Applied Surface Science 120 Ž1997.

81–84

Grand canonical Monte Carlo simulation of the adsorption of CO 2

on silicalite and NaZSM-5
Akiyasu Hirotani, Koichi Mizukami, Ryuji Miura, Hiromitsu Takaba, Takeshi Miya,
´ Stirling, Momoji Kubo, Akira Miyamoto )
Adil Fahmi, Andras
Department of Molecular Chemistry and Engineering, Faculty of Engineering, Tohoku UniÕersity, Aoba-ku, Sendai 980-77, Japan
Received 22 November 1996; accepted 5 February 1997

Abstract

The adsorption of carbon dioxide in silicalite and NaZSM-5 zeolite has been studied using new Monte Carlo software. In
this program, sodium cations and framework are movable during the simulation. The calculated adsorption isotherms are in
good agreement with the experimental results. The energy distribution of carbon dioxide over silicalite and NaZSM-5 shows
that the increase of the adsorption energy for NaZSM-5 is mainly due the electric field generated by sodium cations. q 1997
Elsevier Science B.V.

Keywords: CO 2 ; Adsorption; Silicalite; NaZSM-5; Monte Carlo simulation

1. Introduction tion may induce structural distortions of the zeolite

In recent years, there has been a significant inter-
est in predicting adsorption isotherms for the adsorp-
tion of gases on microporous materials. Grand
canonical ensemble Monte Carlo ŽGCMC. methods
have the advantage to treat systems where the num-
ber of species fluctuates. Therefore, they are suitable
for calculating adsorption isotherms and energy dis-
tributions of adsorbed molecules. GCMC methods
were applied to the adsorption on zeolites: methane
w1x and butane w2x in silicalite; nitrogen, oxygen w3x
and xenon w4x in X- and Y-zeolite types. Most of
these calculations were performed on systems where
the zeolite framework is rigid. However, the adsorp-
lattice. Therefore, GCMC methods which can take
into account the relaxation of the zeolite framework
and displacements of extra framework cations are
needed. In this paper, we present a new GCMC
program where the zeolite can be relaxed. We stud-
ied the adsorption of carbon dioxide on silicalite and
NaZSM-5. In this first application, we relaxed only
sodium cations and determined adsorption isotherms
and energy distributions.
2. Method of calculation
2.1. Features of our software

)
Corresponding author. Tel.: q81-22-2177233; fax: q81-22- In conventional GCMC methods, the simulations
2177235; e-mail: miyamoto@aki.che.tohoku.ac.jp. are performed in cycles, and each cycle consists of

0169-4332r97r$17.00 q 1997 Elsevier Science B.V. All rights reserved.

PII S 0 1 6 9 - 4 3 3 2 Ž 9 7 . 0 0 2 2 2 - 5
82 A. Hirotani et al.r Applied Surface Science 120 (1997) 81–84

randomxy selected attempts either to displace, to Table 1

create or to destroy a molecule. Besides these possi- Potential parameters for GCMC simulation
bilities, it is possible to displace extra framework Atom type ´ 0 ˚. Z
r 0 ŽA
Žkcalrmol.
cations of the metal-exchanged zeolite in our method.
This is the first attempt, to the best of our knowl- C CO 2 0.058 3.13 0.575
edge. Our GCMC software has the following fea- OCO 2 0.165 3.38 y0.288
tures: Ži. either GCMC or NVT simulations with a Ozeolite 0.255 3.04 y0.400
movable zeolite-framework, Žii. calculation and visu- Si 0.037 0.76 0.800 ŽSilicalite.
0.783 ŽNaZSM-5, SirAls94.
alization of the molecule–zeolite potential energy 0.766 ŽNaZSM-5, SirAls 46.
map in 3D space, Žiii. visualization of the interacting Al 0.038 1.14 0.600 ŽSilicate.
system during the simulation. 0.587 ŽNaZSM-5, SirAls94.
0.575 ŽNaZSM-5, SirAls 46.
2.2. Interatomic potentials Na 0.030 2.98 1

2.2.1. Preparation of the zeolite framework

We used crystallographic data of the silicalite
obtained from X-ray diffraction studies w5x. The
NaZSM-5 structures are made by replacing Si atoms
of T-12 sites by Al atoms, and adding sodium cations
randomly. The location of sodium cations and the
zeolite framework were optimized by molecular dy-
namics w6,7x simulations at 273 K. The interaction
potential has the following form:
U s Zi Z j e 2rr i j q f 0 Ž bi q bj .
= exp  Ž a i q a j y ri j . r Ž bi q bj . 4 .
The first term is the Coulomb potential, and the
second is the exchange–repulsion potential. Z is the
formal ionic charge, e is the elementary electric
charge and r is the interatomic distance. f 0 is a
constant for unit adaptation that is equal to 6.9511 =
10y1 1. Parameters a and b represent the size and the
stiffness of the atoms respectively.
2.2.2. GCMC simulations of CO2 adsorption
The interaction potential between the adsorbate
and the zeolite is the following:
12
U s Zi Z j e 2rri j q ´ 0 ½ Ž r rr
0 ij . y 2 Ž r 0rri j .
The first term is the Coulomb potential and the
second term is the Lennard-Jones potential. ´ 0 is the
bond strength, r 0 is the bond length. The Ewald
method w8x was applied to calculate Coulomb interac-
tions. For CO 2 , we use the potential parameters
developed by Murthy–Singer–McDonald w9x and the
C–O bond length is fixed to the experimental value
˚
of 1.18 A.
We optimize, using our GCMC program, the ´ 0
parameter of oxygen of the silicalite according to the
following procedure: First, using Si and O parame-
ters from Ref. w3x we performed Ar Žparameters from
Ref. w10x. adsorption simulation on a fixed silicalite
framework. We optimized the ´ 0 parameter of oxy-
gen to reproduce the experimental heat of adsorption
of Ar w11x with Lorentz–Berthelot combination rules
for Ar-silicalite. Next, we optimized the partial
charges of Si to reproduce the heat of adsorption of
CO 2 using the parameters from Table 1. Lorentz–
Berthelot rules are also used for CO 2-silicalite. For
NaZSM-5, sodium has a formal charge of q1. The
charge of oxygen is the same as that of optimized for
silicalite, whereas the charges of Si and Al in
NaZSM-5 are calculated assuming a charge ratio of
4 : 3 with the constraint of a total charge of zero
Žneutral system..
The simulation box for the GCMC calculations is
a zeolite unit cell. For most runs, the initial configu-
ration was chosen as the final configuration from the
previous run. One GCMC calculation corresponds to
10 6 cycles at low loading Žsmall number of adsorbed
6
molecules. and 2.0 = 10 6 for high loading. Tests for
5 several loadings showed that these numbers are suf-
ficient to obtain equilibrium.
3. Results of GCMC simulations
3.1. Adsorption isotherms
The calculated adsorption isotherms of CO 2 on
silicalite at several temperatures are shown in Fig. 1
 A. Hirotani et al.r Applied Surface Science 120 (1997) 81–84
together with experimental data w12,13x. Indeed, there
is a good agreement with experimental data at all
temperatures and pressures. Therefore, using a sim-
ple pair-wise potential model and a GCMC method
we were able to reproduce adsorption isotherms of
CO 2 .
3.2. Energy distributions
Fig. 2 shows the distribution of adsorbed
molecules on silicalite and NaZSM-5 ŽSiO 2rAl 2 O 3
s 46 and 94. at 273 K and 80 kPa. For the silicalite,
there is a single peak around y25 kJrmol. This
corresponds to the adsorption on both straight and
zigzag channel sites. Straight and zigzag channels
have similar adsorption energies. For NaZSM-5
ŽSiO 2rAl 2 O 3 s 94., the peak is shifted up by 4
kJrmol, and a new peak appears around y35
Fig. 1. Adsorption isotherms of CO 2 over silicalite at various
temperatures: Ža. low pressure, experimental values from Ref.
w12x; Žb. high pressure. Experimental values from Ref. w13x.
83
Fig. 2. Energy distribution of CO 2 over silicalite and NaZSM-5
Ž273 K, 80 kPa..
kJrmol. This is related to the decrease of Si atomic
charges. When Al and Na atoms are added, we
adjust the charge of Si to satisfy the charge neutral-
ity. The new peak corresponds to CO 2 molecules
adsorbed on sodium sites. For NaZSM-5
ŽSiO 2rAl 2 O 3 s 46., the increase of the number of
sodium atoms leads to the increase of the peak
around y35 kJrmol, whereas the peak at y25
kJrmol disappears. Therefore, all CO 2 molecules
are adsorbed at cation sites.
4. Conclusion
We performed GCMC simulations of isotherms
and energy distributions of carbon dioxide in sili-
calite and NaZSM-5 using a new GCMC software.
The program takes into account displacements of Na
atoms inside the zeolite. The calculated adsorption
isotherms using pair-wise interaction potentials agree
well with experimental measurements. The energy
distributions of carbon dioxide over silicalite and
NaZSM-5 allow one to distinguish molecules ad-
sorbed on cation sites from molecules adsorbed on
pores. With the increase of the number of Na atoms,
all the CO 2 molecules are adsorbed on cation sites.
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