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Two-dimensional zeolites: dream or reality?
Wieslaw J. Rothw and Jiřı́ Čejka*
Received 25th October 2010, Accepted 10th November 2010
DOI: 10.1039/c0cy00027b
Delaminated and pillared zeolites, called here ‘‘two-dimensional zeolites’’, are a promising and
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exciting area of solid materials research with high practical potential in adsorption and catalysis.
Synthetic approaches for their preparation, crucial issues concerning reliable identification and
characterization of these materials, and examples of their catalytic behaviour are highlighted in
this contribution. Last, but not least, ideas and challenges for future progress of these materials
are addressed.
1. Introduction
Zeolite synthesis, aiming at the discovery of new microporous
structures, has been vigorously explored and developed for
more than half a century to expand the demonstrated and
potential practical benefits of zeolites in heterogeneous catalysis,
adsorption and ion-exchange.1–4 This effort has relied
essentially on trial and error approach: hydrothermal syntheses
carried out at various conditions and starting mixture
compositions, although recently new methodologies like
high-throughput synthesis have been successfully applied.5
The leading strategy has employed the addition of polar
organic molecules, so-called structure directing or templating
agents. While such synthesis routes are less attractive
commercially, compared with non-organic ones due to higher
cost and environmental problems, most zeolites known to date
have not been synthesized yet without templating with an
appropriate organic molecule.
At present, close to 200 different structural types of zeolites
have been formally recognized by the Structure Commission
of the International Zeolite Association6 and this number is
continuously increasing every year. Zeolites are crystalline
microporous aluminosilicates having three-dimensional frame-
works formed by SiO4 and AlO4 corner-sharing tetrahedra as
primary building units. The framework is defined as
4-connected since each T-atom has four different neighbours
and two neighbouring tetrahedra can share only one oxygen
bridge. These combinations lead to secondary building units
like 4-, 5- and 6-rings and double 4-, 5- and 6-rings, etc. A
variety of channel systems with up to three-dimensional
connectivity are formed from the secondary building units.
The number of SiO4 and AlO4 tetrahedra forming the entrance
windows to a zeolite channel system governs the diameter
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of
the Czech Republic, v.v.i., Dolejsˇkova 3, CZ-182 23 Prague 8,
Czech Republic. E-mail: jiri.cejka@jh-inst.cas.cz;
Fax: +420-28658-2307
w Permanent address: 123 Boundbrook Ct., Sewell, NJ, USA.
This journal is c The Royal Society of Chemistry 2011
PERSPECTIVE
of the aperture usually consisting of 6, 8, 10, 12, 14, 18 and 20
tetrahedra.6 For most applications of zeolites in catalysis, the
presence of aluminium is crucial as aluminium introduces
negative charge to the 4-connected aluminosilicate frameworks.
When the charge is compensated by protons solid acids are
formed. The concentration of protons forming Brønsted sites
is controlled by the chemical composition of a zeolite while
their acid strength per acid site decreases with increasing
amount of framework aluminium. For the adsorption, separation
and catalytic purposes the accessibility of Brønsted sites is of
high importance and it is governed by the relation between the
kinetic diameters of organic guest molecules and the size of
entrance windows to the channel system.7 The size of available
zeolite channels is more or less limited to 1 nm, referred to as
‘‘1 nm prison’’, which makes the acid sites in principle
inaccessible for bulkier molecules. The largest pore size in a
zeolite in commercial use is 0.74 nm (faujasite) and there
is ongoing vigorous search for more open structures and
enhanced accessibility.8,9
The above described practice of zeolite synthesis traditionally
afforded microcrystalline products with completed 4-connected
framework, which was not amenable to post-synthesis structural
modification. This is most evident during the standard processing
as the obtained crystals are being activated by ion exchange
and calcination showing little or no apparent change of lattice
parameters, which is readily ascertained based on the corres-
ponding X-ray powder diffraction patterns. In general, no
meaningful structure contraction, expansion or other non-
destructive geometry modification have been observed or
expected as the result of such processing.
New opportunities arose in conjunction with the discovery
of zeolite MCM-22, which exhibited a new fundamental
property of zeolite formation via layered precursor, designated
MCM-22P (variations on this designation include MCM-22(P),
MCM-22-P).10,11 In fact, the MCM-22 framework was found
to form by two pathways as shown in Fig. 1: the mentioned
indirect lamellar one and the traditional direct pathway.
In contrast to the typical 3D zeolite frameworks assembled
Catal. Sci. Technol., 2011, 1, 43–53 43
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Fig. 1 Two pathways to zeolite MCM-22 framework (MWW). The structure on the right represents both the template containing MCM-49 as
well as the final template-free calcined framework of both MCM-22 and MCM-49.

directly with no flexibility for modification, the layered
precursor was viewed11 and demonstrated12 that it could be
structurally modified after the synthesis. At the same time, the
layered precursor versions of other frameworks were found,
expanding the field to other zeolites, most notably some
classical representatives like FER,13,14 SOD,15–17 and recently
MFI.18 Various forms like pillared and delaminated structures
built from framework monolayers (components of the layered
precursors) were being proposed and realized (see ref. 19).
MCM-22 was leading the way in demonstrating novel types of
layered structures, like pillared, delaminated and disordered
layered precursor, summarized in ref. 20, which was expanding
the number and diversity of structurally distinct materials
based on the MWW structures, referred to as the MCM-22
family.
The objective of this contribution is to provide up-to-date
knowledge and challenges associated with ‘‘two-dimensional
zeolites (2D zeolites)’’, which herein means those having the
third dimension limited to about 2–3 nm, thus, the dimension
corresponding to 1–2 unit cells, and to discuss the capability to
modify zeolites structurally to get new adsorbents and catalysts.
The main difference in comparison with conventional zeolites

Table 1 List of existing lamellar or pillared zeolites

Zeolite, calcined Directly 3D assembled Layered precursor Pillared derivative Delaminated Stabilized precursor Other
MWW MCM-49 MCM-22P MCM-36 ITQ-2 IEZ-MWW
MCM-22,-49 MCM-56
FER Ferrierite PreFer, PLS-3 ITQ-36 ITQ-6 IEZ-FER ERS-12 disordered
CDO MCM-65, -47 IEZ-CDO
CDS-1 PLS-1, -4
CAS CAS EU-19 major
EU-20b
NSI NU-6(1) MCM-39(Si) ITQ-18 EU-20 disordered
NU-6(2) EU-19 minor
SOD Sodalite RUB-15
RWR
RUB-24 RUB-18, -51, HLS
RRO RUB-39
RUB-41
AFO AFO PreAFO
MFI Yes Yes
ZSM-5

44 Catal. Sci. Technol., 2011, 1, 43–53 This journal is c The Royal Society of Chemistry 2011

stems from the fact that with 2D zeolites adsorption and
catalysis occur almost exclusively on the surface of these
materials and not inside the zeolite pores. The present
publication outlines some practical benefits while at the same
time discussing future prospects and opportunities. In addition,
we focus on challenges associated with characterization of
these novel materials, which requires systematic and meticulous
approach for their synthesis and proper identification.
In this perspective we refer to (i) pillared materials—they
have permanently expanded interlamellar distance/space
caused by the presence of localized props (pillars) made of
silica or other thermally stable substances. They are typically
produced by initial intercalation of expanding/swelling organic
substance followed by treatment and insertion of a soluble
material that transforms into pillars upon burning off of the
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intercalant. (ii) Delaminated zeolites—separated into constituent
layers, may be understood as any collection of zeolite layers
that are not ordered, without alignment in the third direction,
and ideally without any connections among the layers, except
for incidental. (iii) Stabilized precursors (IEZ—interlamellar
expanded zeolites)21,22 layered precursors with interlayer
separation made permanent, e.g. by treatment with silylating
agents. At present, around 10 zeolites (e.g. MWW,
FER, Table 1) have a layered precursor known. The first
comprehensive review of this emerging subject was published
in 2007 and has not been updated since then.19
2. Synthesis of layered zeolite precursors
The first critical step towards entry into the area of modified
precursors is the actual preparation and identification of a
layered precursor or some other lamellar zeolite forms. Such
syntheses occurred typically unexpectedly upon conventional
organic templated preparations. They are usually recognized
when the as-synthesized product changes XRD pattern upon
calcination.11 New findings have been rare but recent
Fig. 2 Updated MCM-22 ‘family tree’ illustrating proposed layer arrangements and synthesis pathways.
This journal is c The Royal Society of Chemistry 2011
View Article Online
discoveries of the layered precursors of frameworks have
become more frequent.18,19 Generally speaking, the synthesis
mixture compositions and conditions applied to date favoured
direct framework assembly with 3D connectivity, i.e. afforded
traditional zeolites. MWW formation may again provide some
insights into alternative routes as it shows transition from
direct to the lamellar pathway upon slight adjustment of the
reaction mixture composition, namely the case of MCM-22P
and MCM-49 synthesis.10,11 The family of MWW zeolites and
related materials is presented in Fig. 2. A detailed analysis of
the underlying reasons for the formation of MCM-22P and
MCM-49 has not been considered in publications. It is evident
that to achieve formation of a layered precursor the frame-
work growth must be prevented from propagation in the third
dimension. The end effect is the presence of silanol groups or
their deprotonated moieties on the surface of the layers. This
termination happens because of blockage by the template or
other factors preventing sustainable attachment of another
silicate tetrahedra or small units to that site. Further probe
into what factors or maybe particular types of atoms do
stabilize T–OH termination, may enable more designed
approach to the synthesis of layered zeolite structures.
The MWW framework has been, to date, arguably the
major source of diversity and innovation in this area.20,21,23
It marks the advances in terms of new structures, fundamental
insights and modified catalytic properties. MCM-22 was first
to demonstrate formation of the 3D frameworks by 2
pathways, which is at the center of the 2D zeolite area. There
are now 4 different MWW related materials known that were
obtained by direct synthesis:20 3D structure (MCM-49),
layered precursors (ordered MCM-22P and disordered
EMM-10P) and delaminated (MCM-56). Fig. 3 provides
comparison of X-ray powder patterns of these MWW materials
obtained by direct synthesis. The modified derivatives include
pillared MCM-36,12 delaminated ITQ-2,24 and stabilized
precursors (IEZ).21 MWW family also sets the standard
Catal. Sci. Technol., 2011, 1, 43–53 45

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Fig. 3 X-Ray powder patterns of various MCM-22 family materials
obtained by direct synthesis.
for identification of various types of materials (structure
arrangements) by X-ray powder diffraction.20,23 Based on
detailed analysis of positions and appearance of diffraction
lines the procedure allows unambiguous identification of a
particular structure (layer packing, distance and order) and
even detection of mixtures.19 Regarding post-synthesis
modification, XRD is invaluable in confirming the quality
and extent of the intended transformation thus validating
veracity of a particular procedure and sample structural
characteristics. The MCM-22 family has been the template
to follow in developing other layered families in terms of
synthesis, identification and characterization.14,21
The recent lamellar MFI discovery (‘single-unit-cell
nanosheets’) represents a very promising step-out change by
providing a possible general approach to the synthesis of
zeolitic lamellar precursors.18,25 It involves an SDA with one
end designed to template the zeolite framework (in this case
MFI) while the other end is a long chain preventing adjacent
growth of another (connected) layer, simultaneously providing
organic interlayer between the MFI monolayers. The overall
effect is a direct synthesis of a hybrid structure, equivalent to a
swollen product, with alternating inorganic and organic layers.
These layers were reported to have 2.0 and 2.8 nm height,
respectively based on TEM images. Identification also
included XRD, which showed overall similarity to MFI but
only h0l reflections were sufficiently distinct to enable indexing,
i.e. assignment of (hkl) indices. This indication of short
crystallographic order in the b-direction is consistent with
the proposed hybrid structure. Removal of the template by
calcination did not produce well ordered MFI, but the sample
had a considerable mesoporosity, attributed to non-congruent
collapse. A follow up publication reported dimension of the
product somewhat differently with repeat 6.1 nm including
2.0 nm MFI layer and 4.1 nm organic part.25 It also claimed
successful synthesis of the pillared derivative so we will
continue discussion in the corresponding section 5.
Additional attractive feature of the MFI layers is the
presence of perpendicular pores, which enable transport
across, i.e. in three dimensions, through the crystal. Another
material with pores across is AMH-3 with 8-ring apertures,
which are, however, inaccessible for most of organic
46 Catal. Sci. Technol., 2011, 1, 43–53
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molecules.26 The sodalite precursor, designated RUB-15, did
not condense into an ordered framework upon standard
calcinations.15 However, if the template is first removed by
extraction with acetic acid and then calcined an ordered
condensed structure is obtained.16 Further on, refluxing
RUB-18 with C16TMA (cetyltrimethylammonium) induced
the formation of pores on the layer surfaces, though the
mechanism is not well understood.27
FER and CAS layers afford 2 different zeolites each, FER
and CDO, and CAS and NSI, respectively, which was attributed
to the lack of mirror symmetry plane in the layer.28 Depending
on the symmetry relationship between the layers, translation
or reflection in mirror plane, different structures were produced.
The chemical effects determining which layer orientation is
adopted during the synthesis, are not known. Ferrierite sheets
having no internal porosity can be templated by different
SDAs depending on the synthesis conditions. Recent additions
include PLS-3 and PLS-4 providing layered precursors of FER
and CDO.29,30
Several layered zeolite precursors have been identified in the
course of systematic work on templated silicate synthesis by
Gies and co-workers, who designate their products with
acronym RUB. Remarkably one of them turned out to be
layered precursor of the well known framework SOD,15 which
provided a convenient aqueous route to all siliceous sodalite.
Other frameworks reported by this group are also notable as
being obtained by the layered intermediate route only.31,32 The
direct framework synthesis is expected but has not been
observed yet. The group of Gies is also a leader in systematic
and thorough structure determination33 and analysis of
various layered precursors and has revealed valuable insights
including structure of EU-20b, containing both NSI and CAS
frameworks in one sample.34
The framework AFO, AlPO-41, was obtained both directly
and from layered aluminophosphate precursor.35 The latter
was obtained with a bulky macrocycle polyamine as the
structure directing agent. The complete AFO topology
required translation of alternate layers by 0.5a and 0.5b with
condensation.
3. Expansion and swelling of the as-synthesized
precursors
This has been historically the most difficult and critical step in
modification of the precursors, which can be then delaminated
and pillared. Again, MCM-22 provided the first published
example12 indicating that it was a rather demanding treatment
entailing the use of surfactant solution at high pH. The pitfalls
are obvious now—there is a danger of silica solubilization,
which is promoted by basic environment and possible
formation of an M41S phase.36 The first successful swelling
of MCM-22P was achieved with a surfactant hydroxide
solution free from other cations, as the most common ones,
like Na+ and tetramethylammonium, would diffuse
preferentially into the interlayer space.37 It was subsequently
established that it was possible to use a solution with potentially
non-interfering cation supplying hydroxide ions together with
a surfactant salt instead of the less desirable surfactant
hydroxide. That cation had to be excluded by its size from
This journal is c The Royal Society of Chemistry 2011
 View Article Online

competing for the interlayer space and tetrapropylammonium
(TPAOH) was found suitable38 and commonly used since in
swelling/delamination of other zeolite precursors.
The relative complexity of swelling, its severity and potential
undesirable reactions impose a special demand for verification
that indeed the intended effect, i.e. swelling with no mesoporous
MCM-41 or related phase formation, was realized. XRD is in
general the adequate tool that can be used for that. As
illustrated by the first case of MCM-22 some of the new
features in the XRD patterns indicative of interlamellar
expansion were not anticipated and needed validation by
accumulation of evidence. The topic has been described in
great detail12 and here we mention only the final conclusions.
Successful swelling of MCM-22P can be proven based on two
features, a low angle line, typically around 5 nm of d-spacing
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Related studies concluded that efficiency of ITQ-2 production
is better at higher Si/Al ratio.43 This study also showed
significant dissolution of the MWW layers and consequent
diminished yield of the solid product.
In continuation of this research, ITQ-6—the delaminated
form of FER, was prepared again by the group of Corma14
from PreFER.13 For the preparation of PreFER (or FER-P),
4-amino-2,2,6,6-tetramethylpiperidine was used instead of
pyridine, piperidine or other templates usually used for the
direct synthesis of 3D FER. Further treatment of PreFER
resembles that for the synthesis of ITQ-2. It could be inferred
that the addition of four methyl groups to piperidine is
important for blocking of the stacking of the individual
FER layers and enables the post-synthesis treatment, FER-P
to ITQ-6.

and transformation of the diffraction lines initially at 8 and 101
2y CuKa, into a broad band without a dip somewhere in
between these two positions. At the same time the initial
(002) reflection at the d-spacing B1.34 nm had to disappear
completely.
As mentioned, the above synthetic procedure for swelling
using surfactant with TPAOH has been used with other
precursors. Recently, swelling of MCM-22P under milder
conditions has been explored.39,60 It was concluded that
swelling of MCM-22P at room temperature produced less
degradation of the MWW layers and in the end translated
into more ordered and catalytically active MCM-36 material.
MCM-56 deserves a special consideration as the only
apparently delaminated zeolite to date obtained spontaneously
in the course of a standard hydrothermal synthesis.23,40 This
represents a convenient entry to delaminated materials
with enormous advantage in cost and labour for further
experimentation (treatments). The synthesis is somewhat more
demanding than the conventional zeolite preparation because
the MCM-56 is an intermediate that must be intercepted at the
right moment before the onset of slow conversion to the

4. Synthesis of delaminated materials

Delaminated, disordered forms of the following zeolites have
been claimed and are designated as follows: MWW–ITQ-2,24
MCM-56,23,40 FER–ITQ-6,13 and NSI–ITQ-18.41 Except for
MCM-56, all were obtained by firstly pre-swelling or by a
treatment of the corresponding precursors with surfactant
in the presence of TPAOH or other tetralkylammonium
hydroxide sources.
Exploitation of the synthetic opportunities of MCM-22P
materials resulted in the preparation of delaminated ITQ-2
samples by Corma et al.24 The first step in the preparation
of ITQ-2 was swelling of MCM-22P in the solution of
hexadecyltrimethylammonium bromide and tetrapropyl-
ammonium hydroxide38 monitored by XRD. Delamination
was performed by placing the slurry in an ultrasound bath
under controlling pH. While the thickness of the layers is
2.5 nm their distance increased to 4.3 nm after the swelling
step. After calcination, a system of accidentally oriented layers
(‘‘house of cards’’) is produced. Analogy with MWW
structure and TEM study revealed that the surface consists
of 0.7  0.7 nm cups and the 10-ring channel system in the
layer between them. Concentration and particularly location
of aluminium in the cups vs. channel system is critical for their
catalytic application. The benefits of easier site accessibility
and shorter diffusion paths in ITQ-2 resulted in higher
cracking conversions of n-decane, 1,3-diisopropylbenzene,
and vacuum gas oil over ITQ-2 when compared with the
non-delaminated MWW zeolite. The authors indicated the Fig. 4 X-Ray powder patterns of various MCM-22 family materials
danger of surfactant-assisted mesoporous phase formation, obtained by modification of MCM-22P. MCM-22P and MCM-56
e.g. if temperature during sonication is elevated above 50 1C.42 patterns included for comparison.

This journal is c The Royal Society of Chemistry 2011 Catal. Sci. Technol., 2011, 1, 43–53 47

ordered structure MWW (MCM-49) with layer stacking in 3D.
This can be judged based on XRD pattern. The presence of a
dip in the broad band spanning the 8–101 2y region, suggesting
separation into two peaks, indicates MCM-56 is past its
optimal point and the formation of ordered 3D MWW
structure began (Fig. 4). Detailed guidance for distinguishing
different members of the MWW family can be found in a
recent publication.44
An XRD pattern resembling that of MCM-56, specifically a
broad band at 8–101 2y and no diffraction line with hkl indexes
(002) at 6.5 2y has been generated from MCM-22P by
treatment with acetone45 and acid.46 The corresponding
materials are probably different from MCM-56 by still
retaining extensive hydrogen bonding between layers that is
originally present in MCM-22P. As discussed20 this bonding
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does not require orientation perpendicular to MWW and can
result in layers twisting with the loss of vertical alignment.
There may be a simple test of this hypothesis. Earlier only
TPA-OH was shown to be effective as the hydroxide source in
allowing swelling of MCM-22P with surfactant as it is too big to
compete with the latter for entering the interlayer space, which
would thwart swelling. The smaller quaternary ions, like tetra-
methyl and ethyl, were found ineffective as themselves diffusing
between the layers preventing surfactant migration (between the
layers). As reported, MCM-56 can be swollen in the presence of
TMA,19 which is much smaller than TPA, indicating a free access
to its surface and suggests absence of adjacent layers connected
by interlayer H-bonding. These are intriguing basic issues that
may be undertaken in future research.
In addition to the three already mentioned MWW materials
obtained by direct synthesis in the 1990’s, a new one,
designated EMM-10P, apparently missing on theoretical
grounds, has been identified recently.20a The identification is
based on unprecedented XRD combining features of the
MCM-22P and MCM-56. The pattern has a doublet at
6.5–7.21 2y, i.e. indicating expanded layered structure, and a
broad band spanning ca. 8–101 2y indicative of lateral
disorder, i.e. non-aligned stacking. The nature of the disorder
has not been determined but has been tentatively proposed as
having MCM-22P stacking with layers twisted in-plane or
mismatched laterally but with preservation of interlayer
hydrogen bonding through silanols. EMM-10P was obtained
with a diquaternary template, bis(N,N,N-trimethyl)-1,5-
pentanediaminium, Diquat-C5, which may span the adjacent
layers.
The delaminated derivative of zeolite NSI, ITQ-18 was
obtained from the long-known material NU-6(1) based on
the 4,4 0 -bipyridine template.47 The as-synthesized layered
precursor containing the template was treated with a mixture
of surfactant and TPA-OH and then subjected to standard
delamination procedure. Subsequent work48 led to conclusion
that: ‘recipe. . .may lead to materials with high specific areas but,
which not necessarily must have the characteristic long-range
ordering of crystalline ITQ-18’.
In somewhat related work, acid treatment of NU-6(1)
resulted in template removal and then the product,
MCM-39, was reacted with the surfactant hydroxide to
accomplish swelling. The final treatment was transformation
into the pillared product MCM-39(Si).49
48 Catal. Sci. Technol., 2011, 1, 43–53
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In general terms, delaminated zeolites are a rapidly growing
area. There is not enough accumulated information and
validated physical data yet to predict the range of properties
and behaviour to be expected. The problem of proper
identification is of crucial importance. There is an expectation
of structural disorder and implied difficulty with reliability on
the traditional XRD, which is very powerful with regular
zeolites. In fact, an apparently delaminated material
MCM-56 (vide supra) shows that XRD may be quite revealing
about the nature of the product and the extent of disorder but
it does not convey information about structural properties in
the third dimension.
5. Synthesis of pillared materials
The organic expanded interlayer space such as in swollen
materials, can be transformed into permanent large pore
(mesopore) system by the process called pillaring. It entails
treatment with appropriate oxide precursor like liquid
alkoxide, which partially fills the interlayer space. The swelling
organic still left is subsequently removed upon calcination,
which simultaneously generates solid oxide props from
alkoxide keeping the layers apart. The treatment is not
guaranteed to succeed, in which case the interlamellar space
would collapse. An effective and often successful procedure
uses treatment with TEOS followed by hydrolysis with water
and final calcination.50 This generates amorphous silica
between the layers, apparently concentrated in domains
(pillars) while significant amount of void space remains. This
procedure proved very effective for the hexadecyltrimethyl-
ammonium swollen MCM-22P yielding the first pillared
zeolite based material MCM-36 containing interlamellar
mesopores in addition to the layer microporosity.12 The
amount of silica introduced was roughly equal to the amount
of zeolite by weight, judged from changes in Si/Al ratio. The
corresponding TEM of the calcined product shows MCM-22
layers equally spaced with roughly 2.5 nm thick region in
between containing the pillars, which are not visible as amorphous
and without long range periodicity. Successful pillaring for the
entire sample was validated by extensive characterization
including XRD, static and dynamic sorption measurements.
A particular care was taken to prove that the XRD characteristics,
like the low-angle line, and increased BET and sorption
characteristics did not arise from accidentally produced
mesoporous material of the M41S type. Pore size distribution
Fig. 5 TEM images of calcined MCM-36 and MCM-22 showing
permanent separation of the MCM-22 monolayers by pillaring.
This journal is c The Royal Society of Chemistry 2011

obtained based on Ar adsorption indicated mesopores with
maximum at 3–3.5 nm. MCM-36 also showed unique
and valuable catalytic properties, which are discussed in the
corresponding section below.
The exact nature of the pillars, such as lateral dimensions,
spacing and distribution (ordered, disordered) remain a
mystery. The featureless appearance of interlamellar space in
TEM (Fig. 5) of cross-sectioned crystals indicates lack of
regularity and provides no further clue. The typical graphical
representation of pillared materials as regular well shaped
props is unlikely representative of real situation. The most
general description can be that in between zeolite layers there
is a layer of amorphous silica with channels, mainly of the size
2–3 nm, whether regular or not is unknown, but certainly
allowing access to the surface pockets of MWW sheets.
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The very attractive layered MFI derivative announced
recently18 was also subjected to the above pillaring treatment.25
The process was deemed successful and it was claimed that the
generated pillars were not amorphous but also had the MFI
structure concluded from TEM images. The regions identified
as pillars appear commensurate with the adjacent layers. It
results in a continuous regular pattern of apparent MFI pores
suggesting congruent underlying structure extending vertically
through several layers. As the first and clearly unexpected case
of ‘crystalline pillars’ this result requires further validation,
and presents intriguing possibilities for catalytic activity and
structure stability.
Pillaring represents a kind of permanent layer separation,
while as discussed above the pillar structure and distribution
between layers can be generally characterized as disordered
(except for the MFI claim25). The recent stabilization of
MCM-22P in its expanded form by silylation21 may be viewed
as discrete ordered pillaring. In fact, it provides the first
example of ordered pillaring. It was initially demonstrated
with Ti-MWW, as Ti-YNU-1,22 and subsequently extended to
standard MWW and then other layered precursors.21 The net
result of this process is a larger pore version of MCM-22,
effectively with 12-ring channels between the layers vs. 10-ring
in the conventional MWW. The connecting moiety is identified
as Si(OH)2 with remaining 2 valences spanning adjacent
MWW layers though the T1 sites.22,51
The pillaring procedures discussed above were carried out
with silica reagents, which proved most convenient and
effective to date. The corresponding pillaring reagents are liquids
with possibly the right balance of reactivity towards organics,
polymerization and hydrolysis. To date there is no control over
the pillar distribution and size as the intercalated swelling
substance seems to determine final interlayer porosity. These
are clearly variables that may require fundamental studies.
Table 2 Comparison of catalytic performance of different zeolites in C4 alkylation
Catalyst SiO2/Al2O3 T/1C Yield (wt/wt) C8 (wt%)
MCM-22, MCM-49 o 20 150 — —
MCM-36 430 150 2.1 53
Zeolite beta 24–30 90 2.0 69
Faujasite, EMT 10–12 80 1.3–2.0 72–76
HF n.a. 32 2.0 90
H2SO4 n.a. 7 2.0 81
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Alternative pillar compositions have been explored
including Al2O3, MgO–Al2O3, BaO–Al2O3, Al2O3–SiO2,
MgO–Al2O3–SiO2, and BaO–Al2O3–SiO2 yielding new
derivatives of MCM-36.52 Enhanced Lewis acidity was generated
with aluminium oxide-containing pillars, while basic properties
were introduced upon pillaring with alkaline earth oxide
aluminates (MgO/BaO–Al2O3). These approaches represent
promising methodology for tailoring acid–base properties of
zeolitic catalysts.
6. Adsorption and catalytic opportunities
While pillared and delaminated materials exhibit large surface
areas comparable with mesoporous materials not too many
examples of their adsorption studies have appeared in the
literature in contrast to the latter. This might be due to more
complex synthetic procedures when related to easier and
straightforward one-pot syntheses of mesoporous molecular
sieves although some textural features of e.g. SBA-15 (surface
roughness53) can limit application and understanding of
adsorption on them. In contrast, catalytic studies are rather
frequent evidencing some advantages over 3D zeolites.
Mesoporous materials modified with different amines offer
high capacities for CO2 adsorption.54 However, ITQ-6
(delaminated FER material) modified by different aminopropyl
groups exhibits higher adsorption efficiency in the whole
region of CO2 pressures, defined as the number of adsorbed
CO2 molecules per one amine ligand.55 This could indicate
that smooth surface of ITQ-6 layers is more adequate for
the spreading of aminopropyl groups resulting in a higher
adsorbed amount of CO2 per amine group.
In catalysis, the accessibility of large external surface of
delaminated or pillared materials is crucial as most of the
reactions over these catalysts would occur on the external
zeolite surface. Delaminated or pillared catalysts with a large
and well organized external surface of tiny zeolitic crystals
allow accessibility of active sites for bulky organic molecules,
which would be otherwise sterically restricted by the channel
entrances of conventional zeolites.
While the entire area of modified layered zeolite structures is
of general fundamental interest the ultimate practical goal is to
gain advantage compared with the parent zeolite. In fact, in
order to be a viable candidate for development beyond
laboratory the benefits must be substantial to offset the cost
and trouble associated with additional, often demanding
processing steps. Improved performance relative to the parent
zeolite may be also treated as evidence that the attempted
modification has been indeed successful. This may be
exemplified by MWW, which itself is a highly active zeolite,
Stability/g alkylate
Me3C5/Me2C6 Octane # RON/MON per g catalyst
— — —
2.4 91–93 23
2.2 91–93 12.5
4.1–4.2 91–97 2.1–44.8
7.6 94–97 100
6.4 94–96 8.7
Catal. Sci. Technol., 2011, 1, 43–53 49

thus if attempted modification fails the product is still likely to
exhibit high activity.
The evidence of catalytic enhancement upon pillaring of a
zeolite was provided originally by MCM-36.56,57 It must be
appreciated that in its original form it contains roughly 50%
by weight of amorphous silica, which is inactive and in many
processes, such as cracking, MCM-36 performance may
appear like ‘diluted’ MCM-22. However, in some processes
the superiority of MCM-36 was without any doubt. In the
report by Schweitzer and van den Oosterkamp56 the published
patent data were compiled to compare activity of several
zeolites in olefin alkylation of isobutane, which is an important
industrial process currently practised in the refineries with HF
and sulfuric acid as catalysts. Zeolites are in general inferior to
liquid acid catalysts in this process but MCM-36 showed good
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performance in particular with regard to resistance to
deactivation as shown in Table 2. In contrast, MCM-22
activity was poor providing low yields and product quality.
Evidently the expanded interlayer space offered advantages
compensating the acid site dilution (less active zeolite and
presence of amorphous silica pillars). The benefits of more
open structure were revealed in a liquid phase ethylbenzene
synthesis by MCM-56.58 The monolayer MCM-56 showed
higher activity than the conventional 3D zeolites with
analogous framework, MCM-22 and MCM-49.
m-Xylene transformation at 350 1C has been developed to
estimate the activity and selectivity of the three pore systems in
MCM-22 materials (sinusoidal channels, supercages and
external cups).59 Compared with regular MCM-22, pillaring
caused a great change in the distribution of the activity: only
approximately 15% of m-xylene transformation occurred in
the 10-ring intralayer pores in MCM-36 vs. more than 70% in
the parent MCM-22 sample. The rest, i.e. 85% of the activity
of MCM-36 (30% in MCM-22) is attributed to surface
pockets, which may be accessible to larger molecules.
Maheshwari et al.60 reported that a milder swelling and
pillaring process prevents destruction of the material and
improved retention of zeolitic layers. As a result, higher
conversions of MCM-36 prepared at room temperature
compared with those of high temperature treatment were
achieved in vacuum gas–oil cracking and transformations of
aromatics.
ITQ-2 prepared from MWW lamellar precursor and having
surface areas larger than 700 m2 g1, showed superiority over
MWW and MCM-36 in vacuum oil cracking. ITQ-2 exhibited
higher conversion and yield of gasoline than other catalysts
and similar yield of diesel as MCM-36. ITQ-2 is also highly
active in reaction leading to the preparation of fine chemicals.
In particular, ITQ-2 was superior for dimethylacetals and
tetrahydropyranylation of alcohols and phenols over zeolites
Scheme 1 Reaction scheme of the formation of 2-methyl-2-naphthyl-
4-methyl-1,3-dioxolane.
50 Catal. Sci. Technol., 2011, 1, 43–53
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BEA and MWW for bulky substrates.61 When small substrates
were used similar conversions were achieved evidencing the
similar role of acid sites in all materials. Steric exclusion of
bulkier substrates, not accessing zeolite channels, made ITQ-2
favourable for these reactions. The yield of acetalization
of 2-acetonaphthalene with propylene glycol increased in
the order BEA (5%) o MWW (20%) o ITQ-2 (63%)61
(Scheme 1)
The literature reports about catalytic activity of MCM-56
paint a somewhat inconsistent picture. Juttu and Lobo found
their preparation to be largely inactive, which they attributed
to coiling of the sheets observed in micrographs.62 A comparison
between ITQ-2 and MCM-56 in large molecules conversion
was reported to favour the former material.45 As mentioned
above, MCM-56 appeared superior to MWW (MCM-22 and
MCM-49) in liquid phase alkylation, which can be interpreted
as advantage because of disordered/delaminated nature. The
alkylation reactions studied in a gas phase led to the conclusion
that the reactions proceed exclusively on the external surface
of tiny MWW sheet crystals.63,64 This supports the superior
catalytic activity of MCM-56, as this 2D zeolite exhibits much
larger external surface. One must factor in the intermediate
nature of MCM-56 during synthesis, which may cause isolation
of product, either too early or too late and consequently not
having the optimal performance.
Comparison of ITQ-2 and MWW modified with Mo was
carried out by Martinez and co-workers65 for methane
dehydroaromatization. ITQ-2 produced more naphthalene
and less benzene than MWW. The selectivity to benzene was
substantially improved by surface dealumination of the ITQ-2
zeolite with simultaneous decrease in naphthalene formation.
Molecular dynamics simulation and treatment of the external
surface evidenced the primary formation of naphthalene on
the active sites located at the external surface of ITQ-2.65
Recently, Lima et al. reported on the preparation of
delaminated zeolite derived from the layered material
Nu-6(1).66 This delaminated catalyst exhibited conversion of
about 80–85% in the liquid phase cyclodehydration of xylose
to furfural with moderate furfural yields.
Relatively flat external surface of delaminated materials
offers nice opportunity to attached organometallic complexes.
ITQ-2 and ITQ-6 were studied also in Heck and Suzuki
coupling reactions. In this case, Schiff base 2-tert-butyl-
4-methyl-6{(E)-[(2S)-1-(1-arylmethyl)pyrrolidinyl] imino}-
methylphenol (aryl = phenyl, 1-naphthyl, 2-naphthyl) were
used as anchoring ligands. After addition of Pd acetate high
activity was achieved with recyclability and no leaching.67
Continuing this research, group of Corma immobilized
mononuclear asymmetrical N-heterocyclic carbene-gold
complexes on delaminated zeolite (ITQ-2). These complexes
exhibit TOFs up to 400 h1 in hydrogenations of alkenes and
Suzuki coupling without dramatic deactivation.68 In another
work zirconocenes Cp2ZrCl2 and (nBuCp)2ZrCl2 were grafted
to the surface of delaminated and mesoporous supports.
Although SBA-15 modified catalyst achieved the highest
activities in polymerization ethylene, promising results were
obtained also with MWW and ITQ-2 supports.69 Polymerization
reaction proceeded at the presence of methylalumoxane as
co-catalyst.
This journal is c The Royal Society of Chemistry 2011

Catalytic investigations of delaminated materials were
extended to Ti-containing catalysts.70 Corma et al. demonstrated
that Ti-ITQ-6 is highly active in hexene and norbornene
epoxidation and this catalyst showed higher activity than
Ti-FER or Ti-BEA. High stability of the conversion is due
to exclusive tetrahedral coordination of Ti in the silica matrix,
which was maintained even after the reaction.70 High activity
of delaminated Ti-zeolites was confirmed for cyclooctene and
cyclododecene by group of Tatsumi.71 Zeolite MWW with
titanium demonstrated exceptional activity as an oxidation
catalyst and has been extensively studied since.72–74 The
corresponding lamellar precursor form became attractive for
modifications, previously discussed and implemented in
practice, like delaminated and pillared forms. In fact, the first
example of the precursor stabilized in the expanded form, now
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designated IEZ-MWW, was obtained in the Ti-MWW system
and designated Ti-YNU-1.22 Its crystal structure was determined
by Rietveld refinement.22 This material showed enhanced
activity compared with other titanosilicates and attributed
by the authors to ‘formation of twelve-rings. . ., which results
in increased steric accessibility. . .’. Subsequently, attempts
were made to swell Ti-MWW to synthesize delaminated and
pillared derivatives. The former was reported to be superior to
TS-1, Ti-Beta, conventional 3D Ti-MWW and Ti-MCM-41 in
the epoxidation of a wide range of bulky alkenes with
hydrogen peroxide.75 Ti-MCM-36 synthesized by standard
procedure was tested for 1-hexene and propylene epoxidation
reactions using H2O2 as an oxidant and reported superior
performance of Ti-MCM-36 over Ti-MCM-22 or TS-1.76 Both
reports provided XRD patterns of the final catalysts but
without analysis to verify layer packing.
Superior catalytic behaviour of delaminated and pillar
zeolites in some acid and oxidation reactions is usually
attributed to high surface areas of these catalysts and easy
accessibility of the active sites on the external surface. Surface
areas of external surface are at the range of 700–900 cm2 g1
and are comparable with surface areas of mesoporous
molecular sieves. Recent results of Gil et al. showed the
invariance and homogeneity of the concentration of Brønsted
sites on the external surface for the series of MCM-22 and
MCM-49 with different Si/Al ratios.77
Combination of inorganic (zeolitic) layers with organic
pillars represents another interesting approach to prepare
active catalysts. Kuroda et al. showed that layered octosilicate
can be treated with 1,4-bis(trichloro- and dichloromethyl-silyl)
benzenes to prepare microporous inorganic–organic hybrids.78
They subsequently hydrolyzed the chlorosilane moieties and
the resultant silanols were close enough to enable condensation
into a Si–O–Si interlayer bridge. Very recently, a novel layered
zeolitic organic–inorganic material (MWW-BTEB) has been
reported by group of Corma79 combining intercalation and
stabilization of arylic silsesquioxane molecules between inorganic
zeolitic MWW layers. 1,4-Bis(triethoxysilyl)benzene (BTEB)
was used as organic linker being aminated after the synthesis.
The reported approach led to the of bifunctional acid–base
catalysts exhibiting the acid sites of zeolitic nature combined
with basic sites of the organic structure. This bifunctional
catalyst was studied in a two-step cascade reaction that of
benzaldehyde dimethylacetal into benzylidene malononitrile.79
This journal is c The Royal Society of Chemistry 2011
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7. Summary and challenges
Up-to-date, 10 frameworks have been recognized as having a
layered precursor but not all among them have been prepared by
both the direct (3D assembly) and indirect (layered precursor)
synthesis pathway. More layered precursors are expected based
on the fact that some long well-known conventional frameworks
have been found only recently to have a lamellar form.
Particularly encouraging is the case of MFI because of its 3D
pore system. One may wonder if structures with isotropic
distribution of density, i.e. the same in 3D, are also capable of
showing layered precursors but we cannot point to a specific
principle that may rule out lamellar forms for most, possibly all
frameworks, as hypothesized earlier.23 The recent MFI case is
also remarkable as apparently the first one where template was
designed specifically for the purpose. In general, new precursors
have been obtained accidentally thus availability of rational
approaches is needed as it could facilitate further progress and
directed expansion. In short, better understanding of factors
affecting pathway selection for the framework or layer assembly
would be very helpful. As the lamellar MFI provides layers with
10-ring channels through the layer it might be desirable to obtain
layers with bigger channels like 12-ring and higher. This implies
that precursors of zeolites like FAU, EMT or BEA would be
highly valuable.
Simultaneously, the area expands in terms of new layered
architectures demonstrated. Here MCM-22 shows most
diversity with 6 different types of layer assemblies, while the
other frameworks are being gradually modeled on the
known MWW materials. Aside from ‘standard’ layered
precursor forms, MWW afforded rather unexpected remarkable
materials spontaneously (MCM-56) or by post-synthesis
modification (IZE-MWW). This suggests that additional
structure types are possible and should be anticipated with
enough effort and ingenuity. As the number of possibilities is
increasing (different frameworks and layer packings) the
attempts may become more selective with elements of design
and focus on most promising precursors. It is easy to visualize
ordered pillared materials with controlled pillar population
and density, which would enable tailoring of large pore size of
zeolitic structures.
In contrast to the framework rigidity and immutability, the
lamellar forms offer the first and basically open-ended
opportunity for post-synthesis modifications. The structural
aspect has been already discussed in the paragraphs throughout
this narrative. There is of course the option to use additional
compositions, e.g. for pillars or other layer spacers, or just as
deposits on the surface to modify properties. Delaminated
materials may be made into mixtures with different layer
topologies, as a fundamental option, but it may also turn
out to offer practical benefits.
Another area of development may be the synthesis in terms
of direct preparation without pre-swelling or at least without
separation of intermediates of modified structures. Typically
the modifications require several step procedures, which
increases cost offsetting potential benefits offered by the more
open structures. The only example to date is MCM-56, as the
delaminated zeolite obtained in one step, suggesting other may
be possible, too.
Catal. Sci. Technol., 2011, 1, 43–53 51

For now we know very little about the factors deciding
whether the structure will propagate directly in 3D structure or
terminate as a layer. As already suggested, MCM-22 and
MCM-49 may provide the clue as they show the switch from
one pathway to the other upon slight changes in composition.
It was proposed19 that aluminium may play a significant role
in this process but it is not well understood at this time.
Catalytic examples are rather broad covering area of
cracking, some petrochemical applications up to synthesis of
fine chemicals. Having in mind the structure of 2D zeolites and
accessibility of active sites we do not expect some progress in
shape-selective reactions as typical zeolite domain. In contrast,
delaminated and pillared zeolite-based catalysts can offer high
activities for transformations of bulky substrates or might be
site-specific for reactions proceeding on the external surface of
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zeolite layers. On the other hand, the performance of MCM-36
in C4 alkylation, i.e. resistance to deactivation, implies other
benefits that may be possible with open architectures. It may
be that in such cases retention of coke is not favored resulting
in persistence of high activity.
Introduction of active metal sites (e.g. Al, Ti, Ga, Fe, etc.) in
specific crystallographic sites is still a matter of vivid discussion in
classical zeolites. Recently, Perez-Pariente and co-workers
showed80,81 that controlled synthesis of FER can introduce
aluminium exclusively to one crystallographic site. This evidences
the potential of synthesis of zeolite catalysts with pre-defined
catalytic activity and probably also selectivity, as one site might
preferentially catalyze the reaction in the required way. As soon
as this synthetic approach will be applied for other zeolites,
particularly those prepared at first as layered precursors, it could
be possible to obtain e.g. layered zeolitic precursors with or
without any aluminium on the surface. This would open
considerably the application potential of these zeolites.
Based on the knowledge and potential of zeolites numerous
opportunities can be opened for 2D zeolites both from the
fundamental as well as application point of view. Some of the
challenges can be summarized as follows:
The most frequently studied lamellar precursors FER-P and
MCM-22P lead by high-temperature treatment to tiny sheet
zeolitic crystals. We wonder if there is any relationship between
the final crystal shape of zeolites, their inner structure and the
mechanism of the formation of a lamellar precursor. Successful
syntheses of lamellar SOD zeolite provided clear evidence that
even cubic zeolites can be prepared via their lamellar form.
Up to now, we know that active layers and non-active
pillars can be prepared with a possible exception of MFI
pillared materials (as discussed vide supra). Pure siliceous
layers could be used to stabilize some highly active species in
the form of pillars and in optimum way to control size and
shape of the pillars and their catalytic activity.
Post-synthesis treatment of MWW by desilication has been
recently reported attempting to connect two independent
channel systems.82 For some catalytic applications it might
be beneficial to form ordered channels (holes) in c-direction
for delaminated (pillared) materials.
Last but not least, while the ‘‘synthesis–structure’’
relationships are mainly of a fundamental interest, the possible
applications of 2D zeolites in adsorption, catalysis, sensing is
extremely challenging. Optimization of catalytic performance
52 Catal. Sci. Technol., 2011, 1, 43–53
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with cost of large-scale production shall be targeted for
industrial application.
Acknowledgements
J.Č. thanks the Academy of Sciences of the Czech Republic
(KAN100400701) and the Grant Agency of the Czech
Republic (104/09/0561 and 203/08/0604).
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