.r. - -r ..

AB INITIO AND DENSITY FUNCTIONAL STUDIES OF

HYDROCARBON ADSORPTION IN ZEOLITES*

Larry A. Curtiss, 1 Stanislaus A. Zygmunt, l~zand Lennox E. Itonl

lMaterials Science and Chemistry Divisons, Argonne National Laboratory, Argonne, IL 60439
2Department of Physics and Astronomy, Valparaiso University, Valparaiso, IN 46383

submitted for publication in the

Proceedings of the 12th International Zeolite Conference

Baltimore, Maryland

July 5-10, 1998

The submitted manuscript has been created by

the University of Chicago as Operator of
Argonne National Laboratory(“Argonne”) under
Contract No. W-31- 109-ENG-38 with the U.S.
Department of Energy. The U.S. Government
retains for itself. and others acting on its behalf.
a paid-u~, nonexclusive. imevoc=ble worldwide
license m said article to reproduce, prepare
derivative works, $istnbute c?pies to M. public,
and perform publtcl and drsplay pubhcl y, by
or on behalf of the J ovemment.

*Work supported by the U.S. Department

. of Energy,
—. BES-Materials Sciences, under Contract
w-3 1-109-ENG-38.

\
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 .

AB INITIO AND DENSITY FUNCTIONAL STUDIES OF HYDROCARBON

ADSORPTION IN ZEOLITES

LARRY A. CURTISS,* STANISLAUS A. ZYGMUNT,+ AND LENNOX E. ITON*

*Argonne National Laboratory, Argome, IL 60439 USA; curtiss@mlchm.chm. anl.gov

+ Valparaiso University, Valparaiso, IN 46383 USA; szygmunt(ljlexodus.valpo.edu

ABSTRACT

The adsorption energies of methane and ethane in zeolites are investigated with ab initio
molecular orbital theory and density functional theory. In this work we have used zeolite cluster
models containing two, three, and five tetr~edral (Si, Al) atoms and have found equilibrium
structures for complexes of methane, ethane, and propane with an acid site. If a large enough
cluster is used and correlation effects are included via perturbation theory, the calculated
adsorption energy for ethane is about 5 kcal/mol compared with the experimental value of 7.5
kcal/mol. The B3LYP density fictional method gives a much smaller binding of -1 kca~mol
for ethane. The reason for the failure of density fictional theory is unclear.

INTRODUCTION

The transfer of a proton ilom the Bransted acid site to an adsorbed molecule is an
important step in acid catalysis by zeolites. However, this process is not yet fi.dly understood at
an atomic level. We are studying this proton transfer process using quantum chemical
techniques.’ The adsorption process is also important and it is necessary to know the adsorption
energy to investigate the barriers for proton transfer and cracking. While there has been a great
deal of computational work done on the adsorption of polar molecules such as water, ammonia,
and methanol in zeolites,2 little has been reported on hydrocarbon adsorption. Experimental
studies3-Ghave reported adsorption energies for hydrocarbons that range horn -7 kcal/mol for
ethane to -15 kcal/mol for n-hexane. A density fictional (DF) study’ has found ethane to be
unbound at an acid site in a zeolitic cluster. In this study we have carried out high level ab initio
molecular orbital calculations, as well DF calculations, of the adsorption energy of methane and
ethane on zeolitic clusters.
 ,

I THEORETICAL METHODS

The ab initio calculations were done using G2(MP2,SVP) theory.9 This method uses
MP2/6-31 G* geometries and scaled HF/6-3 lG* zero-point energies. Single point energies at the
MPY6-311 +G(3dfi2p) and QCISD(T)/6-3 IG* levels are combined to obtain a final total energy.
The 6-31 l+G(3df,2p) basis set should be large energy enough to handle the interaction between
the hydrocarbon and the acid site. The density fictional method used is the gradient corrected
B3LYP method.8 The geometries were calculated at the B3LYP/6-31 G* level and then a single
point energy was calculated at the B3LYP/6-31 l+G(3df,2p) level. After obtaining each of the
optimized geometries, we also calculated the harmonic zero-point energy (ZPE) of each system
at the B3LYP/6-31 G* level. The adsorption energies are calculated for the reaction ZH-C~H2~
+ ZH + CnH2~.
The cluster models for the zeolite Iia.mework used in this study have two, three, and five
tetrahedral (Si, Al) atoms and are denoted 2T (SiAIOHG),3T (SizAKhH*), ~d 5 T (S~O&lG),
respectively. The clusters having an acid site are denoted ZH and the all silicon clusters are
denoted Z. All of the structures were filly optimized and have all positive frequencies.

I RESULTS AND DISCUSSION

The MP2/6-31 G(d) structures of the ethane-ZH and methane-ZH complex using the 2T
cluster are shown in Fig. 1. Selected geometrical parameters are shown in the figure. In both
complexes the two hydrogens of the hydrocarbon are bonded to the acidic proton with H-H .
distances of about 2 &
The optimized structures of the ethane-ZH complex using the 3T and 5T clusters are
shown in Fig. 2. Selected geometrical parameters are shown in the figure. Ethane is bonded to
the acidic proton with H-H distances of about 2 ~. Also, only one end of the ethane is bonded to
the ZH cluster even though the clusters are large enough to allow for interaction of both ends of
ethane.
The adsorption energies of the methane and ethane complexes with the 2T and 3T
clusters from the G2(MP2,SVP) calculation (based on the MP2/6-31 G(d)) optimized clusters are
summarized in Table 1. The results indicate that the ethane is bound by 2.8 kcal/mol (including
zero-point effects) to the acid site. This increases slightly to 3.3 kcal/mol for the larger 3T
cluster. Methane is bound by 2.1 kcal/mol to the acid site, The larger binding for ethane than
methane agrees with the trend of larger adsorption energies as the hydrocarbon size increases.
The adsorption energies from the B3LYP/6-31 l+G(3df,2p) calculations (B3LYP/6-
31G(d) geometries) are listed in Table 2. This method, which is generally considered the most
reliable density fi.mctional method for bond energies in molecules,’0 indicates that ethane is
bound by only 0.1 to 0.6 kcal/mol to the acid site. This is considerably smaller than the
G2(MP2,SVP) results which should be more reliable. The adsorption energy for propane, 1.0
kcal/mol, is slightly more than that of ethane (see Table 2). It is known that for weak van der
Wads interactions large basis sets and a good account of correlation effects are required for
obtaining accurate binding energies. Apparently the treatment of correlation in density functional
theory is not adequate for calculating these weak interaction energies.

Figure 1. MP2/6-31 G(d) optimized structures for ethane-ZH and methane-ZH complexes using
the 2T cluster model for the zeolitic acid site.

There have been numerous experimental measurements of the hydrocarbon adsorption

energies in zeolites and generally they are significantly larger than what is given by our
calculations. The adsorption energy of methane in ZSM-5 has been measured to be about 6
kcal/mo13 compared to our value of 2.8 kcal/mol. The adsorption energy of ethane in ZSM-5 has
been measured to be about 7.5 kcal/mo14 compared to our value of 3.3 kcal/mol. The adsorption
energies of other hydrocarbons increase by about 2 kcal/mol per CH2 group.
 c
%
2.046 i“, ‘
1
, ,“;.01
,,
2.1

4
Figure 2. Optimized structures for ethane-ZH complexes using the 3T cluster (MP2/6-31G(d))
and 5T cluster (133LYW6-3lG(d)).

Adsorbed
Cluster Size Cluster Type Molecule AE.,kcal/mol AEO,kcal/mol
2T ZH CH4 2.7 2.1
CZH6 3.3 2.8
z C& 1.1 0.8
CzH(j 2.2 2.0
3T ZH CZH6 3.8 3.3

Table 1. Adsorption energies for methane and ethane complexes with ZH and Z
clusters from G2(MP2,SVP) calculations.

The reason for the discrepancy for between experiment and theory is not clear. The
theoretical calculations indicate that ethane and methane form a weak van der Waals bond with
the acid site, which is what is to be expected when a nonpolar molecule interacts with a strong
dipole. Results for the all silicon clusters (Z) in Table 1 indicate that the bonding to a non-acidic
site is also weak (2 kcal/mol or less).
.

Adsorbed
Cluster Size Cluster Type Molecule AEO,kcal/mol
2T ZH CH4 0.1
3T ZH CZH6 0.2
5T ZH CZH6 0.6
5T ZH c3Hg 1.0

Table 2. Adsorption energies for methane, ethane, and propane

complexes with ZH clusters fromB3LYP/6-31 l+G(3df,2p)
//B3LYP/6-3 lG(d) calculations.

Adsorbed
Cluster Size Molecule HF/6-3 lG(d) MP2/6-31 G(d)
2T CZHfj “ 0.9 2.8
3T CZHG 1.0 3.2
5T CzH(j 1.0 4.3

Table 3. Adsorption energies (A&, kcal/mol) for the ethane complex

with different size ZH clusters flom MP2/6-3 lG(d) andHF/6-31 G(d) calculations.

In order to fhrther investigate the cluster size effect, we have compiled MP2/6-31G(d)
and HF/6-31 G(d) adsorption energies of ethane-ZH in 2T, 3T and 5T clusters in Table 3. At the
HF/6-31 G(d) level there is little dependence of the binding on the cluster size. In contrast, at the
MP2/6-3 lG(d) level the results indicate that the binding of the ethane to the acid site increases
significantly with cluster size. Since the 3T result of 3.2 kcal/mol (MP2/6-31 G(d)) is close to the
more accurate G2(MP2,SVP) result of 3.3 kcal/mol in Table 1, there appears to be a
cancellation of higher level effects (correlation, basis set, and zero-point energies). Thus, the
MP2/6-3 lG(d) values for the binding may be reasonably reliable. For the 5T cluster the
adsorption energy is 4.3 kcah’mol at the MP2/6-31 G(d) level. We have also investigated the
effect of using a much larger cluster, 38T, on the adsorption energy. At the HF/6-31 G(d) level
the binding increases by 0.8 kcal/mol tlom 5T to 38T. If the long-range electrostatic effects are
described reasonably well at the Hartree-Fock level, this gives an estimate for the ethane
adsorption energy of 5.1 kcal/mol (4.3 kcal/mol from 5T and 0.8 kcal/mol flom 5T ~ 38T). The
experimental value is 7.5 kcal/mol. It may be necessary to do a more complete study with larger
clusters to account for the remaining difference between experiment and theory.
u

CONCLUSIONS

The interaction of methane and ethane with an zeolitic acid site using cluster models
containing two and three tetrahedral (Si, Al) atoms is found to be very weak with binding of 2-3
kcal/mol. This is significantly less than experimental measurements of hydrocarbon adsorption,
which give an adsorption energy of-6-7 kcal/mol for these molecules. Using larger clusters the
adsorption energy of CzHfj increases to -5 kcal/mol compared to the experimental value of 7.5
kcal/mol. The B3LYP density fictional method appears to greatly underestimate the binding
energies compared to the ab initio molecular orbital methods. In work in progress we are using
larger basis sets and larger zeolitic clusters to fin-ther investigate theoretical adsorption energies
of hydrocarbons in zeolites.

Acknowledgement

This work was supported by the Division of Materials Sciences, Office of Basic Energy
Sciences, Department of Energy, under Contract No. W-31-109-ENG-38.

REFERENCES

1. S. A. Zygrnunt, L. A. Curtiss, L. E. Iton, to be published.

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1006663 (1996).
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4. R. E. Richards and L. V.S.Rees,Langmuir,3335 (1987).
5. F. Eder and J. A. Lercher, J Phys. Chem., B101 1273 (1997).
6. J. A. Dunne, R. Maiwala, M. Rae, S. Sircar, R. J. Gorte, and A. L. Myers, Langmuir, 125888
(1996).
7. S. Blaszkowski, M. Nascimento, R. van Santen, 1 Phy.s. Chem., 1003463 (1996).
8. L, A. Curtiss, P. Redfem, B. J. Smith, and L.Radom, J Chem. Phy.s., 1045148 (1996).
9. M. J. Frisch et al., Gaussian 94, Gaussian, Inc. Pittsburgh, PA.
10. L. A. Curtiss, K. Raghavachari, P. C. Redfem, J. A. Pople, J Chem. Phy.s., 1061063 (1997).