Monatsh Chem (2017) 148:1727–1731
DOI 10.1007/s00706-017-2003-z
ORIGINAL PAPER
Adsorption and decomposition of formaldehyde on the B12N12
nanostructure: a density functional theory study
Esmail Vessally1 • Elaheh Ahmadi1 • Sima alibabaei1 • Mehdi D. Esrafili2 • Akram Hosseinian3
Received: 7 May 2016 / Accepted: 21 May 2017 / Published online: 26 July 2017
 Springer-Verlag Wien 2017
Abstract Minnesota functionals computations DFT/M06-
2X is carried out to study the adsorption and breakdown of
formaldehyde (H2CO) on the top of a boron nitride
nanostructure, B12N12, BNn. Two chemical and physical
adsorption types and two reaction routes are recognized.
The electrical properties of the nanostructure can be
changed when the adsorption of H2CO occurs on the top of
BNn. The routes of H2CO dissociation via breaking of the
C–O and C–H bonds are investigated. For the H2CO dis-
sociation on the top of B12N12, the rate determining step
follows the reaction CH2O ? CHO ? H. The computa-
tions suggest that the C–H bond cleavage is the most
desirable route on the top of BNn.
Graphical abstract
& Esmail Vessally
vessally@yahoo.com
1
Department of Chemistry, Payame Noor University, Tehran,
Iran
2
Department of Chemistry, Faculty of Sciences, University of
Maragheh, Maragheh, Iran
3
Department of Engineering Science, College of Engineering,
University of Tehran, P.O. Box 11365-4563, Tehran, Iran
Keywords Formaldehyde  Nanostructure  B12N12 
Adsorption  Decomposition
Introduction
Monitoring air pollution became very important in recent
years. In particular, formaldehyde (H2CO), which is vola-
tile at room temperature is highly toxic and a potential
carcinogenic. Thus, it seems necessary to monitor and
remove it in both industrial and living environments. The
decomposition and breakdown of formaldehyde has been
studied on a number of transition-metal surfaces including
W (111) [1], Ru (110) [2], Ni (110) [3], clean and sulfide
pre-covered Pt (111) [4], clean and oxygen pre-covered Cu
(110) [5], and oxygen pre-covered Ag (110) [6]. Recently,
attempts were undertaken to develop simple, rapid, and
sensitive methods for the elimination of H2CO [7, 8].
It has been found that the boron nitride nanoparticles
could be good candidates for breakdown of toxic gasses
[9]. The polar character of the B–N bonds in the boron
nitride nanoparticles leads to a higher reactivity than in
their carbon homologues. In addition, the considerable
charge difference between the nitrogen and boron atoms,
the boron and nitrogen atoms can act as Lewis acid and
base. Therefore, we can conclude that the boron nitride
nanoparticles can be regarded as a non-metal catalyst. In
the boron nitride category, B12N12 (BNn) was reported to
be the smallest stable nanocage particles [10, 11].
Recently, we have found that the BNn nanoparticles
could be applied as a catalyst in association with methanol
[12]. The results indicated that the BNn nanostructure
could be applied as a suitable catalyst to separate the
hydrogen atoms from methanol compound and subse-
quently intermix them with hydrogen gas. The BNn
123
1728 E. Vessally et al.

nanostructure has been theoretically investigated to apply

as an effective catalyst in the decomposition of methy-
lamine (CH3NH2) [13].
Experimental and theoretical investigations reported that
a BN catalyst shows two paths [14, 15]. For example, the
breakdown of formaldehyde on a clean (110)-oriented Cu/
Ni single crystal has been studied by flash desorption
spectroscopy and Auger electron spectroscopy [14]. At
190 K, formaldehyde adsorb dissociatively on a clean
(110)-oriented Cu/Ni to form H2 and CO. The desorption
of CO was first order while the desorption of H2 follows a
complex kinetics.
The BNn nanostructures with covalent or ionic features
in the chemical bond [16–18] appear to be very efficient
catalysts in some reactions such as the formaldehyde
decomposition.
In this research, we report the interaction between
formaldehyde and the BNn nanostructure using M062X
calculations. The target of this research is (a) to scrutinize
how the nanostructure and formaldehyde interacts with
each other, (b) to investigate the bonding character of the
Configuration A
H2CO–BNn complexes, and (c) to find a mechanism of
formaldehyde breakdown on top of the nanostructure.

Results and discussion

Formaldehyde adsorption on surface of BNn

nanostructure

The fully optimized structure of BNn with Th symmetry is

shown in Fig. 1. There are two types of B–N bonds, one
occurs between two six-membered rings, and the other one
is occurred between a four-membered ring and six-mem-
bered ring with bond distances of 1.44 and 1.48 Å,
respectively. Their bond lengths are close to the related
bonds in B2N2H4 (1.45 Å) and B3N3H6 (1.43 Å), which
were optimized at the same level of theory [23].
The bond angles in B–N–B and N–B–N angles in the
six-membered ring are 80.0 and 98.6 and in the four-
membered ring 110.7 and 125.9. The calculated geo-
metrical parameters are in accordance with values
calculated by other methods [10, 11], which confirms the
method used in this study. The M06-2X calculations clarify
that the boron atoms are positively charged by 1.2e and the
nitrogen atoms are negatively charged by -1.2e. Thus, the
electron-poor boron and electron-rich nitrogen atoms can
act as Lewis acid and Lewis base. In Fig. 1, the most
stable adsorption sites of the H2CO molecule adsorbed on
the BNn nanostructure surface is schematically illustrated.
In configuration A, H2CO is adsorbed on top of BNn via its
oxygen lone pair with boron atoms of the nanostructure.
The configuration A is the most stable one with an
Configuration B
Fig. 1 Optimized geometries and frontier orbitals (iso-
value = 0.02 e/Bohr3) for BNn, and two configurations (A and
B) of CH2O–BNn complexes. Color for each optimized structure:
blue N, brown B, gray C, red O, white H (color figure online)
adsorption energy of -74.98 kJ/mol. Strong overlap
between the oxygen lone pair electrons in H2CO and empty
boron p orbital in BNn attributed the formation of the
strong B–O bond.
In configuration A, the boron atom is more or less drawn
out of the surface, which causes a structural deformation at
the interaction positions (Fig. 1). Moreover, the DFT cal-
culations indicate the hybridization of the B atom in BNn
changed from sp2 to sp3 when the formaldehyde molecule
absorbs on the nanostructure surfaces. The C–O bond
distance of formaldehyde is stretched in comparison with
the isolated formaldehyde which indicates a considerable
interaction between the oxygen atom in H2CO and the B
atom in BNn. In addition, the O–C bond length was

123
Adsorption and decomposition of formaldehyde on the B12N12 nanostructure: a density…
increased to 1.223 from 1.209 Å in the isolated H2CO
molecule. The DFT calculations also show a large charge
transfer of 0.30e from the H2CO molecule to the BNn
nanostructure. Therefore, the activity of H2CO molecule on
top of the BNn nanostructure was increased.
In configuration B, the C–H bond of the H2CO molecule
is vertical to the surface of the BNn nanostructure. The
distance between the hydrogen and boron atoms is 2.70 Å
and the adsorption process is slightly exothermic
(Ead = -3.3 kJ/mol and DH298 = -4.2 kJ/mol). Then, the
calculated positive DG298 amount shows that the formation
of this configuration is not a spontaneous process while the
complex being thermodynamically slightly stable in the gas
phase at 298 K.
Slight elongation of the O–C bond distance from
1.209 Å in formaldehyde molecule compared to 1.223 Å in
the complex confirmed a small value of charge transfer
from H2CO molecule to the BNn nanostructure. The sta-
bility of the H2CO–BNn complex could mostly be related
to the electrostatic effects.
The interaction between the H2CO molecule and BNn
seems to change the electronic structure of the nanos-
tructure. The highest occupied molecular orbitals
(HOMO) and the lowest unoccupied molecular orbitals
(LUMO) of the nanostructure and H2CO–BNn complexes
are shown in Fig. 1. The calculated HOMO–LUMO
energy gap (Eg) of the BNn nanostructure is about
9.25 eV, which is close to other DFT calculations [24].
The Eg of H2CO–BNn (A) was found to be 7.89 eV. The
DOSs of the H2CO–BNn complex indicates that the
electronic property of the nanostructure is improved when
the adsorption of the H2CO molecule was carried out on
BNn. When a new donor phase forms near the conduction
band edge in the BNn nanostructure upon H2CO
adsorption in configuration A, the band gap near the
Fermi level becomes smaller. This is related to the charge
transfer between the H2CO molecule and the BNn
nanostructure in configuration A.
Formaldehyde decomposition on the BNn
nanostructure
Decomposition of H2CO could start with the adsorption of
H2CO on top of BNn. The dissociation can occur through a
series of stages into various products. It should be noted
that we do not investigate the reaction pathway of H–BNn
cleavage in our calculations in configuration B since,
interactions in configuration B is very weak and the reac-
tion pathway is not suitable. Therefore, we considered
configuration A as an initial complex to calculate the
reaction mechanism for H2CO breakdown on the nanos-
1729
tructure surface. Since H2CO has two different types of
heteroatom bonds, C–O and C–H, the breakdown step
consists of the breaking of these two bonds. It was found
that the dissociation reaction mechanism consists of C–H
bond breaking as the most favorable route. The relative
energy vs. reaction coordinate diagram for the various
reaction routes of H2CO breakdown on the BNn nanos-
tructure are presented in Fig. 2. The related activation
energies (Eact), imaginary frequencies (m), Gibbs free
energy differences (DG298), and enthalpy differences
(DH298) are presented in Table 1.
The reaction route R1 starts by breaking the C–H bond
through TS-1 which generates CHO (Fig. 2). The energy
barrier of C–H bond cleavage is obtained to be
172.8 kJ/mol with a m of 1256i cm-1 at the transition state
which was obtained by means of vibrational frequency
computations. This activation energy is comparable with
those found for catalysis using a clean (110)-oriented Cu/
Ni single crystal [14]. In the first transition state (TS1), the
H atom of formaldehyde goes to the top position of the N
atom in BNn. This hydrogen atom transfer leads to an
increased C–H bond length of 1.29 Å. The hydrogen atom
disconnected from formaldehyde group is then bound at the
top position of N atom in BNn, with a bond length of N
surf-H 1.02 Å in the P1 complex. The bond length of B
surf-OCH be 1.46 Å. The bond length of C–O increases
significantly from 1.23 to 1.30 Å in P1. Nevertheless,
dissociation of CHO from the top of BNn is an important
reaction because of the relative stable structure of CHO. It
is evident that the TS1 is more product-like, indicating a
late-barrier reaction.
The CHO group goes on to convert at the top of BNn to
liberate another hydrogen atom and yield CO (P2). The
DFT calculations indicate this route is an exothermic step
which is thermodynamically favorable (DH298 = -50.2 -
kJ/mol and DG298 = -54.0 kJ/mol). The activation energy
from P1 to P2 is obtained to be 119.7 kJ/mol and the
imaginary m of the transition state is about 870i cm-1. The
bond length of CO–H is found to be 1.55 Å in the transition
state (TS2), and the bond length of surface-H is about
1.24 Å). By the way, the bond length of C–O in the CO
group is decreased from 1.46 Å in formaldehyde to 1.24 Å.
It is evident that TS2 is more reactant-like, indicating an
early barrier reaction. The P2 can readily convert to CO
and the BNn–H2 complex (P20 ).
Despite of a C–H cleavage on the R1 pathway, the C–O
cleavage of CH2=O can occur at the top of BNn. The C–O
cleavage produces two particles of CH2 and O. The dis-
tance between C and O atom is 2.09 Å in the transition
state (TS3) while that distance is 1.57 Å in the configura-
tion A. The bond distance of Bsurf–O is decreased to
123
1730 E. Vessally et al.

Fig. 2 Reaction pathways of

CH2O decomposition on the
BNn nanostructure

300 R1
(307.9)

(286.6)
200
(203.8)
P3 (201.2)

(157.7)
100

+ (97.9) P1
P2
(84.1)
(33.9) P2
0 B (27.2)
(0.0)
(-3.3)

A
+
-100 (-75.0)

Table 1 Obtained activation Reactions Eact/kJ mol-1 m/cm-1 DG298/kJ mol-1 DH298/kJ mol-1
energies, imaginary frequencies,
change of Gibbs free energies H2CO ? CH2 ? O 361.5 1278 229.28 232.63
(DG298), change of enthalpies
H2CO ? HCO ? H 172.8 1256 155.64 158.99
(DH298) of decomposition of
CH2O on BNn HCO ? CO ? H 119.66 870 -53.97 -50.21
HCO ? H ? HC–OH 223.84 650 119.66 117.15

1.47 Å. This route has a high energy barrier of Conclusion

361.5 kJ/mol which indicates the impossibility of the C–O
cleavage and CH2O decomposition. This is consistent with
the experimental results of CH2O decomposition [14].
Thus, we can conclude that the production of CH2 and O
particles is limited due to high energy barrier.
The last route which is discussed here is the conversion
of P1–P3. This route indicates that decomposition of CH2O
can continue to form P3, which can later produce the C and
H2O products. This route consists of several reactions
including; CH2O ? CHO ? H ? CH–OH ? C–
OH ? H ? C ? H2O. However, these steps must pass
from conversion of P1–P3 by a barrier energy of
223.8 kJ/mol. This barrier energy is sufficiently high to
prohibit conversion of P1–P3.
The adsorption and breakdown of the formaldehyde
molecule on the BNn nanostructure was studied by M06-
2X method together with the interaction energies and
electronic properties of the CH2O adsorption on the surface
of BNn.
In the most stable configuration (A) of the H2CO–BNn
complex, the H2CO is adsorbed on the surface through its
oxygen lone pair with an adsorption energy of
-75.0 kJ/mol. This means that BNn can be applied as a
useful gas sensor of formaldehyde.
Based on these results, we can predict the outcomes of
the decomposition of CH2O on the surface of the BNn
nanostructure. The results indicate that C–H bond disso-

123
Adsorption and decomposition of formaldehyde on the B12N12 nanostructure: a density…
ciation is the most favorable reaction route for CH2O
decomposition on BNn. The obtained reaction energies and
the activation barriers predict that in the CH2O decompo-
sition on the BNn surface, the rate-determining step is the
dehydrogenation of adsorbed CH2O. As a result, the
decomposition of CH2O, which produces CHO may take
place under normal conditions or proceed at relatively high
temperature because the energy-barrier is as high as
172.8 kJ/mol. Accordingly, decomposition of CH2O to C
and H2O on the BNn nanostructure surface would need to
make modifications, such as introducing structural defects,
chemical functionalization, or doping of the BNn surface
with metal atoms, because of the very high energy-barrier
of 361.5 kJ/mol.
Computational details
The theoretical calculations on the H2CO–BNn complexes
and its interactions were carried out using a hybrid func-
tional closed-shell M06-2X and 6-31??G** basis set,
employing the GAMESS program package [19]. All cal-
culations were carried out for gas phase condition under
1 atm pressure and 298 K temperature. The frequency
calculations were performed at the mentioned level. A pure
imaginary frequency was obtained for the transition state
structures at the same level of theory.
Theoretical studies [20, 21] proposed that the M06-2X
method can give the best results to compute the absorption
energies, strength of noncovalent interactions, barrier
energy amounts and thermochemistry properties. The
adsorption energies (Ead) of the CH2O–BNn systems were
computed using the M06-2X/6-31??G** level of theory.
The Ead was obtained via differences between the total
energies of the CH2O–BNn systems and the energies of
each monomer. The interaction energies were corrected for
the basis set superposition error (BSSE) in all the com-
plexes using the full counterpoise method [22].
1731
Acknowledgements We gratefully acknowledged from Payame
Noor University for financial support of this research work.
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