ISSN 2548-9011 Physics treatise Vol. 3 no.

2 (2019) 33-36

Study of Functional Theory of Density in Determination of Solving Reaction Pathways H 2 O

on the Surface of PtMo (111)
(login / received May 25, 2019, received / accepted July 18, 2019) )

A Density Functional Theory Based Study in Determining the H 2 O Discosiation Pathway in a

PtMo (111) Surface

Dian Bayuaji, Wahyu Tri Cahyanto, R. Farzand Abdullatif

Physics Department, Faculty of Mathematics and Natural Sciences, Jenderal Soedirman University Jl. dr. Soeparno No. 61,
Karangwangkal, Purwokerto 53123, Indonesia
wahyu.cahyanto@unsoed.ac.id https://doi.org/10.35895/rf.v3i2.156

Abstract - Research on quantum simulations for the breakdown of water molecules (H) has been carried out 2 O) on the surface of PtMo (111) based on
Density Functional Theory (DFT). This research was conducted to determine the most effective reaction pathway in the process of solving H. 2 O and the
reaction mechanism. The calculation results show that the path is most likely for solving H 2 O. ads be H ads and OH ads is the movement of H from position H 2 O
on top of Mo2 to the HCP Pt41-Mo2-Pt42 site, proceed to the FCC Pt42-Mo2-Pt46 site, then to the Pt42-Pt46 bridge site, continue to the HCP
Pt42-Pt43-Pt46 site, and end at the FCC Pt38-Pt42- site Pt43. OH position ads top of Mo2. The activation energy needed to break down H 2 O of 0.68 eV.
Next, the reaction mechanism of solving H 2 O is discussed with the analysis of the geometrical structure of the adsorption H 2 O on the site corresponding to
the course of the reaction.

Keywords: solving H 2 O, DFT, PtMo (111), activation energy, reaction mechanism

Abstract - Quantum simulation studies for the decomposition of water molecules (H 2 O) on the surface of PtMo (111) based on the density functional
theory (DFT) were performed. This study was conducted to determine the most preferred pathways of the H 2 O dissociation process and its reaction
mechanism. The calculation results show that the most preferential pathway to decompose H 2 O. ads into H ads and OH ads is the movement of H from the
original position of adsorbed H 2 O atop Mo2 to the HCP Pt41-Mo2-Pt42 site, then to the FCC Pt42-Mo2-Pt46 and then to the bridge site of neighboring
Pt42-Pt46 atoms followed by HCP Pt42-Pt43-Pt46 site and terminate at the FCC Pt38- Pt42-Pt43 site. The position of OH ads remains on top of Mo2. The
activation energy is required to break H 2 O is 0.68 eV. In addition, the reaction mechanism for H 2 O dissociation is discussed by analyzing the adsorption
geometry corresponding to each site of reaction paths.

Key words: dissociation of H 2 O, DFT, PtMo (111), activation energy, reaction mechanism

I. Introduction it is hoped that it will be easier to break down H 2 O. ads

be H ads and OH ads, because the adsorption energy produced becomes
Solution reaction H 2 O. ads becomes very important in a variety of chemical
greater [3]. Reaction results
reactions. One example is in technology Direct Methanol Fuel Cell ( DMFC),
solving H 2 O. ads it can improve
which is a source of oxidants to oxidize methanol in its anode. This
methanol oxidation [4]. In this regard, research on the reaction of H
hydroxyl (OH) oxidant is obtained by an intermediate reaction in the form of
solution 2 O. ads important to do. Furthermore, this paper provides a
H solution 2 O. ads be H ads and OH ads [ 1]. The process of solving H. 2 O. ads at this
simulation of the reaction path process as well as the design of catalyst
anode is facilitated by a metal catalyst [2]. The catalyst commonly used for
material for H separation 2 O. ads on the surface of PtMo (111) which has
DMFC anodes is platinum metal (Pt).
never been found in previous studies.

This explanation is expected to be able

provide an understanding of the mechanism of the H separation reaction 2 O
On its development, catalyst Pt has
on the metal surface alloy.
deficiencies in its application, including poisoning by CO molecules
produced from the intermediate reaction part of the dehydrogenation of II. RESEARCH / EXPERIMENT METHOD
methanol (CO poisoning). In this research, a method is used Density Functional Theory ( DFT) to
To overcome the poisoning effect, one way to do this is by modifying the calculate the total system energy.
material. This is intended to facilitate the complete disposal of CO through DFT calculation itself is done through the application
oxidation. To achieve this goal, material modification is done by adding the program Vienna Ab initio Simulation Package
element molybdenum (Mo) to the Pt catalyst. (VASP) [5-8]. The accuracy of calculations is guaranteed by
use exchange-correlation from PW91 type [9, 10] from the approach Generalized
Gradient Approximation
With the additional Mo, (GGA). To illustrate the interaction between ions and

33
34 Dian Bayuaji - Study of Functional Theory of Density in Determination of Solving Reaction Pathways H 2 O on the Surface ...

electron used method Projected Augmented Wave absorption This can be seen in Figure 2.
(PAW) [7]. To anticipate the convergence of fairly heavy O atom nuclei, OH bond lengths are known to be no different from the results
energy is used
cut-off equal to 400 eV for the basic set of wave fields ( Plane Wave). The
Brillouin zone is integrated in the mesh (5 × 5 × 1) with a Monkhorst Pack
k-point sampling [11].
For surface models, Pt metals are mixed with a small amount of Mo
atoms to form a PtMo surface. The crystal structure follows the Pt metal viz Face
Centered Cubic ( FCC), and the selected field index ( Miller-index) 111 which
repeats periodically. The surface consists of three layers with each layer
consisting of 4 × 4 atoms in each cell unit [12]. So the total number of
atoms studied is 48 atoms, with 46 platinum atoms and 2 molybdenum
atoms. To anticipate

Picture 1. Initial state H 2 O is on Mo2's top site

(top view) [3].
interaction between gas with
the closest slab, then the distance between each surface is given a
vacuum along the z axis of 15 Å [13].

Next, to find the reaction pathway for solving H 2 O is done by scanning

potential surface energy ( Potential Energy Surfaces = PES) of proposed
reaction pathways. Determination of this pathway refers to the initial
position in the form of H molecules 2 O in the gas phase is absorbed and
the final position is hydrogen gas absorbed and the hydroxyl group is
absorbed. From these two points of reference, several possible sites are
taken between the initial and final states. After that, the total system
energy from each site is calculated and altitude variations are performed
Figure 2 The final state is H at the FCC site Pt38-Pt42-Pt43
to find the most stable position. Among the most stable positions on each
and OH at the top Mo2 site (top view) [14].
site will form a reaction path. The reaction path is most likely to be defined
as the pathway with the least activation energy. The activation energy is adsorption H 2 O. ads which is 0.979 Å, and the height of the separated H
determined from the maximum between the minimum values ​obtained at atom is 1.04 Å, much lower than the height at the time of adsorption of H 2 O.
each site. ads.

A. Reaction Pathway 1

Molecule H 2 O who come will be directly absorbed at the sites on the

surface of PtMo (111). The stronger the compound is absorbed, the easier

III. RESULTS AND DISCUSSION
Solving reaction pathway H 2 O can be determined by knowing the
position of H 2 O. ads in the initial state and position H ads and OH ads in its final
state. A study by Septikasari [3] regarding the adsorption of H 2 O. ads
on the same surface. It is known that the position of adsorption H 2 O. ads tends goes to the FCC Pt42-Mo2-Pt46 site, continues to the Pt42-Pt46 bridge
to be strongly absorbed at the top Mo2 sites compared to Pt sites. This
situation can be seen in Figure 1. As a result of the absorption, it is known
that the bond length between O and H is equal
it is to split [15]. To understand the process of solving the reaction it is
very important to know the mechanism, namely the reaction path and
geometry analysis. Solving reaction pathway H 2 O. ads be H ads and OH ads it
was discovered through several sites among the initial conditions when it
was still H 2 O. ads and the final state when it has split into H ads and OH ads. These
sites are OH at the top of Mo2, and H goes to HCP Pt41-Mo2-Pt42, then
site, then to the HCP Pt42-Pt43-Pt46 site . The reaction pathway scheme
is described sequentially (ab-cdef) as shown in Figure 3.

0.979 Å and the height of the H atom from the top surface (third layer) is
2,515 Å. Gray atoms denote platinum atoms, green denotes molybdenum
atoms, red denotes oxygen atoms, and small pink circles denote hydrogen
atoms.
For the final state when it is split into H ads
and OH ads, has been investigated by Saepulloh [14] regarding the
absorption of H ads and OH ads on the same surface. From these studies it is
known that H tends to be at the FCC site Pt38-Pt42-Pt43 and OH is at the
top Mo2 site. Molybdenum atom itself is known to be able to maximize CO
oxidation by absorbing OH from H 2 O [4]. As for the model
Based on calculations using DFT software
VASP, the total system energy of each site is known. In the initial state
when H 2 O is on the top site of Mo2 has an energy of -297.38 eV. When the
H atom moves to the HC41 Pt41-Mo2-Pt42 site, the system has an energy
of -296.70 eV. Furthermore, on the FCC site Pt42-Mo2-Pt46 the energy is
known as -296.74 eV. After that on the Pt42-Pt46 bridge site it was -297.24
eV. At the HCP site Pt42-Pt43-Pt46 an energy of -297.31 eV was obtained.
And the final state at the FCC site Pt38-Pt42-Pt43 is -297.33 eV.

Physics treatise Vol. 3 no. 2 (2019) 33-36

ISSN 2548-9011
Dian Bayuaji - Study of Functional Theory of Density in Determination of Solving Reaction Pathways H 2 O on the Surface ....
Figure 3 Schematic transfer of H atoms during the process
solving H 2 O (top view), in alphabetical order are: a) initial
state of top Mo2 b) HCP Pt41-Mo2-Pt42 c) FCC
Pt42-Mo2-Pt46 d) bridge Pt42-Pt46 e)
Based on the energy data, it can be seen that the transition state is
when the maximum energy value is between the minimum values, namely
when the H atom is at the HCP Pt41-Mo2-Pt42 site.
From transition point
the activation energy information obtained to break down H 2 O. ads be H ads and each site. In the initial state on the top site Mo2 had as much energy
OH ads, which is 0.68 eV. The activation energy value is lower than our
previous study when using a pure Pt surface, which is 0.91 eV. This
indicates that the catalyst design with the addition of Mo metal alloys
reduces the price paid for the H separation reaction 2 O. Next,
lane reaction breakdown H 2 O got it
illustrated by the contours of PES by entering energy, distance and
altitude variables.
Figure 4 shows the results of the first reaction path, where the x-axis
represents the distance of the H atom from its initial state, the y-axis
represents the height of the measured H atom from the top surface layer,
and the color represents the total energy of the system. Black dots
Figure 4 Contour Potential energy Surface ( PES) for paths
reaction 1
states the proposed sites. The first point of the contour represents the
position at the initial state. Furthermore, the second point states the H
atom at
35
the HCP Pt41-Mo2-Pt42 website. The third, fourth, fifth and sixth points
consecutively represent the FCC site Pt42-Mo2-Pt46, Pt42-Pt46 bridge,
PtP-Pt43-Pt46 HCP, and Pt38-Pt42-Pt43 FCC sites (final state). From
Figure 4 it can be seen that when the second position there is an increase
in energy, which is when the transition occurs. The thick black lines
illustrate the prediction of reaction pathways at sites not included in the
study. The height of the H atom is seen decreasing during the transition
state, which indicates the absorption of the H atom is very optimal. Based
on the data obtained there is also a reduction in the OH bond length to
0.975 Å, slightly shorter than in the initial state. It also obtained an
additional charge on H and OH of 0.7387 eV, which was calculated using a
bader application [16].
B. Reaction Pathway 2
As for other possible reaction pathways for the process of solving H 2 O is
through several sites after the initial state, namely OH at the top of Mo2,
and H goes to HCP Pt36-Mo2-Pt46, then goes to the Mo2-Pt46 bridge
site, continues to the Pt42-Pt46 bridge site, then to the Pt42-Pt43 bridge
site. The reaction pathway scheme is described sequentially (abcde-
that, f) as in Figure 5. After the calculation, total system energy is obtained from
- 297.38 eV. At the HCP site Pt36-Mo2-Pt46 has an energy of -296.69 eV.
Next on the site bridge
Mo2-Pt46 is known to have an energy of -297.10 eV.
Figure 5 Schematic transfer of H atoms during the process
solving H 2 O (top view), in alphabetical order is a) initial
state of top Mo2 b) HCP Pt36-Mo2-Pt46 c) bridge
Mo2-Pt46 d) bridge bridge Pt42-Pt46 e) bridge Pt42-Pt43 f)
Final state of FCC Pt38-Pt42-Pt43
Physics treatise Vol. 3 no. 2 (2019)
ISSN 2548-9011
36 Dian Bayuaji - Study of Functional Theory of Density in Determination of Solving Reaction Pathways H 2 O on the Surface ...
2 VS Silva, AM Mendes, LM Madeira, et al.,
Figure 6 Contour Potential energy Surface ( PES) for
reaction pathway 2
After that on the site bridge Pt42-Pt46 is -297.24 eV. On the site bridge Pt42-Pt43
3 T. Septikasari, Simulation of Quantum Adsorption H 2 O on
obtained energy of
- 297.24 eV, and ends at the FCC site Pt38-Pt42-Pt43 for -297.33 eV.
From some of these sites,
it is known that the transition state occurs when the H atom is at the
Pt36-Mo2-Pt46 HCP site, so the activation energy obtained is 0.69 eV,
slightly greater than in the first reaction path. The low activation energy
indicates the more easily the molecule splits.
From the contours of PES in Figure 6, it can be seen that the transition
state occurs at the second point when the H atom is at the HCP
Pt36-Mo2-Pt46 site. The height of the H atom from the surface also
decreases compared to the initial state. The OH bond distance is known to
be the same as in the transition state in the first reaction path, which is
equal to
0.975 Å. It is also known that the charge increment that occurs at H and
OH is 0.72 eV, smaller
compared to what happened in the first reaction path.
IV. CONCLUSION
It has been determined that the reaction path most likely for solving H has
been determined 2 O on the surface of PtMo (111). The most likely path is
to break one of the H atoms from the H molecule 2 O which moves through
the HCP Pt41-Mo2-Pt42, then goes to the FCC Pt42-Mo2-Pt46 site,
continues to the Pt42-Pt46 bridge site, then to the HCP Pt42-Pt43-Pt46
site, and ends at the FCC Pt38-Pt42-Pt43 site. For this breakdown
reaction an activation energy of 11 is required
0.68 eV. This value is smaller than that obtained when using a pure Pt
catalyst. On solving H 2 O is also observed that the O atom retains its
position to adsorb on the Mo atom both before and after the dissociation
process.
With
thus it is evident that the modification of the addition of Mo to Pt will
facilitate the running of the H termination reaction 2 O, so it will also make
the overall reaction more efficient.
THANK-YOU NOTE
This research was funded by the Directorate of Research and Community
Service, Director General of Research and Development Strengthening,
Ministry of Research, Technology,
Physics treatise Vol. 3 no. 2 (2019) 33-36
ISSN 2548-9011
and Higher Education through the Basic Research scheme for the 2019
Fiscal Year with a contract Number: P / 1805 / UN23 / 14 / PN / 2019.
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