Journal of ELECTRONIC MATERIALS, Vol. 46, No.

10, 2017
DOI: 10.1007/s11664-017-5626-2
Ó 2017 The Minerals, Metals & Materials Society

Electronic Structure Calculations of Ammonia Adsorption

on Graphene and Graphene Oxide with Epoxide
and Hydroxyl Groups

A. NANCY ANNA ANASTHASIYA,1,3 MAMTA KHANEJA,2,4

and B.G. JEYAPRAKASH1,5

1.—Functional Nanomaterials Lab @ Centre for Nanotechnology and Advanced Biomaterials

(CeNTAB), School of Electrical and Electronics Engineering, SASTRA University,
Thanjavur 613401, Tamil Nadu, India. 2.—Solid State Physics Laboratory, Defence
Research and Development Organisation, Ministry of Defence, Timarpur, Delhi 110054,
India. 3.—e-mail: [email protected]. 4.—e-mail: [email protected].
5.—e-mail: [email protected]

Ammonia adsorption on graphene (G) and graphene oxide (GO) was investi-
gated through density functional theory calculations. In the GO system, the
obtained binding energy, band gap, charge transfer and electronic structure
revealed that the epoxide (GO-O) and hydroxyl groups (GO-OH) in GO en-
hance the NH3 adsorption, which leads to the chemisorption of NH3 on GO.
The dissociation of NH3 to NH2 and formation of OH was also observed when
the O and H atoms were separated at 0.985 Å, 1.019 Å, 1.035 Å, and 1.044 Å
for various GO systems. The maximum charge transfer value was found to be
0.054 |e| with the binding energy of 1.143 eV for GO with a single epoxide
(GO-1O) group. The charge transfer from NH3 to G or GO and the bond for-
mation in this study agree with the reported experimental results.

Key words: Density functional theory, electronic structure, epoxide,

hydroxyl, graphene, graphene oxide

INTRODUCTION as an active site for the interaction between

2 molecules and GO. However, GO becomes an insu-
Graphene (G) is composed of sp hybridized
lator when increasing the oxygen functional groups,
carbons in a two-dimensional honeycomb structure
which is generally not suitable for chemosensitivity-
and is highly sensitive to the adsorption and
based sensing applications. The maximum concen-
desorption of molecules.1 Also, ultrahigh electron
tration of oxygen in G is about 30 at.%, which is
mobility (200,000 cm2 V1 s1),2 linear energy disper-
poor for conduction.5 Hence, it is essential to
sion, and zero energy gap3 means that G has a wide
understand the electronic structural changes by
range of applications. However, the zero band gap,
the addition of the hydroxyl and epoxy groups in G
large-scale high-quality graphene production, and
to make GO an effective sensing element for detect-
the fragile boundary integrality have been chal-
ing the targeted molecules. It has been reported
lenging factors in using it as a sensor. On the other
that G is highly sensitive to NH3 and NO2 at
hand, the synthesis of large-scale graphene oxide
ambient temperature, in the order of ppm.1,6
(GO) from G by the chemical method is simple and
Recently, NH3 adsorption studies on G and GO
cost effective. In general, GO consists of epoxy (–O–),
have been reported by Yue PEG7 through density
hydroxyl (–OH), carbonyl (–C=O) and carboxyl
functional theory (DFT) using the DMol3 package.
(–COOH) groups.4 These functionalized groups act
Similarly, adsorption and dissociation of NH3 on GO
have been reported by Tang and Cao8 by analyzing
the binding energy and charge transfer.7,8 Further-
(Received January 31, 2017; accepted May 25, 2017; more, the computational study on the interaction of
published online June 12, 2017)

5642
Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5643
with Epoxide and Hydroxyl Groups

NH3 with materials like boron nitride nanotubes,9 The bonding and antibonding states of the p bands
MoO3,10 aluminum nitride nanotubes,11,12 ZnO,13 meet at the k point in the Fermi level, which makes
TiO2,14 Ni- and Si-doped graphenes,15 and RuO216 G a zero-band-gap material. The pz orbitals of two
have also been reported for detection application. carbon atoms in the honeycomb lattice alone con-
The DFT-based computational approach either tribute to the p and p* bands, while px and py orbital
with local density or generalized gradient approxi- contributions are small.17 However, the density of
mations is widely used to study the gas adsorption states at the Fermi level is zero for G. A Dirac cone
properties of various materials in their ground was clearly observed in the band structure at the K-
states. In the present work, the local density point. Dispersions of the valence and conduction
approximation including spin was adopted, which bands around the Fermi level at the K-point were
gives precise bond length changes with errors of less found to be linear.
than a few percent.17 The overall objective of the
present study is to analyze the band gap, density of Oxidation with Epoxy Group (GO-O)
states and Fermi level shift during the interaction of
Figure 1b shows the optimized structure of GO
NH3 with G and GO [epoxy (–O–) and hydroxyl
with a single epoxy group (GO-1O). A nearly
(–OH)] for the better understanding of chemiresis-
equilateral triangle is formed when the epoxy group
tive-based ammonia detection.
bonds with the two nearby carbons atoms in a
honeycomb structure. The O 2p orbital is hybridized
COMPUTATIONAL DETAILS
with the p bands in G, which shifts the Dirac point
Density functional theory calculations were car- in K-space,18 as shown in Fig. 3a. The band gap is
ried out to study the interaction of NH3 with G and created because of the substitution of an epoxide
GO using the atomistic tool kit (ATK) package. All group in the G sheet leads to the formation of strong
the calculations were executed with Perdew and covalent bonds between the C and O atoms. The
Wang parameterized exchange–correlation poten- C–O and C–C bond lengths in GO-1O are 1.438 Å
tial in the self-consistency convergence criteria and 1.503 Å, respectively. The increase in the bond
framework. During the calculations, the functional length after adsorption was found to be 0.082 Å,
was chosen as the local spin density approximation8 and hence the symmetry of the honeycomb lattice
along with spin polarization. The hexagonal 4 9 4 was disturbed. This leads to the creation of a band
supercell graphene was considered as the base gap in the GO-1O system and its value was found to
system to simulate GO and carry out the adsorption be 0.677 eV. The total energy, band gap and binding
studies. A vacuum region of 20 Å and 4 Å was energy are given in Table I. The magnitude of the
considered on the top and the bottom sides of the total energy of the system increases in negative
slab, respectively. The Brillouin zone was sampled values, indicating the stabilization of the system.
with 6 9 6 9 1 k-point with FFT solver. High-sym- The binding energy of the GO-1O is 3.461 eV19 and
metry points such as C, K, and M of graphene were that of the GO-2O is 7.551 eV. Figure 1c shows the
considered during the band structure analysis. The GO structure with a double epoxide group (GO-2O).
binding energy was calculated using Eq. 1. The C1–O1, O1–C2, and C3–C4 bond lengths are
1.455 Å, 1.403 Å, and 1.490 Å, respectively. The
O1–C2 and C3–O2 bond lengths are decreased, while
Eb ¼ ½EA þ EB   EAB ð1Þ those in other positions are increased. Due to the
where EA and EB represent the total energy of the presence of the two epoxide groups in nearby carbon
individual systems and EAB is the total energy of the atoms of a honeycomb lattice, the overall distortion
full system.8 Ammonia adsorption studies were in G lattice was found to be minimum. This was
carried out by placing the N atom of NH3 towards confirmed with the decrease in the band gap when
the adsorbent (G/GO). The charge transfer from compared to the GO-1O system. Figure 3b shows
NH3 to G and GO was analyzed on the basis of the electronic structure of the GO-2O system. The
Mulliken population analysis. The structure of GO Dirac point was shifted towards the C point and the
contained the epoxy (–O–) and hydroxyl (OH). intensity of the peaks in density of states are
located at 4 eV, 2 eV, and 2.2 eV, which is
increased due to the formation of additional energy
RESULTS AND DISCUSSION levels.
Graphene and Graphene Oxide
Oxidation with Hydroxyl Group (GO-OH)
Graphene (G)
The top and side views of GO with a single hydroxyl
An optimized structure of 4 9 4 monolayer G is group (GO-1OH) are shown in Fig. 1d. Figure 1e
given in Fig. 1a. The C–C bond length is 1.421 Å. corresponds to the top and side views of GO with a
The total energy and band gap of the 4 9 4 G slab double hydroxyl group (GO-2OH). The corresponding
were found to be 5052.432 eV and 0 eV, respec- electronic structure, including the band structure
tively. The electronic structure, including the band and density of states, are shown in Fig. 4. The flat
structure and density of states, are shown in Fig. 2. band at the Fermi level is observed in the GO-1OH,18
5644 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

Fig. 1. Optimized structure of 4 9 4 (a) G, (b) GO-1O, (c) GO-2O, (d) GO-1OH, (e) GO-2OH, and (f) GO-1O1OH slab top view and side view.

Fig. 2. Band structure and density of states of graphene slab.

and it leads to small peaks in the density of states, as Fermi level vanishes due to the shift in the band
shown in Fig. 4a. While introducing the other OH above the Fermi level (Fig. 4b). The band gap value
group on the opposite side, the small peak at the for GO-1OH is 0.519 eV. The band gap is created as a
Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5645
with Epoxide and Hydroxyl Groups

Fig. 3. (a) GO-1O and (b) GO-2O band structure and density of states.

Table I. Total energy, band gap and binding energy of G and GO systems
System Total energy (eV) Band gap (eV) Binding energy (eV)

G 5052.432 0.000
GO-1O 5483.987 0.677 3.461
GO-2O 5916.170 0.314 7.551
GO-1OH 5500.651 0.519 1.854
GO-2OH 5950.431 0.825 5.268
GO-1O1OH 5933.126 0.718 6.236

result of sublattice symmetry changes and the Oxidation with both Epoxy and Hydroxyl Groups
change of hybridization from sp2 to sp3. The total (GO-1O1OH)
energy and binding energy shows that the system is
Figure 1f shows both the epoxy and hydroxyl
stabilized due to the substitution of the OH group. In
groups in the basal plane of G. The total energy,
the GO-1OH system, the C–O and O–H bond lengths
band gap and binding energy values are given in
are 1. 463 Å and 0.975 Å, respectively. On the other
Table I. Predominant peaks at the Fermi level,
hand, in the GO-2OH system, C1–O1, C2–O2, O1–H1,
shown in Fig. 5, arise from the OH group with an
and O2–H2 are separated by a distance of 1.478 Å,
odd number of electrons in the supercell. In the
1.435 Å, 0.983 Å, and 0.995 Å, respectively. This
hydroxyl group, the O–H bond length is 0.993 Å,
leads to the increase in the band gap of 0.825 eV. The
which was found to be higher than in the GO-1OH
band gap value of GO-2OH was found to be higher
system. This is due to the effect of the epoxide
than the GO-1OH system, because of an increase in
group, which attracts hydrogen atoms towards it.
the lattice distortion with respect to the degree of
The highest band gap value is 0.718 eV, observed
substitution.
5646 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

Fig. 4. Band structure and density of states of (a) GO-1OH and (b) GO-2OH systems.

Fig. 5. Electronic structure of the GO-1O1OH system.

Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5647
with Epoxide and Hydroxyl Groups

Fig. 6. Adsorption sites in (a) G, (b) GO-1O, (c) GO-2O, (d) GO-1OH, (e) GO-2OH, and (f) GO-1O1OH systems.

for the GO-1O1OH system, because of two different site. The C–N bond length at the G-C site is 2.538 Å.
groups in a G lattice. An additional energy level is observed near the
Fermi level in the band structure of G, as shown in
Ammonia Adsorption Fig. 8a, b, and c. This leads to unusual peaks at
1 eV in the valence band of G after adsorption.
Figure 6 shows the adsorption sites for ammonia
This reveals that NH3 adsorption over the G layer
over (a) G, (b) GO-1O, (c) GO-2O, (d) GO-OH, (e)
significantly alters the p band rather than the p*
GO-2OH, and (f) GO-1O1OH systems. The corre-
band, due to the interaction of the N atom with G.
sponding electronic structural changes in the sys-
The obtained results are in agreement with the
tem are discussed in the following sections.
results of Kaloni et al.17 The intensity of the density
Adsorption of ammonia over G and GO was found
of states was found to be high for the bridging site
to be exothermic,7,8 and hence exothermic reactions
and low for the carbon site, respectively. However,
are only considered in a later section. The endother-
significant changes in the band gap were observed
mic characteristic interactions in the chosen sites
in the carbon site, as compared to the other site.
were considered as unfavorable.
Charge transfer from the adsorbate to G at the
carbon site is determined to be high.
Interaction of Ammonia with Graphene
Interaction of Ammonia with Graphene Oxide
Three main adsorption sites are found in the
study of ammonia adsorption on a G slab: carbon, Previous work by Fowler et al.,20 Dan et al.21 and
bridging and hollow sites, as shown in Fig. 7a, b, Tang et al.22 reveals that molecular sensors with a
and c, respectively. The corresponding results are high performance are possible by converting G to
given in Table II. The binding energy and band gap reduced GO. During the conversion of G to GO, the
values were found to be low, which reveals that NH3 introduced oxygen-containing group acts as an
adsorption over the G site occurs through a active site to enhance the performance of the GO.
physisorptive process. Even though physisorptive This enhancement in performance is due to the
charge transfer is observed at all sites, the charge formation of a covalent C–N bond and due to the
transfer value is found to be higher at the carbon electrostatic attraction between O and H. Hence, in
5648 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

Fig. 7. (a), (b) and (c) are the NH3 adsorption over the carbon, bridging and hollow sites on graphene, respectively.

Table II. Total energy, bottom of the CB, top of the VB, band gap, binding energy and charge transfer after
adsorption of NH3
Total energy CB position VB position Band gap Binding Charge transfer
System/site (eV) (eV) (eV) (eV) energy (eV) (electrons)

Adsorption of NH3 over graphenea

G-H 5371.270 0.002 0.003 0.005 0.290 0.009
G-B 5371.170 0.005 0.005 0.010 0.191 0.016
G-C 5370.849 0.027 0.039 0.066 0.131 0.029
Adsorption of NH3 over graphene oxide
GO-1O
A 5803.539 0.480 0.300 0.780 1.005 0.049
B 5803.677 0.408 0.369 0.777 1.143 0.054
C 5803.015 0.342 0.258 0.600 0.480 0.018
GO-2O
A 6236.030 0.169 0.174 0.343 1.313 0.049
B 6235.561 0.153 0.183 0.336 0.845 0.007
GO-1OH
A 5819.644 0.266 0.518 0.784 0.445 0.017
B 5817.764 0.101 0.946 1.047 1.435 0.034
C 5819.571 0.100 0.719 0.819 0.373 0.010
GO-2OH
A 6268.582 0.407 0.295 0.702 0.396 0.122
B 6266.732 0.155 0.197 0.352 2.246 0.021
C 6269.570 0.426 0.383 0.809 0.592 0.047
GO-1O1OH
A 6252.276 0.154 0.390 0.544 0.602 0.006
B 6252.038 0.095 0.553 0.648 0.364 0.016
a
H Hollow, B bridging, C carbon.

the present work, carbon was chosen as the adsorp- different positions and calculating the correspond-
tion site for nitrogen, and the influence of the ing optimized structures, which are shown in Fig. 9.
position of the ammonia molecule in the honeycomb The site positions were named as A, B and C, and
structure was studied. the distances between C and N at these sites are
1.482 Å, 1.491 Å, and 2.629 Å, respectively. The
(a) Epoxide group large C–N separation at the C site may be the
reason for the lesser charge transfer at this site. At
The interaction of GO-1O with the NH3 molecule sites A and B, the NH3 molecule is fixed in such a
was studied by placing the NH3 molecules in three way that H points towards O. On the other, the
Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5649
with Epoxide and Hydroxyl Groups

Fig. 8. (a), (b) and (c) band structure and density of states of NH3 adsorbed graphene in C, B and H sites.

pointing of H towards O is intentionally avoided at Table II. The positive value of the binding energy
the C site. The separation between the O and H reveals that the interaction of NH3 with GO is an
atoms at the three sites is 1.019 Å, 1.044 Å, and exothermic reaction. The obtained binding energy
1.892 Å. The dissociation of NH3 to NH2, epoxide value discloses that site C is energetically unfavor-
ring opening and the formation of the OH bond were able as compared to sites A and B. The maximum
observed, as shown in Fig. 9a and b. Similar epoxide charge transfer is found to be 0.054 |e|, when the
ring opening and dissociation of the NH3 was NH3 is placed at site B. It reveals the electron
reported theoretically by Tang et al.8 and Matt- donating nature of NH3 molecule which was also
son.23 This might be of C–N covalent bond formation experimentally proven by Schedin et al.1 The charge
and the strong electrostatic attractive interaction transfer was also verified through shift in the Fermi
between the O and H atoms. Dissociation of NH3 level. Figure 10a and b shows the density of states
and epoxide ring opening are not observed in spectra of GO-1O and NH3-adsorbed GO-1O, and its
Fig. 9c. However, after the optimization process, Fermi level positions were 4.25 eV and 4.11 eV,
the hydrogen of NH3 points towards O. At site C, the respectively. The shift in the Fermi level towards
distance between O and the nearby H atom is found the conduction band confirms the charge transfer
to be high and, hence, OH formation and band from NH3 to GO-1O. The corresponding binding
opening are not observed. energy and total energy values are 1.143 eV and
The calculated values of total energy, band gap, 5803.677 eV, respectively. Significant alterations
charge transfer and binding energy are given in are not observed in the density of states near the
5650 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

Fig. 9. (a), (b) and (c) are the top and side views of the optimized structure of NH3 adsorption on the A, B and C sites in GO-1O.

Fig. 10. Density of states of (a) before and (b) after adsorption of NH3 on B site in GO-1O.

Fermi level, as shown in Fig. 10. This is because, in density of states at 2.5 eV and 4 eV were found
the oxygen-functionalized G, the highest-valence to be high (Fig. 13a), which might be because of the
band corresponds to the O 2p orbital. The unusual presence of an additional epoxide in the honeycomb
intense peaks located at 2.5 eV and 4 eV in structure. The O1–H and C–N bond lengths were
Fig. 11a and b are due to the interactions of C and 1.035 Å and 1.481 Å, respectively. The distance
N, and O and H, respectively. These peaks show between the epoxide and the nearby hydrogen was
negligible intensity in Fig. 11c. Therefore, the ori- 2.208 Å. The larger distance prevents bond-opening
entation of the NH3 molecule also has a role, of the O2 epoxide group. The NH3 molecule was
resulting in significant changes in the adsorption placed in such a way that its H pointed to O2
analysis. separately. The corresponding optimized structure
The degree of substitution of the epoxide in the is shown in Fig. 12b. C–N bonds were created before
single honeycomb was also studied. For this, two optimization but were not observed after optimiza-
adsorption positions were chosen for the study of the tion. Formation of NH2 and OH was not observed.
interactions of NH3 with GO-2O. NH2 and OH Hence, the peaks at 2.5 eV and 4 eV vanished
formation along with epoxide bonding were (Fig. 13b). The charge transfer value was found to
observed, as shown in Fig. 12a. The total energy be 0.007 |e|. The O2–H, O1–H and C–N distances
and band gap after adsorption were found to be were found to be 2.072 Å, 2.786 Å, and 3.282 Å,
larger for site A than site B. The charge transfer respectively. The larger C–N distance might be the
value was found to be 0.049 |e| and the obtained reason for the smaller charge transfer. Significant
electronic structure mimics the structure shown in O1–H and O2–H separations were also observed.
Fig. 11a. However, the relative intensities of the These results reveal that the number of active sites
Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5651
with Epoxide and Hydroxyl Groups

Fig. 11. NH3-adsorbed (a) A site, (b) B site and (c) C site GO with a single epoxide-substituted GO electronic structure, respectively.

present in the G does not enhance charge transfer

between NH3 and GO.
(b) Hydroxyl group

The NH3 molecule was located exactly opposite to

the OH group, but, after optimization, bonding
between C and N was not observed. The corre-
sponding image is given in Fig. 14a and the charge
transfer value was 0.017 |e|. The distance between
O and H atoms in the hydroxyl group was 0.989 Å.
The closest O–H and C–N distances were 2.192 Å
and 2.955 Å, respectively. The separation between
the OH and N may be the reason for the larger
binding energy. In general, there is a possibility of
the formation of NH4 ions and H2O molecules.
Fig. 12. Optimized structure of NH3 adsorption at the (a) A site and
Therefore, while checking the influence of the NH3
(b) B site of GO-2O. position, the formation of the by-product was
5652 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

Fig. 13. Electronic structure of NH3-adsorbed GO-2O in (a) A and (b) B sites, respectively.

Fig. 14. Adsorption of NH3 in (a) A site, (b) B site and (c) C site of GO-1OH system.

verified. Thus, the N and H of ammonia are placed H of NH3 was oriented towards the O of the OH
very close to the OH group and the corresponding group. The optimized structure for the correspond-
optimized structure is shown in Fig. 14b. The ing input is given in Fig. 14c. The O atom acquires
binding energy of the system was found to be an H atom from NH3 leaving the G surface, and this
negative, which reveals that the system is unfavor- position is filled by NH2. The chemisorption of NH2
able. To observe the formation of H2O molecules, the and formation of H2O during dissociation agrees
Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5653
with Epoxide and Hydroxyl Groups

Fig. 15. Electronic structure of NH3-adsorbed GO-1OH at the (a) A site and (b) C site.

Fig. 16. Optimized structure of NH3 adsorption over (a) A site, (b) B site and (c) C site in GO-2OH.

with the work reported by Tang et al.8 The O–H formation of a peak at 1 eV is observed, confirming
bond lengths in the H2O molecule are 0.985 Å and the C–N bonding (Fig. 15). The interaction of NH3
0.978 Å, respectively. The N–C bond length is with a GO-2OH honeycomb structure was studied.
1.488 Å. The charge transfer value was found to The optimized structure of the NH3-adsorbed sys-
be 0.010 |e|, which is lower than that at site A. The tem is shown in Fig. 16.
5654 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

Fig. 17. Electronic structure of GO-2OH system after adsorption of NH3 in C site.

structure (Fig. 17). The bond length between the

nearest hydrogen of NH3 and the oxygen of the OH
group was 2.559 Å. Hence, formation of H2O was
not observed. Conversely, the smallest C–N dis-
tance was 3.154 Å. The large distance might be the
reason for the absence of additional changes in
energy levels in spite of significant charge transfer.
(c) Epoxy and Hydroxyl group

Typically, GO consists of both epoxide and hydroxyl

groups. Hence, the ammonia adsorption studies
were extended to GO with both these groups. The
corresponding optimized structure with the adsorp-
tion sites is shown in Fig. 18a and b. The corre-
sponding electronic structural changes are shown in
Fig. 19a and b. In these changes, a small peak at the
Fig. 18. Optimized structure of NH3 adsorption over (a) A site and Fermi level was observed, corresponding to the
(b) B site GO-1O1OH. characteristic peak of OH. The high-intensity peak
at 0.4 eV is due to the creation of additional
The carbon site at which NH3 adsorption occurs in energy levels close to the Fermi level. The charge
the two-hydroxyl group-functionalized honeycomb transfer value for site A is found to be 0.006 |e|,
structure is considered as site A. However, the which was lower than for all other sites. The total
binding energy of the system was found to be energy and band gap were found to be
negative, revealing that the reaction is endother- 6252.276 eV and 0.544 eV, respectively. The C–N
mic, which is not possible. The position of NH3 at distance was 2.987 Å. The smallest distance
the B site was similar to that of GO-1OH as shown between H of NH3 and O of the epoxide group in
in Fig. 14b. Hence, one OH group did not contribute GO was found to be 2.066 Å. When NH3 was placed
and the total energy of the system was found to be close to the epoxide group, the intensity of the peak
negative, which is unfavorable. Therefore, it is at 2.4 eV increased and the peak at 4 eV
concluded that the adsorption of an NH3 molecule decreased. All peaks appeared to be broader as
in the same honeycomb structure is not possible. compared to Fig. 8. This is because of the creation of
Hence, the NH3 molecule was placed in the hollow discrete energy levels after adsorption. The sharp
site of the nearby honeycomb structure. The corre- energy level observed at 0.4 eV in Fig. 19a was
sponding site was named as the C site. The total also observed in Fig. 11b. However, the intensity of
energy and charge transfer values were the peak was small and a broad instead of a sharp
6269.570 eV, and 0.047 |e|, respectively. The peak was observedk. The separation between bands
binding energy of the system was found to be higher near the Fermi level increased after the interaction,
than in all other combinations, indicating that this and this might be the reason for the broad peak at
system is more stable. No significant alterations 0.4 eV. Formation of NH2 and OH was not
were observed in the density of states and band observed. The charge transfer, band gap and
Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide 5655
with Epoxide and Hydroxyl Groups

Fig. 19. Band structure and density of states of NH3 adsorption over GO-1O1OH at the (a) A site and (b) B site.

binding energy values were found to be 0.016 |e|, cial support under ER & IPR Project (ERIPR/ER/
0.648 eV and 0.364 eV, respectively. The closest 1003908/M/01/1541). The authors acknowledge to
distance between O of the epoxide group and H of Dr. Arkaprava Bhattacharyya, SASTRA University
NH3 was 1.986 Å. The smallest C–N distance was for providing ATK QuantumWise software package
2.934 Å. At both sites, neither epoxide bond opening to carry out the DFT studies. Also, the authors ex-
nor OH formation were observed due to the large tend to thank the SASTRA University for providing
bond separation. infrastructural facility to carry out the research
work.
CONCLUSION CONFLICTS OF INTEREST
The studies show that the epoxide and hydroxyl Manuscript do not include any content with a
groups in the GO act as active sites for ammonia conflict of interest.
adsorption and enhance the sensing performance
REFERENCES
compared with G. Better binding energy and charge
transfer were observed in the NH3-adsorbed GO-O 1. F. Schedin, A.K. Geim, S.V. Morozov, E.W. Hill, P. Blake,
systems. It was observed that the epoxide bond M.I. Katsnelson, and K.S. Novoselov, Nat. Mater. 6, 652
(2007).
opening, OH formation, and NH2 formation occurs 2. K.I. Bolotin, K.J. Sikes, Z. Jiang, M. Klima, G. Fudenberg,
when the C–N and O–H separation distance was J. Hone, P. Kim, and H.L. Stormer, Solid State Commun.
less than that of 2.629 Å and 1.892 Å, respectively. 146, 351 (2008).
Thus, the result indicates that GO is a promising 3. K.-C. Zhang, Y.-F. Li, Y. Liu, and Y. Zhu, Carbon 102, 39
(2016).
candidate to detect ammonia at ambient tempera- 4. W.-H. Zhao, L.-J. Yang, L.-H. Qing, X.-M. Lv, L.-Y. Yi, H.
ture, and further work can be extended for chemire- Li, and Z.-Q. Chen, Comput. Theor. Chem. 1068, 1 (2015).
sistive-based device fabrication. 5. A.S. Dobrota, I.A. Pasti, and N.V. Skorodumova, Elec-
trochim. Acta 176, 1092 (2015).
ACKNOWLEDGEMENTS 6. F. Yavari, E. Castillo, H. Gullapalli, P.M. Ajayan, and N.
Koratkar, Appl. Phys. Lett. 100, 203120 (2012).
The authors thank Defence Research and Devel- 7. Y. Peng and J. Li, Front. Environ. Sci. Eng. 7, 403 (2013).
opment Organisation (DRDO), India for the finan- 8. S. Tang and Z. Cao, J. Phys. Chem. C 116, 8778 (2012).
5656 Nancy Anna Anasthasiya, Khaneja, and Jeyaprakash

9. A. Ahmadi, J. Beheshtian, and N.L. Hadipour, Struct. 16. C.-C. Wang, Y.-J. Yang, and J.-C. Jiang, J. Phys. Chem. C
Chem. 22, 183 (2011). 113, 2816 (2009).
10. Z. Yana, J. Fanc, Z. Zuod, Z. Li, and J. Zhang, Appl. Surf. 17. T.P. Kaloni, Y.C. Cheng, and U. Schwingenschlogl, J.
Sci. 288, 690 (2014). Mater. Chem. 22, 919 (2012).
11. A. Ahmadi, J. Beheshtian, and N.L. Hadipour, Physica E 18. J.-A. Yan and M.Y. Chou, Phys. Rev. B 82, 125403 (2010).
43, 1717 (2011). 19. M.J. Lundie, S. Tomić, and Ž. Šljivančanin, Phys. Scr. 162,
12. A. Ahmadi Peyghan, A. Omidvar, N.L. Hadipour, Z. 014019 (2014).
Bagheri, and M. Kamfiroozi, Physica E 44, 1357 20. J.D. Fowler, M.J. Allen, V.C. Tung, Y. Yang, R.B. Kaner,
(2012). and B.H. Weiller, ACS Nano 3, 301 (2009).
13. Q. Yuan, Y.-P. Zhao, L. Li, and T. Wang, J. Phys. Chem. C 21. Y. Dan, Y. Lu, N.J. Kybert, Z. Luo, and A.T.C. Johnson,
113, 6107 (2009). Nano Lett. 9, 1472 (2009).
14. I. Onal, S. Soyer, and S. Senkan, Surf. Sci. 600, 2457 22. S. Tang and Z. Cao, J. Chem. Phys. 134, 044710 (2011).
(2006). 23. E.C. Mattson, K. Pande, M. Unger, S. Cui, G. Lu, M. Gaj-
15. A. Ahmadi Peyghan, S.F. Rastegar, and N.L. Hadipour, dardziska-Josifovska, M. Weinert, J. Chen, and C.J.
Phys. Lett. A 378, 2184 (2014). Hirschmugl, J. Phys. Chem. C 117, 10698 (2013).