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A dft study of hydrogen dissociation over MoP

(001) plane
ARTICLE in COMPTES RENDUS DE L'ACADEMIE BULGARE DES SCIENCES: SCIENCES MATHEMATIQUES ET
NATURELLES AUGUST 2014
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Lachezar Petrov

King Abdulaziz University

Bulgarian Academy of Sciences

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Comptes rendus de lAcad
emie bulgare des Sciences
Tome 67, No 6, 2014

CHIMIE
Cinetique et catalyse

A DFT STUDY OF HYDROGEN DISSOCIATION

OVER MoP (001) PLANE
Sharif F. Zaman, Mohammad Daous, Lachezar Petrov
(Submitted on January 8, 2014)

Abstract
Density functional theory was employed to investigate the H2 adsorption
and dissociation energy over MoP (001) surface. Hydrogen atom preferred
the fcc adsorption site with a binding energy of 72.41 kcal mol1 whereas
hydrogen molecule adsorbed over an Mo atom on top arrangement, showed
lower binding energy, 16.8 kcal mol1 , compared to atomic adsorption. H2
dissociation over MoP (001) plane was found not to be catalytically activated.
The dissociation activation barrier is 113.4 kcal/mol, which is close to the gas
phase molecular H2 dissociation.
Key words: H2 dissociation, activation energy, MoP, DFT

Introduction. The important areas of petrochemical industry are catalytic

hydrogenation- dehydrogenation processes for production of fine chemicals, intermediates for pharmaceutical industry, monomers for various polymers, etc. Selective, catalytic hydrogenation of functional groups contained in organic molecules
is one of most useful, versatile and environmentally acceptable reaction routes
available for organic synthesis. Hydrogenation catalytic processes are used to
produce about 20 % of the fine chemicals and pharmaceutical products.
A wide variety of catalysts are used in these reactions like supported noble
metals Pt, Pd, Rh, supported transition metals Ni, Co, Fe, Cu, Mo, oxide catalysts Cr2 O3 , Fe2 O3 , Al2 O3 -Cr2 O3 , sulfides catalysts MoS2 /Al2 O3 , WS2 /Al2 O3 ,
NiS/Al2 O3 , CoS/Al2 O3 , and others. The reaction mechanisms of those processes
are multistep and complex. Most of the noble metals, i.e. Pt, Ru, Rh, Pd show
This work was supported by the Deanship of Scientific Research of King Abdulaziz University, Jeddah, Saudi Arabia under grant No (D-005/431).

777

extraordinary activity and selectivity. In search for less expensive and more selective catalysts, molybdenum based catalysts, especially MoS2 , Mo2 C, MoN2 , and
MoP are of recent interest.
The hydrogen is a key reagent in hydrogenation-dehydrogenation processes
and the participation of hydrogen in different elementary steps of reaction mechanism might have a strong impact on the proceeding of the given reaction. Thus,
to reveal the reaction mechanism and to find way of improving the performance
of the particular catalyst in a given reaction, it is necessary to study adsorption of
hydrogen over the catalyst surface. MoP has demonstrated promising properties
as catalyst in reactions of H2 and CO. For these reasons, we decided to study the
adsorption of H2 over this catalyst.
Density functional theory (DFT) can give an insight of the microscopic factors determining the reactivity of hydrogen on the solid surface. Adsorption and
dissociation energies of hydrogen have been successfully estimated over various
transition metals, oxide and sulfide catalyst surfaces. Facile dissociative adsorption of hydrogen molecule and strong hydrogen atom binding energy was reported
for most of the transition metals except for Au, Ag and Cu, where binding is
weaker and H2 dissociation is highly activated [1 ].
Kitchin at al. [2 ] reported the adsorption of H atom on both the Mo and C
terminated surface of Mo2 C. In this case, the H atom was more strongly attached
to the Mo terminated surface. For MoS2 catalyst [3 ], much smaller energy barrier
was calculated for dissociative adsorption preferentially taking place on the metal
sites. This energy barrier is also smaller compared to the energy barrier for the
transition metals [4 ].
In this paper, we are reporting the dissociative adsorption energies of hydrogen molecule and hydrogen atom over MoP (001) plane obtained by using Density
functional theory.
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. Accordingly, the wave functions of the electrons are expanded in
numerical atomic basis sets defined on an atomic-centered spherical polar mesh.
The double-numerical plus P-function (DNP) of all electron basis sets was used
for all the calculations. The DND basis set includes one numerical function for
each occupied atomic orbital and a second set of functions for valence atomic
orbitals, plus a polarisation p-function on all atoms. Each basis function was
restricted to a cutoff radius of 5.5
A, allowing for efficient calculations without
loss of accuracy. The KohnSham equations [5 ] were solved by a self-consistent
field procedure using PW91 functional with GGA for exchange correlation [6, 7 ].
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 optimisation convergence thresholds for energy change, maximum force and
maximum displacement between the optimisation cycles were 0.00001 Ha, 0.002
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S. Zaman, Mo. Daous, L. Petrov

 and 0.005
Ha/A
A, respectively. The k-point set of (3 3 3) was used for all
calculations. The activation energy of interaction between two surface species
was identified by complete linear synchronous transit and quadratic synchronous
transit search methods [8 ] followed by TS confirmation through the nudge elastic
band method [911 ]. Spin polarisation was imposed in all the 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 }

MoP has a hexagonal crystal structure belonging to P6m2 space group with
A. The unit cell of MoP crystal
A and c = 3.165
lattice parameter a = b = 3.235
was build according to the following atomic coordinate position (x, y, z); Mo at
(0, 0, 0) and P at (0.667, 0.333, 0.5) [12 ]. The unit cell of MoP was built by the
cleavage of the (001) surface plane from the unit cell. The size of the plane was
increased to 4 4 by supercell addition. The final cell unit had four atomic layers
in depth. The possible adsorption location for H atom over a MoP (001) surface
can be on top of an Mo atom, bridge between two Mo atoms, a fcc site
bonding with three different Mo atoms with no underneath phosphorous atom
and finally, a hcp site bonding with three different Mo atoms with an underneath
phosphorous atom.
Adsorption energy of atomic hydrogen. Adsorption energy of hydrogen
atom was initially calculated for H atom adsorbed over the MoP (001) plane at
different preferred locations, fcc, hcp, bridge and on top sites. The obtained
energies of adsorption are presented in Table 1. The formation of surface complex
consisted of three-fold binding of H atom with three Mo atoms at the fcc site which
needed the highest adsorption energy of activation. The adsorption activation
energy for forming this surface complex was 3.14 eV or 72.40 kcal mol1 .
Table

Atomic hydrogen adsorption at different sites over MoP(001) plane

Adsorption arrangement
Adsorption energy
Charge on H atom (e)
dM oH (
A)

fcc site
3.14 eV
72.41 kcal/mol
0.15
2.03

hcp site
2.88 eV
66.41 kcal/mol
0.134
2.07

On top
2.33 eV
53.73 kacl/mol
0.173
1.78

Pictorial description

Compt. rend. Acad. bulg. Sci., 67, No 6, 2014

779

The adsorption energy for the other two forms of adsorption complexes of H
atom with the surface of MoP (001) were lower, at hcp and on top sites the
adsorption energy was 66.41 kcal mol1 and 53.73 kcal mol1 , respectively.
Bridge bonded adsorption arrangement was not favourable over MoP (001) plane.
Adsorbed hydrogen atom had negative charge in all arrangements, while the free
hydrogen atom had a zero charge. The charge on Mo atoms to which the bond
with H was build was also decreased from +0.1095e to +0.04e, and neutral atomic
hydrogen gained negative charge of 0.155 e. Similar result was also obtained
from modelling the CO adsorption on MoP (001) plane. The reason for these
results could be the electrons attraction from the underneath P atoms, which are
bonded to the Mo atoms. There was no significant change in density of state
upon adsorption of H atom over the MoP plane.
In [2 ] authors reported that the atomic hydrogen adsorption at the threefold sites over Mo (100) surface was of 70.01 kcal mol1 . For atomic hydrogen
adsorption energy over the Mo terminated surface of Mo2 C (0001) energy of
adsorption is 76.55 kcal mol1 . These values are very close to the value of atomic
hydrogen adsorption energy on the fcc site MoP (001) plane. This suggests that
the mechanism of the strongest adsorption of H atom for all of Mo containing
solids might be the same. The adsorption proceeds via formation of adsorption
complex containing H atom adsorbed at a three-fold site on the Mo surface
atoms. The precious transition metals, i.e. Pd, Pt, Rh, Ru [1 ] showed lower
adsorption energy for hydrogen atom 2.74 eV < E < 3.0 eV.
Adsorption energy of molecular hydrogen and H2 bond dissociation. Molecular hydrogen was absorbed in a planar arrangement horizontal to
the MoP surface and bonded to one Mo atom as shown in Fig. 1a. This configuration was accepted as the initial configuration for the H2 dissociation calculation
using NEB method. The MoH bond length was 1.909
A. Molecular hydrogen
showed low adsorption energy, of 0.73 eV (16.88 kcal mol1 ). The distance
between the two H atoms in adsorbed molecule was 0.843
A, whereas the distance
between atoms in hydrogen molecule was 0.75
A. We found that both hydrogen
atoms had small negative charge of 0.0328 e. Hence, hydrogen molecule was
activated upon adsorption over the MoP surface.
Hydrogen molecular adsorption energy on MoS2 (1010) surface [12 ] is 1.4
eV (32.28 kcal mol1 ), which is about 2 times larger than adsorption energy
on MoP. In the literature, there are no other available data about the activation
energy of the adsorption of molecular hydrogen, as well as about hydrogen dissociation over Mo based catalysts. The DOS structure, Fig. 2, showed an interaction
peak at low energy value, 0.3 Ha, (s orbital interaction) for the molecular adsorption of H2 . Vibrational frequency for hydrogen molecule was 3674.80 cm1 ,
whereas free H2 molecule has a vibrational frequency of 4358.43 cm1 .
For comparison, we studied two hydrogen atoms adsorbed on their preferred
fcc adsorption sites of MoP surface, which were adjacent to each other as displayed
780

S. Zaman, Mo. Daous, L. Petrov

Fig. 1. Transition state search for H2 dissociation over MoP (001) plane

in Fig 1b. The adsorption energy for each adsorbed H atom was 3.13 eV (72.35
kcal mol1 ) close to the value of the single H atom adsorption on fcc site. The
adsorbed hydrogen atoms on the MoP (001) surface as a result of dissociative
adsorption are energetically stabilised. This configuration was used as initial
approximation for the search of possible transition state of the molecular hydrogen
adsorption process. The initial distance between H atoms was 3.238
A and the
H atoms after adsorption obtained charges of 0.1487 e.
After performing complete transition state search, we found that the activation barrier, Ea , for dissociation of adsorbed H2 was 113.4 kcal mol1 . This
value is slightly higher than the activation barrier for gas phase dissociation of

Fig. 2. DOS analysis of H2 adsorption over MoP (001) plane

4

Compt. rend. Acad. bulg. Sci., 67, No 6, 2014

781

molecular hydrogen, which is equal to 104.3 kcal mol1 [13 ], though the hydrogen
dissociation proceeds with a high heat of the reaction of Er = 22.29 kcal/mol.
The most probable transition structure is shown in Fig. 1c.
Therefore, the results obtained after the performed calculations indicate that
MoP (001) plane has no potential for catalysing processes in which formation of
atomic hydrogen is part of reaction mechanism. Probably it might be catalyst
for reactions in which H2 reacts in molecular form.
Conclusions. A DFT calculation of the activation energy of hydrogen atom
adsorption over MoP (001) plane was performed. The fcc sites on MoP (001)
plane are the preferred locations for atomic H adsorption with Ea = 72.41 kcal
mol1 .
Hydrogen dissociative adsorption on MoP (001) plane needs very high activation energy Ea = 113.4 kcal mol1 , which means that this process does not
take place on this surface.

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http://www.nist.gov/data/nsrds/NSRDS-NBS31.pdf
Chemical and Materials
Engineering Department
Faculty of Engineering
King Abdulaziz University
P.O. Box 80204
Jeddah 21589, Saudi Arabia
e-mail: zfsharif@gmail.com
sfzaman@kau.edu.sa
782

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, Mo. Daous, L. Petrov