International Scholarly Research Network

ISRN Renewable Energy

Volume 2012, Article ID 491396, 4 pages
doi:10.5402/2012/491396

Research Article
High-Pressure Hydrogen Adsorption in the Zeolites:
A Grand Canonical Monte Carlo Study

Xiuying Liu, Jie He, and Rui Li

College of Science, Henan University of Technology, Henan, Zhengzhou 450001, China

Correspondence should be addressed to Xiuying Liu, liuxiuyingzx@126.com

Received 22 April 2012; Accepted 15 June 2012

Academic Editors: F. E. Little and R. P. Saini

Copyright © 2012 Xiuying Liu et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The adsorption of hydrogen molecules on different zeolites at near room temperature and extremely high pressures has been
simulated employing Grand Canonical Monte Carlo (GCMC) method. Some important physical amounts under different
temperatures and pressures, such as adsorption isotherms, adsorption amounts, and isosteric heats were studied. We predict the
storage capacity of hydrogen in ZON and CHA zeolites at different conditions. The results show that the hydrogen storage capacity
of CHA is superior to that of ZON. The different hydrogen adsorption behavior between them is explained by the isosteric heats
of adsorption at different temperatures. These results may help us to understand different hydrogen adsorption properties of these
two zeolites, thus facilitate exploring new hydrogen storage candidates experimentally.

1. Introduction the measurement and computation of the adsorption of

Hydrogen storage is a key enabling technology for the
extensive use of hydrogen as an energy carrier. The aim
is to develop economically and environmentally attractive
solutions for storage options. Therefore, a number of novel
storage techniques are being investigated to complement the
currently available methods. These methods mainly include
high pressure gas, liquid hydrogen, adsorption on porous
materials, complex hydrides, and hydrogen intercalation in
metals [1–5]. However, none of these methods completely
satisfy all the criteria for the amount of hydrogen that can be
supplied from a given weight or volume of tank for transport
purposes. Therefore, alternative possibilities for hydrogen
storage have to be considered. Recently, physisorption has
attracted more attention because the adsorption is reversible,
and thus the adsorbent can be recycled. Moreover, physisorp-
tion offers the possibility of high hydrogen storage capacity
and quick hydrogen desorption. As a result, many investiga-
tions have focused on encapsulating hydrogen molecules in
microporous materials [6–8].
Zeolites are aluminosilicate crystals extensively used in
industrial applications involving separation, adsorption, or
preferential adsorption of gases [9]. These applications have
motivated theoretical and experimental works devoted to
simple gases or complex molecular fluids on these materials.
Numerical simulations have been realized using a sound
model of the interactions between the zeolite crystal and
gas molecules, with the aim of evaluating the possibility of
computing the amount of gas adsorbed at a given pressure
and temperature with acceptable precision.
The objective of the present work is concerned with the
adsorption of H2 on the different zeolites. Here, we have
investigated three zeolites with different channel diameters
and pore volumes. The physisorption properties of hydrogen
molecules on RHO, ZON, and CHA zeolites have been simu-
lated employing GCMC method. Figure 1 shows a schematic
drawing of the zeolite pore structure investigated [10].
2. Simulation Details
Investigation on the adsorption isotherms of H2 molecules
in zeolites were based on the GCMC method. For the
grand canonical statistical ensemble, the chemical potential,
volume, and system temperature were all fixed. The average
number of adsorbate molecules at the imposed chemical
potential (or fugacity) was obtained from the simulation. To
describe the interactions between adsorbates and adsorbents,
2 ISRN Renewable Energy
RHO
Figure 1: Framework structures of RHO, ZON, and CHA zeolites.
COMPASS force field was used. The COMPASS force field
employs the Lennard-Jones (LJ) potential to describe the
van der Waals interactions and the Coulomb potentials to
describe the electrostatic interactions. Most parameters of
the COMPASS force field were derived based on ab initio
data, and the COMPASS force field had been parameterized
to predict various properties for covalent molecules includ-
ing most common organics, small inorganic molecules, and
polymers in isolation and in condensed phases.
During the simulation, the zeolites structure was as-
sumed to be rigid structure during the adsorption process.
Eight unit cells of zeolites are used to construct the simula-
tion box (2 × 2 × 2 cells), and periodic boundary conditions
are applied in three dimensions in order to simulate an
infinite system.
3. Results and Discussion
At room temperature, experimental data of hydrogen
adsorption on zeolites is rare, and larger storage capacities
are possible when the pressure is high. The adsorption
isotherms are given in the form of uptake plots, that is,
the uptake as a weight percentage is given as a function of
gas pressure. Figure 2 shows that the calculated adsorption
isotherms of hydrogen at 80 K obtained from the GCMC
simulations are compared with the experimental results of
Kumer et al. [10]. It can be seen that our computed adsorp-
tion isotherms are in good agreement with experimental
results. Therefore, the model and COMPASS force field used
in this work are correct and reliable.
Then, we predict the hydrogen storage capacity of ZON
and CHA zeolites at near room temperature and extremely
high pressures. Figure 3 shows the adsorption isotherms of
the ZON and CHA zeolites in a broad range of temperature
(273 K, 298 K, and 350 K) and pressure (0–2000 MPa). Their
physisorption amounts under different temperatures and
pressures were obtained, which may compare their hydrogen
storage capacity. It can be seen from Figure 3 that the adsorp-
tion amounts increase and saturate with increasing pressure,
which are in agreement with experiments on porous carbons
[11]. And the adsorption amounts correspondingly increase
ZON CHA
with decreasing temperature. This is because zeolite has a
characteristic high internal surface area, approximately of a
similar order of magnitude to the surface area of activated
carbon, a material which can exhibit appreciable hydrogen
uptake values at cryogenic temperatures. Differently, the
adsorbed amounts of CHA are larger than those of ZON at
the same conditions. This is because the hydrogen adsorption
capacity of zeolite mainly depends on the framework,
channel size, pore volume and the interaction of molecular
hydrogen with the internal surfaces of the micropores.
In order to explain the reason causing such differences
of hydrogen storage in ZON and CHA zeolites, isosteric
heats of adsorption of the later were calculated by applying
the Clausius-Clapeyron equation at different temperatures.
Isosteric heat is a physical quantity which may estimate
the energetic interaction between zeolites and hydrogen
molecule. The isosteric heat of adsorption versus the
adsorbed amounts is shown at 298 K, as shown in Figure 4.
We may see that the isosteric heat decreases with increasing
the adsorbed amounts. This is due to the existence of
different adsorption sites in these porous materials where
the strongest binding sites are occupied at lower adsorbed
amounts, while those possessing a lower adsorption enthalpy
are occupied only at higher hydrogen concentrations. On
the other hand, repulsive interaction between the adsorbed
hydrogen molecules might appear at higher loading which
then decreases at the heat of adsorption. The mean value of
isosteric heat of adsorption Qst of each zeolite may reflect
the interaction of zeolite with hydrogen molecule. We can
see that the value Qst of in CHA is larger than that in ZON.
This is why the storage capacity of CHA is superior to that of
ZON.
4. Conclusions
Using GCMC method, we have studied the physisorption
properties of ZON and CHA zeolites at the different condi-
tions. Firstly, in order to validate correctness and accuracy of
the model and compass parameters, the computed adsorp-
tion isotherms of RHO at 80 K and pressures (0–100 mbar)
were compared with corresponding experimental results.
ISRN Renewable Energy 3

0.7 1.7

0.6 1.65
Adsorbed hydrogen (wt%)

Isosteric heat (kcal/mol)

1.6
0.5
1.55
0.4
1.5
0.3
1.45
0.2
1.4
0.1 1.35

0 1.3
0 2 4 6 8 10 12 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6
Pressure (mbar) Adsorbed hydrogen (wt%)
Exp CHA
Sim ZON

Figure 2: Comparison between simulation results and experimen- Figure 4: Isosteric heat of adsorption for ZON and CHA zeolites
tal data of hydrogen adsorption in RHO zeolite at 80 K. versus the adsorbed amounts at 298 K.

3.6
3.2 no. 2011B140005) and Henan University of Technology
Foundation (Grant no. 2009BS025).
Adsorbed hydrogen (wt%)

2.8

2.4
2 References
1.6
1.2
0.8
0.4
0 36, pp. 17776–17783, 2006.
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Pressure (MPa)
CHA273K
CHA298K
CHA350K
Figure 3: The adsorption isotherms of hydrogen in ZON and CHA
zeolites.
Then, we predicted the hydrogen storage of CHA and ZON
zeolites using the GCMC method. Some important physical
amounts under different temperatures and pressures, such
as adsorption isotherms and adsorption amounts, were ob-
tained. The results show that the physisorption properties
of CHA zeolite are superior to those of ZON zeolite at all
conditions. The reasonable theoretical explanations are given
by calculating the isosteric heats of adsorption at the different
temperatures.
Acknowledgments
This work was supported by the Natural Science Foundation
of Education Bureau of Henan Province, China (Grant
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