DFT Study of Methanol Conversion to

Hydrocarbons in a Zeolite Catalyst

JAN ANDZELM, NIRANJAN GOVIND, GEORGE FITZGERALD,
AMITESH MAITI
Accelrys Inc., 9685 Scranton Road, San Diego, California 92121 USA

Received 19 October 2001; accepted 9 March 2002

DOI 10.1002/qua.10417

ABSTRACT: First-principles calculations using the density functional theory code

DMol3 were performed to investigate important pathways in the methanol-to-gasoline
conversion process over zeolite catalysts. Reaction paths and energy barriers involving
the COO bond cleavage and the first COC bond formation were explored using all-
electron periodic supercell calculations and newly implemented algorithms for the
optimization of intermediates and transition states. The simulations indicate that the
formation of surface ylide involves prohibitively high barriers, whereas surface
methoxyl species can easily react with methanol to form ethanol. © 2002 Wiley
Periodicals, Inc. Int J Quantum Chem 91: 467– 473, 2003

formed in the zeolite cage [5, 6]. At that stage di-

Introduction methyl ether can be formed [7], as confirmed by
experiment [1]. However, it is unclear whether di-

T he conversion of methanol to gasoline (MTG)

in zeolites is an important industrial process
that has attracted considerable interest from both
industrial and academic researchers. The main in-
terest is in the mechanism of the first COC bond
formation and cleavage of the COO bond of meth-
anol. Several reaction mechanisms have been pro-
posed, and some have supporting experimental ev-
idence [1–3]. A commonly accepted mechanism
involves the initial physisorption of methanol at a
Brønsted acid site of the Al-substituted zeolite [4].
As the concentration of methanol increases, clusters
of hydrogen-bonded methanol molecules are
Correspondence to: J. Andzelm; e-mail: JWA@ACCELERYS.
COM
methyl ether is a necessary intermediate for the first
COC bond formation [8]. As for the cleavage of the
COO bond of methanol, it can occur through the
formation of surface methoxyl species [5, 9 –11].
This reactive species can then be a starting point for
the formation of the initial COC bond in a reaction
leading to the formation of ethanol or ethyl-methyl-
ether [12]. Those intermediates can be easily dehy-
drated, thereby producing ethylene, which upon
further reactions can lead to the formation of higher
olefins, alkanes, etc. [12]. More recently, yet another
mechanism for the COC bond formation was pro-
posed: this involves the formation of a surface ylide
neighboring a Brønsted acid site [8, 11]. In princi-
ple, the surface ylide species could form from the

International Journal of Quantum Chemistry, Vol 91, 467– 473 (2003)

© 2002 Wiley Periodicals, Inc.
ANDZELM ET AL.
methoxyl species by the transfer of a proton to a
neighboring bridging oxygen. However, it is also
possible that the ylide carbon atom is incorporated
into the zeolite framework, leading to a significant
reorganization of a large number of atoms around
the Brønsted acid site.
Most first-principles computational studies em-
ploy cluster models to represent the neighborhood
of the Brønsted acid site of a zeolite [3, 5, 8 –11].
There are only a few studies using periodic bound-
ary conditions to represent realistic crystalline en-
vironment for the MTG reaction [4, 6, 7]. The plane
wave code CASTEP, for instance, has previously
been used to study the physisorption and clustering
of methanol molecules leading to the formation of
dimethyl ether [6, 7]. Here we report the first peri-
odic calculations investigating the formation of a
surface methoxyl species and the formation of an
initial COC bond within a zeolite cage, ultimately
leading to ethanol. The possibility of ylide forma-
tion close to a Brønsted acid site is investigated, as
well.
Density functional theory (DFT) calculations
were performed using the DMol3 [13, 14] program.
Recently developed algorithms to find transition
states [15] and to optimize structures of a crystal
[16] were employed to investigate reaction mecha-
nisms. The accuracy of DMol3 to predict structures
of adsorbed species in zeolites was verified in cal-
culations on hydrogen-bonded model systems and
bridging hydroxyl groups within the zeolite cage.
Computational Details
The DFT calculations reported here were per-
formed using the DMol3 program from Accelrys (Ma-
terial Studio 2.0) [13, 14]. The electronic wavefunc-
tions are expanded in atom-centered basis functions
defined on a dense numerical grid. We used the dou-
ble-numeric-polarized (DNP) [13] basis set, and a fine
level of integration grid, amounting to approximately
5500 grid points per atom. The DNP, all-electron basis
set is composed of two numerical functions per va-
lence orbital, supplemented with a polarization func-
tion. Each basis function was restricted to within a
cutoff radius of Rcut ⫽ 4.0 Å, thereby allowing for
efficient calculations without a significant loss of ac-
curacy. The electron density was approximated using
a multipolar expansion up to hexadecapole. Typical
overbinding associated with local density functionals
was rectified through the use of the gradient-cor-
rected Perdew-Burke-Ernzerhof (PBE) functional [17].
468
The Brillouin-zone integration was performed using a
2 ⫻ 2 ⫻ 2 Monkhorst–Pack (MP) grid [18].
All geometries were optimized using the re-
cently developed scheme based on delocalized in-
ternal coordinates generalized to periodic bound-
ary conditions [16]. It was already demonstrated
that for systems such as zeolites this algorithm can
be several times more efficient than the one based
on Cartesian coordinates. Methanol and water mol-
ecules in zeolite pores present additional challenge
for the optimization algorithm, because such spe-
cies are typically not connected to the zeolite frame-
work. However, the DMol3 optimizer allows for a
treatment of such disconnected fragments without
having to introduce any artificial connecting bonds.
Several reaction paths investigated here require ap-
proximate scanning of the potential energy surface.
That was accomplished by using internal con-
straints that were imposed on connected or discon-
nected fragments. Precise determination of the tran-
sition states (TS) involving several species in
concerted-like reactions in zeolite is obviously a
formidable challenge. The traditional method of
calculating a Hessian and following the reaction
mode can be very costly for any zeolites of practical
importance. Moreover, the success of such calcula-
tions is not guaranteed unless the initial structure is
already close to the transition state. In this article
we employ a recently developed method [15] that
blends a generalization of the synchronous transit
(ST) method of Halgren and Lipscomb with the
conjugate gradient (CG) technique. In this approach
only structures of reactants and products are
needed to locate TS via a series of ST/CG steps.
This method was found to be robust, efficient, and
accurate in calculations for many complicated TS of
reactions in the gas as well as the condensed phase.
Results
HYDROGEN BONDING
The mechanism of MTG reaction is determined
to a large extent by the network of hydrogen bonds
connecting methanol, water molecules, and the H
atom at the Brønsted acid site. A quantitatively
accurate treatment of hydrogen bonds is, therefore,
important for this work. To test the accuracy of
DMol3 in describing H-bond strengths, the interac-
tion energies between two methanol molecules and
between two water molecules were computed us-
ing the PBE/DNP/Rcut ⫽ 4.0 Å settings, as de-
scribed in the previous section. The calculated val-
VOL. 91, NO. 3

TABLE I ______________________________________________________________________________________________
Relative energies and selected geometrical parameters for the four bridging OH groups in H-Faujasite (FAU).a
Occupation site rAlH (Å)
O1H 2.54 (2.48 ⫾ 0.4)
O2H 2.43
O3H 2.46 (2.40 ⫾ 0.4)
O4H 2.44
a
Experimental values are given in parentheses [22, 23].
b
Results of Ref. [23].
ues of 5.8 and 5.7 kcal/mol for methanol and water
dimers compare well with experimentally esti-
mated ranges of 4.6 –5.9 and 5.0 –5.4 kcal/mol [19],
respectively. This good agreement is due to the fact
that the interaction is dominated by the electrostat-
ics, and DFT predicts dipole moments for both
methanol and water with reasonable accuracy [20].
Dispersion forces that are missing in DFT [21] and
contribute perhaps as much as 25% to the total
interaction energy of water dimer [19] are appar-
ently compensated by other terms in the interaction
energy.
The standard procedure in ab initio calculations
of interaction energies uses the so-called basis set
superposition error (BSSE) approach [19] to account
for incomplete atomic basis sets. The DMol3 pro-
gram uses numerical functions that are far more
complete than the traditional Gaussian functions,
and therefore we expect BSSE contribution to be
small. We verified this by performing DMol3 calcu-
lations on a water dimer using a much larger basis
set (five numerical functions per every valence or-
bital, supplemented with three sets of polarization
functions, diffuse functions, and Rcut ⫽ 8 Å). This
calculation affects the interaction energy by less
than 0.6 kcal/mol. Therefore, indirectly, we dem-
onstrate that any BSSE contributions or further ba-
sis set extensions have a small effect of a fraction of
kcal/mol on the interaction energy. We are confi-
dent that the PBE/DNP/Rcut ⫽ 4.0 Å DMol3 calcu-
lations are an accurate and practical approach to
study complicated reactions in the unit cell of zeo-
lites.
ZEOLITE MODELS AND BRIDGING
HYDROXYL GROUPS
Most commercially used zeolite structures are
too large for a detailed study of all reactions in-
volved in the MTG process. The unit cell of a ZSM-5
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
METHANOL CONVERSION
␣SiO(H)A1 Energy (kJ/mol)
(deg) PBE/DNP VWN/DNPb
130.1 (135.7) 0 0
141.1 (144.6) 7.8 9.8
136.8 (139.8) 4.1 4.9
135.9 (141.9) 9.4 7.9
catalyst, for instance, has 288 atoms. In this article
we use the Ferrierite (FER) structure that has eight-
and 10-ring channels—somewhat similar to the 10-
rings channels of ZSM-5. The primitive cell of FER
contains only 54 atoms and makes the calculations
feasible. Recent calculations by Haase and Sauer [4]
on the physisorption of a single methanol molecule
in the FER and ZSM-5 zeolites show similar com-
plexes in both zeolites. The methanol adsorption
energies in both zeolites differ by less than 4 kcal/
mol, which is only 15% of the adsorption energy.
Most results from the calculations on a FER zeolite
are therefore expected to be valid for a commercial
zeolite such as ZSM-5.
To assess the accuracy of the DMol3 settings in
a periodic geometry of a zeolite, we performed
calculations on bridging hydroxyl groups at the
alumino-silicate Brønsted acid site of Faujasite
(FAU) and FER zeolites. Experimental studies
[22] on the FAU zeolite have revealed that only
three of the four possible bridging OH groups are
observed, and their relative occupations are as
follows: 3:1:1.6:0 for O1H:O2H:O3H:O4H sites,
respectively. In the work by Hill et al. [23] DMol3
was applied at the Vosko-Wilk-Nusait (VWN)/
DNP level using unit cell parameters obtained
from the shell model. Hill et al. [23] found excel-
lent correlation between the relative energies of
the four bridging OH groups and the relative
experimental occupations. In the current work
full geometry optimization was performed for the
primitive rhombohedral cell with 145 atoms and
fixed cell parameters. Table I summarizes our
results as compared with the results of Ref. [23].
It is evident that the relative energies from our
calculations correspond well with the experimen-
tal site occupations as well as with previous
DMol3 calculations. The bond lengths and bond
angles associated with bridging hydroxyl groups
469
ANDZELM ET AL.
2
FIGURE 1. The SN pathway for surface methylation with single methanol. Dotted lines represent hydrogen bonds.
(a) Methanol-hydrogen complex at Brønsted acid site; (b) transition state; (c) surface methoxyl and water hydrogen-
bonded to zeolite.
are within 0.06 Å and 6° of experimental values.
The O1H site, which is open to the largest channel
of a zeolite, is a preferable location for the hy-
droxyl group in both FAU and FER zeolites. In
the case of FER zeolite, the relative energies are 0,
7.5, 9.5, and 14.2 kJ/mol for the O1H, O2H, O3H,
and O4H sites, respectively. The O1H, being the
lowest energy site, was selected as the Brønsted
acid site for our MTG study with the FER zeolite.
FORMATION OF SURFACE METHOXYL
SPECIES
A single molecule of methanol forms multiple
hydrogen bonds with the Brønsted acid site of
FER zeolite. There are several adsorption sites
possible that are within 1 kcal/mol; Figure 1(a)
displays the most stable structure, with an ad-
sorption energy of 18.5 kcal/mol. This value com-
pares well the experimental estimates of the heat
of adsorption in acidic zeolites, ranging from 15
to 27 kcal/mol [5, 24]. No protonation of metha-
nol by the Brønsted acid site was found, in agree-
ment with the recent study by Haase and Sauer
[4]. The calculated transition state for the meth-
ylation of a surface oxygen at the alumino-silicate
Brønsted acid site of FER zeolite is presented in
Fig. 1(b). Clearly this is a concerted reaction in-
volving breaking of the COO bond in methanol
and bond formation between C and surface oxy-
gen. Simultaneously the proton from the Brøn-
sted acid site is transferred to the hydroxyl
470
group, thereby forming a water molecule [Fig.
2
1(c)]. This is a strained SN -type reaction with an
activation barrier of 54 kcal/mol. Other DFT or
ab initio cluster studies [9 –11] have reported a
barrier of 44 to 65 kcal/mol. Interestingly, the
presence of a second methanol molecule lowers
the above activation barrier to 44 kcal/mol, as the
TS now corresponds to an unstrained SN 2
pathway
(see Fig. 2). At the TS the surface oxygen, methyl
carbon, and oxygen of the leaving water molecule
are roughly collinear [Fig. 2(b)]. The water mol-
ecule is formed as a result of proton transfer to
the methanol hydroxyl group from the methoxo-
nium ion. Our computed barrier of 44 kcal/mol is
comparable with the 32– 46 kcal/mol barrier pre-
dicted by the MP2/6-31G*//HF/3-21G studies of
Sinclair and Catlow [5] on clusters of various
sizes.
This reaction is facilitated by the hydrogen-
bonded methanol and methoxonium ion [Fig. 2(a)].
Methoxonium ion is formed spontaneously when a
methanol molecule captures the proton from the
Brønsted acid site. No barrier for that reaction is
found, in agreement with the work by Sandre et al.
[7]. Clearly, the presence of the second methanol
molecule in the zeolite cage facilitates methoxo-
nium ion formation because with one methanol
molecule, no spontaneous deprotonation of zeolite
was found. Further analysis of other possible path-
ways for surface methoxyl formation is given in a
separate study.
VOL. 91, NO. 3
 METHANOL CONVERSION

2
FIGURE 2. The SN pathway for surface methylation with two methanol molecules: (a) methoxonium–methanol com-
plex; (b) transition state; (c) surface methoxyl and methanol–water complex.

REACTIONS OF SURFACE METHOXYL possible pathways, which are discussed in details

SPECIES
Surface methoxyl species can react with metha-
nol or dimethyl ether to form ethanol or methyl-
ethyl-ether, respectively [12]. Those are the first
species containing a COC bond. In this study we
investigated the formation of ethanol. Using the
structure presented in Figure 3(a) as a reactant for
the COC bond formation, we investigated several
elsewhere. The most successful pathway involved
water as an important catalytic agent, which
through the network of hydrogen bonds stabilized
ethanol molecule and facilitated transfer of the pro-
ton from the methyl group of the methanol to the
Brønsted acid site of zeolite [Figs. 3(b) and 3(c)].
The importance of the water molecule in assist-
ing in this reaction was already noticed by Blasz-

FIGURE 3. Ethanol formation via a methoxyl/water–mediated mechanism. (a) Surface methoxyl and water–methanol
complex; (b) transition state; (c) ethanol, water, and hydrogen bonded to zeolite.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 471

ANDZELM ET AL.
FIGURE 4. Formation of the surface ylide species: (a) surface methoxyl species; (b) transition state; (c) surface ylide
species.
kowski and van Santen [12]. The transition state
2
[Fig. 3(b)] indicates that this is an SN -type reaction
involving CH3 species already separated from the
zeolite surface with structure close to the trigonal
planar. Our computed barrier for that reaction is
25.4 kcal/mol, which is significantly less than the 60
kcal/mol barrier reported from the cluster calcula-
tions of Ref. [12]. The net reaction is exothermic and
the final product adsorbed via hydrogen bonds
[Fig. 3(c)] to the zeolite surface has an energy lower
than the reactant by 49.2 kcal/mol. The correspond-
ing reaction energy from Ref. [12] is about 24 kcal/
mol. This disparity can be attributed to differences
in (1) the choice of the model: cluster models were
used in Ref. [12], as compared with the periodic
models used in this work; and (2) the method:
self-consistent GGA calculations were performed
here, whereas only perturbative GGA corrections
were used in Ref. [12]. From comparing activation
barriers for methoxyl formation we can conclude
that the rate-limiting step is the breaking of the
COO bond of methanol and the formation of the
surface methoxyl species [Fig. 2(b)]. The activation
energy for such reaction, 44 kcal/mol, is signifi-
cantly higher than the barrier for the first COC
bond formation of 25 kcal/mol [Fig. 3(b)], as found
in this work.
Finally, we investigated a recent hypothesis [8,
25] that the surface ylide (CH2) may provide a
reactive C atom for the first COC bond formation.
According to that hypothesis, the methoxyl species
loses a proton, which is transferred to the neighbor-
ing Brønsted acid site. Our initial attempts to find a
stable structure with a surface ylide separated from
472
a proton were not successful. The proton always
comes back, without any barrier to form a stable
methoxyl species. However, if there is a rearrange-
ment of the zeolite framework and the ylide (CH2)
species is inserted into the AlOO bond, a stable
intermediate structure is indeed possible. Cluster
calculations [8, 25] reveal that the barrier for such
reaction methoxyl f ylide built in surface is about
50 kcal/mol. We expect a small cluster model to be
inadequate to study reactions that may significantly
affect the entire framework of a zeolite. We inves-
tigated this reaction (Fig. 4) using a consistent pe-
riodic zeolite model. The calculated barrier of 78.5
kcal/mol is significantly larger than our previously
calculated barriers for methoxyl (44 kcal/mol) and
the ethanol (25 kcal/mol) formation. Therefore, we
can rule out the possibility of a surface ylide for-
mation. One can notice a significant reorganization
of the zeolite framework upon surface ylide forma-
tion, underlining a need for consistent calculations
in a periodic environment.
Conclusion
Using a DMol3 PBE/DNP approach we per-
formed calculations on periodic FER zeolite to elu-
cidate the mechanism of key reactions involved in
the first COO bond breaking and COC bond for-
mation for the MTG process. This is a consistent
approach that allows us to study significant reor-
ganization of the zeolite cages, which may occur if
an adsorbed species is built into the zeolite frame-
VOL. 91, NO. 3

work. The main findings of this work are summa-
rized below:
▪ The current approach allows us to calculate
hydrogen bonding with a reasonable accuracy
of ⬃0.5 kcal/mol for interaction energies.
▪ Periodic DFT calculations can describe well
the neighborhood of a Brønsted acid site in
alumino-silicate Faujasite zeolite. The experi-
mentally known positions of the bridging hy-
droxyl groups and their relative stabilities are
correctly reproduced in our calculations.
▪ Single methanol molecule is adsorbed in zeo-
lite cages via hydrogen bonds, whereas the
presence of the two methanol molecules al-
lows for spontaneous formation of the meth-
oxonium ion.
▪ Formation of surface methoxyl species occurs
2
in SN -type concerted reaction with a barrier of
44 kcal/mol if two methanol molecules are
present.
▪ Surface methoxyl species can undergo a reac-
tion to form an ethanol molecule. The barrier
for such a reaction is 25 kcal/mol if the water
molecule is present.
▪ Formation of the ylide that is built into the
zeolite cage surface has to be ruled out as the
barrier for such a reaction exceeds 78 kcal/
mol.
▪ The synchronous transit coupled with conju-
gated gradient refinement to optimize transi-
tion states [15] and delocalized internals to
optimize structures of reaction intermediates
[16], under periodic boundary conditions and
internal constraints, allowed fast and accurate
exploration of reaction pathways and associ-
ated heats and barriers.
Further details of the calculations and structures
of transition states will be published elsewhere. The
next step in our study of MTG process is likely to
include investigations on the role of ether and the
process of dehydration of ethanol to form ethylene.
ACKNOWLEDGMENT
The authors are grateful to Prof. Joachim Sauer
(Humboldt University, Berlin) and Prof. Richard
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
METHANOL CONVERSION
Catlow (Royal Institute of Great Britain, London)
for valuable discussions. We thank our colleagues
at Accelrys for help in this study and acknowledge
members of Accelrys’s Catalysis 2000 Consortium
for their support of this work.
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