Comptes rendus de lAcademie bulgare des Sciences

Tome 66, No 11, 2013

CHIMIE
Cinetique et catalyse

A DFT STUDY OF CO ADSORPTION AND DISSOCIATION

OVER MoP(001) PLANE
Sharif F. Zaman, Mohammad Daous, Lachezar Petrov
(Submitted on July 3, 2013)

Abstract
Density functional theory was employed to investigate the CO dissociation
energy over MoP(001) surface. CO dissociation over MoP(001) plane was found
unfavourable in comparison to the molecular adsorption of CO. The dissociation
activation energy is 385.3 kJ/mol which is much higher than the adsorption
energy of CO molecule, 212.30 kJ/mol. The CO adsorption process did not
alter the d orbital DOS structure. A significant electronic contribution from
the phosphorus ligand underneath the surface layer was observed.
Key words: CO dissociation, activation energy, density of state (DOS),
MoP, DFT

1. Introduction. Nowadays, intensive research activities are devoted to

the search for new highly active and selective catalytic systems for FTS and HAS
processes. One of the key issues we have to reveal for each new catalyst system
is the information about the mechanism of CO participation in the reaction.
Since the adsorption of CO is the first step of its activation, it is very important
to understand how CO predominantly is adsorbed on a catalyst active surface
and what type of surface complexes are formed. Because the dissociative CO
adsorption is leading to formation of coke precursors and active oxygen, this
reaction route should be depressed by selecting catalysts components, on which
CO is adsorbed nondissociatively. Therefore, we have to be able to exclude such
components beforehand by suggesting a suitable criterion.
This work was supported by the Deanship of Scientific Research of King Abdulaziz University, Jeddah, Saudi Arabia, under Grant No D-005/431.

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As an effective criterion for such discrimination might be used the energy

of CO dissociative adsorption on particular component. At the same time, the
energy of CO adsorption can be used as a criterion of the CO hydrogenation capability of the particular metal [1 ]. Mo based catalysts possess high hydrogenation
capability and have been used by many authors as effective catalysts in FTS and
higher HAS from syngas [24 ]. Addition of p orbital ligands to Mo reduces the CO
adsorption energies following the sequence Mo > MoP > -MoC > -MoN [5 ].
According to results published in [5 ], MoP has properties, which show a good
potential possibility for preparation on its base an active catalyst for alcohol synthesis from syngas. Still, however, in the literature there is no reported data
about the value of energy of CO dissociation on MoP surface.
In this study, we report the adsorption and dissociation energies of CO over
MoP(001) plane calculated by using DFT. To understand the mechanism of CO
hydrogenation over the MoP catalyst we set our focus on finding the preferable
adsorption arrangement of COads and [Cad +Oad ] and the calculation of the activation energies of CO bond dissociation over MoP catalyst.
2. Calculation procedure. The DMol3 module of Material Studio (version 6.0) from Accelrys Inc. (San Diego, CA, USA) was used to perform the DFT
calculations. The double-numerical plus P-function (DNP) of all electron basis
set was used for all the calculations. Each basis function was restricted to a cutoff
radius of 4.9
A, allowing for efficient calculations without loss of accuracy. The
KohnSham equations were solved by a self-consistent field procedure using PW91
functional with GGA for exchange correlation. The techniques of direct inversion
in an iterative subspace with a size value of six and thermal smearing of 0.005 Ha
were applied to accelerate convergence. The optimization convergence thresholds
for energy change, maximum force and maximum displacement between the optimization cycles were 0.00001 Ha, 0.002 Ha/
A and 0.005
A, respectively. The
k-point set of (333) was used for all calculations. The transition state between
two stable surface species was identified by complete linear synchronous transit
and quadratic synchronous transit search methods followed by TS confirmation
through the nudge elastic band method. Spin polarization was imposed in all
calculations. The adsorption energy of an element (i.e. molecule or atom) was
found according to the following formula:
Ead = Eslab+element + Eempty

slab

+ Eelement .

3. Building unit cell structure of MoP crystal. MoP has a hexagonal

crystal structure belonging to P6m2 space group with lattice parameter a = b =
3.235
A and c = 3.165
A [6 ]. The investigation plane (001) was cleaved from
the MoP unit cell and increased to five atomic layers and 4 4 supercell slab to
provide large surface area for favourable adsorption locations for CO, C and O
species.
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S. Zaman, M. Daous, L. Petrov

4. Results. 4.1. Preferred adsorption location for C and O over

MoP(001). Before calculating the dissociation energies of CO, the preferred
adsorption position of oxygen (O) and carbon (C) atom on the MoP(001) surface
were investigated separately. The results of simulation of preferred adsorption
location of C and O atoms were performed by adsorbing C and O atoms separately
and then placing them together on the surface, i.e. surface product configuration.
The adsorption energy results are tabulated on Table 1. Our calculations have
Table

Total and adsorption energies of C and O atoms and CO

molecule over MoP(001) plane

O
C
CO
MoP(001)
COad + MoP(001)
Oad (3 fold at fcc) + MoP
Oad (3 fold at hcp) + MoP
Cad (3 fold at fcc) + MoP
Cad (3 fold at hcp) + MoP
Oad (fcc) + Cad (fcc) + MoP
Oad (fcc) + Cad (hcp) + MoP
Oad (hcp) + Cad (fcc) + MoP
Oad (hcp) + Cad (hcp) + MoP

Etotal (Hartree)
75.0731
37.8452
113.3201
151402.0499
151515.4509
151477.3539
151477.3683
151440.1498
151440.1564
151515.4865
151515.4612
151515.5088
151515.5183

Ead (kJ/mol)

212.27
605.93
643.52
668.64
686.01
1360.44
1294.83
1419.29
1444.38

1 Hartee = 27.212 eV = 2625.50 kJ/mol

shown that bridge and on top sites are not favourable for adsorption of C
and O atoms. We have found that hcp and fcc sites are the preferred location
but both atoms have the lowest energy arrangement when adsorbed at the hcp
site. The adsorption energy of O atom at fcc site is 605.92 kJ/mol while on
hcp site it is 644.52 kJ/mol, the adsorption energy of C atom on fcc site is
668.64 kJ/mol and on hcp site it is 686.01 kJ/mol when C and O atoms were
placed . The lowest energy configuration was found when O and C atoms were
adsorbed at two different hcp sites with an adsorption energy of 1444.38 kJ/mol.
When both C and O atoms were placed at their preferred location (two nearby
hcp sites) together on MoP(001) plane, they were stabilized on two different hcp
sites not adjacent to each other. The initial distance between C and O atoms,
placed at two adjacent hcp sites, was 3.23
A while the optimized final distance
was 5.62
A.
4.2. Adsorption and dissociation energies of CO over MoP(001)
plane. Different molecular adsorption arrangements, i.e. ontop, bridge and three
fold position, of CO on MoP(001) slab were investigated and every configuration
converged to the preferred ontop adsorption arrangement with an adsorption
Compt. rend. Acad. bulg. Sci., 66, No 11, 2013

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energy of 212.3 kJ/mol. The CO bond length in on top nondissociatively

adsorbed CO was found to be equal to 1.173
A. This length is greater than the
molecular CO bond length of 1.14
A. Therefore, CO adsorption on MoP(001) slab
makes the CO bond relaxed. The vibrational frequency of CO over MoP(001)
plane was found 2028 cm1 close to the previously reported one by Feng et al. [7 ].
The obtained value of CO adsorption energy over MoP(001) plane is 2.20 eV,
which is close to the reported by other authors value of adsorption energy of 1.98
to 2.2 eV [5, 7, 8 ]. The calculated values of Mullikan atomic charges of C and
O are +0.038 eV and 0.208 eV. The corresponding atomic charges for free CO
molecule are +0.105 eV and 0.105 eV. The decrease in charge on adsorbed CO
molecule indicates that a process of the electron donation from Mo is taking place.
An increased distance between C and O atoms in the adsorbed CO molecule shows
that the adsorbed on top on MoP CO molecule was activated by the charge
donation process. Therefore, the activated CO molecule is prepared for further
transformations.
We can regard the optimized structure configuration of the dissociated C
and O over MoP(001) plane, as a reaction product. The on top CO adsorbed
over MoP(001) plane will be regarded as an initial reagent. A transition state
search was performed between the reactant and the product. The obtained energy
barrier Ea of the dissociation reaction is 385.3 kJ/mol which is much higher than
the molecular adsorption of CO on the MoP(001) plane, 211.30 kJ/mol (2.19 eV).
The CO dissociation activation barrier reported in the literature [6 ] over Mo(100)
plane is 58.03 kJ/mol, over C terminated Mo2 C(0001) plane is 85.87 kJ/mol,
over Mo terminated Mo2 C(0001) plane is 185.25 kJ/mol, and over Mo edge of
MoS2 (1010) plane is 250.86 kJ/mol. Over MoP(001) plane, it shows highest CO
dissociation activation barrier among the Mo based catalysts.
Therefore, from these data it follows that CO will remain undissociated over
the MoP(001) surface. The exothermic heat effect is 176.57 kJ/mol. The reaction
pathway is shown in Fig. 1.
4.3. Density of state (DOS) analysis. Densities of state (DOS) have
been generated for empty MoP(001) plane and for MoP(001) plane with adsorbed
CO molecule, C and O atoms are depicted in Fig. 2. When CO is molecularly
adsorbed on the surface DOS interaction show a new peak at 0.33 Ha at both
s and p orbital DOS structures. Also small alteration of p orbital DOS was
observed at 0.22 Ha. Interaction of electron orbitals during the CO adsorption
process over several transition metals are well explained by Sung and Hoffmann[9 ]. The 5 bonding orbital of CO interacts with the d orbitals of transition
metals, mainly dz 2 orbital, and the electron is transferred from CO to metal (Mo)
by donation-back donation mechanism to establish the bond. A shift in d band
centre is also observed for CO adsorption on Pd (210) [10 ] (non dissociative CO
adsorption) in later DFT works, which stabilizes the fact of d orbital contribution of transition metals in CO adsorption more profoundly. Interestingly, for CO
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S. Zaman, M. Daous, L. Petrov

Fig. 1. CO dissociation reaction pathway over MoP(100) plane

adsorption MoP(001) no alteration in the shape of d orbital, hence, the d band

centre, is observed (Fig. 2 (III) a and b). The s and p orbital should come from
the CO molecule and p orbital ligand element phosphorus. Therefore phosphorus
has a significant electronic contribution in the nondissociative adsorption of CO

Fig. 2. DOS of s, p and d orbital (a) empty MoP(001) (b) CO adsorbed on MoP(001) (c) C and
O dissociative adsorbed over MoP(001) plane
Compt. rend. Acad. bulg. Sci., 66, No 11, 2013

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over MoP(001), where as over Mo(110) plane CO is adsorbed dissociatively. In

the DOS structure of dissociated C and O atoms adsorbed on the surface we
observe two low energy peaks on the s, p and d orbitals DOS. The peak at
0.7 Ha is representative for oxygen atom binding and the peak at 0.33 Ha
corresponds to the carbon atom bound to the surface. The intensity of the peaks
for p and d orbital DOS is very low. There is also a slight alteration of the height
at 0.05 Ha in the d orbital DOS. From DOS structures for C and O adsorbed
on the MoP surface, we can conclude that the main interaction comes at the s
orbital.
5. Conclusions. Density functional theory (DFT) was employed to investigate the CO dissociation energy over MoP(001) surface. Nondissociative
ontop adsorption of CO is favoured over the surface with an adsorption energy
of 212.3 kJ/mol. Both C and O atoms prefer hcp three-fold binding location
on the surface. The dissociation activation energy is 385.3 kJ/mol which is much
higher than the adsorption energy of CO molecule, 212.3 kJ/mol. Hence, CO
molecule would prefer to desorb from the surface rather than undergoing the CO
dissociative adsorption.

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Chemical and Materials
Engineering Department
Faculty of Engineering
King Abdulaziz University
P. O. Box 80204
Jeddah 21589, Saudi Arabia
e-mails: zfsharif@gmail.com
sfzaman@kau.edu.sa
1540

SABIC Chair of Catalysis

Chemical and Materials
Engineering Department
Faculty of Engineering
King Abdulaziz University
P. O. Box 80204
Jeddah 21589, Saudi Arabia

S. Zaman, M. Daous, L. Petrov