Article

pubs.acs.org/cm

Swelling and Interlayer Chemistry of Layered MWW Zeolites MCM-22

and MCM-56 with High Al Content
Wieslaw J. Roth,*,, Jiri C ejka,, Roberto Millini, Erica Montanari, Barbara Gil, and Martin Kubu

Faculty of Chemistry, Jagiellonian University in Krakow, ul. Ingardena 3, 30-060 Krakow, Poland

J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of Czech Republic, Dolejskova 2155/3, 182 23 Prague 8, Czech
Republic

King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

Renewable Energy & Environmental Laboratories, Eni S.p.A., Via Fauser 4, I-28100 Novara, Italy

Physical Chemistry Dept., Downstream Laboratories, Eni S.p.A., Via F. Maritano 26, I-20097 San Donato Milanese, Italy
*
S Supporting Information

ABSTRACT: Swelling of layered zeolite precursors such as

MCM-22P with cationic surfactants at high pH is the key step in
their subsequent conversion into expanded lamellar materials by
pillaring and delamination. Increasing Al content in the precursors
can yield more active catalysts but aects their swelling eciency
especially at lower temperature, which was reported as favorable
for layer structure preservation with more siliceous MCM-22P.
The latter, a (multi)layered precursor, was investigated in this work
and showed inadequate swelling of its high-Al representatives with
organic hydroxide/surfactant mixtures and especially when NaOH
is the source of high pH. In contrast, the unilamellar MCM-56 was
found to swell readily at room temperature with various hydroxide
sources, and notably with NaOH, in combination with the
surfactant. The observed dierences between MCM-56 and
MCM-22P, especially with regard to swelling with NaOH, are attributed to the fundamentally dierent nature of their layer
surface and interlayer linking. The former has surface terminated with AlOHNa+ moieties, producing weak connections,
instead of the pyramidal SiOHs populating the MCM-22P surface and forming interlayer H-bonding. The methods used for
validating the swelling and product characterization included XRD, nitrogen sorption, IR spectroscopy and TEM imaging. The
microscopy conrmed, by direct visualization, the extensive but not complete swelling of MCM-56, which can be enhanced by
treatment at higher temperature.

INTRODUCTION
Zeolites are well-known and widely used in commercial
applications as exceptional heterogeneous catalysts1,2 and
selective sorbents3 with extraordinary properties arising from
their framework structures with uniform micropores. They had
been known exclusively as networks extended continuously in
3D until framework MWW revealed formation via a layered
precursor, denoted MCM-22P4,5 and also ERB-1.6 Subse-
quently other frameworks such as ferrierite,7 sodalite,8 and
recently MFI,9 showed formation of layered forms as well.
There are now approximately 15 frameworks, out of over 200
known, recognized to produce layered precursors and other
lamellar forms10 consisting of monolayers with thickness of
approximately 13 nm.4,6,7 This was a signicant fundamental
development but it also has very benecial practical side. In
contrast to virtually immutable 3D zeolite structures, their 2D
lamellar derivatives can be modied11,12 into new architectures
and compositions like the well-established 2-dimensional
solids.1315 In particular, they can be converted into more
open materials with enhanced accessibility to zeolitic active
centers,1619 which is often quite limited in the conventional
3D frameworks. A more general concept of zeolite structures,
integrating the 3D and 2D forms as a two-dimensional
representation, has been proposed.10,20 The starting layered
zeolites have been obtained by three dierent pathways:
bottom-up direct syntheses using organic templates21 that are
usually discovered by accident but recently also by design9,22
and the novel top-down process from other frameworks
conducive to selective degradation.2326
The principal transformations of layered zeolite precursors
are illustrated in Figure 1 based on the framework MWW, and
in principle they are applicable to all others. The intercalation
of large organic molecules such as surfactants, which is called
swelling,27 is the rst step toward generation of expanded
Received: March 19, 2015
Revised: June 9, 2015

XXXX American Chemical Society A DOI: 10.1021/acs.chemmater.5b01030

Chem. Mater. XXXX, XXX, XXXXXX
Chemistry of Materials Article

was proposed as an alternative allowing better layer

Figure 1. Principal transformations reported for MCM-22P and
MCM-56 with representative interlayer d001 spacing distances from
XRD. Filled pores indicate presence of SDA molecules. The idealized
representation of MCM-22P as ordered stacks of MWW layers is
explained in the rst section below.
structures with permanently separated layers by processes like
pillaring and delamination.28 It is typically the most dicult and
crucial stage that in the case of 2D zeolites requires
unprecedented severity, namely, high pH of 12.5 and above.29
This calls for a particular attention because, in addition to the
possibility of incomplete swelling, other undesirable eects like
partial layer dissolution with accompanying degradation and
even formation of mesophases like the M41S materials30,31 may
occur.32 The dierence between swelling and the undesired
reactions may be dicult to detect. There are in fact quite a few
literature reports that erroneously claim zeolite swelling and
successful pillaring or delamination. The breaking of interlayer
hydrogen bonding between the layers is considered the main
reason for the needed high severity, i.e., pH, of the swelling
conditions.33,34
Swelling was initially developed as a high temperature
process carried out at near 100 C (using MCM-22P with a
high Al content).27 Later on, room temperature swelling (RT)
preservation and avoidance of degradation.35 It was developed
with precursors having relatively low Al content. Subsequent
catalytic evaluation postulated that layer preservation (through
swelling at RT) resulted in a better catalytic activity of the
MCM-36 obtained after pillaring of swollen precursors.36
Although the best MCM-36 performance was observed with
MCM-22P swollen at RT it was also the most Al-rich precursor
used in this study. Direct comparison of MCM-36 samples
prepared from the same precursor swollen at RT and higher
temperatures indicated very similar catalytic performance. This
observation of minimal activity dierence proves that the
choice of lower (RT) vs higher temperature has secondary
inuence on catalytic activity, provided that the swelling
eciency is comparable.36 At the same time it was evident that
the initial higher Al content in the starting MCM-22P was the
primary source of higher catalytic activity in its derivatives. The
increasing activity with Al content is a general trend for
zeolites37 and therefore it is important to understand the
behavior of representatives with maximized Al content,
although it does not ensure the best ultimate performance.
The framework MWW is so far unique by oering several
modiable layered forms with high Al content down to Si/Al
around 10/1.38 They are also available via convenient
straightforward syntheses amenable to a scale-up. As the
essentially only example of a layered precursor that can achieve
high Al content, MCM-22P shows that the swelling eciency is
strongly inuenced by Si/Al ratio of the layers.39 This was also
observed40 in the preparation of ITQ-2, which exhibited lower
BET area and pore volume with increasing Al content of the
precursor. In addition, mild swelling conditions were found to
be insucient to enable ITQ-2 formation by delamination.35
This work concerns swelling and characterization of high-Al
MWW materials MCM-22P and MCM-56. The former shows
sensitivity to the type of hydroxide added to provide high pH in
the surfactant solution. In particular, NaOH, which would be
the most convenient reagent to use, is found to be very
ineective,29 while some of the organic quaternary hydroxides
allow only partial swelling. In contrast, MCM-56, which has
intrinsic high Al content,41 shows easy swelling under mild

Table 1. Summary of Preparation Conditions, Positions of Low Angle XRD Maxima (Cu K radiation, = 0.154178 nm) and
Textural Properties of the Studied Materialsa
XRDlow angle peak maximum
swollen pillared textural properties
alkalinity, MOH estd. swell 2 2 BET pore vol.
material swelling, MOH (mol/dm3) (%) (deg) d (nm) (deg) d (nm) (m2/g) (cm3/g)
MCM-22P + calc 6.5 1.36 520 0.34
MCM-22P + swell NaOH 0.54 0 6.0 1.47 N/A
TMA-OH 0.39 80 1.8 4.90 1.9 4.65 593 0.51
HD-OH/Cl 0.31 100 1.7 5.20 1.8 4.90 735 0.55
TPA-OH 0.40 10 1.8 4.90 N/A
TPA-OH 95C 0.40 50 1.8 4.90 N/A
MCM-56 + calc 419 0.53
MCM-56 + swell TPAOH/calc 0.51 100 1.75 5.04 N/A 499 0.60
NaOH 0.52 100 1.6 5.52 N/A
NaOH 0.66 100 1.6 5.52 1.8 4.90 697 0.59
HD-OH/Cl 0.16 100 1.55 5.69 1.7 5.20 676 0.85
HD-OH/Cl 99C 0.16 100 1.55 5.69 1.75 5.04 970 0.68
HD-OH/Cl 99C, hydr 0.16 100 1.55 5.69 1.8 4.90 851 0.57

a
HD = hexadecyltrimethylammonium.

B DOI: 10.1021/acs.chemmater.5b01030
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Chemistry of Materials
conditions even with the use of NaOH/surfactant. MCM-56 is
considered to be a unilamellar zeolite with MWW topology
comprising layers stacked disorderly without interlayer
connectivity, except for possible incidental silanol condensa-
tions.28,41,42 It crystallizes as a distinct intermediate during
preparation of the three-dimensional MCM-49 (high-Al
MWW) and must be intercepted at the right time in the
course of synthesis.41 If quenched prematurely or too late the
MCM-56 monolayers end up contaminated with either
unreacted amorphous solid or partially condensed (MCM-
49), respectively. For example, a recent article34 quotes MCM-
56 as consisting of 70% submerged layers, i.e., disordered or,
in our view, monolayers, and 30% condensed, i.e., equivalent to
MCM-49. This result can be attributed to overcrystallized
MCM-56 (synthesis too long), while the sample we use here is
judged to be close to the idealized MCM-56. The present
results show MCM-56 swelling readily without interference
from other cations, which contrasts the behavior of MCM-22P.
This supports its proposed unilamellar character and provides
new insights into the nature of MCM-56 and its formation,
which have been quite elusive so far.42,43
A study concerning preparation and testing of pillared
MCM-36 materials obtained from MCM-22P and MCM-56
but with dierent Al content has been reported recently.44 The
MCM-36 obtained from the former had much lower BET area,
which is indicative of inferior sample quality.
EXPERIMENTAL SECTION
Preparation of High-Al MCM-22. The preparation was described
earlier.39,43 It is similar to the MCM-56 synthesis below except for the
Si/Al of the gel equal to 15/1.
Preparation of MCM-56. MCM-56 was prepared according to the
published procedure.41,45 The synthesis mixture comprised water, 50%
NaOH solution, sodium aluminate (Riedel-de-Haen, 4045% Na2O,
5056% Al2O3), hexamethylenimine (HMI), and Ultrasil VN3 in the
following molar ratios: Si/Al = 11.5, OH/Si = 0.21, HMI/Si = 0.35,
water/Si = 19.2. The hydrothermal synthesis was carried out with
agitation in a Teon lined Parr reactor at 143 C. The crystallization
was interrupted after 29 h, sampled for crystallinity, and continued for
an additional 4 h. The product was isolated by ltration, washed with
water, and dried at 110 C.
Swelling of MCM-22P and MCM-56. The swelling solutions
were prepared using 25% aqueous solution of hexadecyltrimethylam-
monium chloride (HDTMA-Cl) either original or partially converted
to hydroxide (vide infra) with additions of the hydroxides of Na,
tetramethylammonium (TMA), or tetrapropylammonium (TPA) and
water. The calculated alkalinities are given in Table 1. Swelling was
typically carried out overnight at room temperature and in some cases
near boiling as indicated. Solids were isolated by centrifugation,
washing with water and decantation, two times, and dried at
temperatures no higher than 65 C.
The HDTMAhydroxide solution was obtained as previously
reported45 by contacting 100 g of the 25% solution of HDTMA-Cl
with 80 mL of anion exchange resin AG 1-X8. The slurry was slowly
stirred overnight and ltered. The [OH] concentration was
approximately 0.4 M.
Pillaring. Pillaring was carried out with 0.30.4 g of the dried
swollen solid in 20 mL of TEOS. The mixture was stirred and heated
under reux at 95 C for 24 h. The solid was isolated by centrifugation,
dried at room temperature, hydrolyzed in water (20 mL), and dried at
100 C. In one case no hydrolysis was applied. The nal product was
obtained upon calcination at 540 C for 48 h.
Characterization. The characterization by X-ray powder dirac-
tion was carried out using a Bruker AXS D8 Advance diractometer in
the ranges 110 and 350 2 with Cu K ( = 0.154178 nm)
radiation.
Article
Adsorption isotherms of nitrogen were determined at 196 C
using an ASAP 2020 (Micromeritics) volumetric apparatus as
described earlier.43 The detailed procedure is provided in the
Supporting Information.
The concentration of Lewis (LAS) and Brnsted (BAS) acid sites
was determined using adsorption of pyridine (Py, Sigma-Aldrich,
analytical grade) followed by IR spectroscopy (Tensor 27 from Bruker,
MTC detector, spectral resolution 2 cm1).43 Full details are available
in Supporting Information. Concentrations of Lewis and Brnsted acid
sites were evaluated from the intensities of bands at 1454 cm1 (LAS)
and at 1545 cm1 (BAS) after desorption at 250 C based on
absorption coecients determined in the laboratory using external
standards,46 (LAS) = 0.165 cm2/mol and (BAS) = 0.044 cm2/
mol.
27
Al NMR spectra were recorded as described earlier, using
APOLLO console (Tecmag) at the magnetic eld of 7.05 T
(Magnex).43 Additional details are in Supporting Information.
TEM investigations were carried out using a JEOL JEM 3010
instrument operating at 200 kV accelerating voltage, equipped with an
energy dispersive spectrometer (EDS) by Oxford (Isis). The powders
were embedded in epoxy resin, and 3540 nm thick sections were
obtained with a Reichert-Jung ULTRACUT ultramicrotome equipped
with a diamond knife.
RESULTS AND DISCUSSION
Since evaluation of the swelling eciency of dierent high-Al
MWW materials under various conditions is the main
experimental objective in this work the criteria used for this
are briey reviewed rst.20 Table 1 summarizes details of the
performed syntheses and treatments with physical character-
istics of the starting MWW materials and the products after
calcinations.
Criteria for Estimation of Swelling Eciency and the
Problem of MCM-22P Disorder. The evaluation of the
swelling eciency of MCM-22P is based on XRD and its four
specic features shown in Figure 2. In practice one can focus on
Figure 2. XRD patterns of MCM-22P treated with various swelling
mixtures (hexadecyltrimethylammonium chloride (HDTMA-Cl) +
MOH) and nitric acid with features for diagnosing the extent of
MCM-22P conversion.
just one: the disappearing separation between the original
(101) and (102) reections at 8 and 10 2, resulting in a
broad band without a dip/valley in the center. The other three,
i.e., new peaks at 5 and 1.7 nm ((001) and (003) reections)
and disappearance of the initial (002) reection at 6.5 2, are
known from experience to follow suit when the valley is absent.
For MCM-56 the broad band at 810 2 is its dening
C DOI: 10.1021/acs.chemmater.5b01030
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Chemistry of Materials
feature,41 which leaves only the (001) and (003) peaks as the
criteria for swelling evaluation. They provide only visual
semiquantitative measure and must be supplemented by a
more reliable test, which involves pillaring and BET surface area
determination. The BET area value indicative of satisfactory
swelling/pillaring is approximately 700 m2/g and higher. It is
the typical minimal value obtained when the XRD criteria,
especially the no-valley condition for MCM-22P swelling, are
fullled.
These criteria for complete or satisfactory swelling are not
synonymous with separating all layers in the sample. This is a
complex problem, which is further illustrated and discussed
based on TEM microscopy.
MCM-22P has been often described38 and is represented in
Figure 1 as having ordered stacking of its MWW layers with ca.
2.7 nm repeat. This apparent 3D order was postulated because
of the XRD pattern containing discrete interlayer reections
with nonzero h and/or k indices (i.e., hkl, with l and h or k
0),47 which implies periodic repeat in the stacking direction.
Other observations6 and techniques, like electron diraction
showing streaking along c*,48 and theoretical simulations,34
suggest limited order or even stacking faults. This is dicult to
quantify but is evidently quite limited in comparison to MCM-
56 and the other multilayered MWW materials EMM-10P,
which are distinguished by not having distinct (101) and (102)
reections like in MCM-22P. Because of this contrast in XRD
we will consider and represent MCM-22P as relatively ordered.
It will allow us to clearly dierentiate from the situation when
swelling of MCM-22P produces obliteration of any lateral
order/3D periodicity evidenced by the absence of (101) and
(102) reections in the properly swollen product. Interestingly,
as-made ERB-1 precursor can produce a 3D ordered structure
by intercalating [2,2,2]-azabicyclooctane.6
Swelling of High-Al MCM-22P. MCM-22P precursor
investigated in this work was prepared according to the most
common formulation resulting in Al content at or near the
possible maximum corresponding to Si/Al 11/149 (if more Al
is added the transition to MCM-56 occurs). As shown in the
literature it could be swollen with high eciency with surfactant
hydroxide at the temperature near 100 C.27 It is evident from
the XRD patterns (Figure 2) and the data in Table 1 that high-
Al MCM-22P is completely swollen by the surfactant hydroxide
solution at room temperature but in general its swelling
eciency varies depending on the type of cation-hydroxide
used to generate high pH in the swelling mixture. Even
increasing temperature may be only partially eective as
illustrated by the TPA-OH case. This contrasts the apparent
ease of swelling of the more siliceous MCM-22P reported
earlier35,36 and the MCM-56 described here. Especially notable
is the fact that the multilayered MCM-22P shows hardly any
swelling with the NaOH/surfactant solution. It is particularly
consequential as behavior contrasting that of MCM-56 and is
analyzed further in comparison to it in the next section.
The high Al content in MCM-22P aects its ability toward
the other transformations as exemplied by the already
mentioned delamination to ITQ-2.40 It is seen here to also
extend to the reaction with acid (XRD shown in Figure 2). This
treatment was reported previously with more siliceous samples
to cause collapse of the interlayer space (c-cell d-spacing change
from 2.7 to 2.5 nm) accompanied by considerable disorder,
which was concluded from the XRD pattern resembling MCM-
56. The product is called MCM-56 analogue,50,51 but it is still
unknown if it is the same as MCM-56; the present authors
D DOI: 10.1021/acs.chemmater.5b01030
Article
believe the answer is negative since the analogue may retain its
original interlayer H-bonding and possibly show swelling
behavior like MCM-22P rather than MCM-56.16 The XRD
shown in Figure 2 indicates that treatment of the studied here
high-Al MCM-22P with acid produces only partial collapse
and disorder, i.e., incomplete conversion into the MCM-56
analogue. This is evidenced by the remaining (002) reection at
6.5 2 and largely unchanged valley around 9 2, which
suggest that some parts of MCM-22P resisted the collapse. The
third transformation of MCM-22P shown in Figure 1 aording
the Interlayer Expanded Zeolite (IEZ) form,52 is also known to
diminish in eciency as the Al content increases toward lowest
Si/Al.53
The observed more dicult and incomplete conversion of
Al-rich MCM-22P, demonstrated in various conversions, is
hard to justify with specic explanation at this point. It may
result from dierent inherent chemistries during treatments and
transformations when more Al is present in the framework and
apparently at the surface. Alternatively, having more Al in the
MCM-22P synthesis mixture may favor formation of sites or
regions with regular TOT bridges, i.e., 3-D framework
fragments (MCM-49), instead of the hydrogen bonded silanol
pairs shown in Figure 3.33,34 This would preclude local swelling,
Figure 3. Dierence between Si and Al centers on the MWW layer
leading to MCM-22P34 and MCM-56, respectively. There are two
pyramidal sites per unit cell (72 T atoms) on each side. (MWW layer
rendition was adopted from IZA Web site).
IEZ-stabilization, and disordering that are possible for the
layered MCM-22P structure but not the condensed framework.
The corresponding materials would be eectively MCM-22P/
49 mixtures, and they may go undetected as such by XRD
unless suciently extensive47 or specically looked for. We also
observed time aging eects upon storage of high-Al precursors
demonstrated by some dry MCM-22P samples examined 2
years after preparation. They manifested much lower eciency
of swelling than the original fresh samples. This suggests the
possibility of spontaneous condensation of the interlayer
hydrogen bonded silanol bridges into TOT moieties
occurring upon prolonged storage.
Swelling of MCM-56Comparison to MCM-22P. In
contrast to MCM-22P, the swelling of MCM-56 having slightly
greater Al content occurs with high eciency irrespective of the
type of hydroxide used as was already seen in the previous
studies that included TMA-OH.45 It is conrmed and
signicantly extended here by the novel outcome of ecient
swelling occurring when NaOH is used in combination with the
surfactant to generate basic pH. It is notable and a bit surprising
because MCM-22P shows little swelling with this medium.
Chem. Mater. XXXX, XXX, XXXXXX
Chemistry of Materials
The dierence between NaOH/surfactant treatment of
MCM-22P and that of MCM-56 is shown in Figure 4. High-
Figure 4. XRD of MCM-56 and MCM-22P treated with various
swelling mixtures comprising the surfactant (HDTMA-Cl) plus a
hydroxide NaOH or HDTMA-OH; the corresponding pillared
derivatives are shown in blue.
Al MCM-22P is seen as practically unswollen because of the
intense maximum at 6 2, assigned to the (002) reection and
especially due to the almost unchanged valley at 9 2. The
presumed shift of the (002) reection to 6 2 from 6.5 2
indicates slight expansion of MCM-22P from the original d002-
spacing 1.36 to 1.47 nm. This expansion is attributed to
intercalation of surfactant molecules in lateral rather than
vertical orientation.54 It may be envisioned when interlayer
hydrogen bonds remain unbroken and continue holding the
layers together allowing intercalation but preventing larger
expansion, i.e., true swelling. The low angle region shows
increased broad scattering around 2 2, which may indicate
some swelling, but overall it is considered quite incomplete.
The rationale for the lack of MCM-22P swelling with
surfactants when NaOH or smaller organic bases were used
to generate high pH was proposed before.33 It presumed that
small cations diused faster or more eectively than surfactants
into the interlayer space, thus interfering in some way with the
swelling. Some new observations came to light since this
original proposal, especially that swelling may occur in the
presence of tetramethylammonium hydroxide TMA-OH (vide
supra).45 Overall, there is no simple explanation to account for
the observed behavior of MCM-22P toward swelling reagents.
MCM-56 shows facile swelling judging from XRD and pore
characteristics of its pillared products. It provides a convenient
alternative route to high-Al expanded MWW materials.
Rationalizing Dierences between MCM-56 and
MCM-22P. MCM-22P is more dicult to swell than MCM-
56 because its layers are strongly interconnected by hydrogen
bonds between surface silanols. These bonds must be severed
by high pH environment, but there is also dependence on the
cations present in the swelling mixture. MCM-56 comprises
disorganized monolayers with much weaker interlayer inter-
actions indicated by its much easier swelling. In both materials
the layers are assumed to have the same structure so there must
be a particular reason for their dierent disposition and
bonding. An explanation is provided by the fact that MCM-56
is formed from the MCM-22P synthesis mixture when its
eective Al content becomes increased (directly or through
increased alkalinity) near Si/Al 11/1.49,55 Furthermore,
MCM-56 is an intermediate that converts into fully condensed
Article
3D framework MCM-49 with Al content higher than in MCM-
22P, as the synthesis progresses. The observed switch from
MCM-22P formation to MCM-56 can be attributed to Al
incorporation on the layer in the T6 site (initially denoted T1)
because the Al amount is greater than can be accommodated in
the layer. The rst ve to six Al atoms per unit cell of MWW
(72 T atoms; Si/Al 12/1), if present, are accommodated
inside the layer judging from the amount of hexamethyleni-
mine in the intralayer 10R channels and the surface
pockets.47,56 The unique pyramidal T6 are populated
predominantly or entirely with silica atoms as surface Si
OH groups (see Figure 3). These silanols connect opposite
layers via H-bonding producing relatively rigid and stable
multilayered structure MCM-22P. The formation of MCM-56
occurs as the eective content of Al increases above 56 and
the extra Al atoms cannot be accommodated in the layer but
must populate the surface, i.e., the pyramidal T6-sites. This has
a chemical consequence since the replacement of SiOH
on the surface with AlOH generates a negative charge
(Al3+ replacing Si4+) and requires presence of a cation for
neutrality producing AlOHNa+ moieties. In agreement
with this is the fact that solid MCM-56 (and MCM-49) shows
higher content of Na and lower of the organic SDA,
hexamethylenimine (HMI), than MCM-22P. The latter
contains more HMI than acid sites (molar HMI > Al). This
excess is accommodated between layers as neutral molecules
forming the interlayer H-bonding with silanols. MCM-56
contains more Al than HMI, which requires additional
compensating cations, like Na+.
The observed contrast between swelling of MCM-56 and
MCM-22P and their dierent surface populations of Al
OHNa+ and SiOH, respectively, suggests that the former
moieties form a rather weak interlayer bond and, during MCM-
56 synthesis, thwart attachment of additional layers causing
disorder and monolayer nature. What remains to be explained
is what triggers the formation of MCM-49, i.e., onset of the
multilayered structure, which occurs when nearly all gel is
converted into MCM-56. Usually there is a sudden pH jump
near the end of templated zeolite syntheses, which may activate
the OH attached to Al and initiate the second layer (MCM-49
begins). The presence of AlOHNa+ moieties has further
consequences with regard acid site generation, as is evident if
one carries out exchange and calcination, which can be
expressed formally by the following reactions:
AlOHNa + + NH4NO3 AlOHNH4 +
Al + NH3 + H 2O
This shows that Al sites on the surface produce trigonal,
pyramidal Al Lewis not Brnsted acid sites. A similar case
was reported recently and attributed to defects.57 MCM-56 may
contain similar centers but as the consequence of its structure.
Additional discussion about detectability of this Al site is carried
out in the NMR section right before conclusions.
The MCM-22P crystal growth shows simultaneous prop-
agation in three directions: very fast growth of layers and their
more or less ordered stacking. This is evidenced by XRD
patterns, which show early on the separate (101) and (102)
maxima (valley in the region 810 2) and are indicative of
multilayered nature when crystallinity is low and the
amorphous component still evident. The XRDs during
MCM-56 crystallization show proles without the valley. It
E DOI: 10.1021/acs.chemmater.5b01030
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Chemistry of Materials Article

begins to show up only when the amorphous solid is almost

exhausted, marking the onset of MCM-49.
MCM-56 Swelling with Dierent NaOH Amounts. The
corresponding XRD patterns are shown in Figure 5. The

Figure 5. XRD of MCM-56 treated with swelling mixtures comprising

HDTMA-Cl and various amounts of NaOH in mol/kg of the swelling
solution (25% surfactant salt). Materials considered fully swollen are
shown in red.

experiment started with MCM-56 suspension in a neutral

surfactant chloride. Portions of NaOH were added, the slurry
stirred overnight, and a sample withdrawn for XRD; more
hydroxide was added, and the cycle was repeated several times.
There is a gradual increase in the swollen portion judging from
the low angle peaks at ca. 2 and 5.5 2. Complete swelling is
observed with 0.31 mol of NaOH per kg of the swelling
solution. Lower NaOH concentrations produce incomplete
partial or negligibleswelling.
TEM Evaluation of Swelling and Pillaring. The images
of selected swollen and pillared samples, presented in Figure 6,
conrm extensive separation of the MWW layers consistent
with the analysis based on the XRD patterns. The layers can be
identied unequivocally in the edge-on view because of distinct
light lines in the middle corresponding to the unique intralayer
sinusoidal pores.
Although swelling was judged to be quite ecient based on
XRD and BET, the images reveal the presence of some
unseparated layers, i.e., formally MCM-22 domains. This
suggests that the extent of swelling and pillaring can be still
improved. The observed gaps between layers in the pillared
calcined sample indicate the presence of thermally stable pillars.
They are not distinct, which proves their nonperiodic
distribution and/or amorphous character.
The crystals are maximum 100 nm wide and sometimes
appear disordered or bent; the layers are often arranged almost
parallel to each other with a relative distance that varies but are
in general not less than about 1.5 nm (except for the unswollen
parts). The average distances are estimated from positions of
the low angle line in XRD: between about 2.5 and 2 nm for the
swollen and pillared samples.
TEM image of the pillared sample also reveals the presence
of an amorphous phase, which is most likely originating from
the TEOS pillaring treatment. It is considered to be a
contamination and together with the mentioned presence of
unseparated layers should be minimized. The possibility for
better swelling was examined by treatment at higher temper-
ature, namely, 99 C, for overnight using the surfactant
hydroxide/chloride solution 1:1. The analogous room temper-
ature swelling was reported earlier.43 Subsequent pillaring of
F DOI: 10.1021/acs.chemmater.5b01030
Figure 6. TEM micrographs evaluating dierent swelling eciencies of
MCM-56: swollen with NaOH as base (a,b), pillared (c,d) compared
with MCM-56 swollen with HDTMA-OH/Cl at 99 C, and pillared
without TEOS hydrolysis before calcination (e,f).
the sample treated at elevated temperature was carried out in
two ways: with and without hydrolysis of the TEOS treated
swollen MCM-56 before nal calcination.54 As can be seen in
Table 1, the high temperature swelling resulted in enhanced
BET area of the pillared derivatives approaching 1000 m2/g.
Calcination without hydrolysis after TEOS pillaring gave higher
BET than with hydrolysis.
According to TEM observations, the sample of MCM-56
swollen at 99 C and pillared without TEOS hydrolysis
contains a majority of MWW zeolite layers separated as single
unit cell lamellae. This conrms the potential for improved
swelling eciency by increasing temperature of the treatment.
It also appears that crystals are wider/longer in comparison to
those treated with the NaOH/surfactant mixture. This suggests
that swelling with NaOH in solution may cause more crystal
breakage.
Evaluation of Pillared MCM-56 by Nitrogen Iso-
therms. Nitrogen isotherms obtained for the pillared MCM-
56 derivatives show the expected signicant increase of porosity
compared to the starting MCM-56 (lowest prole). The
observed hysteresis loops are typical for layered solids like
MCM-56/36.58 The notable feature is the dierence between
MCM-56 swollen with NaOH/HDTMA-Cl (red curve) and
HDTMA-OH/Cl at room temperature (green one) in the
Chem. Mater. XXXX, XXX, XXXXXX
Chemistry of Materials Article

region above p/p0. Both materials show almost identical
overlapping proles below p/p0 = 0.5. At higher pressure the
former is horizontal with a at hysteresis loop, while the latter
shows continuous increase with an upward incline.
The isotherms in Figure 7 also conrm that swelling at
elevated temperature can lead to enhanced porosity of the
Figure 7. Nitrogen isotherms of the original MCM-56 and its pillared
derivatives swollen with HDTMA-Cl plus NaOH (red) and with
HDTMA-OH (50/50) at RT (green) and 99 C (blue without
hydrolysis, purple with hydrolysis prior to calcinations). The isotherms
are not shifted, represent actual values, and indicate gradual increase in
porosity.
pillared MCM-56. This may be due to both increased amount
of separated layers, as seen in TEM, and desilication causing
some layer fragmentation and additional porosity.
Surfactant Extraction from Swollen MWW. Swelling is
typically carried out in order to produce permanently expanded
or delaminated solids, and so, the reverse process, which has
been dubbed deswelling, appears to have little practical
signicance. On the other hand, it may be quite valuable for
appraising the state of the treated precursor layers by freeing it
from the swelling agent. The other alternative is calcination at
over 500 C, which by comparison is quite severe and may
cause additional damage especially due to heat because of the
enormous amount of organic that is burned o.
Tsapatsis et al. described deswelling of MCM-22P swollen at
room temperature by acidication.35 The recovered product
was identied as the 3D ordered MCM-22P precursor. This is
an unexpected outcome because acid treatment of as-
synthesized MCM-22P50 induces disorder and collapse to the
MCM-56 analogue with disorganized layer stacking. It is
possible that acid deswelling did not remove all of the
surfactant present between layers and its residual amount
remained in horizontal orientation producing in eect an
intercalated MCM-22P with slight expansion and layer
ordering.
Acid deswelling of Al rich swollen zeolite precursors has a
drawback as it may result in dealumination by leaching of the
framework Al. An alternative treatment with salts instead of
acid, such as ammonium nitrate in alcoholic solution, which was
applied here, provides a milder approach. An aqueous
environment is less conducive to surfactant extraction,
producing little deswelling. Salts of organic cations can be
also used for deswelling, in which case they would aord
organic intercalates of layered zeolites.
Acidity Evaluation by FT-IR Studies; 27Al NMR. Table 2
summarizes acid site concentration values for the studied
MCM-22 and MCM-56 materials including those deswollen by
exchange with ammonium nitrate in alcohol. Two types of
zeolite activation were applied: air/vacuum involving calcina-
tion in air at 550 C, ammonium exchange and heating in
vacuum to 450 C in situ in the IR cell; and vacuum
activationas-synthesized material heated in situ in vacuum to
550 C with elimination of organic and other degradable/
volatile compounds. The latter did not entail cation exchange,
and the nal numbers could be aected by the presence of Na+
as indeed is observed with the starting MCM-56.
Both starting MCM-22 and MCM-56 demonstrate high acid
site concentration (>900 mol/g) consistent with their high Al
content. MCM-56 was reported earlier to be sensitive to
postsynthesis treatments and activation, which could result in
dealumination and structural deformation producing low acid
site concentration and poor catalytic activity.42 More recent
studies have shown that MCM-56 can show high acid site
concentrations comparable to MCM-22 and MCM-49,43,46
which may be consistent with its demonstrated high catalytic
activity in some processes like ethylbenzene synthesis.59
Swelling produces a decrease in the Brnsted acid site
concentration (BAS) by about 1/3 to around 600 mol/g
while the Lewis sites (LAS) remain about the same. Pillaring,
which introduces amorphous silica, produces further decrease
of BAS to around 400500 mol/g.43
Swelling at elevated temperature, which produces more
extensive layer separation observed in TEM and enhanced
porosity in comparison to the RT treatment, makes hardly any

Table 2. Concentration of Brnsted (BAS) and Lewis (LAS) Acid Sites in MCM-22P and MCM-56 Samples after Various
Treatmentsa
sample type heat activation BAS, mol/g LAS, mol/g Si/Al BAS + LAS Si/Al BAS ref
MCM-22 as synthesized Vac 1092 156 12 14
MCM-22 calc, NH4NO3 exchange Air/Vac 828 167 16 19 41
MCM-56, as synth, with original Na+ Vac 585 55 29 33
MCM-56 calc, NH4NO3 exchange Air/Vac 942 139 15 17
MCM-56 sw HDTMA-OH/Cl Vac N/A
MCM-56-sw HDTMA-OH/Cl calc, NH4NO3 Air/Vac 635 179 19 25 41
MCM-56 sw NaOH, deswell Vac 1577 251 8 10
MCM-56 sw NaOH, deswell Air/Vac 564 154 22 29
MCM-56 sw HDTAMA-OH/Cl 99C, deswell Vac 1227 162 11 13
MCM-56 sw HDTAMA-OH/Cl 99C, deswell Air/Vac 649 154 20 25

a
Samples were activated by heating under vacuum at 550 C (Vac) and air (550 C) followed by cation exchange and heating under vacuum, at 450
C (Air/Vac).

G DOI: 10.1021/acs.chemmater.5b01030
Chem. Mater. XXXX, XXX, XXXXXX
Chemistry of Materials
dierence for the BAS values. The MCM-56 swollen with
HDTMA-OH/Cl at RT and 99 C have BAS equal to 635 and
649 mol/g, respectively. A signicant dierence is seen by IR
in the silanol region (Figure 8). The intensities of maxima due
Figure 8. FTIR of MCM-56 pillared at dierent temperatures in the
OH stretching region.
to terminal silanol and bridging hydroxide are quite similar.
However, for the high temperature treatments the background
is elevated substantially, which can be attributed to the presence
of various (additional) silanol groups interacting with each
other. This is consistent with much more extensive desilication
than at RT, which is believed to occur upon swelling at higher
temperature.
The activation in vacuum can produce initially much higher
BAS values than the standard air/vacuum procedure (see Table
2). This potentially attractive enhancement of acidity is
especially evident in the cases of mild deswelling with
ammonium nitrate in alcohol. These high concentrations revert
to typical values when followed by regular calcination.
27
Al NMR spectra recorded for selected samples showed
preservation of tetrahedral Al coordination until nal
calcinations. There was very little octahedral Al seen in the
swollen and calcined MCM-56. Deswelling followed by
calcinations produced a signicant amount of octahedral Al
especially upon calcinations in air. Typically for MWW
materials the signals were broad, preventing detection of
dierent structural environments in the framework. Swollen
MCM-56 shows the expected less intense signal than the parent
zeolite. This signal does not regain all of the original intensity
after surfactant removal by calcinations or chemical deswelling,
suggesting formation of undetectable Al centers.
The notable issue with the proposed Al site on the surface is
the problem of its detectability. As observed here and in ref 57,
the 27Al NMR spectrum of the Na forms does not show signals
that could be assigned to it. It may be possible to obtain
evidence through advanced NMR methods like 27Al{1H}
REDOR (3Q) combined with computational methods.57 The
complexity of this issue is quite obvious, and most likely
extensive investigation will be required to settle outstanding
problems.
CONCLUSIONS
The eciency of swelling and other transformations of MCM-
22P, a multilayered precursor to zeolite MCM-22, are aected
by the increasing Al content in the framework. In contrast, the
unilamellar analogue MCM-56 can be readily swollen under
mild conditions and notably with NaOH as the source of the
required high pH. Swelling at higher temperature increases the
amount of separated layers and results in the pillared product
with increased porosity. MCM-22, MCM-56, and their various
H DOI: 10.1021/acs.chemmater.5b01030
Article
forms show high acid site concentrations. This can result in
high catalytic activity in processes like benzene alkylation with
small olens, in which MWW zeolites play a prominent
commercial role.
*
ASSOCIATED CONTENT
S Supporting Information
Detailed description of characterization by adsorption, FTIR
and 27Al NMR NMR spectra, compilation of MCM-22 catalytic
data from ref 36. The Supporting Information is available free
of charge on the ACS Publications website at DOI: 10.1021/
acs.chemmater.5b01030.
AUTHOR INFORMATION
Corresponding Author
*Phone: +48-126632016. E-mail: wieslaw.roth@uj.edu.pl.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
J.C. acknowledges the Czech Science Foundation for the
project of the Centre of Excellence (P106/12/0189). The
research leading to these results has received also a partial
funding for J.C . from the European Union Seventh Framework
Programme (FP7/2007-2013) under Grant Agreement No.
604307. This work was nanced with the funds from the
Narodowe Centrum Nauki provided on the basis of decision
number DEC-2011/03/B/ST5/01551. The IR measurements
were carried out with the equipment purchased thanks to the
nancial support of the European Regional Development Fund
in the framework of the Polish Innovation Economy Opera-
tional Program (Contract No. POIG.02.01.00-12-023/08).
REFERENCES
(1) Masters, A. F.; Maschmeyer, T. Zeolites - From Curiosity to
Cornerstone. Microporous Mesoporous Mater. 2011, 142, 423438.
(2) Fechete, I.; Wang, Y.; Vedrine, J. C. The Past, Present and Future
of Heterogeneous Catalysis. Catal. Today 2012, 189, 227.
(3) Breck, D. W. Zeolite Molecular Sieves: Structure, Chemistry, and
Use; Wiley: New York, 1973.
(4) Leonowicz, M. E.; Lawton, J. A.; Lawton, S. L.; Rubin, M. K.
MCM-22 - A Molecular Sieve with 2 Independent Multidimensional
Channel Systems. Science 1994, 264, 19101913.
(5) Rubin, M. K.; Chu, P. Composition of Synthetic Porous
Crystalline Material, Its Synthesis and Use. U.S. Patent 4,954,325,
1990.
(6) Millini, R.; Perego, G.; Parker, W. O., Jr.; Bellussi, G.; Carluccio,
L. Layered Structure of ERB-1 Microporous Borosilicate Precursor and
Its Intercalation Properties towards Polar Molecules. Microporous
Mater. 1995, 4, 221230.
(7) Schreyeck, L.; Caullet, P.; Mougenel, J. C.; Guth, J. L.; Marler, B.
A Layered Microporous Aluminosilicate Precursor of FER-Type
Zeolite. J. Chem. Soc., Chem. Commun. 1995, 21872188.
(8) Moteki, T.; Chaikittisilp, W.; Shimojima, A.; Okubo, T. Silica
Sodalite without Occluded Organic Matters by Topotactic Conversion
of Lamellar Precursor. J. Am. Chem. Soc. 2008, 130, 1578015781.
(9) Choi, M.; Na, K.; Kim, J.; Sakamoto, Y.; Terasaki, O.; Ryoo, R.
Stable Single-Unit-Cell Nanosheets of Zeolite MFI as Active and
Long-Lived Catalysts. Nature 2009, 461, 246249.
(10) Roth, W. J.; Gil, B.; Marszalek, B. Comprehensive System
Integrating 3D and 2D Zeolite Structures with Recent New Types of
Layered Geometries. Catal. Today 2014, 227, 914.
(11) Roth, W. J. Synthesis of Delaminated and Pillared Zeolitic
Materials. Stud. Surf. Sci. Catal. 2007, 168, 221239.
Chem. Mater. XXXX, XXX, XXXXXX
Chemistry of Materials
(12) Ramos, F. S. O.; De Pietre, M. K.; Pastore, H. O. Lamellar
Zeolites: An Oxymoron? RSC Adv. 2013, 3, 20842111.
(13) Auerbach, S. M.; Carrado, K. A.; Dutta, P. K. Handbook of
Layered Materials; Marcel Dekker: New York, 2004.
(14) Selvam, T.; Inayat, A.; Schwieger, W. Reactivity and
Applications of Layered Silicates and Layered Double Hydroxides.
Dalton Trans. 2014, 43, 1036510387.
(15) Lerf, A. Storylines in Intercalation Chemistry. Dalton Trans.
2014, 43, 1027610291.
(16) Roth, W. J.; Cejka, J. Two-dimensional Zeolites: Dream or
Reality? Catal. Sci. Technol. 2011, 1, 4353.
(17) Daz, U.; Corma, A. Layered Zeolitic Materials: An Approach to
Designing Versatile Functional Solids. Dalton Trans. 2014, 43, 10292
10316.
(18) Roth, W. J.; Nachtigall, P.; Morris, R. E.; C ejka, J. Two-
Dimensional Zeolites: Current Status and Perspectives. Chem. Rev.
2014, 114, 48074837.
(19) Hartmann, M. Hierarchical Zeolites: A Proven Strategy to
Combine Shape Selectivity with Efficient Mass Transport. Angew.
Chem., Int. Ed. 2004, 43, 58805882.
(20) Roth, W. J.; Dorset, D. L. Expanded View of Zeolite Structures
and Their Variability Based on Layered Nature of 3-D Frameworks.
Microporous Mesoporous Mater. 2011, 142, 3236.
(21) Marler, B.; Gies, H. Hydrous Layer Silicates as Precursors for
Zeolites Obtained through Topotactic Condensation: A Review. Eur. J.
Mineral. 2012, 24, 405428.
(22) Na, K.; Park, W.; Seo, Y.; Ryoo, R. Disordered Assembly of MFI
Zeolite Nanosheets with a Large Volume of Intersheet Mesopores.
Chem. Mater. 2011, 23, 12731279.
(23) Chlubna-Eliaso va, P.; Tian, Y.; Pinar, A. B.; Kubu, M.; C ejka, J.;
Morris, R. E. The Assembly-Disassembly-Organization-Reassembly
Mechanism for 3D-2D-3D Transformation of Germanosilicate IWW
Zeolite. Angew. Chem., Int. Ed. 2014, 53, 70487052.
(24) Roth, W. J.; Nachtigall, P.; Morris, R. E.; Wheatley, P. S.;
Seymour, V. R.; Ashbrook, S. E.; Chlubna, P.; Grajciar, L.; Polozij, M.;
Zukal, A.; Shvets, O.; C ejka, J. A Family of Zeolites with Controlled
Pore Size Prepared Using a Top-Down Method. Nat. Chem. 2013, 5,
628633.
(25) Roth, W. J.; Shvets, O. V.; Shamzhy, M.; Chlubna, P.; Kubu, M.;
Nachtigall, P.; Cejka, J. Postsynthesis Transformation of Three-
Dimensional Framework into a Lamellar Zeolite with Modifiable
Architecture. J. Am. Chem. Soc. 2011, 133, 61306133.
(26) Shamzhy, M.; Opanasenko, M.; Tian, Y. Y.; Konysheya, K.;
Shyets, O.; Morris, R. E.; Cejka, J. Germanosilicate Precursors of
ADORable Zeolites Obtained by Disassembly of ITH, ITR, and IWR
Zeolites. Chem. Mater. 2014, 26, 57895798.
(27) Roth, W. J.; Kresge, C. T.; Vartuli, J. C.; Leonowicz, M. E.;
Fung, A. S.; McCullen, S. B. MCM-36: The First Pillared Molecular
Sieve with Zeolite Properties. Stud. Surf. Sci. Catal. 1995, 94, 3018.
(28) Corma, A.; Fornes, V.; Pergher, S. B.; Maesen, T. L. M.; Buglass,
J. G. Delaminated Zeolite Precursors as Selective Acidic Catalysts.
Nature 1998, 396, 353356.
(29) Roth, W. J.; Vartuli, J. C. Preparation of Exfoliated Zeolites from
Layered Precursors: The Role of pH and Nature of Intercalating
Media. Stud. Surf. Sci. Catal. 2002, 141, 273279.
(30) Kresge, C. T.; Roth, W. J. The Discovery of Mesoporous
Molecular Sieves from the Twenty Year Perspective. Chem. Soc. Rev.
2013, 42, 36633670.
(31) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck,
J. S. Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-
Crystal Template Mechanism. Nature 1992, 359, 71012.
(32) Roth, W. J.; Vartuli, J. C.; Kresge, C. T. Characterization of
Mesoporous Molecular Sieves: Differences between M41S and Pillared
Layered Zeolites. Stud. Surf. Sci. Catal. 2000, 129, 501508.
(33) Roth, W. J. Cation Size Effects in Swelling of the Layered
Zeolite Precursor MCM-22-P. Pol. J. Chem. 2006, 80, 703708.
(34) Polozij, M.; Thang, H. V.; Rubes, M.; Eliaso va, P.; C ejka, J.;
Nachtigall, P. Theoretical Investigation of Layered Zeolites with
Article
MWW Topology: MCM-22P vs. MCM-56. Dalton Trans. 2014, 43,
1044310450.
(35) Maheshwari, S.; Jordan, E.; Kumar, S.; Bates, F. S.; Penn, R. L.;
Shantz, D. F.; Tsapatsis, M. Layer Structure Preservation during
Swelling, Pillaring, and Exfoliation of a Zeolite Precursor. J. Am. Chem.
Soc. 2008, 130, 15071516.
(36) Maheshwari, S.; Martnez, C.; Teresa Portilla, M.; Llopis, F. J.;
Corma, A.; Tsapatsis, M. Influence of Layer Structure Preservation on
the Catalytic Properties of the Pillared Zeolite MCM-36. J. Catal.
2010, 272, 298308.
(37) Haag, W. O.; Lago, R. M.; Weisz, P. B. The Active Site of Acidic
Aluminosilicate Catalysts. Nature 1984, 309, 589591.
(38) Roth, W. J.; Dorset, D. L.; Kennedy, G. J. Discovery of New
MWW Family Zeolite EMM-10: Identification of EMM-10P as the
Missing MWW Precursor with Disordered Layers. Microporous
Mesoporous Mater. 2011, 142, 168177.
(39) Chlubna, P.; Roth, W. J.; Zukal, A.; Kubu, M.; Pavlatova, J.
Pillared MWW Zeolites MCM-36 Prepared by Swelling MCM-22P in
Concentrated Surfactant Solutions. Catal. Today 2012, 179, 3542.
(40) Frontera, P.; Testa, F.; Aiello, R.; Candamano, S.; Nagy, J. B.
Transformation of MCM-22(P) into ITQ-2: The Role of Framework
Aluminium. Microporous Mesoporous Mater. 2007, 106, 107114.
(41) Roth, W. J. MCM-22 Zeolite Family and the Delaminated
Zeolite MCM-56 Obtained in One-Step Synthesis. Stud. Surf. Sci.
Catal. 2005, 158A and B, 1926.
(42) Juttu, G. G.; Lobo, R. F. Characterization and Catalytic
Properties of MCM-56 and MCM-22 Zeolites. Microporous Meso-
porous Mater. 2000, 40, 923.
(43) Gil, B.; Makowski, W.; Marszalek, B.; Roth, W. J.; Kubu, M.;
C ejka, J.; Olejniczak, Z. High Acidity Unilamellar Zeolite MCM-56
and Its Pillared and Delaminated Derivatives. Dalton Trans. 2014, 43,
1050110511.
(44) Zhang, Z.; Zhu, W.; Zai, S.; Jia, M.; Zhang, W.; Wang, Z.
Synthesis, Characterization and Catalytic Properties of MCM-36
Pillared via the MCM-56 Precursor. J. Porous Mater. 2013, 20, 531
538.
(45) Roth, W. J.; Chlubna, P.; Kubu, M.; Vitvarova, D. Swelling of
MCM-56 and MCM-22P with a New Medium - Surfactant-
Tetramethylammonium Hydroxide Mixtures. Catal. Today 2013,
204, 814.
(46) Gil, B.; Marszaek, B.; Micek-Ilnicka, A.; Olejniczak, Z. The
Influence of Si/Al Ratio on the Distribution of OH Groups in Zeolites
with MWW Topology. Top. Catal. 2010, 53, 13401348.
(47) Lawton, S. L.; Fung, A. S.; Kennedy, G. J.; Alemany, L. B.;
Chang, C. D.; Hatzikos, G. H.; Lissy, D. N.; Rubin, M. K.; Timken, H.
K. C.; Steuernagel, S.; Woessner, D. E. Zeolite MCM-49: A Three-
Dimensional MCM-22 Analogue Synthesized by in situ Crystallization.
J. Phys. Chem. 1996, 100, 37883798.
(48) Dorset, D. L.; Roth, W. J. Electron Crystallography of MWW
zeolites - Filling the Missing Cone. Z. Kristallogr. 2011, 226, 254263.
(49) Pawlesa, J.; Bejblova, M.; Sommer, L.; Bouzga, A. M.; Stocker,
M.; Cejka, J. Synthesis, Modification and Characterization of MWW
Framework Topology Materials. Stud. Surf. Sci. Catal. 2007, 170, 610
615.
(50) Wang, L. L.; Wang, Y.; Liu, Y. M.; Chen, L.; Cheng, S. F.; Gao,
G. H.; He, M. Y.; Wu, P. Post-transformation of MWW-type Lamellar
Precursors into MCM-56 Analogues. Microporous Mesoporous Mater.
2008, 113, 435444.
(51) Wang, Y.; Liu, Y. M.; Wang, L. L.; Wu, H. H.; Li, X. H.; He, M.
Y.; Wu, P. Postsynthesis, Characterization, and Catalytic Properties of
Aluminosilicates Analogous to MCM-56. J. Phys. Chem. C 2009, 113,
1875318760.
(52) Wu, P.; Ruan, J. F.; Wang, L. L.; Wu, L. L.; Wang, Y.; Liu, Y. M.;
Fan, W. B.; He, M. Y.; Terasaki, O.; Tatsumi, T. Methodology for
Synthesizing Crystalline Metallosilicates with Expanded Pore Windows
through Molecular Alkoxysilylation of Zeolitic Lamellar Precursors. J.
Am. Chem. Soc. 2008, 130, 81788187.
(53) Yokoi, T.; Mizuno, S.; Imai, H.; Tatsumi, T. Synthesis and
Structural Characterization of Al-Containing Interlayer-Expanded-
I DOI: 10.1021/acs.chemmater.5b01030
Chem. Mater. XXXX, XXX, XXXXXX
Chemistry of Materials Article

MWW Zeolite with High Catalytic Performance. Dalton Trans. 2014,

43, 1058410592.
(54) Shamzhy, M.; Mazur, M.; Opanasenko, M.; Roth, W. J.; C ejka, J.
Swelling and Pillaring of the Layered Precursor IPC-1P: Tiny Details
Determine Everything. Dalton Trans. 2014, 43, 1054810557.
(55) Pawlesa, J.; Zukal, A.; C ejka, J. Synthesis and Adsorption
Investigations of Zeolites MCM-22 and MCM-49 Modified by Alkali
Metal Cations. Adsorption 2007, 13, 257265.
(56) Palin, L.; Croce, G.; Viterbo, D.; Milanesio, M. Monitoring the
Formation of H-MCM-22 by a Combined XRPD and Computational
Study of the Decomposition of the Structure Directing Agent. Chem.
Mater. 2011, 23, 49004909.
(57) Brus, J.; Kobera, L.; Schoefberger, W.; Urbanova, M.; Klein, P.;
Sazama, P.; Tabor, E.; Sklenak, S.; Fishchuk, A. V.; Dedecek, J.
Structure of Framework Aluminum Lewis Sites and Perturbed
Aluminum Atoms in Zeolites as Determined by 27Al{1H} REDOR
(3Q) MAS NMR Spectroscopy and DFT/Molecular Mechanics.
Angew. Chem., Int. Ed. 2015, 54, 541545.
(58) Zukal, A.; Kubu, M. High-resolution Adsorption Analysis of
Pillared Zeolites IPC-3PI and MCM-36. Dalton Trans. 2014, 43,
1055810565.
(59) Cheng, J. C.; Fung, A. S.; Klocke, D. J.; Lawton, S. L.; Lissy, D.
N.; Roth, W. J.; Smith, C. M.; Walsh, D. E. Manufacture of Short-
Chain Alkylaromatic Compounds with a Zeolite Catalyst. U.S. Patent
5,453,554, 1995.

J DOI: 10.1021/acs.chemmater.5b01030
Chem. Mater. XXXX, XXX, XXXXXX