Accepted Manuscript

Research paper

N2O + CO reaction over a single Si or P atom incorporated nitrogen-doped gra-

phene: A comparative DFT study

Mehdi D. Esrafili

PII: S0009-2614(18)30623-7
DOI: https://doi.org/10.1016/j.cplett.2018.08.006
Reference: CPLETT 35836

To appear in: Chemical Physics Letters

Received Date: 27 June 2018

Revised Date: 31 July 2018
Accepted Date: 2 August 2018

Please cite this article as: M.D. Esrafili, N2O + CO reaction over a single Si or P atom incorporated nitrogen-doped
graphene: A comparative DFT study, Chemical Physics Letters (2018), doi: https://doi.org/10.1016/j.cplett.
2018.08.006

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
 N2O + CO reaction over a single Si or P atom incorporated
nitrogen-doped graphene: A comparative DFT study

Mehdi D. Esrafili

Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, Maragheh, Iran

Phone: (+98) 4137276008-108. Fax: (+98) 4137276008. P.O. Box: 55136-553. E-mail:
esrafili@maragheh.ac.ir.

Abstract
The catalytic reduction of N2O on a single Si or P atom incorporated nitrogen-doped
graphene (SiN4-Gr/PN4-Gr) is investigated by means of DFT calculations. It is found that for
both surfaces, the dopant atom prefers to reside in the divacancy site. The N2O reduction by CO
molecule over these surfaces proceeds via a two-step mechanism: (a) N2O → N2 + O*, and (b)
O* + CO → CO2. Our results indicate that the catalytic activity of SiN4-Gr is higher than that of
PN4-Gr, due to the more favorable orbital interaction between CO molecule and Si atom in the
corresponding transition state.

Keywords: graphene; N2O reduction; pyridinic nitrogen; divacancy; DFT.

1
 1. Introduction
The continuous increasing of atmospheric concentration of hazardous air pollutants is one
of the main challenging issues facing the world today. In particular, one of the great
environmental problem is to control the concentration level of greenhouse gases since they
contribute to the global warming, ozone depletion, and acidic rain formation [1, 2]. Nitrous oxide
(N2O) is an important greenhouse gas, with a global warming potential (GWP) of about 300
times larger than that of carbon dioxide (CO2). Besides, N2O is a dominant ozone-depleting
substance, since it is able to release active chemicals when it reaches the stratosphere [3]. Hence,
the development of an efficient technology to control or reduce the N2O emission can play an
important role in solving the increasing environmental problems caused by this gas. It is known
that the catalytic reduction of N2O by CO molecule is one of the most promising and effective
approaches, since CO is cheap and readily available [4-6]. As the conventional catalysts, noble
metal catalysts like Au, Pt and Pd have been widely investigated for the N 2O reduction [7-12].
However, these catalysts are rare, expensive and often need high reaction temperatures for
efficient operation. Therefore, scientists have been paid lots of attention to find non-noble metal-
based catalysts with higher activity and lower operating temperature to reduce N2O molecule
[13-16].
Graphene is a one-atom-thick carbon sheet with exceptional thermal, mechanical, and
electrical properties [17, 18]. In particular, due to its huge surface to volume ratio, graphene can
serve as an ideal support to host metal atoms and clusters in heterogeneous catalysis [19-22]. For
instance, the experimental study of Fu and co-workers [23] have shown high catalytic activity of
Pd nanoparticles supported on graphene in the oxidation of formic acid. However, it is found that
the interaction between perfect graphene and the deposited metal atom is generally weak due to
its π-conjugated structure. To improve surface reactivity, various vacancy defects are usually
introduced into the carbon network of graphene. Through these defect sites, nonmetal atoms such
as B, P, Si could be embedded into graphene structure and modify its surface reactivity by tuning
the electronic structures and local curvature [24-29]. The calculated diffusion barrier of dopants
is quite large, indicating that the doped graphene is stable enough to use in catalysis applications.
Numerous theoretical and experimental studies have shown that doped graphene with a single Si
[5, 29], B [30] or Al [31, 32] atom exhibits superior catalytic activity toward the low temperature
oxidation of the CO molecule. Moreover, recent studies indicated that the incorporation of

2
pyridinic N atoms around the vacancy site of graphene could further improve its catalytic activity
[33, 34]. For instance, Sun and co-workers [35] have reported that a single Co atom stabilized
over a defective nitrogen-doped graphene can be considered as a novel catalyst for the oxygen
reduction reaction. Tang and coworkers [36] have recently found that incorporation of pyridinic
N atoms around the Si atom doped divacancy graphene could render it as an efficient catalyst for
CO oxidation. However, the catalytic activity of such modified graphene structures towards N 2O
reduction seems to be scarce to date.
The present work investigates the possible reaction mechanism of the N2O reduction on
Si or P atom incorporated with pyridinic nitrogen graphene (SiN4-Gr/PN4-Gr). We systematically
studied the most stable adsorption configurations, their electronic structure as well as the
possible reaction mechanism of the N2O reduction on SiN4-Gr and PN4-Gr using the first-
principles calculations. According to our results, the SiN4-Gr exhibits higher catalytic activity to
reduce N2O compared to the PN4-Gr .

2. Computational details
All the periodic DFT calculations were performed by means of the Dmol3 code [37, 38].
The Perdew-Burke-Ernzerhof (PBE) [39] density functional and double numerical plus
polarization (DNP) basis set were used for unconstrained geometry optimization and IR
frequency calculations. To consider the van der Waals forces, the DFT+D method within the
Grimme scheme [40, 41] was used in all calculations. A Fermi smearing parameter of 0.005 Ha
was used in the calculations (1 Ha = 27.212 eV). The basis set cut-off was set to be 4.6 Å. The
convergence tolerances for the geometry optimization were set to 10 -5 Ha for the energy, 0.001
Ha/Å for the force, and 0.005 Å for the displacement.
A modified hexagonal graphene with a 5 × 5 supercell was adopted, and a vacuum layer
of 15 Å was set to avoid the inter-layer interactions. The Brillouin zone integration was sampled
using a 3 × 3 × 1 Monkhorst–Pack grid. The minimum-energy pathway (MEP) for elementary
reaction steps was computed using the nudged elastic band (NEB) method.
The formation energy of SiN4-Gr and PN4-Gr was obtained using the following
equation:
Eform=Esupport + 6 μC - (EGr+ 4 μN + ESi/P) (1)

3
where Esupport is the total energy of SiN4-Gr or PN4-Gr, and EGr refers to the energy of pristine
graphene. μC and μN are the chemical potential of one single carbon atom in the graphene and the
chemical potential of the nitrogen atom which is defined as half of N2 molecule energy,
respectively. ESi/P represents the energy of a single Si or P atom in the gas phase.
The adsorption energy (Eads) of each adsorbate was calculated as
Eads = Eadsorbate/support - Eadsorbate - Esupport (2)
where Eadsorbate/support, Eadsorbate and Esupport are the total energies of the adsorbate/substrate
complex, the adsorbate and substrate, respectively. By this definition, a negative E ads value
indicates an exothermic adsorption. The charge-transfer values was calculated using the
Hirshfeld charge density analysis [42].

3. Results and discussion

3.1. Geometry, electronic structure and stability of SiN4-Gr and PN4-Gr
Recent studies [33, 34, 43] have shown that the incorporation of pyridinic nitrogen
atoms can effectively stabilize a vacancy defect in the graphene. Orellana [44] has found that the
substitution of undercoordinated carbons with pyridinic nitrogen atoms could lead to a
considerable decrease in the formation energy of the divacancy defect in the graphene. Hence,
the formation of a divacancy defect should be energetically more favorable under N-rich
conditions. Besides, the resulting N-modified graphene is quite active to stabilize a foreign atom
at the vacancy site more efficiently. Figure 1 indicates the optimized structure of a divacancy N-
doped graphene (N4-Gr). One can see that the planar structure of graphene is still preserved in
N4-Gr. The relaxed C-N bond distances are calculated to be 1.33 Å, which are much smaller than
the C-C bonds in the pristine graphene (1.42 Å). The Hirshfeld analysis reveals that the nitrogen
atoms are negatively charged (≈ -0.15 e) which can be attributed to their larger electronegativity
compared to the C atoms. Our results show that a single Si or P atom can be easily trapped at the
center of these negatively charged nitrogen atoms forming four covalent bonds. The optimized
geometry of SiN4-Gr and PN4-Gr are depicted in Figure 1. The formation energy of SiN4-Gr and
PN4-Gr is -2.80 and -0.44 eV, respectively, which suggests that the Si and P atoms can be easily
doped at the divacancy site of N4-Gr. This may be understood by the nitrogen dangling bonds at
the vacancy site that are able to stabilize the unpaired electrons on the Si and P atoms. The Si-N
bond distances in SiN4-Gr are 1.96 Å, which are nearly identical to those of P-N bonds in PN4-

4
Gr (1.97 Å). In the both surfaces, the dopant Si or P atom protrudes out of the graphene plane,
due to the larger size and more favorable sp3 hybridization. According to the Hirshfeld analysis,
the Si and N atoms in the SiN4-Gr are positively (0.25 e) and negatively (-0.09 e) charged,
respectively, and therefore, the SiN4 moiety is negatively charged by 0.11 e. On the other hand,
our results indicate that in PN4-Gr about 0.31 e are transferred from the P atom into its
neighboring nitrogen atoms indicating that the N4-Gr acts as an electron withdrawing support in
the system. The adsorption energy of the Si and P atom on N4-Gr is Eads = -7.50 eV and Eads = -
4.18 eV, respectively. The high adsorption energies confirm the strong chemical bonding
between Si or P atom and pyridinic nitrogens that makes the whole structure stable enough to
start the N2O reduction reaction. Note also that the adsorption energy of Si atom on the N4-Gr is
in good agreement with that of Tang et al. (-7.25 eV) [36] and to those Si atom doped into a
monovacancy (-7.41 eV) [26] or divacancy graphene sheet (ca. -7.33 eV).
The calculated electronic density of states of N4-Gr, SiN4-Gr and PN4-Gr structures are
shown in Figure 1. One can see that the partial density of states (PDOS) of nitrogen atoms in
SiN4-Gr and PN4-Gr are clearly altered as compared with N4-Gr. Also, there is a significant
overlap between the states of the incorporated pyridinic N atoms and Si or P atoms, which can be
regarded as an evidence for the formation of covalent Si-N and P-N chemical bonds in SiN4-Gr
and PN4-Gr, respectively. Moreover, one can see that the sizable electronic states exist near the
Fermi level of the mentioned substrates can facilitate the charge transfer between these substrates
and the adsorbed species as discussed later.

3.2. Adsorption of N2O and CO molecules

A favorable adsorption configuration of adsorbates is a prerequisite for a catalytic
reaction to proceed over the catalyst. Hence, before studying the mechanisms of N2O reduction
reaction, the most stable adsorption configurations of N2O and CO molecules on SiN4-Gr and
PN4-Gr are studied firstly. The optimized geometry of all adsorbed configurations along with the
corresponding PDOS plots are depicted in Figure 2. Also, the calculated adsorption energies and
charge-transfer values are summarized in Table 1.
Adsorption of N2O on SiN4-Gr and PN4-Gr is characterized by two alternative
configurations, namely N-end and O-end modes (see Figure 2). In the N-end mode, which is
energetically less favorable than the O-end, N2O is tilted over SiN4-Gr and PN4-Gr surfaces with

5
the binding distance of 1.77 and 1.69 Å, respectively. The corresponding Eads values are
calculated to be -0.65 and -0.38 eV, which indicates the chemisorption of N2O molecule over
these surfaces. According to the Hirshfeld analysis, N2O molecule gains 0.38 e from the SiN4-Gr
surface, which is slightly larger than that on PN4-Gr (0.23 e). These electrons are mainly donated
by the embedded Si or P atom, and occupy the 2π* orbital of the N2O molecule. Consequently,
the N-N bond distance in the adsorbed N2O becomes longer than that of its isolated state (1.14
Å). The PDOS analysis in Figure 2 also shows that due to the charge transfer from the surface to
N2O, the 2π* states of N2O downward with respect to the Fermi level and become slightly
populated. On the other hand, upon the adsorption of N2O molecule on both SiN4-Gr and PN4-Gr
surfaces from its O-site, it spontaneously dissociate into the N2 molecule and an actived oxygen
atom (O*) adsorbed over the Si or P atom. The associated large adsorption energy for the latter
configuration clearly indicates that adsorption of N2O on the O-end mode is energetically more
favored than that of N-end mode, which is consistent with those of other studies [5, 6, 15, 16,
45]. The Hirshfeld analysis reveals that a large negative charge of -0.47 and -0.35 e is localized
over O* moiety in SiN4-Gr and PN4-Gr, respectively. Meanwhile, the positive charge on the Si
and P atom is calculated to be 0.38 and 0.44 e, respectively, which is larger than the
corresponding value in the bare SiN4-Gr and PN4-Gr systems. According to the PDOS analysis,
the N2O adsorption from its O-end is associated with an orbital hybridization between the N2O-
2π and Si or P states below the Fermi level. Meanwhile, there are some electron density shift
from the surface to empty N2O-2π* states, which is responsible for the stabilization of the latter
states in the adsorbed N2O configuration compared to its isolated state.
In the case of CO adsorption, it is found that it adopts an end-on configuration over SiN4-
Gr and PN4-Gr, similar to those reported in other related investigations [22, 30, 32, 34]. The
binding distance between CO and Si atom in SiN4-Gr is 1.91 Å, which is much smaller than that
of PN4-Gr (3.23 Å). It should be noted that the calculated binding distance for the adsorption of
CO over SiN4-Gr is in excellent agreement with those reported in the previous studies [36]. As
expected, CO molecule has a larger Eads value over SiN4-Gr than PN4-Gr, showing its strong
interaction with the former surface. For both surfaces, adsorption of CO molecule is associated
with a charge transfer from Si or P atom into the empty 2π* orbital of the CO molecule.
However, this orbital interaction is much stronger for the SiN4-Gr surface than PN4-Gr (Table 1).
This is consistent with the PDOS analysis results, where CO adsorption over the former surface

6
induces a larger shift in the energy of CO-2π* states. Besides, due to the strong interaction with
Si atom, the 2π* states of the adsorbed CO molecule are considerably broadened in SiN4-Gr.

3.3. N2O reduction mechanism

In the next step, we studied the probable mechanisms of N2O reduction by CO
molecule on both SiN4-Gr and PN4-Gr surfaces. Since the Eads value of the N2O molecule on
both surfaces is higher than that of CO, the N2O adsorption should be energetically more
favorable than the CO adsorption. Hence, the adsorption of N2O is considered as the starting
point for its catalytic reduction over both surfaces.
The proposed mechanisms and corresponding energy profile for the reduction of N 2O
by CO molecule over SiN4-Gr and PN4-Gr are shown in Figure 3. As mentioned before, the
catalytic reduction of N2O starts with the dissociative adsorption of N2O over the surfaces
leading to the formation of N2 molecule and an activated oxygen atom (O*). Since the adsorption
energy of the N2 molecule on the SiN4-Gr and PN4-Gr is very low (≈ -0.05 eV), it easily desorbs
from these surfaces at room temperature. Then, the CO molecule interacts with the activated O*
in order to form the initial state structure (see the IS-1 and IS-2 configurations in Figure 3). The
binding distance between CO and O* in IS-1 and IS-2 is 2.81 and 3.14 Å, respectively, that
indicates the weak interaction of CO molecule with the surface. Meanwhile, a small charge is
transferred from the O* into CO molecule. As CO approaches the O* moiety, the Si-O* or P-O*
bond distance is continuously decreased until CO2 molecule is formed. Although the process is
exothermic, the calculated energy barrier needed to reach the CO2 molecule over SiN4-Gr (0.55
eV) is much smaller than that on PN4-Gr (1.81 eV). To understand the origin of high catalytic
activity of SiN4-Gr, the PDOS analysis is performed on the corresponding transition states during
the CO + O* reaction (see Figure 4). Compared to TS-2, one can see that there is a quite larger
hybridization between the CO-5σ and Si states of SiN4-Gr in TS-1. Meanwhile, the orbital
interaction between the O* and CO-2π* states above the Fermi level is also important, which can
facilitate the breaking of the Si-O* bond in the TS-1. We note that the calculated activation
energy for CO + O* reaction over SiN4-Gr is slightly smaller than that of reported by Tang et al.
[36]. It is also much smaller than those of noble-metal catalysts like Pd (0.91 eV) or Pt (0.79 eV)
[46]. In addition, due to the presence of pyridinic nitrogens, the energy barrier to remove O*
moiety by CO molecule over PN4-Gr is larger than that of P-doped divacancy graphene [47].

7
Finally, the formed CO2 molecule in FS-1 or FS-2 can easily detach from the surface due to its
small adsorption energy (≈ -0.3 eV).
As another possibility to remove O* moiety, we also study the N2O + O* → N2 + O2
reaction over the title surfaces. Figure 5 depicts the energy profile and the corresponding
optimized stationary points along this reaction. As seen, the reaction starts with the adsorption of
N2O over the activated O*, followed by the elongation of Si-O* or P-O* bond distance. By
overcoming a large activation energy, the N-O bond length of N2O is further elongated and
finally O2 and N2 molecules are formed over the surface. This reaction is endothermic over both
surfaces, indicating that it is a thermodynamically unfavorable process. Moreover, the large
activation energies show that the N2O + O* → N2 + O2 reaction is kinetically impossible at
ambient temperature.
3.4. The effect of O2 molecule
Although N2O and CO molecules can be present in oxygen-free media, the effect of O2
molecule during the N2O reduction could be important when an aerobic environment is
considered. To this aim, we also studied the adsorption of O2 molecule over SiN4-Gr and PN4-
Gr. Figure 6 indicates the most stable adsorption configuration of a single O 2 molecule over
SiN4-Gr and PN4-Gr. It is found that the O2 molecule could be chemisorbed on the top site of Si
or P atom, as evident from the calculated short binding distance and negative adsorption energy.
As those in the N2O and CO adsorptions, there is a large charge-transfer from the surface to the
2π* orbitals of the O2 molecule which leads to the elongation of O-O bond distance. The
adsorption energy of O2 over the SiN4-Gr and PN4-Gr surfaces is -2.21 and -0.46 eV,
respectively, which are much smaller than the corresponding value for the N2O adsorption. This
means that the tendency of N2O molecule to interact with the Si or P atom of the surface is larger
than that of O2. Therefore, it can be concluded that the N2O + CO reaction should be more
probable than the O2 + CO reaction on the SiN4-Gr and PN4-Gr surfaces and the N2O reduction
could proceed in the aerobic environment.

4. Conclusion
In summary, DFT calculations were performed to investigate the catalytic reduction of
N2O by CO molecule over SiN4-Gr and PN4-Gr. It is found that the adsorption of N2O molecule
is energetically preferred over SiN4-Gr and PN4-Gr surfaces due to its larger adsorption energy

8
than that of CO molecule. Meanwhile, the N2O molecule undergoes dissociative adsorption over
both surfaces, yielding a N2 molecule and an active oxygen atom (O*) adsorbed over the Si or P
atom. According to our results, the elimination of O* moiety over both surfaces is an exothermic
process, however, the corresponding activation energy over SiN4-Gr (Eact =0.55 eV) is much
smaller than that on PN4-Gr (Eact =1.81 eV). Besides, the competing N2O + O* → N2 + O2
reaction is impossible over these surfaces due to its large energy barrier. The larger adsorption
energy of N2O molecule with respect to O2 indicates that the N2O reduction could proceed in the
aerobic environment. The results of the present study may provide a valuable guidance on design
graphene-based single-atom catalysts to remove toxic molecules.

9
References
[1] J.F. Mitchell, The “greenhouse” effect and climate change, Reviews of Geophysics, 27
(1989) 115-139.
[2] D.J. Beerling, A. Fox, D.S. Stevenson, P.J. Valdes, Enhanced chemistry-climate feedbacks in
past greenhouse worlds, Proc. Natl. Acad. Sci. U.S.A., 108 (2011) 9770-9775.
[3] S.A. Montzka, E.J. Dlugokencky, J.H. Butler, Non-CO2 greenhouse gases and climate
change, Nature, 476 (2011) 43-50.
[4] Y. Chen, B. Gao, J.-X. Zhao, Q.-H. Cai, H.-G. Fu, Si-doped graphene: an ideal sensor for
NO-or NO2-detection and metal-free catalyst for N2O-reduction, J. Mol. Model., 18 (2012) 2043-
2054.
[5] R. Gholizadeh, Y.-X. Yu, N2O+ CO reaction over Si-and Se-doped graphenes: An ab initio
DFT study, Appl. Surf. Sci., 357 (2015) 1187-1195.
[6] P. Nematollahi, M.D. Esrafili, A DFT study on the N 2O reduction by CO molecule over
silicon carbide nanotubes and nanosheets, RSC Adv., 6 (2016) 59091-59099.
[7] A. Gluhoi, M. Dekkers, B. Nieuwenhuys, Comparative studies of the N 2O/H2, N2O/CO,
H2/O2 and CO/O2 reactions on supported gold catalysts: effect of the addition of various oxides,
J. Catal., 219 (2003) 197-205.
[8] O.P. Balaj, I. Balteanu, T.T. Roßteuscher, M.K. Beyer, V.E. Bondybey, Catalytic oxidation
of CO with N2O on gas‐phase platinum clusters, Angew. Chem. Int. Ed., 43 (2004) 6519-6522.
[9] V. Tzitzios, V. Georgakilas, Catalytic reduction of N2O over Ag–Pd/Al2O3 bimetallic
catalysts, Chemosphere, 59 (2005) 887-891.
[10] V. Blagojevic, G. Orlova, D.K. Bohme, O-atom transport catalysis by atomic cations in the
gas phase: reduction of N2O by CO, J. Am. Chem. Soc., 127 (2005) 3545-3555.
[11] F. Rondinelli, N. Russo, M. Toscano, On the Pt + and Rh+ catalytic activity in the nitrous
oxide reduction by carbon monoxide, J. Chem. Theory Comput., 4 (2008) 1886-1890.
[12] X.L. Xu, E. Yang, J.Q. Li, Y. Li, W.K. Chen, A DFT study of CO catalytic oxidation by
N2O or O2 on the Co3O4 (110) surface, ChemCatChem, 1 (2009) 384-392.
[13] Y.-a. Lv, G.-l. Zhuang, J.-g. Wang, Y.-b. Jia, Q. Xie, Enhanced role of Al or Ga-doped
graphene on the adsorption and dissociation of N 2O under electric field, Phys. Chem. Chem.
Phys., 13 (2011) 12472-12477.
[14] E.H. Song, J.M. Yan, J.S. Lian, Q. Jiang, External electric field catalyzed N2O
decomposition on Mn-Embedded graphene, J. Phys. Chem. C, 116 (2012) 20342-20348.
[15] M.D. Esrafili, F. Mohammadian-Sabet, P. Nematollahi, Oxidation of CO by N2O over Al-
and Ti-doped graphene: a comparative study, RSC Adv., 6 (2016) 64832-64840.
[16] R. Gholizadeh, Y.-X. Yu, Y. Wang, N2O adsorption and decomposition over ZnO (0001)
doped graphene: density functional theory calculations, Appl. Surf. Sci., (2017).
[17] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, M.I. Katsnelson, I.V. Grigorieva,
S.V. Dubonos, A.A. Firsov, Two-dimensional gas of massless Dirac fermions in graphene,
Nature, 438 (2005) 197-200.
[18] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater., 6 (2007) 183-191.
[19] Y. Li, Z. Zhou, G. Yu, W. Chen, Z. Chen, CO catalytic oxidation on iron-embedded
graphene: computational quest for low-cost nanocatalysts, J. Phys. Chem. C, 114 (2010) 6250-
6254.
[20] Y. Tang, X. Dai, Z. Yang, L. Pan, W. Chen, D. Ma, Z. Lu, Formation and catalytic activity
of Pt supported on oxidized graphene for the CO oxidation reaction, Phys. Chem. Chem. Phys.,
16 (2014) 7887-7895.

10
[21] X.-Y. Xu, J. Li, H. Xu, X. Xu, C. Zhao, DFT investigation of Ni-doped graphene: catalytic
ability to CO oxidation, New J. Chem., 40 (2016) 9361-9369.
[22] Y. Tang, W. Chen, Z. Shen, C. Li, D. Ma, X. Dai, A computational study of CO oxidation
reactions on metal impurities in graphene divacancies, Phys. Chem. Chem. Phys., 20 (2018)
2284-2295.
[23] J. Yang, C. Tian, L. Wang, H. Fu, An effective strategy for small-sized and highly-dispersed
palladium nanoparticles supported on graphene with excellent performance for formic acid
oxidation, J. Mater. Chem., 21 (2011) 3384-3390.
[24] Y. Zou, F. Li, Z. Zhu, M. Zhao, X. Xu, X. Su, An ab initio study on gas sensing properties
of graphene and Si-doped graphene, Eur. Phys. J. B, 81 (2011) 475-479.
[25] S. Nachimuthu, P.-J. Lai, J.-C. Jiang, Efficient hydrogen storage in boron doped graphene
decorated by transition metals - A first-principles study, Carbon, 73 (2014) 132-140.
[26] Y. Tang, Z. Liu, X. Dai, Z. Yang, W. Chen, D. Ma, Z. Lu, Theoretical study on the Si-
doped graphene as an efficient metal-free catalyst for CO oxidation, Appl. Surf. Sci., 308 (2014)
402-407.
[27] L. Ferrighi, M.I. Trioni, C. Di Valentin, Boron-doped, nitrogen-doped, and codoped
graphene on Cu (111): A DFT+ vdW study, J. Phys. Chem. C, 119 (2015) 6056-6064.
[28] H. Jiang, T. Zhao, L. Shi, P. Tan, L. An, First-principles study of nitrogen-, boron-doped
graphene and co-doped graphene as the potential catalysts in nonaqueous Li–O2 batteries, J.
Phys. Chem. C, 120 (2016) 6612-6618.
[29] M.D. Esrafili, N. Saeidi, P. Nematollahi, Si-doped graphene: A promising metal-free
catalyst for oxidation of SO2, Chem. Phys. Lett., 649 (2016) 37-43.
[30] M.D. Esrafili, P. Mousavian, Boosting graphene reactivity with co-doping of boron and
nitrogen atoms: CO oxidation by O2 molecule, Appl. Surf. Sci., 455 (2018) 808-814.
[31] Q. Jiang, Z. Ao, S. Li, Z. Wen, Density functional theory calculations on the CO catalytic
oxidation on Al-embedded graphene, RSC Adv., 4 (2014) 20290-20296.
[32] M.D. Esrafili, P. Nematollahi, H. Abdollahpour, A comparative DFT study on the CO
oxidation reaction over Al-and Ge-embedded graphene as efficient metal-free catalysts, Appl.
Surf. Sci., 378 (2016) 418-425.
[33] X. Zhang, Z. Lu, Z. Yang, Single non-noble-metal cobalt atom stabilized by pyridinic
vacancy graphene: An efficient catalyst for CO oxidation, J. Mol. Catal. A: Chem., 417 (2016)
28-35.
[34] M. Wang, Z. Wang, Single Ni atom incorporated with pyridinic nitrogen graphene as an
efficient catalyst for CO oxidation: first-principles investigation, RSC Adv., 7 (2017) 48819-
48824.
[35] X. Sun, K. Li, C. Yin, Y. Wang, F. He, H. Tang, Z. Wu, CoN 3 embedded graphene, a
potential catalyst for the oxygen reduction reaction from a theoretical perspective, Phys. Chem.
Chem. Phys., 19 (2017) 17670-17676.
[36] Y. Tang, W. Chen, Z. Shen, S. Chang, M. Zhao, X. Dai, Nitrogen coordinated silicon-doped
graphene as a potential alternative metal-free catalyst for CO oxidation, Carbon, 111 (2017) 448-
458.
[37] B. Delley, An all‐electron numerical method for solving the local density functional for
polyatomic molecules, J. Chem. Phys., 92 (1990) 508-517.
[38] B. Delley, From molecules to solids with the DMol3 approach, J. Chem. Phys., 113 (2000)
7756-7764.

11
[39] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple,
Phys. Rev. Lett., 77 (1996) 3865.
[40] S. Grimme, Accurate description of van der Waals complexes by density functional theory
including empirical corrections, J. Comput. Chem., 25 (2004) 1463-1473.
[41] S. Grimme, Semiempirical GGA‐type density functional constructed with a long‐range
dispersion correction, J. Comput. Chem., 27 (2006) 1787-1799.
[42] F.L. Hirshfeld, Bonded-atom fragments for describing molecular charge densities, Theor.
Chim. Acta, 44 (1977) 129-138.
[43] X. Liu, Y. Sui, T. Duan, C. Meng, Y. Han, Monodisperse Pt atoms anchored on N-doped
graphene as efficient catalysts for CO oxidation: a first-principles investigation, Catal. Sci.
Technol., 5 (2015) 1658-1667.
[44] W. Orellana, Catalytic properties of transition metal–N4 moieties in graphene for the oxygen
reduction reaction: evidence of spin-dependent mechanisms, J. Phys. Chem. C, 117 (2013) 9812-
9818.
[45] M.D. Esrafili, BN co-doped graphene monolayers as promising metal-free catalysts for N2O
reduction: A DFT study, Chem. Phys. Lett., 705 (2018) 44-49.
[46] X.-Q. Gong, Z.-P. Liu, R. Raval, P. Hu, A systematic study of CO oxidation on metals and
metal oxides: density functional theory calculations, J. Am. Chem. Soc., 126 (2004) 8-9.
[47] M.D. Esrafili, P. Mousavian, Probing reaction pathways for oxidation of CO by O 2
molecule over P-doped divacancy graphene: A DFT study, Appl. Surf. Sci., 440 (2018) 580-585.

Figure 1. The optimized structure (from both top and side views) and the corresponding PDOS
plot of N4-Gr, SiN4-Gr and PN4-Gr. In the PDOS plots, the dashed line indicates the Fermi level,
which set to be zero. The 4N in the PDOS plots refers to the pyridinic nitrogen atom.

12
13
Figure 2. Optimized geometries and corresponding PDOS plots of N2O (from N-end and O-end) and CO molecules over SiN4-Gr and
PN4-Gr. All bond distances are in Å. In the PDOS plots, the dashed line indicates the Fermi level, which set to be zero.

14
Figure 3. The potential energy profile and optimized stationary points for the CO + O* reaction
over SiN4-Gr (above) and PN4-Gr (below). All bond distances are in Å.

15
Figure 4. PDOS analysis of TS-1 (left) and TS-2 (right). The dashed line indicates the Fermi
level, which set to be zero.

16
Figure 5. The potential energy profile and optimized stationary points for the N2O + O* reaction
over SiN4-Gr (above) and PN4-Gr (below). All bond distances are in Å.

17
Figure 6. The most stable geometry, corresponding adsorption energy and charge-transfer for O2
molecule adsorbed over SiN4-Gr (above) and PN4-Gr (below). All bond distances are in Å.

18
Research highlights:

1) N2O is dissociated over a single Si or P atom incorporated nitrogen-doped graphene.

2) N2O reduction by CO proceeds via a two-step mechanism.
3) Catalytic activity of SiN4-Gr is higher than that of PN4-Gr.

19
Graphical Abstract

20