, Ho Chi Minh 721337, Vietnam

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

Keywords: The topological of sp and sp2- C hybridization of graphdiyne (GDY) structure gives GDY the uique and fascinating
Carbon-based properties compared to the other carbon allotropes which contain only sp2- or sp3-hybridized C existence. The
Graphdiyne π*-conjugated and Van der Waals interlayer interaction between layers and stacking mode alter the electronic
Nitrogen doping
conductivity, mobility, and capacity of bilayer GDY over monolayer structure. Herein, pristine and N-doped
Bilayer graphdiyne
Density functional theory
bilayer GDY are investigated for equilibrium structure, electronic properties, and gas molecules (O2, CO, CO2,
HCHO) interaction. The pristine AB(β1) and AB(β2) are the antiferromagnetic semiconductors with an energy
gap of 0.41 eV and 0.29 eV, respectively. N doping on bilayer GDYs shows a lower energy gap than pristine
bilayer GDY. N prefers doped at the sp-N2 site on both AB(β1) and AB(β2) stacking models of bilayer GDY, and
N2-AB(β1) indicates higher thermodynamic stability and higher HOMO-LUMO energy gap at Γ path than that of
N2-AB(β2) configuration. Both N2-AB(β1) and N2-AB(β2) show poor selectively of toxic gas molecules (CO, CO2,
HCHO). On the other hand, the -0.305 eV (-0.547 eV) of O2 adsorption energy on N2-AB(β1) (N2-AB(β2)) and the
elongate of O-O bond distance demonstrates that N2-AB(β1) and N2-AB(β2) can be active for oxygen reduction.
This work provides the physical-chemistry properties of N-doped stacking bilayer GDY and a potential idea for
designing the new efficient and high CO tolerance for electrocatalyst systems.

Introduction electrical conductivity [13]. The GDY is a magnetic semiconductor [9,

Carbon has attracted a great deal of attention from the scientific
community over the past several decades because of its unique ability to
form many allotropes, such as zero-dimensional (OD) fullerene [1],
one-dimensional (1D) single-walled carbon nanotube [2], and
two-dimensional (2D) graphene [3] have been synthesized. Carbon
materials are promising candidates and the great supporting layer
applied for energy conversion materials since the interaction between
the active phase, and carbon support can alter electron transportation.
The high conjugated of carbon-rich materials with tunable optoelec­
tronic and structural properties could act as potential systems for the
next-generation energy conversion and storage devices [4, 5, 6, 7]. A
new 2D carbon allotrope is graphdiyne (GDY), which features topolog­
ical two acetylenic linkages ( − C ≡ C − C ≡ C − ) sp and sp2-C hybrid­
ization [8,9,10] which is unlike the other carbon allotropes that contain
only sp2- or sp3- C hybridization [11,12]. The presence of sp-hybridized
gives GDY distinctive structures, unique and fascinating properties that
differ from other forms of carbon, such as abundant C − C chemical
bonds, unique electronic property, physicochemical stability, and
14], with low thermal conductivity and ultrahigh capacity [15], which
are very potential properties to take the idea for designing the new
efficient batteries or fuel cell devices.
The high porosity along with the coexistence of sp and sp2 hybridi­
zation in GDY structure, shows that the π/π* orbitals can rotate
perpendicular to − C– – C− bonds [18], which is more suitable for
–
anchoring single atoms. Nowadays, N-doped GDYs are paid much
attention in the scientific community as the potential candidate for en­
ergy conversion, especially for Oxygen reduction reaction (ORR) cata­
lysts with high performance, small crossover effect, and long-term
stability [16,17,18]. Liu et al. [19] synthesized the N-doped single GDY
with the high ORR catalytic activity (Eonset≈ 0.899 V vs. RHE) and good
tolerance to methanol in alkaline solution. Notably, N can be doped to
GDY surface on five different sites: sp2 (graphitic and pyridinic)-N, two
sites for sp-N depending on which hybridized carbon and the amino-N
[20]. The sp2-N (pyridinic N) and the sp-N dopants can promote the
capacity and electrocatalytic performance of graphdiynes [21,22,23].
Liu et al. [19] proposed that the sp-N plays a more important role than
sp2-N on the charge distribution and gas sensor adsorption.

E-mail address: ptnnguyet@hcmus.edu.vn.

https://doi.org/10.1016/j.apsadv.2022.100301
Received 29 June 2022; Received in revised form 1 September 2022; Accepted 4 September 2022
Available online 14 September 2022
2666-5239/© 2022 The Author. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
N.N.T. Pham Applied Surface Science Advances 11 (2022) 100301

Fig. 1. The geometry structure and band structure of (a) monolayer graphdiyne, bilayer graphdiyne (b) AB(β1) and AB(β2).

Moreover, the stacking models of few layers of GDY can alter the
Table 1
physicochemical properties, and the interspacing between GDY layers
The interlayer distance (Å) of bilayer GDY AB (β1) and AB (β2). (The configu­
can also increase the capacity and conductivity over the GDY monolayer
rations as shown in Figure 1); the bonds lengths (Å) of Csp2 − Csp2, Csp2 − Csp,
[24], especially bilayer of GDY. The stacking models and the electronic Csp − Csp single and triple bonds on single GQY and GDY bilayer.
properties of bilayer and N-doped bilayer GDYs should be figured out in
Interlayer C-C bond length (Å)
both theoretical and experimental. AB (β1) and AB (β2) have been re­
(Å) Aromatic Csp2 − Csp Single Triple
ported as the most stacking models of bilayer GDT [24]. Moreover, the Csp2 − Csp2 Csp − Csp Csp − Csp
N-doped bilayer of GDY has not yet been studied in previous theoretical
Single 1.43 1.43 1.40 1.40 1.34 1.34 1.23 1.23
and experimental studies. Thus, the structural and electronic properties GDY [46, 51, 52, [46, 51, 52, [53, 54, [46,
of pristine and N-doped bilayer GDY AB (β1) and AB (β2) were investi­ 53] 53, 54, 55] 55] 52-55]
gated by using density functional theory (DFT) calculations. Besides, the AB (β1) 3.42 (3.42 1.43 1.40 1.34 1.23
O2 and toxic gas molecules (CO, CO2, HCHO) adsorption on N-doped [53])
AB (β2) 3.40 (3.40 1.46 1.42 1.36 1.24
bilayer GDYs are also delivered to provide the essential perspective for
[53])
designing the new efficient eco-friendly materials which can be applied
in fuel cell, batteries, or transistor devices.
Results and discussion
Methodology
Equilibrium graphdiyne structures
The all DFT calculations were figured out based on the projector-
augmented wave (PAW) method [25] within the Vienna Ab Initio The optimized structure of single GDY and two most stable stacking
Simulation Package (VASP) [26,27]. We applied the generalized models of AB(β1) and AB(β2) of bilayer GDY are shown in Fig. 1. The AB
gradient approximation (GGA) with Perdew–Burke–Ernzerhof (PBE) (β1) configuration resembles that of the Bernal AB stacking bilayer
[28] for describing the exchange-correlation potential, which well de­ graphene concerning the relative position of the hexagonal benzene
scribes the carbon-based systems in other studies [29–42]. The 600 eV of ring. The AB(β2) configuration is obtained by moving the hexagonal ring
energy cut-off is used for all calculations. Grimme’s DFT-D3 [43] is on the top layer perpendicular to the edge of the lower hexagonal ring by
applied to describe the van der Waals interactions between the layers of 3.93 Å and is located in the triangle region of the diyne chain of the
AB-stacked bilayer GDY. Ground state geometries were obtained with 3 second layer.
× 3 × 1 Monkhorst-Pack set of k-points and the k-points of 6 × 6 × 1 was As shown in Table 1, with vdW correction included, the relaxed
applied for all electronic calculations. The dipole correction [44] along interlayer spacing of AB(β1) and AB(β2) configurations are 3.42 and
the z-direction is involved in all our calculations. The self-consistent 3.40 Å, respectively (Table 1), which well agrees with the previous study
field (SCF) for force and energy conversion are applied to 10− 5 eV and [24]. Fig. 1(a) shows the geometry and band structure of the GDY
0.02 eV A− 1, respectively. The crystal structure of GDY was optimized as monolayer. The energy gap of single layer GDY is calculated as 0.50 eV,
a = b = 9.45 Å; well agrees with other theoretical and experimental which is well agreement with those reported in previous works using the
studies [9,14,45,46,47,48,49]. A 2 × 2 unit cell with a vacuum of 30 Å DFT method (0.44 [14], 0.46 [9], or 0.53 [50] and 0.52 eV [14]).
along the z-direction (18.92 × 18.92 × 20.00 Å) was build for all As shown in Fig. 1(b)(c), AB(β1) stacking indicates an antiferro­
configurations. magnetic semiconductor with a direct band gap of 0.41 eV, whereas the
AB(β2) is also a non-magnetic semiconductor accompanied by 0.29 eV of
energy gap. The stacking mode and the number of GDY layers influence
its electrical features with the energy gap decreases as the order of single
GDY > AB(β1) > AB(β2), but that not effect to the magnetic property.

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N.N.T. Pham Applied Surface Science Advances 11 (2022) 100301

Fig. 2. (a) Geometries of N atoms doped in GDY include graphitic-N (N1), sp-N (N2 and N3), pyridinic-N (N4); amino-N(N5). The configurations of N doped (b) AB
(β1) and (c) AB (β2).

The sp and sp2 co-hybridization in structure makes four kinds of C − C

Table 2
bonds in GDY: aromatic Csp2 − Csp2 bonds; Csp2 − Csp bonds between
The cohesive energy (Ecoh), Magnetic moment (Mag), energy gap (Egap) and
adjacent C = C and triple C≡C bonds; Csp≡Csp alkyne triple bonds; and
various N − C bond lengths of the optimized Nx-AB(β1) and Nx-AB(β2) (x = 1, 2,
single Csp − Csp bonds between adjacent C≡C bonds. The diversity of C–C 3, 4 and 5) configurations.
bonds in GDY makes its structure more flexible than that of graphene,
Ecoh (eV) Mag (µB) Egap (eV) Bond distance (Å)
which is beneficial for synthesizing curved structures such as nanotubes.
N − C1 N − C2 N − C3
As single GDY, the bond lengths of Csp2 − Csp2 (aromatic bonds), Csp2 −
N1-AB(β1) -8.483 0.00 0.19 1.42 1.34 1.42
Csp bonds, single and triple Csp − Csp bonds are calculated to be 1.43,
N2-AB(β1) -8.490 0.00 0.16 1.35 1.20
1.40,1.34, and 1.23 Å, respectively. The interior coupling between ar­ N3-AB(β1) -8.488 0.00 0.14 1.20 1.28
omatic ring moiety and alkynyl unit leads to the narrowing of the single N4-AB(β1) -8.091 0.00 0.35 1.33 1.36
C–C and the elongating of aromatic C–C as compared to that of an iso­ N5-AB(β1) -8.344 2.80 0.11 1.50 1.50
lated benzene ring (1.39 Å), which indicates the hybridization effect of N1-AB(β2) -8.465 0.00 0.13 1.45 1.36 1.45
N2-AB(β2) -8.472 0.00 0.13 1.37 1.21
coexisting of sp- and sp2-hybridized carbon atoms in GDY configuration.
N3-AB(β2) -8.470 0.00 0.17 1.21 1.30
The van der Waals interaction, π-conjugation interlayer interaction be­ N4-AB(β2) -8.077 0.00 0.31 1.33 1.36
tween layers, and the higher porous density over monolayer of GDY, N5-AB(β2) -8.329 0.00 0.22 1.54 11.54
make stacking bilayer GDY a potential candidate for energy materials,
including battery, fuel cell and storage devices.
along with around 120.8o of C-N-C angle. These geometric distortions
can be ascribed to the radius of the N atom being slightly smaller than
N-doped bilayer graphdiyne that of the C atom, leading to the flat structure of N-doped AB GDYs.
The cohesive energy was computed to be evaluating the stability of
Heteroatom doping carbon-based has been demonstrated to be an structures through Eq. 1 as follow [58]:
efficient structure for tuning physical and chemical properties, EN− − (nEC + mEN )
frequently employed in catalysts, batteries, and supercapacitors devices (1)
GDY
Ecoh =
n+m
[56,57]. N as heteroatoms are introduced through five different doping
sites on GDY, namely graphitic-N (N1), two sp-hybridized (N2, N3), where EN− GDY and EC are the DFT total energies of doped GDY and
pyridinic N (N4) and amino-N (N5) [23], as shown in Fig. 2. isolated carbon, respectively. EN denote the energy of isolated N. n and
For both N-AB(β1) and N-AB(β2), the bond lengths of N-C (sp2) is m represent the number of C and N atoms, respectively. The more
longer than that of N-C (sp). The angle of C-C-C near a dopant N atom site negative cohesive energy, the more thermodynamic stability. As re­
in the hexagon environment has changed from 120 to 119.639◦ in the ported in Table 2, our all N-doped AB GDYs have negative cohesive
graphitic, pyridinic, and sp- doping site of N on GDY surface. In contrast, energies, indicating the high thermodynamic stability. N prefers doped
the bond distance between N and two neighbor C atoms is almost equal,

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N.N.T. Pham Applied Surface Science Advances 11 (2022) 100301

Fig. 3. The band structure of (a) Nx-AB(β1) and Nx-AB(β2) (x = 1, 2, 3, 4 and 5) structures.

at N2 site on both Bernal stacking models of bilayer GDYs with the
highest negative cohesive energy of -8.490 eV (-8.472 eV) for N2-AB(β1)
(N2-AB(β2)), which show the same most stable doping site of N on a
single layer of GDY [59,60]. AB(β1) is the most stable of the bilayer GDY
Bernal stacking mode with a higher negative cohesive energy, consistent
with the previous study [59]. The effect of electronic properties for
N-doped systems is studied through the band structure investigation, as
shown in Fig. 3.
Moreover, N doping induced the Fermi energy (EF) to shift to a
higher energy level, accompanied by some electronic states crossing the
EF. The band structures shown in Fig. 3 exhibit that the band gap of N
doped bilayer GDYs is lower than that of systems without N dopant for
all considered models. The graphitic, sp-N and amino-N doping trans­
formed the GDY from being semiconductive to metallic. In contrast, the

Fig. 4. The most stable configuration of O2, CO, CO2, HCHO adsorption on (a) N2-AB(β1) and (b) N2-AB(β2).

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N.N.T. Pham Applied Surface Science Advances 11 (2022) 100301

Table 3 Conclusion
The calculated adsorption energy (Eads), Bader charge (ΔQ), interfacial distance
(dgas-sub) and band gap (Egap) of the most stable gas molecules (O2, CO, CO2, The structural and electronic properties of pristine and N-doped
HCHO). Bernal stacking mode of bilayer graphdiyne (GDY) are studied using
Gas Eads (eV) ΔQ (e) dgas-sub (Å) Egap (eV) density functional theory (DFT) calculations involving van der Waals
O2 -0.305 -0.265 1.906 0.102 interaction. The stacking arrangement influences the electronic prop­
CO -0.076 -0.010 3.145 0.158 erties and thermodynamic stability of bilayer GDY structures. The AB
N2-AB(β1) CO2 -0.013 -0.004 2.865 0.161 (β1) indicates higher thermodynamic stability and higher band gap than
HCHO -0.078 0.003 2.434 0.160 AB(β2) configuration. The coexistence of sp and sp2-hybridized C and
O2 -0.547 -0.413 1.724 0.085
CO -0.089 -0.014 3.023 0.124
high π* conjunction interaction between layers explained the reduced
N2-AB(β2) CO2 -0.095 -0.021 2.608 0.123 energy gap of bilayer GDY over single layer GDY system.
HCHO -0.107 0.012 2.315 0.116 As the N-doped AB bilayer GDY in five different dopant sites at
graphitic, pyridinic, amino and two sp-N on both AB(β1) and AB(β2)
structure; the results indicate that N prefers doped at sp site of C, espe­
Pyridinic-N doped AB-GDYs are semiconductors with a decreasing en­
cially at sp-N2 doping site configuration. The weak adsorption energy
ergy gap compared to the pristine AB-GDYs. The N-doped AB(β2) sys­
and charge transfer of CO, CO2, HCHO gas molecules on both N2-AB(β1)
tems present non-magnetic structures in all doping site configurations.
and N2-AB(β2) exhibit that N2-doped stacking AB bilayer GDY have
The amino-N doped AB(β2) indicates the ferromagnetic semiconductor
poor selectively to these toxic gases. The O2 adsorption energies on both
on the Γ− M path. The decreasing bandgaps are beneficial to the electron
N2-AB(β1) and N2-AB(β2) are -0. 305 eV and -0.547 eV, respectively.
transfer when these doped graphdiynes are utilized as electrode
The more negative O2 indicates the stronger O2 adsorption, which
materials.
translated into N2-AB(β1) and N2-AB(β2) can be active for oxygen
reduction mechanism, and N2-AB(β2) can be predicted for higher ki­
The gas sensor absorbed on the N-doped bilayer GDYs
netic oxygen reduction activity over N2-AB(β1). Notably, CO interacts
very weakly with N2-AB(β1) and N2-AB(β2), demonstrating the high
Based on the optimized configurations and cohesive energies, the
tolerance of N-doped Bernal stacking bilayer GDY. Overall, the stacking
results reveal that N prefers to be located in sp-N2 on both AB(β1) and
models and N doping on bilayer GDY effect of the stability and electronic
AB(β2), indicating their high structural stability. These findings are
properties of GDY and N2 doped AB bilayer GDYs are potential to per­
consistent with N doped monolayer GDY configuration [58,60]. Based
forming the oxygen reduction mechanism towards efficient eco-friendly
on the most stable doped structures of N2-AB(β1) and N2-AB(β2), here
electrocatalyst materials.
we investigate different adsorption position of O2 molecule and toxic gas
molecules (CO, CO2, HCHO) on the top of the doping atom and the
adjacent C atoms (labeled as C1, C2 in Fig. 2). The interaction between
Declaration of Competing Interest
gas molecules and substrates are evaluated through the adsorption en­
ergy (Eads ) as follow:
The authors declare that they have no known competing financial
Eads = Esub− gas − Esub − Egas (2) interests or personal relationships that could have appeared to influence
the work reported in this paper.
where Esub− gas , Esub and Egas represent the total DFT energy of structure
with the gas molecules adsorption, pristine N doped AB bilayer GDY and
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