Ab initio DFT study of urea adsorption and decomposition on the

ZnO 10

10 surface
Yangyan Gao
a,b
, Ning Zhao
a
, Wei Wei
a,
, Yuhan Sun
a,c,
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, PR China
b
Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China
c
Low Carbon Energy Conversion Technology Research Center, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201203, PR China
a r t i c l e i n f o
Article history:
Received 20 March 2012
Received in revised form 9 April 2012
Accepted 16 April 2012
Available online 2 May 2012
Keywords:
Density functional theory (DFT)
Urea
ZnO 10

10 surface
Adsorption
Decomposition into HNCO and NH
3
a b s t r a c t
The mechanisms of urea decomposition into isocyanic acid (HNCO) and ammonia (NH
3
) in gas-phase and
on the ZnO 10

10 surface have been investigated by using density functional theory. In gas-phase, urea
decomposes into HNCO and NH
3
in one step, which is a concert reaction. However, on the ZnO 10

10
surface urea is found to decompose gradually, in which urea molecule rst adsorbs on the ZnO surface,
followed by the NAH and the NAC bonds breaking, and eventually rebinds to form NH
3
and HNCO. The
presence of ZnO 10

10 surface decreases the energy barrier of urea decomposition. And as the intense
interaction between the surface and urea, urea decomposition is exothermic by 48.0 kcal/mol on the
surface, which is endothermic by 22.0 kcal/mol in the gas-phase.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Dimethyl carbonate (DMC) has received considerable attention
due to its wide application in green chemistry [15], and much
effort has been devoted to exploring the DMC synthesis methods
in the past three decades. A direct synthetic method had been
developed recently, which is urea methanolysis process [69]. This
process is a two-step reaction. The intermediate, methyl carbamate
(MC) is produced via the reaction of urea and methanol (CH
3
OH) in
the rst step, and then interacts with another CH
3
OH molecule to
form DMC. The second step reaction (MC to DMC) is the rate-
limiting step in the whole urea methanolysis reaction [1014].
H
2
N
C
O
NH
2
+CH
3
OH
-NH
3
H
2
N
C
O
OCH
3
+CH
3
OH
-NH
3
H
3
CO
C
O
OCH
3
Rate-limiting step Quick step
Despite the extensive investigation of ZnO as highly active
catalysts [911], the catalytic mechanism of the ZnO in the urea
methanolysis process is still mysterious. Initially, ZnO was consid-
ered to activate CH
3
OH to form CH
3
O

group, which then attaches

the carbonyl C atoms of urea or MC to produce DMC [9]. However,
it was found that, as a typical heterogeneous catalyst, it is difcult
for ZnO to directly interact with MC. According to the results of
FTIR and element analysis for the precipitate after reaction, Zhao
et al. believed that the real catalyst in the urea methanolysis reac-
tion was zinc complex formed by ZnO and urea, namely
Zn(NH
3
)
2
(NCO)
2
. Accordingly ZnO is considered as the precursor
of homogenous catalyst [14]. Thus, the interaction between urea
and ZnO to form the complex is very important for the urea meth-
anolysis process. Although there have been several experimental
paper investigating the interaction of urea and ZnO, to the best
of our knowledge, the relevant theoretical investigation has not
been published yet [1517]. The detailed investigation of the sur-
face reaction is vital for elucidating the reaction mechanismof urea
methanolysis to synthesize DMC, which is difcult to implement
only by the available experimental methods. Thus, the theoretical
simulation is applied in our study to describe the adsorption of
urea on ZnO and its possible surface reactions, which is expected
to provide with a deeper insight into catalysis mechanism.
Generally speaking, over the reaction temperature range of
DMC synthesis (170190 C), the urea decomposition paths and
products is complicated. The isocyanato group (NCO

) and ammo-
nia (NH
3
) were observed by Schaber et al. when urea was heated to
2210-271X/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.comptc.2012.04.022

Corresponding authors. Address: State Key Laboratory of Coal Conversion,

Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan 030001, PR China
(Y. Sun). Tel.: +86 351 4049612; fax: +86 351 4041153.
E-mail addresses: weiwei@sxicc.ac.cn (W. Wei), yhsun@sxicc.ac.cn (Y. Sun).
Computational and Theoretical Chemistry 992 (2012) 18
Contents lists available at SciVerse ScienceDirect
Computational and Theoretical Chemistry
j our nal homepage: www. el sevi er . com/ l ocat e/ compt c
160 C under open reaction vessel [18], while Stradella and Argen-
tero believed that the isocyanic acid (HNCO) was formed in the
evolved gases at this temperature [19]. Based on these experimen-
tal observations, all the possible process of the urea decomposition
on the ZnO 10

10 surface [20] are simulated. For comparison, the

similar reactions without the substrate for urea decomposition into
NH
3
and HNCO are also investigated. In addition, the correspond-
ing vibrational frequencies of adsorbed urea and its decomposition
products on the ZnO 10

10 surface are calculated and compared

with the experimental results.
2. Computational methods
All the DFT calculations are performed using the Dmol
3
program
available in Materials studio 3.2 package [21,22]. The doubled
numerical basis set witha set of polarizationfunctions (DNP) is used,
which is comparable to Gaussian 6-31G

[21]. The generalized gra-

dient approximation (GGA) with PerdewWang 1991 function is
used [23,24], whichis generally used in ZnO10

10 surface calcula-
tion [25,26]. The real space cutoff radius is 4.4 . All electron basis
set are used for all the elements except Zn, which is treated by effec-
tive core potentials [27,28]. And a k-point of 4 4 1 is used. The
following thresholds are used for the geometry optimization: 1
10
5
Hartree for the maximum energy change, 2 10
3
Hartree/
for the maximum force, and 5 10
3
for the maximum displace-
ment. To determine the activation energy for a specic path for urea
decomposition, complete linear synchronous transit and quadratic
synchronous transit (LST/QST) calculations are performed to obtain
the structures of transitionstate (TS) [29,30]. Intrinsic reactioncoor-
dinate (IRC) calculationfromTS is carried out to conrmthat its cor-
relation with the desired reactant and product. Vibrational
frequencies are calculated at the optimized geometries to identify
the nature of the stationary points (no imaginary frequency) and
the TS (only one imaginary frequency).
The ZnO bulk structure is optimized before cleaving to generate
surface. The computed bulk lattice constants is found to be
a = b = 3.249 and c = 5.205 , in good agreement with the exper-
imental values and the previously reported theoretical results [31
33]. A (3 2)-ZnO 10

10 surface supercell with three double

layers is chosen as surface model (Fig. 1). A series of tests are per-
formed with this surface model and it is found that increasing the
slab thickness and supercell size changed the relative adsorption
energies by <1 kcal/mol. The rst bilayer is set to relax during
geometry optimization and the surface ZnAO bond length shortens
to 1.881 after relaxation, which is close to the literature [33].
3. Results and discussion
3.1. Gas-phase mechanism proposal
The reaction of urea decomposition into HNCO and NH
3
can be
described as the H atom rebinding process. During the process, one
NAH bond of the amino group breaks and the split H atom forms
bond with the N atom of the other amino group which breaks with
the carbonyl C atom simultaneously. There are two possible path-
ways as one N atom binds two H atoms in the amino group, as
shown in Scheme 1. The indirect transfer process via carbonyl O
atom for H
A
atom is proposed in Path A. The long distance between
H
A
and N
2
atoms makes the direct transfer (from N
1
to N
2
) unfea-
sible. By TS searching, three transition structures are located along
this reaction process. The optimized geometries of reactant (urea),
TS, intermediates (IM) and product complex (P) are illustrated in
Fig. 2. The corresponding potential energy is shown in Fig. 3.
Firstly, one of amino NAH bond breaks and the split amino H atom
(H
A
) binds to the carbonyl O atom to form the intermediate A-M1
via A-TS1. In A-TS1, the N
1
AH
A
bond is elongated to 1.338 and
the H
A
atom is ready to bond with the carbonyl O atom with the
distance between them of 1.331 . With the approaching of H
A
,
the electron density in the C@O bond is pulled to the O end, leading
to the double bond changes to the CAO single bond with the bond
length of 1.303 . Meanwhile, the N
1
@C double bond is formed and
the bond length decreases from 1.392 in free urea to 1.322 .
With the further adjustment of the structure, the A-M1 is obtained,
in which the OAH, CAO, and N
1
@C bond is 0.976 , 1.367 and
1.280 in length, respectively. This step is endothermic by
16.1 kcal/mol with the energy barrier of 44.6 kcal/mol. The high
energy barrier probably attributes to the difculty of H
A
breaking
with N
1
atom and rebinding to O atom since the urea N atom with
lone pair electrons is more electronegative than the carbonyl O
atom, which is conrm by the calculated electrostatic potential t-
ted charges (N: 0.516e and O: 0.396e). The process from A-IM1
to A-IM2 is endothermic by 7.7 kcal/mol with a small energy bar-
rier of 9.9 kcal/mol, and the N
2
AC bond length increases from
1.382 to 1.404 . Then the H
A
atom breaks from the carbonyl O
atom and binds to the N
2
atom with the newly formed NAH bond
of 1.238 in A-TS3, accompanying with the recovery of carbonyl
C@O double bond. At the nal state AP, the N
2
AC bond breaks
to generate HNCO and NH
3
. As the amino N atom with lone pair
electrons is more electronegative, this transfer process from the
O to N atoms is probably easier. The calculated energy barrier of
this step is 12.6 kcal/mol lower than that of the rst step
(32.0 kcal/mol), which can be explained by the different electro-
negativity of O and N atom. The last step is exothermic by14.6 -
kcal/mol.
A direct H atom rebinding pathway is proposed in Path B, in
which the amino H
B
atom splits from N
1
atom and binds to N
2
atom directly. And there is not any intermediate during the pro-
cess. Since the new bonds formation (the N
1
@C double bond and
N
2
AH
B
bond) and the old bond breaking (N
2
AC bond and amino
N
1
AH
B
bond) occur in one step, it is considered as a concerted reac-
tion. The transition structure (B-TS) and the product complex (BP)
are illustrated in Fig. 2. The potential energy surface is shown in
Fig. 4. In the transition structure B-TS, the H
B
atom has been broken
with the N
1
atom to bind to the N
2
atom with the newly formed
N
2
AH
B
bond of 1.210 in length. And the N
2
AC bond lengthens
from 1.391 in the free urea to 1.432 . Then N
2
AC bond totally
breaks and the hydrogen-bonded product complex consisted of
HNCO and NH
3
(BP) is formed. This step is predicted to be endo-
thermic by 18.9 kcal/mol, with energy barrier of 41.8 kcal/mol.
Path B is considered as a more possible pathway for urea
decomposition in gas-phase as the energy barrier is 2.8 kcal/mol
X
Z
Fig. 1. The schematic representation of ZnO 10

10 surface (red atoms and gray

atoms represent O and Zn, respectively) (For interpretation of the references to
color in this gure legend, the reader is referred to the web version of this article.).
2 Y. Gao et al. / Computational and Theoretical Chemistry 992 (2012) 18
less than that for Path A. Moreover the existence of the intermedi-
ate (A-IM1 or A-IM2) has not been observed by experiments, which
further conrms our conclusion.
3.2. Urea adsorption on the ZnO 10

10 surface
To evaluate the interaction between a urea molecule and the
adsorption surface, we rst calculated the adsorption energy of
urea on the ZnO 10

10 surface, which is dened as E

ads
=
E
total
(E
ZnO
+ E
urea
), where the E
total
, E
ZnO
and E
urea
stand for the to-
tal energies of adsorbed system, bare ZnO slab and a urea molecule,
respectively. The negative value represents a stable adsorption
system.
There are two kinds of adsorption sites on the ZnO 10

10 sur-
face, and urea can be adsorbed on either Zn or O atom. Different
congurations of urea adsorption on ZnO 10

10 surface have
been simulated and the most stable structure (M1) is obtained,
as shown in Fig. 5a. The adsorption of urea on the surface is exo-
thermic by 37.2 kcal/mol without any energy barrier, where both
of the amino N atoms from urea bind to surface Zn atoms with
the bond length of 2.231 . The bond length of N
1
AC in urea
N
1
C
N
2
O
H
A
H
B
H
H
H
A
C
O
N N
H
H
H
H
C
O
N
N
H
H
H
H
C
O
N
N
H
H
H
H
HNCO + NH
3
A-TS1 A-TS2 A-TS3
Urea
A-IM1 A-IM2 A-P
B-TS
C
O
N
N
H
H H H
B-P
Path A
Path B
Scheme 1. Possible pathways of the free urea decomposition into HNCO and NH
3
(Dash lines indicate Coulomb interactions or hydrogen bonds).
C
O
N N
H
H
H
H
C
O
N
N
H
H
H
H
A-TS1
A-TS2 A-TS3
1.227
1
.3
9
2
1
.0
1
5
Urea
C
O
N N
H
H
0
.9
7
6
1.022
1
.3
2
2
1
.2
8
0
1.338
1.018
1.331
1.367 1.303
1.016
0.971
1.024
1
.2
7
5
1.388
A-IM1
A-IM2
A-P
1
.3
8
8
1
.3
9
1
1
.3
8
2
1
.3
6
0
0
.9
7
3
1
.2
7
4
1.371
1
.4
0
4
1.023
1
.
2
3
8
1
.2
7
0
1.286
1.026
1.642
1
.
1
8
7
1
.
2
1
4
1.811
1.021 1.049
1.213
1
.3
3
2
1
.3
6
2
1
.4
3
2
B-TS
B-P
1
.
2
1
0
C
O
N
N
H
H H H
H
H
C
O
N N
H
H
H
H
C
O
N N
H
H
H
H
C
O
N N
H
H
H
H
C
O
N
N
H
H
H
H
C
O
N N
H
H
H
H
1.176
1.226
1
.
0
1
3
2
.4
2
0
1
.0
2
3
Fig. 2. The optimized geometries of various species involved in Paths A and B
described in Scheme 1 (IM-intermediate, TS-transition state, P-product complex.
Dash lines indicate Coulomb interaction or hydrogen bonds). Bond length is in
angstroms.
0
10
20
30
40
50
60
55.8
26.0
44.6
22.0
9.2
23.8
16.1
32.0
9.9
44.6
HNCO
+NH
3
A-P
A-IM2
A-IM1
A-TS3
A-TS2
0.0
A-TS1
Urea
R
e
l
a
t
i
v
e

E
n
e
r
g
y

(
k
c
a
l
/
m
o
l
)
Reaction coordinate
Fig. 3. Energy prole of the Path A. The energy barriers are presented in italics and
bolds.
0
10
20
30
40
50
41.8
B-P
B-TS
22.0
18.9
41.8
HNCO
+NH
3
0.0
Urea
R
e
l
a
t
i
v
e

E
n
e
r
g
y

(
k
c
a
l
/
m
o
l
)
Reaction coordinate
Fig. 4. Energy prole of the Path B. The energy barrier is presented in italics and
bolds.
Y. Gao et al. / Computational and Theoretical Chemistry 992 (2012) 18 3
increases from 1.392 (N
2
AC 1.391 ) to 1.418 (N
2
AC 1.418 ).
The hydrogen bonds of 1.674 in length between the amino H
atoms of urea and the adjacent O atoms on the surface are formed,
which leads to the slight increase of the amino NAH bonds length
from 1.016 in the free urea to 1.068 .
The metastable adsorption structures (M2) are illustrated in
Fig. 5b and c, where the urea molecule is parallel to the ZnO
10

10 surface with the adsorption energy of 33.2 kcal/mol. The

carbonyl O atom of urea binds to the surface Zn atom, accompany-
ing with the formation of hydrogen bonds between the amino H
atoms and the adjacent O atoms on the surface. The carbonyl
C@O double bond and the N
1
AC bond increases from 1.227 and
1.392 to 1.255 and 1.415 respectively, while the N
2
AC bond
decreases to 1.340 . In literature [34], our calculation for the
adsorption of urea onto ZnO10

10 surface with the VASP program

also believed the conguration of M1 and M2 are the most stable.
We also obtained some other adsorption structures with lower
adsorption energies (at least 13 kcal/mol lower than the metastable
one). However, according to Boltzmann population analysis, these
energy differences are large enough to ignore the existence of the
less stable ones [35,36]. Thus, structures M1 and M2 are applied
for further discussion of the possible decomposition pathways.
3.3. Urea decomposition on ZnO 10

10 surface
The processes for urea decomposition on the ZnO 10

10 sur-
face are explored in our calculations, which is probably different
from the conclusion we obtained in the previous discussion as
the reaction is more complicated on the metal oxide surface than
in gas-phase. Thus, we investigated all the possible processes,
and the proposed pathways of urea decomposition on the ZnO
10

10 surface on the base of M1 and M2 are illustrated in

Schemes 2 and 3, respectively.
3.3.1. Decomposition process on the base of M1
As shown in Scheme 2, there are three possible decomposition
pathways on the base of M1: H
A
and H
B
atoms transfer from N
1
to N
2
involving the H migration on the ZnO surface (Path 1 and
Path 2), as well as the direct rebinding of H
B
to N
2
atom (Path 3).
3.3.1.1. Path 1. The proposed process of Path 1 can be described as
following: H
A
atom breaks from N
1
atom to bind to the surface O
3
atom, then migrates to the surface O
4
atom, and nally binds to the
urea N
2
atom to form HNCO and NH
3
. The optimized structures for
surface intermediate, transition state and product are illustrated in
Fig. 6 and the energy prole is presented in Fig. 7, with the energy
of the clean surface and free urea molecule as reference.
However, the whole process is more complicated. Our calcula-
tion shows that after H
A
atom breaks with the N
1
atom, it rstly
binds to the carbonyl O atom to form IM1-1 rather than the surface
O
3
atom, which is probably because of the long distance between
H
A
and the surface O
3
atom. In TS1-1, the H
A
AN
1
bond breaks
and H
A
has bound to the urea O atom to form H
A
AO bond
1.275 in length, which results in the former C@O double
bond changing into CAO bond of 1.288 in length and the N
1
AC
bond shortens to 1.358 . This step is endothermic by 17.8 kcal/
mol with the energy barrier of 42.8 kcal/mol. Then H
A
atom mi-
grates to bind to the surface O
3
atom, leading to the formation of
IM1-2. This step is exothermic by 11.8 kcal/mol with energy bar-
rier of 4.1 kcal/mol. Before investigating the H
A
atom surface
migration from the surface O
3
to O
4
atoms, we consider another
possible pathway from IM1-1 to IM1-3 via the surface intermedi-
ate denoted as IM1-2
0
. In this case, the OAH bond from IM1-1
rstly bends to form IM1-2
0
, in which the H
A
atom is approaching
to the surface O
4
atom. The distance between the H
A
and surface O
4
atoms is 1.411 and the OAH bond lengthens from 0.977 in
IM1-1 to 1.106 . The IM1-2
0
formation is exothermic by 1.9 kcal/
mol without any energy barrier, which because this step does
not involve any bonds breaking and formation. Then the H
A
atom
breaks from the urea O atom and binds to the surface O
4
atom to
form IM1-3. In IM1-3, the OAH bond totally splits, leading to the
surface hydroxyl formation (R
O4HA
: 0.984 ). Meanwhile, the dis-
tance between the urea C and O atoms shortens to 1.238 to re-
cover the C@O double bond. This step is exothermic by 8.0 kcal/
H
A
H
B
N
2
N
1
O
1
O
2 O
3
O
4
H
A
H
B
N
2
N
1
O
1
O
2
(a) (c) (b)
M2 M1
Fig. 5. The optimized structures of urea molecular adsorption on the ZnO 10

10 surface. (a) and (b) are the side view of the optimized surface structures (M1 and M2). (c) is
the top view of M2. The element name is assigned to the respective atom.
M1
IM1-1
IM2-1
Path 1
Path 3
Path 2
Dissociation of
amino H atom
H
A
H
B
H
A
surface
migration
H
B
binding
to N
2
P3
P1
H
B
surface
migration
IM2-2
P2
IM1-2
H
A
binding
to N
2
H
B
direct
rebinding to N
2
Scheme 2. Possible pathways of the urea decomposition into HNCO and NH
3
on the
ZnO 10

10 surface started from M1.

P4
M2
IM4 Path 4
Path 5
H
A
binding
to carbonyl O
H
A
binding
to N
2
H
B
direct
rebinding to N
2
P5
Scheme 3. Possible pathways for the urea decomposition into HNCO and NH
3
on
the ZnO 10

10 surface started from M2.

4 Y. Gao et al. / Computational and Theoretical Chemistry 992 (2012) 18
mol without any energy barrier. Thus, it is concluded that the IM1-
3 formation is more likely in this barrierless pathway.
The nal step is to give the product complex (P1) via TS1-3, in
which H
A
atom binds to the N
2
atom and the urea N
2
AC bond
breaks simultaneously. In TS1-3, H
A
atom is on the way to the ami-
no N
2
atom with the distance of 1.333 . And the N
2
AC bond has
broken, accompanying with the formation of C@N
1
double bond
of 1.223 in length. At last, in P1, when NH
3
is formed, the H
B
atom
trends to bind to the neighboring surface O atom (O
1
) which leads
to the N
1
AH
B
bond breaking. In this process, P1 is energetically
preferred by 12.7 kcal/mol. The energy barrier for the product for-
mation is as high as 45.4 kcal/mol, which is probably because that
H
A
atom not only requires energy to break from the surface O
4
atom, but also has to overcome the Coulomb interaction with the
carbonyl O atom during the process of binding to the N
2
atom.
In Path 1, the energy barriers for the process of H
A
atom binding
to the urea carbonyl O atom is 1.8 kcal/mol lower than that in Path
A, but the energy barrier for H
A
binding to N
2
atom is 13.4 kcal/mol
higher than that in Path A, which suggests the rebinding process of
H
A
to N
2
in free urea is much easier than that on ZnO surface. The
negative inuence of the ZnO 10

10 surface probably results from

the strong surface hydroxyl formed between the split H
A
atom and
surface O atom, which cause the additional energy in H
A
rebinding
to N
2
atom process.
3.3.1.2. Path 2. In addition to the H
A
atom transfer, we investigate
another possible reaction pathway involved in the H
B
atom rebind-
ing, Path 2. The optimized structures for surface intermediate
species, transition structures and product are illustrated in Fig. 8
and the energy prole is presented in Fig. 9, with the clean surface
and free urea molecule as energetic reference.
As shown in Scheme 2, there are three steps in Path 2. Firstly, H
B
atom breaks from the urea N
1
atom and binds to the adjacent sur-
face O atom (O
1
) to form the dissociative adsorption conguration
(IM2-1) via TS2-1. In TS2-1, the H
B
atom has broken from the N
1
atom with the bond length of 1.336 and the surface hydroxyl
(O
1
AH
A
) has thus formed with the bond length of 1.222 . Then,
the surface hydroxyl in IM2-1 further shortens to 1.018 . The re-
moval of H
B
from urea results in the shortening of N
1
AC bond from
1.418 in M1 to 1.374 , while the carbonyl C@O double bond
scarcely changes. This step is endothermic by 2.9 kcal/mol with
the energy barrier of only 4.7 kcal/mol. It demonstrates that urea
could dissociatively adsorb on the ZnO 10

10 surface via the

NAH bond breaking.
Subsequently, the H
A
atom migrates to the surface O
2
atom to
approach the N
2
atom via TS2-2. In the surface migration process,
in order to facilitate the H
A
atomtransfer, the surface ZnOdimers in-
volved in O
1
and O
2
atoms slightly moves to close each other, which
are allowed to relax in our calculation. In TS2-2, H
B
atom is on the
way to the surface O
2
atom. The distance between H
B
and the surface
O
1
and O
2
atoms is 1.248 and 1.302 , respectively. Meanwhile the
urea N
1
AC bond further shortens to 1.340 , while the N
2
AC bond
lengthens from 1.418 in M1 to 1.469 . The newly formed surface
hydroxyl (O
2
AH
B
) is 0.972 in length and the urea N
1
AC and N
2
AC
bond further shortens and lengthens to 1.336 and 1.514 , respec-
tively. This step is endothermic by 16.5 kcal/mol. The energy barrier
for the H
B
surface migration is 35.2 kcal/mol, which probably results
from the surface dimers movement and the steric repulsion caused
by the adjacent H atom from N
2
atom.
After that, IM2-2 converts to P2 via TS2-3. In TS2-3, the H
B
atom
is on the way to the amino N
2
atom and the distance between H
B
and N
2
atom is 1.678 . And the N
1
AC bond has been broken, lead-
ing to the formation of N
1
@C double bond of 1.222 in length.
Meanwhile, HNCO is formed and adsorbs on the surface with the
H
A
atom trending to bind to the adjacent surface O
3
atom. The
N
1
AH
A
bond lengthens from 1.022 in IM2-2 to 1.200 and the
distance between H
A
and surface O
3
atoms is 1.411 . Finally,
TS1-1
IM1-1
IM1-2' P1
IM1-2 TS1-2
TS1-3 IM1-3
Fig. 6. The optimized geometries of various species involved in the urea decomposition reaction on the ZnO 10

10 surface in Path 1 described in Scheme 2.

-40
-30
-20
-10
0
10
20
Reaction coordinate
R
e
l
a
t
i
v
e

E
n
e
r
g
y

(
k
c
a
l
/
m
o
l
)
42.8
ZnO+
Urea
-37.2
0.0
-19.4
5.7
M1
IM1-1
TS1-1
4.1
45.4
-42.0
16.1
-31.2
-21.3
-29.3
-15.3
IM1-2'
IM1-3
TS1-2
P1
IM1-2
TS1-3
Fig. 7. Energy prole of the urea decomposition process on the ZnO 10

10 surface
in Path 1 described in Scheme 2. The clean surface and free urea molecule are taken
as energetic references. The energy barriers are presented in italics and bolds. The
dot lines indicate another proposed path started from IM1-1.
Y. Gao et al. / Computational and Theoretical Chemistry 992 (2012) 18 5
NH
3
has been formed and molecularly adsorbs on the surface Zn
atom via N atom, while the HNCO dissociatively adsorbs on the
surface via the N
1
AH
A
bond breaking. The last step is exothermic
by 30.2 kcal/mol with a moderate energy barrier of 16.4 kcal/mol,
which is 29.0 kcal/mol lower than that of the last step in Path 1.
As the highest energy barrier along the process of Path 2
(35.2 kcal/mol) is 10.2 kcal/mol lower than that of Path 1
(45.4 kcal/mol), it is concluded that urea decomposes on the ZnO
10

10 surface in Path 2 is more feasible. Compared with Path B,

the process of urea decomposition via H
B
atom rebinding in gas-
phase, the energy barrier for H
B
atom rebinding process is
effectively decreased. It is probably because that the transition
structure adsorbed on the surface is stabilized by the interaction
with surface atoms. Thus, the presence of ZnO 10

10 surface
changes the former concerted reaction into a stepwise process
and effectively decreases the energy barrier for H
B
atom rebinding
process. Moreover, as the intense interaction between the ZnO
10

10 surface and urea, the urea decomposition process is exo-

thermic by 48.0 kcal/mol, which promotes the urea decomposition.
3.3.1.3. Path 3. For comparison with the indirect H
B
atom rebinding
process, the direct pathway is proposed without any surface inter-
mediate, which is denoted as Path 3. The energy prole is
presented in Fig. 10, with the clean surface and free urea molecule
as energetic reference and the transition structure.
In the only transition structure (TS3), the N
2
AC bond has broken
and the N
1
AC shortens to convert to the N
1
@C double bond of
1.287 in length. At the same time, the N
1
AH
B
bond lengthens
to 1.181 , which results in H
B
atom approaching to N
2
atom with
the distance of 1.532 . The product (P3) is then formed, which is
the same as P1 structurally. This step is exothermic by 4.8 kcal/
mol and the energy barrier is as high as 84.7 kcal/mol, which indi-
cates the impossibility of urea decomposition in this pathway. The
high energy barrier probably results from the following two
reasons: rstly, during the process of rebinding to N
2
atom, H
B
atom not only requires energy to break from N
1
atom, but also
has to overcome the interaction with surface O
1
atom. Secondly,
because of the hydrogen bond formed with the surface O
2
atom,
the N
2
AH bond hardly bends which results in the steric repulsion
to hinder the approaching of H
B
to N
2
atom.
3.3.2. Decomposition process stated from M2
Starting from the metastable molecular adsorption congura-
tion M2, two possible reaction pathways for the rebinding process
TS2-1 IM2-1 TS2-2
IM2-2 TS2-3 P2
Fig. 8. The optimized geometries of various species involved in the urea decomposition reaction on the ZnO 10

10 surface in Path 2 described in Scheme 2.

-50
-40
-30
-20
-10
0
10
35.2
3.7
16.4
ZnO+
Urea
-37.2
Reaction coordinate
R
e
l
a
t
i
v
e

E
n
e
r
g
y

(
k
c
a
l
/
m
o
l
)0.0
-17.8
-48.0
-1.4
-32.5
-34.3
0.9
P2
IM2-2
M1
TS2-3
TS2-2
IM2-1
TS2-1
Fig. 9. Energy prole of the urea decomposition process on the ZnO 10

10 surface
in Path 2 described in Scheme 2. The clean surface and free urea molecule are taken
as energetic references. The energy barriers are presented in italics and bolds.
-40
-20
0
20
40
60
47.5
84.7
ZnO+
Urea
-37.2
Reaction coordinate
R
e
l
a
t
i
v
e

E
n
e
r
g
y

(
k
c
a
l
/
m
o
l
)
0.0
-42.0
P3(P1)
M1
TS3
Fig. 10. Energy prole and transition structure (TS3) of the urea decomposition
reaction on the ZnO 10

10 surface in Path 3 described in Scheme 2. The clean

surface and free urea molecule are taken as energetic references. The energy barrier
is presented in italics and bolds.
6 Y. Gao et al. / Computational and Theoretical Chemistry 992 (2012) 18
of H
A
and H
B
atoms are proposed, which are denoted as Path 4 and
Path 5, respectively (Scheme 3).
3.3.2.1. Path 4. In Path 4, H
A
atom is supposed to indirectly rebind
to the N
2
atom via carbonyl O atom. The transition structure, sur-
face intermediate and the energy surface are shown in Figs. 11 and
12, respectively.
Firstly, H
A
atom binds to the urea carbonyl O atom to form IM4
via TS4. In TS4, the H
A
atom has broken from N
1
atom with the
breaking N
1
AH
A
bond length of 1.363 , while the bond between
O and H
A
has not been formed with the distance of 1.300 . At
the same time, the N
1
AC bond shortens from 1.415 in M2 to
1.363 and the carbonyl C@O double bond lengthens from
1.255 in M2 to 1.323 . Then, IM4 is formed, in which the H
A
atom has bound to the carbonyl O atom with the newly formed
OAH
A
bond of 0.997 in length. Accordingly, the C@O double bond
converts to CAO single bond of 1.407 in length. The distance be-
tween N
1
and C atom shortens to form the N@C double bond of
1.314 in length. This step is endothermic by 15.2 kcal/mol with
the energy barrier of 43.2 kcal/mol. In view of activation barrier,
Path 4 is less favorable than Path 2, regardless of the energy barrier
for the following steps, in which H
A
atom will bind to N
2
atom to
form the product.
3.3.2.2. Path 5. The process of H
B
atom direct rebinding to the N
2
atom is investigated, rather than the indirect process in which H
B
atom adsorbs on the surface O
1
atom. It is because the surface O
1
atom is further away from H
B
than N
2
atom and the H formed
hydrogen bond with surface O
1
atom will create the steric repul-
sion upon H
B
approaching to O
1
atom, which probably results in
more energy required in the indirect process. The transition
structure and surface intermediate are shown in Fig. 11. The
energy surface can be found in Fig. 12 (dash line).
H
B
atom directly rebinds to N
2
atom via TS5. In TS5, the H
B
has
broken fromthe N
1
atom with the broken bond of 1.428 in length
and it is on the way to the N
2
atom with the distance of 1.375 .
The surface intermediate (IM5) is then formed. In IM5, H
B
atom
has bound to the N
2
atom with the newly formed NAH bond of
1.028 in length, and the N
2
AC bond lengthens from 1.340 in
M2 to 1.500 , but not breaks. Meanwhile, the N
1
AC bond shortens
from 1.415 in M2 to 1.329 . The formation of this surface inter-
mediate is strongly endothermic by 51.4 kcal/mol, which indicates
its instability. Subsequently, IM5 should convert to the nal prod-
uct HNCO and NH
3
via N
2
AC bond breaking. However, as the en-
ergy barrier of this step is as high as 64.6 kcal/mol, which is
29.4 kcal/mol higher than that in Path 2, it is concluded that urea
may not decomposes in this pathway and the subsequent step is
not further investigated.
According to the energy barriers of the ve reaction pathways
discussed above, it is concluded that on the ZnO 10

10 surface
urea decomposes into HNCO and NH
3
in Path 2, in which H
B
atom
indirectly rebinds to the urea N
2
atom via surface migration.
3.4. Vibrational frequencies of urea and its decomposition products on
the ZnO 10

10 surface
As discussed above, upon urea decomposition in Path 2, HNCO
and NH
3
may dissociatively and molecularly adsorb on the ZnO
10

10 surface, respectively. In order to support the existence of

the decomposition products, their vibrational frequencies are cal-
culated, as well as molecularly adsorbed urea (M1 and M2). In
the calculation, the NAH asymmetry and symmetry stretching
vibration of urea are around 3480 cm
1
and 3426 cm
1
, respec-
tively. The C@O stretching vibration and NAH bending vibration
of urea are around 1747 cm
1
and 1634 cm
1
, respectively. Exper-
iments had reported the similar NAH asymmetry and symmetry
stretching vibration at around 3440 cm
1
and 3350 cm
1
, accom-
panying with the C@O stretching vibration and NAH bending
vibration of urea at around 1670 cm
1
and 1623 cm
1
, respectively
[37]. As for the N@C@O group, the calculated vibrational frequency
is at 2238 cm
1
. Wang et al. reported the similar absorbance band
of N@C@O group at 2205 cm
1
by FTIR experiment [15]. The accor-
dance between the calculated vibration frequencies and experi-
ments results suggests the accuracy of the simulation.
4. Conclusions
The present calculations demonstrate the mechanism for urea
decomposition into HNCO and NH
3
on the ZnO 10

10 surface.
The free urea decomposition is a concerted reaction via one of ami-
no H atom direct rebinding to the N atom, which is endothermic by
22.0 kcal/mol with energy barrier of 41.8 kcal/mol. However, on
the ZnO 10

10 surface, the decomposition occurs in consecutive

steps. Firstly, one of NAH bond breaks leading to the dissociative
TS4 IM4 TS5 IM5
Fig. 11. The optimized geometries for transition structures and surface intermediates involved in the urea decomposition reaction on the ZnO 10

10 surface in Path 4 and 5

described in Scheme 3.
-40
-30
-20
-10
0
10
20
30
40
-18.0
IM4
64.6
TS5
18.2
31.4
10.0
IM5
43.2
ZnO+
Urea
Reaction coordinate
R
e
l
a
t
i
v
e

E
n
e
r
g
y

(
k
c
a
l
/
m
o
l
)
0.0
TS4
-33.2
M2
Fig. 12. Energy prole of the urea decomposition process on the ZnO 10

10
surface in Paths 4 and 5 described in Scheme 3. The clean surface and free urea
molecule are taken as energetic references. The energy barriers are presented in
italics and bolds.
Y. Gao et al. / Computational and Theoretical Chemistry 992 (2012) 18 7
adsorbed urea. Then, the split H atom migrates on the surface O
atom to approach the other amino N atom. Finally, the H atom is
removed from the surface to bind to the N atom, accompanying
with the breaking of urea NAC bond to produce HNCO and NH
3
.
The process is exothermic by 48.0 kcal/mol with the highest energy
barrier of 35.2 kcal/mol. Compared with the free urea decomposi-
tion process, the presence of ZnO 10

10 surface effectively
decreases the reaction energy barrier for the H atom rebinding pro-
cess. Moreover, upon urea adsorbing on this surface, the intensely
exothermic process could promote urea decomposition. That is, in
our calculation the ZnO 10

10 surface is conrmed to catalyze the

urea decomposition, which is accordance with the deduction in
former experimental investigation [15]. In order to support the
existence of the decomposition product, the vibrational frequen-
cies are also calculated and the results are found to agree well with
the experimental results.
Acknowledgment
The authors acknowledge the nancial support from State Key
Program for Development and Research of China (No. 2006BAC
02A08).
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