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Kinetics and thermodynamics of polymethylbenzene

formation over zeolites with different pore sizes
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Cite this: DOI: 10.1039/c6cy00465b

for understanding the mechanisms of methanol to
olefin conversion – a computational study†
Yan-Yan Chen,a Zhihong Wei,a Sen Wang,ab Junfen Li,a Mei Dong,a Zhangfeng Qin,a
Jianguo Wang,a Haijun Jiao*ac and Weibin Fan*a

Received 1st March 2016,
Accepted 13th April 2016
DOI: 10.1039/c6cy00465b
www.rsc.org/catalysis
On the basis of density functional theory including dispersion correction (ωB97XD), the thermodynamics
and kinetics of the formation of polymethylbenzene intermediates in methanol to olefin conversion over
zeolites with different pore sizes have been systematically computed. The agreement between the experi-
mental and theoretical adsorption enthalpies of the several polymethylbenzenes over H-FAU reasonably
validates the applied models and methods, and reveals the importance of dispersion correction in the
space confinement and electrostatic stabilization of the zeolite framework. The free energies of the step-
wise formation of the polymethylbenzenes show that the most favorable active hydrocarbon pool interme-
diates are pentamethylbenzene and hexamethylbenzene over H-BEA and H-SAPO-34, as well as tetra-
methylbenzene over H-ZSM-5 and H-ZSM-22. These stable polymethylbenzenes are also precursors for
the formation of geminal methylated cationic intermediates on the basis of kinetic and thermodynamic
analyses. The agreement of the thermodynamic and kinetic results on the favorable intermediates validates
the use of Gibbs free reaction energies to estimate the primary component of the intermediates in the var-
ious zeolites. All these pore-size-dependent differences among the zeolites show their enhanced confine-
ment effect, which is mainly influenced by the short-range electrostatic potential including stabilization
and repulsion.

1. Introduction co-catalysts. One of the most important active HCP species is

polymethylbenzenes (polyMBs).15,16
Methanol can be expediently produced via synthesis gas from
multifarious carbon sources such as coal, natural gas and
biomass,1–5 and the conversion of methanol to olefins (MTO)
over acidic zeolite catalysts has been turning into a gradually
important alternative to naphtha cracking for obtaining light
olefins.6–8 In the past few decades, a great deal of effort has
been devoted to elucidate the mechanisms of methanol to
olefin conversion on the basis of experimental and theoretical
studies.9–14 The hydrocarbon pool (HCP) mechanism pro-
posed by Dahl and Kolboe6–8 has received wide recognition,
where it is assumed that hydrocarbon species trapped in zeo-
lite pores interplay with the inorganic framework and serve as

a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese
Academy of Sciences, Taiyuan, Shanxi 030001, China.
E-mail: haijun.jiao@catalysis.de, fanwb@sxicc.ac.cn
b
University of Chinese Academy of Sciences, Beijing 100049, China
c
Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-
Strasse 29a, 18059 Rostock, Germany Scheme 1 Schematic representation of the paring and side-chain re-
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ action mechanisms in MTO catalysis (Z–H and Z− stand for the proton-
c6cy00465b ated and deprotonated form of zeolite, respectively).29

This journal is © The Royal Society of Chemistry 2016 Catal. Sci. Technol.

Paper
For polyMBs as active HCP species, two reaction routes, a
side-chain route17–20 and a paring route,21 have been proposed
for the formation of light olefins (Scheme 1). Both routes start
with repeated methylation until the formation of a geminal
methylated cation (e.g.; 1,2,3,4,4,5,6-heptamethylcyclohexa-2,5-
dien-1-ylium ion, 7MB+). Subsequently, the side-chain route
starts with the formation of an exocyclic double bond by de-
protonation, followed by successive side-chain methylation
and side-chain elimination, resulting in olefins. The alterna-
tive paring route involves contraction and expansion steps
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with the elimination of propene. The difference between both
routes is that the paring reaction involves the use of a ring
carbon to grow an alkyl chain, while in the side-chain reaction,
the six-membered ring is conserved during the reaction.
Haw et al.,19 found the side-chain route to be predominant
in the production of olefins through direct pulse experiments
of different polyMBs and 13C-methanol in a large H-BEA pore
at 723 K. However, Bjørgen et al.,22 reported the rearrangement
of 7MB+ by 12C-benzene and 13C-methanol co-reacted at tem-
peratures below 573 K to be the major reaction route for olefin
formation on a H-BEA zeolite. These results are reconcilable if
a change in the dealkylation mechanism occurs with tempera-
ture.23 Another possible route for light olefin formation, origi-
nally proposed by Dessau on the basis of successive methyla-
tion and cracking reactions of C3+ alkenes, has already
attracted extensive attention.24 In more detailed studies using
13
C labeling, a complete dual cycle mechanism in a H-ZSM-5
zeolite was proposed, and both the polyMBs cycle and alkene
cycle can produce light olefins.25,26 This concept has been fur-
ther corroborated by theoretical studies on H-ZSM-5.27,28
MTO mechanisms are determined by intermediates or
HCP species which are further controlled by the structure to-
pology of zeolites. Identifying intermediates is of great impor-
tance to understand reaction mechanisms as well as the
structure and activity correlation of a reaction. Although
many experimental techniques have been used to detect HCP
intermediates, and some intermediates over only a few zeo-
lites have been found, specific HCP intermediates over differ-
ent zeolites are less known. Some carbenium ions in the
MTO reaction, such as 5MB+, cyclopentenyl cation and 7MB+,
were identified by using in situ solid-state NMR, whereas the
formation of these carbenium ions in catalysts was verified
mostly indirectly or by the aid of the reaction of co-feeding
methanol and benzene or methylbenzene.20,30–33 Dai et al.,34
observed several initial species (i.e., three-membered ring
compounds, dienes, polymethylcyclopentenyl, and poly-
methylcyclohexenyl cations) on a H-SAPO-34 model catalyst
during the early stages of MTO conversion via 1H MAS NMR
and 13C MAS NMR, and proposed an olefin-based catalytic cy-
cle as the primary reaction pathway before the steady-state,
with highly active polymethylbenzenium ions as the most im-
portant intermediates. Until now, only cyclopentenyl cations
and 5MB+ ions on H-ZSM-5 (ref. 35 and 36) and cyclopentenyl
cations on H-ZSM-5 by applying in situ ultraviolet-visible
spectroscopy,37 and 7MB+ ions on DNL-6 (ref. 38) and CHA
(H-SAPO-34 and H-SSZ-13)39 by applying MAS NMR spectro-
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scopy were observed directly under working conditions using
only methanol as the reactant. The precursors of these
carbenium ion intermediates are HCP species of polyMBs
(for aromatic cycle as an example) which are relatively stable
and easily observable, and some HCP species over a few zeo-
lites were identified using isotopic switch experiments.40 On
H-ZSM-5, lower polyMBs, especially for tetramethylbenzene
(4MB), were found to act as HCP species.41,42 The main reac-
tion centers were identified as pentamethylbenzene (5MB)
and hexamethylbenzene (6MB) in the wide-cavity of H-SAPO-
34 (ref. 43 and 44) and in the wide-channel of H-BEA.19,22,36,41
The confinement effect of zeolite frameworks, which re-
flects the attractive or repulsive interaction between intermedi-
ates and frameworks, is decisive for the specific intermediates.
Although some knowledge has been gained about the
HCP species and MTO reaction mechanism over various
zeolites,45–51 quantitative analyses of the confinement effect
on the stability and activity of HCP species in zeolites are not
carried out. The confinement effect includes analysis of ther-
modynamics about reaction energies and kinetics about activa-
tion energies. Investigating the activity of HCP species, the
probability and favorability of the formation of these species
in zeolites should be considered at first by thermodynamics.
Smit et al.52 examined the confinement effect in zeolite catalysis
and argued that simple thermodynamics of molecules adsorbed
inside zeolite pores can explain the selective formation of prod-
ucts and guide the identification of zeolite structures which
are particularly suitable for desired catalytic applications.
In our work, thermodynamic and kinetic analyses on the ba-
sis of density functional theory computations including disper-
sive interactions are carried out to quantify the stability and ac-
tivity of HCP species in various zeolite topologies of H-SAPO-34,
H-ZSM-5, H-BEA and H-ZSM-22, and the confinement effect of
the zeolite frameworks on the HCP species is also discussed.
For clear presentation, only the HCP species of polyMBs are
considered in this work. Kinetic analyses about the gem-
methylation of polyMBs on H-CHA, H-ZSM-5 and H-BEA with-
out dispersion correction were reported by Waroquier et al.,53
and a similar protocol for thermodynamic analyses on free en-
ergies of methylbenzenes was recently reported by Wang et al.54
In contrast to the above two references, we also included the
interconversion of different MBs proceeding through a methyla-
tion step in our calculations. The advantages of our work are:
(a) identification of more favorable reactions as well as active
hydrocarbon intermediates by comparing the energy barriers of
the competitive reactions of methylation and gem-methylation
of polyMBs; (b) the validity of the Gibbs free reaction energies
to estimate the primary component of intermediates in zeolites
on the basis of the agreement between thermodynamic and ki-
netic results; (c) the essence of the confinement effect analyzed
by comparing the energies in the four zeolites.
2. Computational model and methods
To model zeolite catalysts, it is essential to choose appropri-
ate systems, taking into account both the space confinement
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Catalysis Science & Technology
and electrostatic effects of the framework. Principally, peri-
odic models taking an entire unit cell into account should be
the most suitable in capturing the true nature of nano-
porous materials. Indeed, such models were utilized to inves-
tigate the mechanism and kinetics of MTO processes.55,56
Contrary to periodic models, small clusters might not reason-
ably represent real structures, but clusters large enough can
be used to account for the distinguishing topological features
of zeolite catalysts,57–59 and to rationally describe the space
confinement and electrostatic stabilization effects of zeolite
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frameworks.
In our work, 52T H-BEA, 49T H-ZSM-5, 61T H-FAU, 45T H-
ZSM-22 and 46T H-SAPO-34 cluster models were used
(Fig. 1). The initial structures of these zeolites were taken
from the database of the Structure Commission of the Inter-
national Zeolite Association (IZA).60,61 The H-SAPO-34 struc-
ture consists of a super-cage (the maximum diameter of a
sphere that can be included is 7.4 Å) made up of small pores
(3.8 × 3.8 Å), which is derived from a silicalite-CHA structure,
where all the symmetrically equivalent Si atoms are
substituted by P and Al atoms in an alternating manner, and
one P atom is replaced by one Si atom to generate one
Brønsted acid site per cage.62 The H-BEA structure consists of
three-dimensional large intersecting straight channels (5.5 ×
6.7 Å), with an Al atom located at T9,63 and the maximum di-
ameter of a sphere that can be included is 6.68 Å. The H-
ZSM-5 structure consists of an intersecting channel between
a straight channel (5.3 × 5.6 Å) and a zigzag channel (5.1 ×
5.5 Å), with an Al atom located at T12 (ref. 64) and the maxi-
mum diameter of a sphere that can be included is 6.4 Å. The
H-ZSM-22 structure consists of a one-dimensional straight
channel (5.7 × 4.6 Å) with an Al atom located at T4,65 and the
maximum diameter of a sphere that can be included is 5.7 Å.
The H-FAU structure consists of super-cages that are inter-
connected by 12-membered rings with dimensions of 7.4 ×
7.4 Å; the same as H-SAPO-34, all its tetrahedral Si atoms are
symmetrically equivalent, and the maximum diameter of a
sphere that can be included is 11.2 Å.66 All the peripheral Si
(Al and P for H-SAPO-34) atoms were saturated by H atoms
Fig. 1 H-SAPO-34-46T, H-BEA-52T, H-ZSM-22-45T, H-ZSM-5-49T, H-FAU-61T cluster models.
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along the pre-existing Si–O bonds, and the terminal Si–H
(Al–H and P–H for H-SAPO-34) distances are 1.47 Å (1.55 and
1.35 Å for H-SAPO-34). We used these cluster models
containing a 5T [6T for H-SAPO-34] active region for
SiOHAlIJOSi)2OSi [(PO)2SiOHAl(OSi)2 for H-SAPO-34] along
with the adsorbates in the channels to be relaxed, while the
rest of the structure is fixed at their crystallographic coordi-
nates during geometry optimization.
In this work, all calculations were done using large clus-
ters with the Gaussian 09 package.67 All the transition states
(TS) were guessed by using the OPT = TS method and con-
firmed by the quasi-internal reaction coordinate approach to
verify each authentic transition state bridging the corre-
sponding reactants and products. Furthermore, the transition
state is a first-order saddle point on the potential energy sur-
face with only a single imaginary frequency, and the obtained
reactants and products were verified to be situated in the en-
ergy minima points of the potential energy surface with only
real frequencies. The B3LYP functional and the 6-31G(d,p)
basis set are used in all the geometry optimizations and fre-
quency calculations.
To obtain accurate interaction schemes, single-point en-
ergy was calculated using the ωB97X-D functional including
dispersion corrections on the B3LYP/6-31G(d,p) optimized ge-
ometries. The ωB97X-D functional is promising for main
group thermochemistry, kinetics and non-covalent interac-
tion;68,69 and the 6-311+G(2df,2p) basis set was used. The
ωB97X-D functional was recently found to perform very well
for the adsorption and reactions on zeolites.70
The dispersion corrected adsorption energy (Eads-d) was
calculated using eqn (1), where Etot-d(HCP/Z) is the dispersion
corrected total energy for a zeolite with absorbed species in
its equilibrium geometry, Etot-d(Z) is the dispersion corrected
total energy of a zeolite, and Etot-d(HCP) is the dispersion
corrected total energy of the free hydrocarbon species in the
gas phase. The adsorption energy without dispersion correc-
tion (Eads) was calculated using a similar method as in
eqn (1), but the Etot value used is the total energy using
B3LYP/6-31G(d,p). The adsorption energy without dispersion
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correction (Eads') using ωB97X/6-311+G(2df,2p) was also calcu-
lated, and the results are shown in Table S1.†
Eads‐d = Etot‐d(HCP/Z) − Etot‐d(HCP) − Etot‐d(Z)
3. Results and discussion
3.1. Adsorption enthalpies of polyMBs
The initial configurations of each polyMB in the zeolite pores
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−1.30 eV, respectively). Over H-BEA, 5MB has the strongest
adsorption enthalpy (−1.37 eV). Over H-ZSM-5, 1,3,5-3MB and
1,2,3,5-4MB have the strongest adsorption enthalpies (−1.42
(1) and −1.41 eV, respectively). Over H-ZSM-22, both p- and
m-xylenes have the strongest adsorption enthalpies (−1.32
and −1.37 eV, respectively), while 6MB has a very positive ad-
sorption energy (1.56 eV), indicating its considerable repul-
sive interaction. It is interesting to note that the strongest ad-
sorption enthalpies of polyMBs over the four zeolites are
within 1.33–1.42 eV.

are multitudinous, but their energetic differences are small

(within 0.2 eV). The optimized configurations with the stron-
gest adsorption enthalpies are used in this work. Table 1 lists
the adsorption enthalpies of polyMBs at 525 K. On the basis
of the adsorption enthalpies of some polyMBs in a H-FAU ze-
olite calculated through experiment at 525 K,71 we validated
our method on the basis of a 61T-FAU cluster model at first.
As given in Table 1, the dispersion corrected adsorption en-
thalpies agree well with the experimental data and the corre-
lation coefficient (R 2) is 0.895, while those without dispersion
correction are much smaller. This indicates that it is crucial
to include dispersion correction for calculating the adsorp-
tion of polyMBs in the zeolites. It also indicates that disper-
sion correction depends on the size of the adsorbed mole-
cules; the larger the adsorbed molecule, the larger the
correction, e.g. the dispersion correction is 0.45 eV for ben-
zene, while 1.07 eV for 6MB. Benchmark studies with even
larger cluster models and different methods show that our
current model is sufficient enough in reproducing the ad-
sorption enthalpy of hexamethylbenzene in the H-FAU zeolite
in comparison with the experimental data. It is also found
that increasing the size of the model for H-ZSM-5 does not af-
fect the adsorption enthalpy of hexamethylbenzene signifi-
cantly (Table S2†). Therefore, we used our current models in
discussing the adsorption enthalpies of polymethylbenzene
over different zeolites.
Based on the agreement between the theoretical and ex-
perimental results over H-FAU, we computed the adsorption
enthalpies over other zeolites. Over H-SAPO-34, 1,2,4,5-4MB
and 5MB have the strongest adsorption enthalpies (−1.33 and
3.2. Free energies of polyMB formation
To identify the formed polyMB intermediates in the zeolite
pores, it is crucial to consider their Gibbs free energy (ΔRGn)
of formation on the basis of the reaction eqn (2), where
methanol is the only starting material and interacts with zeo-
lite (ZOH) leading to the formation of polyMBs, and n can be
considered as the number of the methyl groups on the ben-
zene ring. To balance the mass, we simply used molecular H2
as the gas product; however, the contribution of H2 is a con-
stant and does not change with the change in the methyl
groups. This will not affect the relative energies and also does
not affect our results and conclusion. The computed ΔRGn
value allows the discrimination of the preferred intermediate,
i.e., the more negative the ΔRGn value, the more preferred the
formed intermediate. Table 2 shows the computed free ener-
gies of formation at 725 K, and this is because the typical
MTO reaction conditions are 625–725 K. The temperature
effect at 525 and 725 K on the stability of the polymethyl-
benzenes is calculated and analyzed. The same trend is
found, and the gap is basically identical (Fig. S1†). Thus, the
result at 725 K is used in this work.
ZOH + (6 + n)CH3OH(g) = ZOH − C6H6−n(CH3)n
+ (6 + n)H2O(g) + 3H2(g) (2)
Within the four zeolites, the free reaction energies of ben-
zene formation are very close, indicating that benzene is a
rather small molecule, and its formation is not significantly
affected by the framework of these zeolites. The same results

Table 1 Adsorption enthalpies (eV) with (Hads-d) and without (Hads; in parenthesis) dispersion correction at 525 K

PolyMBs H-SAPO-34 H-BEA H-ZSM-5 H-ZSM-22 H-FAU H-FAU (expt)71

Benzene (B) −0.77 (−0.16) −0.80 (−0.20) −0.88 (−0.22) −1.0 (−0.07) −0.74 (−0.29) −0.78
Toluene (MB) −0.91 (−0.15) −0.94 (−0.24) −1.06 (−0.23) −1.16 (−0.05) −0.88 (−0.31) −0.85
p-Xylene (p-2MB) −1.06 (−0.12) −1.09 (−0.27) −1.20 (−0.17) −1.32 (−0.06) −0.97 (−0.35) −0.93
m-Xylene (m-2MB) −1.07 (−0.13) −1.12 (−0.25) −1.26 (−0.21) −1.37 (−0.06) −0.98 (−0.35)
o-Xylene (o-2MB) −1.0 (−0.08) −1.07 (−0.27) −1.17 (0.01) −1.03 (0.35) −0.99 (−0.34)
Mesitylene (1,3,5-3MB) −1.17 (0.07) −1.13 (−0.23) −1.42 (−0.19) −0.79 (0.91) −1.06 (−0.36) −1.01
1,2,4-Trimethylbenzene (1,2,4-3MB) −1.19 (−0.04) −1.16 (−0.23) −1.23 (−0.01) −1.20 (0.34) −1.06 (−0.35)
1,2,3,5-Tetramethylbenzene (1,2,3,5-4MB) −1.07 (0.3) −1.22 (−0.18) −1.41 (0.11) −0.31 (1.66) −1.08 (−0.29) −1.17
1,2,4,5-Tetramethylbenzene (1,2,4,5-4MB) −1.33 (−0.02) −1.21 (−0.14) −0.68 (0.92) −0.89 (1.01) −1.10 (−0.28)
1,2,3,4-Tetramethylbenzene (1,2,3,4-4MB) −1.17 (0.22) −1.14 (−0.07) −0.55 (1.08) −0.30 (1.57) −0.98 (−0.25)
Pentamethylbenzene (5MB) −1.30 (0.29) −1.37 (−0.18) −0.81 (1.04) −0.04 (2.19) −1.27 (−0.28)
Hexamethylbenzene (6MB) −0.90 (1.01) −1.27 (0.13) −0.09 (2.35) 1.56 (4.26) −1.24 (−0.17) −1.30
Maximum diameter (Å)a 7.4 6.7 6.4 5.7 11.2
a
http://www.iza-structure.org/databases.

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Table 2 Computed Gibbs free energies of the formation reaction of polyMB (ΔRGn, eV, based on eqn (2)) and their sequential difference between (n +
1)MB and nMB (ΔΔRG, eV, based on eqn (3), in square brackets)

Hydrocarbons H-SAPO-34 H-BEA H-ZSM-5 H-ZSM-22 H-FAU

B −4.02 [0.00] −4.07 [0.00] −4.16 [0.00] −4.08 [0.00] −4.07 [0.00]
MB −4.89 [−0.87] −4.82 [−0.75] −4.89 [−0.73] −4.85 [−0.77] −4.85 [−0.78]
p-2MB −5.69 [−0.80] −5.58 [−0.76] −5.59 [−0.70] −5.70 [−0.85] −5.54 [−0.69]
m-2MB −5.51 [−0.62] −5.44 [−0.62] −5.71 [−0.82] −5.71 [−0.86] −5.57 [−0.77]
o-2MB −5.63 [−0.74] −5.35 [−0.53] −5.22 [−0.33] −5.12 [−0.27] −5.47 [−0.67]
1,3,5-3MB −6.02 [−0.51] −6.09 [−0.65] −6.43 [−0.72] −5.48 [+0.23] −6.33 [−0.76]
1,2,4-3MB −6.34 [−0.65a] −6.31 [−0.73] −6.26 [−0.67] −5.94 [−0.24] −6.24 [−0.70]
1,2,3,5-4MB −6.78 [−0.44] −7.02 [−0.71] −6.93 [−0.67] −5.57 [+0.37] −6.89 [−0.65]
−7.03 −6.97 [−0.66] −6.03 [+0.23] −6.16 −6.77
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1,2,4,5-4MB [−0.69] [−0.22] [−0.53]

1,2,3,4-4MB −6.77 [−0.43] −6.86 [−0.55] −5.78 [+0.48] −5.38 [+0.56] −6.64 [−0.40]
5MB −7.22 [−0.44; −0.19b] −7.58 [−0.56; −0.61b] −6.43 [+0.50] −5.53 [+0.63] −7.28 [−0.51]
6MB −7.06 [+0.16] −7.78 [−0.20] −5.87 [+0.56] −3.97 [+1.56] −7.73 [−0.45]
a
−0.65 eV is the difference value between p-2MB and 1,2,4-3MB. b
−0.44 eV is the difference value between 1,2,3,5-4MB and 5MB; −0.19 eV is
the difference value between 1,2,4,5-4MB and 5MB.

are also found for toluene, where the largest difference is
only 0.07 eV.
From the xylene isomers, shape dependence on the cage
size of the zeolites is observed, especially for H-ZSM-5 and
H-ZSM-22. H-ZSM-5 favors m-xylene (−5.71 eV), by 0.49 eV
higher than o-xylene (−5.22 eV); H-ZSM-22 favors both m- and
p-xylenes (−5.71 and −5.70 eV), by 0.59 and 0.58 eV higher
than o-xylene (−5.12 eV); H-SAPO-34 and H-BEA favor p-xylene
(−5.69 and −5.58 eV, respectively); while three xylene isomers
show similar free reaction energies in H-FAU. Although the
most favorable xylenes are not the same isomer, their free en-
ergies are very close, which indicates that their formation is
not significantly affected by the framework of these zeolites.
For both 3MB isomers, H-ZSM-5 and H-FAU favors 1,3,5-
3MB (−6.43 and −6.33 eV), while 1,2,4-3MB is more favored
over H-SAPO-34 (−6.34 eV), H-BEA (−6.31 eV) and H-ZSM-22
(−5.94 eV). It is found that the free energy of 3MB over
H-ZSM-22 is lower than those of the other zeolites, indicating
the larger repulsive interaction between the framework and
3MB. The same results are also found for the 4MB isomers.
H-ZSM-5 favors 1,2,3,5-4MB (−6.93 eV), by 0.90 eV higher
than 1,2,4,5-4MB (−6.03 eV), while H-SAPO-34 (−7.03 eV) and
H-ZSM-22 (−6.16 eV) favor 1,2,4,5-4MB, and H-BEA as well as
H-FAU favors both 4MB isomers.
With increasing size, higher polyMBs experience strong re-
pulsive interactions counterbalancing vdW stabilization. For
5MB, H-BEA has the largest free energy (−7.58 eV), followed
by H-FAU (−7.28 eV) and H-SAPO-34 (−7.22 eV), while those of
H-ZSM-5 (−6.43 eV) and H-ZSM-22 (−5.53 eV) are much lower.
For 6MB, H-BEA has the largest free energy (−7.78 eV),
followed by SAPO-34 (−7.06 eV), while those of H-ZSM-5
(−5.87 eV) and H-ZSM-22 (−3.97 eV) are much lower.
All the computed Gibbs free energies of the formation re-
actions of polyMBs show their thermodynamic probability.
Since the formation of polyMBs is considered as sequential
methylation reactions (Scheme 1), we become interested in
the sequential Gibbs free energy change [ΔΔRG = ΔRGn+1 −
ΔRGn] from ZOH-C6H6−n(CH3)n to ZOH-C6H6−n−1(CH3)n+1, as
shown in eqn (3). Indeed, such sequential Gibbs free energy
change can reveal the methylation probability, i.e., a negative
ΔΔRG value implies the formation of (n + 1)MB to be thermo-
dynamically possible and favorable starting from nMB, a pos-
itive ΔΔRG value reveals the formation of (n + 1)MB to be
thermodynamically less or not possible in the zeolites, and a
ΔΔRG value close zero reveals the possible co-existence and
equilibrium of (n + 1)MB and nMB in a zeolite.
ZOH − C6H6−n(CH3)n + CH3OH(g) = ZOH − C6H6−n−1(CH3)n+1
+ H2O(g) (3)
Within the four zeolites, the formation of toluene from
benzene and the formation of xylenes from toluene are ther-
modynamically favorable (Table 2); therefore, the transforma-
tion from benzene via toluene to xylenes should be easy and
they do not represent stable intermediates in the zeolites.
Starting from toluene, the more favorable methylation routes
are shown in Scheme 2.
In H-SAPO-34, both p-2MB and o-2MB isomers are more
favorable from toluene [ΔΔRG = −0.80 and −0.74 eV, respec-
tively], and they can be transformed into the next more favor-
able 1,2,4-3MB [ΔΔRG = −0.65 and −0.71 eV, respectively]. The
next more favorable intermediate is 1,2,4,5-4MB starting from
1,2,4-3MB [ΔΔRG = −0.69 eV]. Considering the small energy
changes from 1,2,4,5-4MB to 5MB (−0.19 eV), and from 5MB
to 6MB (+0.16 eV), all three intermediates might be formed
in equilibrium and 5MB should be the major isomer.
In H-BEA, the most favored methylation route for the for-
mation of polyMBs is p-2MB → 1,2,4-3MB → 1,2,3,5-4MB and
1,2,4,5-4MB; 5MB and 6MB might be formed in equilibrium,
and 6MB should be the major isomer, since the formation of
6MB is more favorable by 0.20 eV.
In H-ZSM-5, the most favored methylation route for the
formation of polyMBs is m-2MB → 1,3,5-3MB → 1,2,3,5-4MB.
However, the formation of 5MB and 6MB is endergonic by
0.50 and 0.56 eV, respectively, and therefore not accessible.
The most favorable intermediate should be 1,2,3,5-4MB.

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Scheme 2 Most favored methylation route for the formation of polyMBs on the basis of the reaction free energies (eV) in eqn (2) on different
zeolites.
In H-ZSM-22, the most favored methylation route for the
formation of polyMBs is p/m-2MB → 1,2,4-3MB → 1,2,4,5-
4MB. However, the formation of 5MB and 6MB is endergonic
by 0.63 and 1.56 eV, respectively, and not accessible. There-
fore, the most favorable intermediate should be 1,2,4,5-4MB
at equilibrium.
In H-FAU, the situation is very clear and simple, since all
the methylation steps are thermodynamically favorable
(Table 2). The large Gibbs free energy (−0.45 eV) of formation
of 6MB shows that 6MB is the most favorable intermediate at
equilibrium, and there is much less confinement of the cage
on the one hand. On the other hand, the formed 6MB should
be further transformed into polycyclic aromatic hydrocarbons.
The computed free reaction energies show good correla-
tion between the polyMB probability and the cage size. For
example, over the large-sized H-SAPO-34 (7.37 Å) and H-BEA
(6.68 Å), 5MB and 6MB are favorable in equilibrium, while
over the medium-sized H-ZSM-5 (6.36 Å) and small-sized
H-ZSM-22 (5.71 Å), 4MB is the favorable intermediate.
3.3. Kinetics of polyMB methylation
In addition to the computed thermodynamic probability of
polyMB formation on the basis of reaction free energies
starting from methanol, the free energy barriers and reaction
free energies of methylation and gem-methylation of polyMBs
using surface methoxy groups for methylation72–74 are also
calculated to investigate the activity of HCP species of poly-
MBs (Fig. 2 and Table 3). It is noted that methylation of nMB
to (n + 1)MB includes geminal methylation and deproton-
ation. In Fig. 2, the deprotonation step is skipped because of
the much lower energy barriers12,56 where the potential en-
ergy surface of (n + 1)MB can also be seen. Since methylation
Catal. Sci. Technol.
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Catalysis Science & Technology
and gem-methylation are parallel and competitive, their selec-
tivity can be qualitatively estimated by their kinetic accessibil-
ity and thermodynamic stability, i.e., the lower the barrier
and the stronger the formation energy, the more selective the
reaction. Benchmark calculations for the free energy barrier
and reaction enthalpy for the reaction from 4MB to 5MB over
H-ZSM-5 by using larger cluster models and different
methods validated our current model (Table S3†). In addi-
tion, we also compared our current free energy barriers for
the stepwise methylation and gem-methylation over different
zeolites with available data in the literature (Table S4†). In
several cases, large differences are found, and this is mainly
due to the differences in models and methods, such as func-
tional, basis set, dispersion correction, thermal correction
and entropy contribution, as well in reaction paths such as
concerted or stepwise. The critical bond distances of the tran-
sition states of methylation and gem-methylation are given in
Table S5.†
In H-BEA, the methylation free energy barrier from 2MB
to 3MB as well as from 3MB to 4MB is 1.43 and 1.23 eV, re-
spectively, and they are virtually the same as those of the
competitive gem-methylation to 3MB+ and 4MB+ (1.43 and
1.31, respectively). However, the methylation from 2MB to
3MB as well as from 3MB to 4MB is much more thermody-
namically favorable (−0.73 and −0.83 eV, respectively) than
gem-methylation (0.35 and 0.13 eV, respectively), which indi-
cates that the reverse reaction of gem-methylation is more fa-
vorable. The methylation free energy barrier from 4MB to
5MB as well as from 5MB to 6MB is 1.17 and 1.07 eV, respec-
tively, and they are lower than those of the competitive gem-
methylation to 5MB+ and 6MB+ (1.61 and 1.50 eV, respec-
tively). In addition, the methylation from 4MB to 5MB as well
as from 5MB to 6MB is more thermodynamically favorable
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Fig. 2 Potential energy surfaces on the basis of activation free
energies ΔG ≠ and reaction free energies ΔGr at 725 K for polyMB
methylation (nMB → (n + 1)MB) and gem-methylation (nMB → (n + 1)
MB+) using surface methoxy groups for methylation.
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(−0.74 and −0.46 eV, respectively) than gem-methylation (0.04
and −0.06 eV, respectively). The gem-methylation of 6MB to
7MB+ requires a free energy barrier of 1.23 eV and is exer-
gonic by 0.29 eV. Thus, 6MB should be the more active spe-
cies in the aromatic cycle for the gem-methylation reaction to
form 7MB+. The potential energy surface in Fig. 2 shows that
methylation is more kinetically and thermodynamically favor-
able than competitive gem-methylation from 2MB to 6MB;
6MB is the most favored intermediate and 7MB+ is the most
favored geminal methylated intermediate.
In H-SAPO-34, methylation is more kinetically and thermo-
dynamically favorable than competitive gem-methylation from
2MB to 5MB, and the methylation and gem-methylation of
5MB are competitive. Therefore, both 5MB and 6MB should
be the active species in the aromatic cycle for the gem-
methylation reactions to form 6MB+ and 7MB+.
For H-ZSM-5, methylation is more favorable from 2MB to
4MB, but gem-methylation is more kinetically and thermody-
namically favorable than competitive methylation from 4MB
and 5MB. Since 4MB is the most favored intermediate, and
5MB and 6MB are higher in energies and are not kinetically
and thermodynamically accessible, 4MB should be the active
species in the aromatic cycle for the gem-methylation reaction
to form 5MB+, similar to H-ZSM-22.
3.4. Confinement effect on thermodynamic and kinetic
energies
Apart from the analysis of the reaction free energies, the
contributions of entropy (TΔS) at 725 K, electrostatic poten-
tial (ΔEe) and long-range van der Waals dispersion (ΔEdis)
(Table S6†) are also interesting for investigating the confine-
ment effect of the zeolite frameworks on polyMB formation,
where ΔEdis is calculated as the difference of the electronic
energies between ωB97X-D/6-311+G(2df,2p) and ωB97X/6-
311+G(2df,2p).
As shown in Fig. 3, the individual contributions of each
term in the four zeolites are similar for low polyMBs, but dif-
fer to a large extent for high polyMBs. As we know, the dis-
persion correction energy varies directly with C/R 6, where R
represents the distance between a pair of atoms, and C repre-
sents the correction coefficient. Therefore, the shorter the
distance between a pair of atoms, the larger the dispersion
correction energy. Following the decrease in the zeolite chan-
nel size in the order H-BEA > H-SAPO-34 > H-ZSM-5 > H-
ZSM-22, the contributions of ΔEdis increase because of the
larger stabilization by the long-range electrostatic potential
on high polyMBs in the small channel; however, this stabili-
zation conversely leads to a decrease in TΔS, while ΔEe rap-
idly decreases because of the strong steric hindrance between
the framework and high polyMBs in the small channel. For
testing the influence of a relaxed model on steric effect, a
larger 8T relaxed model over H-ZSM-5 was used. The com-
puted Gibbs free reaction energy of hexamethylbenzene for-
mation is lower (−6.05 eV), which corresponds to a change of
only 3%, indicating that the size of the relaxed model shows
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Table 3 Calculated free energy barrier (ΔG ≠), enthalpy barrier (ΔH ≠, eV) and entropy loss (−TΔS ≠, eV) as well as reaction free energies ([ΔGr], in square
brackets) at 725 K of methylation (nMB → (n + 1)MB) and gem-methylation (nMB → (n + 1)MB+) of polyMBs. Here, 2MB is p-2MB; 3MB is 1,2,4-3MB;
4MB is 1,2,3,5-4MB in H-SAPO-34, H-BEA and H-ZSM-5, while 1,2,4,5-4MB in H-ZSM-22; 3MB+ is a 1,4,4-trimethylcyclohexa-2,5-dien-1-ylium ion;
4MB+ is a 1,3,4,4-tetramethylcyclohexa-2,5-dien-1-ylium ion; 5MB+ is a 1,3,4,4,5-pentamethylcyclohexa-2,5-dien-1-ylium ion in H-SAPO-34, H-BEA and
H-ZSM-5, while a 1,2,4,4,5-pentamethylcyclohexa-2,5-dien-1-ylium ion in H-ZSM-22

H-SAPO-34 H-BEA H-ZSM-5 H-ZSM-22

ΔG ≠ [ΔGr] ΔH ≠ −TΔS ≠ ΔG ≠ [ΔGr] ΔH ≠ −TΔS ≠ ΔG ≠ [ΔGr] ΔH ≠ −TΔS ≠ ΔG ≠ [ΔGr] ΔH ≠ −TΔS ≠
2MB → 3MB 1.71 [−0.65] 1.43 0.28 1.43 [−0.73] 1.18 0.25 1.25 [−0.90] 1.03 0.22 0.92 [−0.95] 0.82 0.10
2MB → 3MB+ 1.71 [0.85] 1.45 0.26 1.43 [0.35] 1.12 0.31 1.23 [0.34] 1.02 0.21 1.15 [0.37] 1.08 0.08
3MB → 4MB 1.68 [−0.36] 1.47 0.19 1.23 [−0.83] 1.06 0.17 1.32 [−0.96] 1.16 0.16 0.84 [−0.84] 0.88 −0.04
3MB → 4MB+ 1.59 [0.38] 1.36 0.23 1.31 [0.13] 0.97 0.34 1.09 [−0.09] 0.92 0.17 1.47 [0.34] 1.37 0.10
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4MB → 5MB 1.74 [−0.52] 1.52 0.22 1.17 [−0.74] 0.96 0.21 1.59 [0.24] 1.27 0.32 1.34 [−0.13] 1.10 0.24
4MB → 5MB+ 1.84 [0.16] 1.53 0.31 1.61 [0.04] 1.20 0.41 1.17 [−0.27] 1.23 0.30 1.10 [−0.13] 0.92 0.18
5MB → 6MB 1.71 [0.18] 1.49 0.22 1.07 [−0.46] 0.92 0.15 1.39 [0.32] 1.24 0.15 1.60 [−0.17] 1.42 0.18
5MB → 6MB+ 1.81 [0.09] 1.57 0.24 1.50 [−0.06] 1.15 0.35 0.99 [−0.38] 0.86 0.13 0.90 [0.09] 0.83 0.07
6MB → 7MB+ 1.51 [0.14] 1.34 0.17 1.23 [−0.29] 0.93 0.30 1.04 [−0.44] 0.91 0.13 1.02 [−0.06] 0.93 0.09

goal is to evaluate the confinement effect of the framework

Fig. 3 Individual contributions from entropy (TΔS), electronic
dispersion energy (ΔEdis) and electrostatic energy (ΔEe) at 725 K.
a little influence on steric effect, and the current model sys-
tems are reasonable to describe the formation of polyMBs in
zeolites. In addition, with the size increase of polyMBs, the
degree of individual energies varied as follows: ΔEe > TΔS >
ΔEdis.
Apart from the analysis of activated energies, the enthalpy
barriers and entropy barriers of polyMB methylation are also
analyzed (Table 3). In H-SAPO-34, the intrinsic enthalpy bar-
riers are higher than those of other zeolites owing to the in-
sufficient stabilization of transition states in the large cage
pores. Comparing the enthalpy barriers, the entropy barriers
in the four zeolites are small.
4. Conclusions
on the stability and activity of the specific hydrocarbon pool
species. All the intermediates were optimized and character-
ized at the B3LYP/6-31G(d,p) level. To take dispersion forces
into account, we used the long-range-corrected ωB97XD/6-
311+G(2df,2p) hybrid functional to calculate the energies on
the B3LYP/6-31G(d,p) optimized geometries.
On the basis of the agreement between the experimental
and theoretical adsorption enthalpies of several methyl-
benzenes over H-FAU, it is found that it is very necessary to
include the van der Waals dispersion correction in determin-
ing the space confinement and electrostatic stabilization of
the zeolite framework. Such agreements reasonably validate
our applied cluster models and computational methods.
Without dispersion correction, the computed adsorption en-
ergies are pathologically lower than the experimental values.
The computed free energy of the methylation reactions
shows the correlation between the polymethylbenzene proba-
bility and the cage size. Over the large-sized H-SAPO-34 and
H-BEA, pentamethylbenzene and hexamethylbenzene are favor-
able in equilibrium, while over the medium-sized H-ZSM-5 and
small-sized H-ZSM-22, tetramethylbenzene is the favorable
intermediate. These stable polymethylbenzenes are the precur-
sors for the formation of geminal methylated cationic interme-
diates on the basis of kinetic and thermodynamic analyses.
The same trend of thermodynamics and kinetics on the
favorable intermediates validates the applicability of Gibbs
free reaction energies to estimate the primary component of
the intermediates in the various zeolites. All these differences
among these zeolites with different pore sizes show their
enhanced confinement effects, which is mainly influenced by
the short-range electrostatic potential including stabilization
and repulsion.

The thermodynamics and kinetics of the formation of poly- Acknowledgements

methylbenzene intermediates over H-SAPO-34, H-BEA, H-
ZSM-5 and H-ZSM-22 with different shapes and pore sizes are We are grateful for the financial support from the National
investigated on the basis of density functional theory includ- Basic Research Program (2011CB201406), the National Natu-
ing van der Waals dispersive corrections (ωB97XD). Our ral Science Foundation of China (21573270, 21103216,

Catal. Sci. Technol. This journal is © The Royal Society of Chemistry 2016

Catalysis Science & Technology
21273263 and 21273264), the Natural Science Foundation of
Shanxi Province of China (2013021007-3), the Coal Based Low
Carbon Joint Foundation of NSFC and Shanxi Province of
China, U1510104) and the CAS/SAFEA International Partner-
ship Program for Creative Research Teams. The computa-
tional results were obtained from the ScGrid of the Super-
computing Center, Computer Network Information Center of
Chinese Academy of Sciences.
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