Microporous and Mesoporous Materials 90 (2006) 293–298

www.elsevier.com/locate/micromeso

Water adsorption in hydrophobic nanopores:

Monte Carlo simulations of water in silicalite
Chen E. Ramachandran, Shaji Chempath, Linda J. Broadbelt, Randall Q. Snurr *

Department of Chemical and Biological Engineering, Institute for Environmental Catalysis, Northwestern University, Evanston, IL 60208, USA

Received 15 August 2005; received in revised form 8 October 2005; accepted 14 October 2005
Available online 15 December 2005

Dedicated to the late Denise Bartomeuf, George Kokotailo and Sergey P. Zhdanov in appreciation of their outstanding contributions to zeolite science

Abstract

Grand canonical Monte Carlo simulations have been carried out to investigate the adsorption of water from the vapor phase into the
zeolite silicalite. For truly hydrophobic micropores, the simulations predict essentially no adsorption of water at low pressures, followed
by rapid pore filling as pressure is increased. The effect of silanol defects in real silicalite samples was explored through simulations using
‘‘seeded’’ water molecules to represent hydrophilic defects. These defects promote adsorption of some water at low pressures, as mole-
cules form hydrogen-bonded clusters around the defects. The defects also shift the pore filling to a lower pressure than in the completely
hydrophobic material.
Ó 2005 Elsevier Inc. All rights reserved.

Keywords: Water; Silicalite; Defect; Hydrophobicity; Adsorption

1. Introduction which the system oscillates between pores devoid of water

Understanding the behavior of water in hydrophobic
micropores is important in a wide variety of fields, ranging
from biological membrane transport to applications of car-
bon nanotubes, as well as water purification using zeolites
and activated carbons. It is also an interesting scientific
question whether water will adsorb in a truly hydrophobic
pore.
In the literature, molecular simulations and thermody-
namic models predict very dramatic water isotherms in
hydrophobic micropores [1–4]. At low pressures, hardly
any water molecules exist in the pores. This persists until
a specific pressure is reached, after which rapid pore filling
occurs [3,4]. This has been observed experimentally for
water in activated carbons [3]. A similar steep transition
between empty and filled pores has been observed in a
molecular dynamics study of hydrophobic pores [5], in
*
Corresponding author. Tel.: +1 847 467 2977; fax: +1 847 491 3728.
E-mail address: snurr@northwestern.edu (R.Q. Snurr).
and pores completely filled with water. Hummer et al. [6]
observed similar behavior for MD simulations of water
in hydrophobic carbon nanotubes, in which small changes
in the interaction between pore walls and water molecules
profoundly changed water hydration of pores, leading to
sharp transitions between filled and empty states on a
nanosecond timescale. McCallum et al. [7] studied the
adsorption of water on activated carbon experimentally
as well as through grand canonical Monte Carlo (GCMC)
simulations and found that the density of active surface
sites contributed significantly to the loading before pore
filling occurred.
Silicalite is a zeolite comprised of SiO2 tetrahedra with
the MFI crystal structure [8,9]. It is widely regarded as
hydrophobic, and the earliest studies on silicalite showed
that it readily adsorbs organic molecules over water [8].
These studies, as well as later ones [8,10–12], however,
show that silicalite does adsorb a small amount of water.
MFI zeolites can also be prepared with various Si/Al
ratios, and a direct relationship has been established

1387-1811/$ - see front matter Ó 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.10.021
294 C.E. Ramachandran et al. / Microporous and Mesoporous Materials 90 (2006) 293–298
experimentally between increased Al content and increased
water loading [12].
In this work, we present results of a GCMC study of
water adsorption in silicalite. The curious behavior
observed in simulations of water confined in hydrophobic
nanopores such as carbon nanotubes was also observed
in our simulations of silicalite. This behavior contrasts with
the experimentally observed water adsorption isotherms in
silicalite, which do not show any pore filling1 but which do
show low levels of adsorbed water even at low pressures.
We will show that the water adsorbed at low pressures is
likely associated with adsorption on hydrophilic defects
[14].
2. Simulation methods
2.1. GCMC simulations
Grand canonical Monte Carlo simulations are well
suited for investigating adsorption in zeolites and related
materials on the molecular level. In the grand canonical
ensemble, the volume, temperature, and chemical potential
are held constant while the number of molecules fluctuates.
Simulations were run using the simulation code Music
[15,16], which was written in-house. At the low pressures
used in our simulations, it was assumed that water vapor
is an ideal gas and its fugacity is equal to the gas-phase
pressure. The simulation box was composed of eight silica-
lite unit cells with periodic boundary conditions. All simu-
lations reported here were at a temperature of 291 K.
Properties of interest were calculated based on averaged
values over the equilibrated regime for each simulation.
Even with biasing of insertion moves, the required number
of Monte Carlo steps for each isotherm point ranged from
24 million to 360 million. Other researchers have also
found that unusually long simulations are needed to equil-
ibrate water in hydrophobic pores [7].
The van der Waals interactions between atoms were
represented by a Lennard-Jones 12-6 function, and elec-
trostatic interactions between point charges placed on the
atoms were calculated using CoulombÕs law. For the silica-
lite/water interactions, Ewald summation was used for the
Coulombic interactions and the Lorentz–Berthelot mixing
rules were used to obtain the Lennard-Jones parameters.
For water/water interactions, a spherical cut-off based on
the molecular center of mass was enforced at 13 Å for both
Lennard-Jones and Coulombic interactions.
1 H
As this manuscript was being completed, an experimental report
appeared showing pore filling in silicalite at pressures considerably above
the bulk saturation pressure [13]. It is interesting to note that Desbiens
et al. used GCMC simulations to predict pore filling above the bulk
saturation pressure, using the TIP4P water model, the same silicalite
partial charges as in Table 1, and Lennard-Jones parameters for the
silicalite oxygens of r = 3.0 Å and e/k = 93.53 K.
2.2. Silicalite model
The locations of the silicon and oxygen atoms of the
zeolite framework were taken from XRD data [17], and
the framework was considered to be rigid. The Lennard-
Jones parameters for the zeolite oxygen atoms were
obtained from previous work [15] and are listed in Table
1. Since silicon atoms are recessed behind oxygen atoms
in the pore walls, they are not readily accessible to sorbates.
Therefore, van der Waals interactions between silicon
atoms and the sorbate molecules were not considered.
However, Coulombic interactions between sorbates and
both oxygen and silicon atoms were modeled explicitly.
The silicon atoms carried a + 1.4 partial charge, whereas
oxygen atoms carried a 0.7 partial charge [15]. Interpola-
tion from pre-tabulated Lennard-Jones and Coulombic
interaction grids was used to speed up the calculation of
zeolite/sorbate interactions.
Three different types of sites can be identified in silica-
lite: zig-zag channels, straight channels, and intersections.
The process of defining sites using a methane probe mole-
cule is described elsewhere [18]. In our simulations, the
regions that were inaccessible to the methane probe but
accessible by water molecules were categorized into the
nearest, by distance, defined site.
In some simulations, we introduced defect sites within
silicalite in a simple way by randomly placing ‘‘seed’’ water
molecules within either zig-zag channels, straight channels,
or intersections. Each defect in a unit cell was initially
replicated in the other seven unit cells of the simulation
box. These seeded water molecules are meant to mimic
intracrystalline defect silanol sites. They were allowed to
rotate during the GCMC simulation but were not allowed
to be removed or translated. The resulting silicalite struc-
ture with seeds was then used to generate a water adsorp-
tion isotherm. Seeded water molecules were not counted
in the reported water loadings.
2.3. Water model
Numerous models exist in the literature for bulk water,
each capable of capturing some experimentally observed
characteristics such as the vapor pressure or radial
Table 1
Potential parameters
ri (Å) ei/kb (K) qi References
Water (SPC/E) O 3.16 78.212 0.848 [23]
H – – 0.424
Water (TIP4P) O 3.15 77.941 – [24]
– – +0.52
e – – 1.04
Silicalite O 2.80 107.5 0.7 [15]
Si – – +1.4
For the SPC/E model: rO–H = 1 Å, h = 104.5°, and Psat = 2.2 kPa at
300 K [33]. For the TIP4P model: rO–H = 0.9572 Å, h = 104.5° rO–e =
0.15 Å, and Psat = 4.5 kPa at 300 K [27].
 C.E. Ramachandran et al. / Microporous and Mesoporous Materials 90 (2006) 293–298 295

Fig. 1. Comparison of water models SPC/E (d) and TIP4P (j) for adsorption in silicalite at 291 K versus experimental data (solid line) from Olson et al.
[12] at 298 K. For the experimental curve, the experimental value of Psat was used, and for the simulation results, the Psat values of 2.2 kPa and 4.5 kPa
were used for the SPC/E and TIP4P models, respectively.

distribution function. As of yet, no universal model has 3. Results and discussion

been developed for this important molecule. Several poten-
tial models have been used in the past to simulate water in
silicalite [19–22], mostly to elucidate the diffusion behavior.
For this study, the SPC/E model [23] was chosen to repre-
sent water, and the Lennard-Jones parameters and partial
charges are listed in Table 1. The SPC/E model has been
used extensively in the literature for a wide variety of differ-
ent systems since it was first introduced. Several other water
models were also investigated for comparison purposes (i.e.,
TIP3P, TIP4P, and TIP5P) [24–28]. Results are presented
for the SPC/E model unless otherwise indicated.
The simulated adsorption isotherms of water in silicalite
using the SPC/E and TIP4P models are shown in Fig. 1.
Both isotherms show qualitatively the same behavior: prac-
tically no water molecules are adsorbed at low pressure and
then the pores fill with water. The onset pressure of the
pore filling is different for the two different models, and it
appears that this value is very sensitive to the potential
parameters used [13]. Fleys and Thompson [29] also found
extremely low loadings of water in silicalite from GCMC
simulations with somewhat different potential parameters.

Fig. 2. Water adsorption isotherms with the SPC/E model at 291 K with and without seeds to mimic defects: 0.5 seeds per unit cell (n), 4 seeds per unit
cell (m), base case with no seed molecules (d and dashed line). The seeds were placed in the channel intersections. Experimental data from Olson et al. [12]
are also shown (solid line).
296 C.E. Ramachandran et al. / Microporous and Mesoporous Materials 90 (2006) 293–298
They did not report pore filling, possibly because they did
not simulate high enough pressures to observe this behav-
ior with their model. The maximum loading from our sim-
ulations is 53 molecules per unit cell, which is similar to
the expected pore filling value of 57 molecules per unit cell
[12].
Experimental isotherms for water in silicalite have been
reported by several groups [8,10–12]. There are some differ-
ences, but all show low levels of water adsorption (less
than 10 molecules per unit cell), starting gradually at low
pressures. The experimental results of Olson et al. [12]
are shown in Fig. 1 for comparison with the simulation
results. None of the vapor phase experimental isotherms
indicate pore filling [13], although pore filling has been
observed for adsorption of water in aluminophosphate
molecular sieves [30].
Clearly, the simulated and experimental isotherms in
Fig. 1 show qualitatively different behavior. One possible
reason for this is the presence of silanol and other defects
in the experimental silicalite samples. It is believed that
silanol defects arise from the use of templating agents in
Fig. 3. Snapshot of water clustering around defect seed molecules in
silicalite. Conditions: 1 seed molecule (located in a straight channel) in 8
unit cells, 0.34P/Psat, and 291 K. Oxygen atoms of seed molecules are
represented by the large blue spheres. Adsorbed water moleculesÕ oxygen
atoms are represented by large red spheres, and the hydrogen atoms are
represented by the smaller white spheres. (For interpretation of the
references in colour in this figure legend, the reader is referred to the web
version of this article.)
the synthesis process. Estimates of as many as four defects
per unit cell have been suggested [12].
We reasoned that silanol defects could serve as hydro-
philic sites that might affect adsorption of water at low
loadings. To test this hypothesis, we determined the water
isotherms with various numbers of seeded water molecules
used to mimic these defects, as described in the previous
section. Fig. 2 shows the results with 0.5 seeds per unit cell
and 4 seeds per unit cell. The isotherm with only 0.5 seeds
per unit cell is essentially identical to the base case. It
should be noted that the seeded water molecules, which
occupy some pore volume, are not included in the loading
quantified on the y-axis. Pore blockage by the seed mole-
cules might explain some of the differences with the base
case observed at the higher loadings, but the differences
are also indicative of the difficulties in equilibrating the sys-
tem when the pores are completely full.
Using 4 seeds per unit cell produces qualitative changes
in the isotherm. The loading at low pressures is non-zero
Fig. 4. Snapshot of water clustering around defect seed molecules in
silicalite. Conditions: 4 seed molecules per unit cell (located in channel
intersections), 0.136P/Psat, and 291 K. Oxygen atoms of seed molecules
are represented by the large blue spheres. Adsorbed water moleculesÕ
oxygen atoms are represented by large red spheres, and the hydrogen
atoms are represented by the smaller white spheres. (For interpretation of
the references in colour in this figure legend, the reader is referred to the
web version of this article.)
 C.E. Ramachandran et al. / Microporous and Mesoporous Materials 90 (2006) 293–298 297

and is more consistent with the experimental data. This

supports the suggestion that defect sites within the pores
influence the adsorption of water at low loading. A truly
hydrophobic pore shows essentially zero loading of water,
but real silicalite samples show finite loadings due to
hydrophilic defect sites. Introduction of seeds also shifts
the pressure at which pore filling begins to a lower value.
A snapshot from a simulation with 1 seed molecule in
the simulation box (eight unit cells) is shown in Fig. 3.
The adsorbed water molecules clearly form clusters that
seem to grow around the seed molecule (note that the clus-
ters at the top/bottom and left/right are connected due to
the periodic boundary conditions). Fig. 4 shows a snapshot
from a simulation with 4 seed molecules per unit cell at low
pressure. Again, the adsorbed water molecules are located
preferentially near the seed molecules. Fig. 5 shows a snap-
shot from a simulation with 4 seed molecules per unit cell
at a higher pressure. Here, it can be seen that the pores
are almost full of water molecules.
Pair distribution functions were also calculated. The
pair distribution function based on the centers of mass
between the seeded molecules and non-seeded water mole-
cules, g[rCOM], showed a very structured configuration of Fig. 5. Snapshot of water adsorption in silicalite near saturation. (Note:
water around the defects at low loading, evident from a For better visualization of seed molecules, this figure is shown as viewed
sharp peak at 2.758 Å [31]. The distance and intensity from a different angle compared to Figs. 3 and 4.) Conditions: 4 seed
molecules per unit cell (located in channel intersections), 0.45P/Psat, and
indicate hydrogen bonding occurs between the seeded 291 K. Oxygen atoms of seed molecules are represented by the large blue
and non-seeded water molecules. Using g[rCOM], the num- spheres. Adsorbed water moleculesÕ oxygen atoms are represented by large
ber of nearest neighbors around the seeded water molecules red spheres, and the hydrogen atoms are represented by the smaller white
could be calculated [32]. For the case with 4 seed molecules spheres. (For interpretation of the references in colour in this figure
per unit cell, results showed on average, approximately one legend, the reader is referred to the web version of this article.)
water molecule surrounding each seed within hydrogen
bonding distance at low pressures (corresponding to The radial distribution function between the oxygen of
Fig. 4) and up to four water molecules surrounding each a seeded molecule and the hydrogen of non-seeded water
seed at high pressures (Fig. 5). molecules, g[rO–H], is shown in Fig. 6 for the case

Fig. 6. Radial distribution function between the oxygen atom of seeded water molecules and the hydrogen atom of adsorbed water molecules. Conditions:
0.5 seed molecules per unit cell (located in channel intersections), 0.14P/Psat, and 291 K.
298 C.E. Ramachandran et al. / Microporous and Mesoporous Materials 90 (2006) 293–298
corresponding to 0.5 seed molecules per unit cell and low
pressure. The first g[rO–H] peak occurs at 1.765 Å and the
second at 3.2 Å, again consistent with hydrogen bonding.
4. Conclusions
The molecular simulations presented in this work predict
that in a perfect silicalite crystal, the pore system is hydro-
phobic and essentially no water adsorbs at low pressure.
At some intermediate pressure, a sharp transition occurs
where the pores become saturated with water molecules.
The presence of hydrophilic defects, such as silanol sites,
in experimental samples leads to adsorption of small
amounts of water at low pressures. Water molecules prefer-
entially form hydrogen-bonded clusters around the defects.
The presence of hydrophilic defects also leads to a decrease
in the pressure where pore filling occurs.
Acknowledgements
This research is supported by the Chemical Sciences,
Geosciences and Biosciences Division, Office of Basic
Energy Sciences, Office of Science, US Department of
Energy, Grant No. DE-FG02-03ER15457. Additional sup-
port from the National Science Foundation (CTS-0302428)
is also gratefully acknowledged. The authors thank Prof.
Alain Fuchs for helpful discussions.
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