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Cite this: Catal. Sci. Technol., 2011, 1, 43–53

www.rsc.org/catalysis PERSPECTIVE
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 of the aperture usually consisting of 6, 8, 10, 12, 14, 18 and 20


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

This journal is c The Royal Society of Chemistry 2011 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 layered precursor, summarized in ref. 20, which was expanding
precursor was viewed11 and demonstrated12 that it could be the number and diversity of structurally distinct materials
structurally modified after the synthesis. At the same time, the based on the MWW structures, referred to as the MCM-22
layered precursor versions of other frameworks were found, family.
expanding the field to other zeolites, most notably some The objective of this contribution is to provide up-to-date
classical representatives like FER,13,14 SOD,15–17 and recently knowledge and challenges associated with ‘‘two-dimensional
MFI.18 Various forms like pillared and delaminated structures zeolites (2D zeolites)’’, which herein means those having the
built from framework monolayers (components of the layered third dimension limited to about 2–3 nm, thus, the dimension
precursors) were being proposed and realized (see ref. 19). corresponding to 1–2 unit cells, and to discuss the capability to
MCM-22 was leading the way in demonstrating novel types of modify zeolites structurally to get new adsorbents and catalysts.
layered structures, like pillared, delaminated and disordered 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
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stems from the fact that with 2D zeolites adsorption and discoveries of the layered precursors of frameworks have
catalysis occur almost exclusively on the surface of these become more frequent.18,19 Generally speaking, the synthesis
materials and not inside the zeolite pores. The present mixture compositions and conditions applied to date favoured
publication outlines some practical benefits while at the same direct framework assembly with 3D connectivity, i.e. afforded
time discussing future prospects and opportunities. In addition, traditional zeolites. MWW formation may again provide some
we focus on challenges associated with characterization of insights into alternative routes as it shows transition from
these novel materials, which requires systematic and meticulous direct to the lamellar pathway upon slight adjustment of the
approach for their synthesis and proper identification. reaction mixture composition, namely the case of MCM-22P
In this perspective we refer to (i) pillared materials—they and MCM-49 synthesis.10,11 The family of MWW zeolites and
have permanently expanded interlamellar distance/space related materials is presented in Fig. 2. A detailed analysis of
caused by the presence of localized props (pillars) made of the underlying reasons for the formation of MCM-22P and
silica or other thermally stable substances. They are typically MCM-49 has not been considered in publications. It is evident
produced by initial intercalation of expanding/swelling organic that to achieve formation of a layered precursor the frame-
substance followed by treatment and insertion of a soluble work growth must be prevented from propagation in the third
material that transforms into pillars upon burning off of the dimension. The end effect is the presence of silanol groups or
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intercalant. (ii) Delaminated zeolites—separated into constituent their deprotonated moieties on the surface of the layers. This
layers, may be understood as any collection of zeolite layers termination happens because of blockage by the template or
that are not ordered, without alignment in the third direction, other factors preventing sustainable attachment of another
and ideally without any connections among the layers, except silicate tetrahedra or small units to that site. Further probe
for incidental. (iii) Stabilized precursors (IEZ—interlamellar into what factors or maybe particular types of atoms do
expanded zeolites)21,22 layered precursors with interlayer stabilize T–OH termination, may enable more designed
separation made permanent, e.g. by treatment with silylating approach to the synthesis of layered zeolite structures.
agents. At present, around 10 zeolites (e.g. MWW, The MWW framework has been, to date, arguably the
FER, Table 1) have a layered precursor known. The first major source of diversity and innovation in this area.20,21,23
comprehensive review of this emerging subject was published It marks the advances in terms of new structures, fundamental
in 2007 and has not been updated since then.19 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
2. Synthesis of layered zeolite precursors
are now 4 different MWW related materials known that were
The first critical step towards entry into the area of modified obtained by direct synthesis:20 3D structure (MCM-49),
precursors is the actual preparation and identification of a layered precursors (ordered MCM-22P and disordered
layered precursor or some other lamellar zeolite forms. Such EMM-10P) and delaminated (MCM-56). Fig. 3 provides
syntheses occurred typically unexpectedly upon conventional comparison of X-ray powder patterns of these MWW materials
organic templated preparations. They are usually recognized obtained by direct synthesis. The modified derivatives include
when the as-synthesized product changes XRD pattern upon pillared MCM-36,12 delaminated ITQ-2,24 and stabilized
calcination.11 New findings have been rare but recent precursors (IEZ).21 MWW family also sets the standard

Fig. 2 Updated MCM-22 ‘family tree’ illustrating proposed layer arrangements and synthesis pathways.

This journal is c The Royal Society of Chemistry 2011 Catal. Sci. Technol., 2011, 1, 43–53 45
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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
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Fig. 3 X-Ray powder patterns of various MCM-22 family materials


obtained by direct synthesis. 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
for identification of various types of materials (structure and CDO.29,30
arrangements) by X-ray powder diffraction.20,23 Based on Several layered zeolite precursors have been identified in the
detailed analysis of positions and appearance of diffraction course of systematic work on templated silicate synthesis by
lines the procedure allows unambiguous identification of a Gies and co-workers, who designate their products with
particular structure (layer packing, distance and order) and acronym RUB. Remarkably one of them turned out to be
even detection of mixtures.19 Regarding post-synthesis layered precursor of the well known framework SOD,15 which
modification, XRD is invaluable in confirming the quality provided a convenient aqueous route to all siliceous sodalite.
and extent of the intended transformation thus validating Other frameworks reported by this group are also notable as
veracity of a particular procedure and sample structural being obtained by the layered intermediate route only.31,32 The
characteristics. The MCM-22 family has been the template direct framework synthesis is expected but has not been
to follow in developing other layered families in terms of observed yet. The group of Gies is also a leader in systematic
synthesis, identification and characterization.14,21 and thorough structure determination33 and analysis of
The recent lamellar MFI discovery (‘single-unit-cell various layered precursors and has revealed valuable insights
nanosheets’) represents a very promising step-out change by including structure of EU-20b, containing both NSI and CAS
providing a possible general approach to the synthesis of frameworks in one sample.34
zeolitic lamellar precursors.18,25 It involves an SDA with one The framework AFO, AlPO-41, was obtained both directly
end designed to template the zeolite framework (in this case and from layered aluminophosphate precursor.35 The latter
MFI) while the other end is a long chain preventing adjacent was obtained with a bulky macrocycle polyamine as the
growth of another (connected) layer, simultaneously providing structure directing agent. The complete AFO topology
organic interlayer between the MFI monolayers. The overall required translation of alternate layers by 0.5a and 0.5b with
effect is a direct synthesis of a hybrid structure, equivalent to a condensation.
swollen product, with alternating inorganic and organic layers.
These layers were reported to have 2.0 and 2.8 nm height, 3. Expansion and swelling of the as-synthesized
respectively based on TEM images. Identification also
precursors
included XRD, which showed overall similarity to MFI but
only h0l reflections were sufficiently distinct to enable indexing, This has been historically the most difficult and critical step in
i.e. assignment of (hkl) indices. This indication of short modification of the precursors, which can be then delaminated
crystallographic order in the b-direction is consistent with and pillared. Again, MCM-22 provided the first published
the proposed hybrid structure. Removal of the template by example12 indicating that it was a rather demanding treatment
calcination did not produce well ordered MFI, but the sample entailing the use of surfactant solution at high pH. The pitfalls
had a considerable mesoporosity, attributed to non-congruent are obvious now—there is a danger of silica solubilization,
collapse. A follow up publication reported dimension of the which is promoted by basic environment and possible
product somewhat differently with repeat 6.1 nm including formation of an M41S phase.36 The first successful swelling
2.0 nm MFI layer and 4.1 nm organic part.25 It also claimed of MCM-22P was achieved with a surfactant hydroxide
successful synthesis of the pillared derivative so we will solution free from other cations, as the most common ones,
continue discussion in the corresponding section 5. like Na+ and tetramethylammonium, would diffuse
Additional attractive feature of the MFI layers is the preferentially into the interlayer space.37 It was subsequently
presence of perpendicular pores, which enable transport established that it was possible to use a solution with potentially
across, i.e. in three dimensions, through the crystal. Another non-interfering cation supplying hydroxide ions together with
material with pores across is AMH-3 with 8-ring apertures, a surfactant salt instead of the less desirable surfactant
which are, however, inaccessible for most of organic hydroxide. That cation had to be excluded by its size from

46 Catal. Sci. Technol., 2011, 1, 43–53 This journal is c The Royal Society of Chemistry 2011
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competing for the interlayer space and tetrapropylammonium Related studies concluded that efficiency of ITQ-2 production
(TPAOH) was found suitable38 and commonly used since in is better at higher Si/Al ratio.43 This study also showed
swelling/delamination of other zeolite precursors. significant dissolution of the MWW layers and consequent
The relative complexity of swelling, its severity and potential diminished yield of the solid product.
undesirable reactions impose a special demand for verification In continuation of this research, ITQ-6—the delaminated
that indeed the intended effect, i.e. swelling with no mesoporous form of FER, was prepared again by the group of Corma14
MCM-41 or related phase formation, was realized. XRD is in from PreFER.13 For the preparation of PreFER (or FER-P),
general the adequate tool that can be used for that. As 4-amino-2,2,6,6-tetramethylpiperidine was used instead of
illustrated by the first case of MCM-22 some of the new pyridine, piperidine or other templates usually used for the
features in the XRD patterns indicative of interlamellar direct synthesis of 3D FER. Further treatment of PreFER
expansion were not anticipated and needed validation by resembles that for the synthesis of ITQ-2. It could be inferred
accumulation of evidence. The topic has been described in that the addition of four methyl groups to piperidine is
great detail12 and here we mention only the final conclusions. important for blocking of the stacking of the individual
Successful swelling of MCM-22P can be proven based on two FER layers and enables the post-synthesis treatment, FER-P
features, a low angle line, typically around 5 nm of d-spacing to ITQ-6.
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and transformation of the diffraction lines initially at 8 and 101 MCM-56 deserves a special consideration as the only
2y CuKa, into a broad band without a dip somewhere in apparently delaminated zeolite to date obtained spontaneously
between these two positions. At the same time the initial in the course of a standard hydrothermal synthesis.23,40 This
(002) reflection at the d-spacing B1.34 nm had to disappear represents a convenient entry to delaminated materials
completely. with enormous advantage in cost and labour for further
As mentioned, the above synthetic procedure for swelling experimentation (treatments). The synthesis is somewhat more
using surfactant with TPAOH has been used with other demanding than the conventional zeolite preparation because
precursors. Recently, swelling of MCM-22P under milder the MCM-56 is an intermediate that must be intercepted at the
conditions has been explored.39,60 It was concluded that right moment before the onset of slow conversion to the
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.

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.

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ordered structure MWW (MCM-49) with layer stacking in 3D. In general terms, delaminated zeolites are a rapidly growing
This can be judged based on XRD pattern. The presence of a area. There is not enough accumulated information and
dip in the broad band spanning the 8–101 2y region, suggesting validated physical data yet to predict the range of properties
separation into two peaks, indicates MCM-56 is past its and behaviour to be expected. The problem of proper
optimal point and the formation of ordered 3D MWW identification is of crucial importance. There is an expectation
structure began (Fig. 4). Detailed guidance for distinguishing of structural disorder and implied difficulty with reliability on
different members of the MWW family can be found in a the traditional XRD, which is very powerful with regular
recent publication.44 zeolites. In fact, an apparently delaminated material
An XRD pattern resembling that of MCM-56, specifically a MCM-56 (vide supra) shows that XRD may be quite revealing
broad band at 8–101 2y and no diffraction line with hkl indexes about the nature of the product and the extent of disorder but
(002) at 6.5 2y has been generated from MCM-22P by it does not convey information about structural properties in
treatment with acetone45 and acid.46 The corresponding the third dimension.
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 5. Synthesis of pillared materials
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does not require orientation perpendicular to MWW and can


result in layers twisting with the loss of vertical alignment. The organic expanded interlayer space such as in swollen
There may be a simple test of this hypothesis. Earlier only materials, can be transformed into permanent large pore
TPA-OH was shown to be effective as the hydroxide source in (mesopore) system by the process called pillaring. It entails
allowing swelling of MCM-22P with surfactant as it is too big to treatment with appropriate oxide precursor like liquid
compete with the latter for entering the interlayer space, which alkoxide, which partially fills the interlayer space. The swelling
would thwart swelling. The smaller quaternary ions, like tetra- organic still left is subsequently removed upon calcination,
methyl and ethyl, were found ineffective as themselves diffusing which simultaneously generates solid oxide props from
between the layers preventing surfactant migration (between the alkoxide keeping the layers apart. The treatment is not
layers). As reported, MCM-56 can be swollen in the presence of guaranteed to succeed, in which case the interlamellar space
TMA,19 which is much smaller than TPA, indicating a free access would collapse. An effective and often successful procedure
to its surface and suggests absence of adjacent layers connected uses treatment with TEOS followed by hydrolysis with water
by interlayer H-bonding. These are intriguing basic issues that and final calcination.50 This generates amorphous silica
may be undertaken in future research. between the layers, apparently concentrated in domains
In addition to the three already mentioned MWW materials (pillars) while significant amount of void space remains. This
obtained by direct synthesis in the 1990’s, a new one, procedure proved very effective for the hexadecyltrimethyl-
designated EMM-10P, apparently missing on theoretical ammonium swollen MCM-22P yielding the first pillared
grounds, has been identified recently.20a The identification is zeolite based material MCM-36 containing interlamellar
based on unprecedented XRD combining features of the mesopores in addition to the layer microporosity.12 The
MCM-22P and MCM-56. The pattern has a doublet at amount of silica introduced was roughly equal to the amount
6.5–7.21 2y, i.e. indicating expanded layered structure, and a of zeolite by weight, judged from changes in Si/Al ratio. The
broad band spanning ca. 8–101 2y indicative of lateral corresponding TEM of the calcined product shows MCM-22
disorder, i.e. non-aligned stacking. The nature of the disorder layers equally spaced with roughly 2.5 nm thick region in
has not been determined but has been tentatively proposed as between containing the pillars, which are not visible as amorphous
having MCM-22P stacking with layers twisted in-plane or and without long range periodicity. Successful pillaring for the
mismatched laterally but with preservation of interlayer entire sample was validated by extensive characterization
hydrogen bonding through silanols. EMM-10P was obtained including XRD, static and dynamic sorption measurements.
with a diquaternary template, bis(N,N,N-trimethyl)-1,5- A particular care was taken to prove that the XRD characteristics,
pentanediaminium, Diquat-C5, which may span the adjacent like the low-angle line, and increased BET and sorption
layers. characteristics did not arise from accidentally produced
The delaminated derivative of zeolite NSI, ITQ-18 was mesoporous material of the M41S type. Pore size distribution
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 Fig. 5 TEM images of calcined MCM-36 and MCM-22 showing
into the pillared product MCM-39(Si).49 permanent separation of the MCM-22 monolayers by pillaring.

48 Catal. Sci. Technol., 2011, 1, 43–53 This journal is c The Royal Society of Chemistry 2011
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obtained based on Ar adsorption indicated mesopores with Alternative pillar compositions have been explored
maximum at 3–3.5 nm. MCM-36 also showed unique including Al2O3, MgO–Al2O3, BaO–Al2O3, Al2O3–SiO2,
and valuable catalytic properties, which are discussed in the MgO–Al2O3–SiO2, and BaO–Al2O3–SiO2 yielding new
corresponding section below. derivatives of MCM-36.52 Enhanced Lewis acidity was generated
The exact nature of the pillars, such as lateral dimensions, with aluminium oxide-containing pillars, while basic properties
spacing and distribution (ordered, disordered) remain a were introduced upon pillaring with alkaline earth oxide
mystery. The featureless appearance of interlamellar space in aluminates (MgO/BaO–Al2O3). These approaches represent
TEM (Fig. 5) of cross-sectioned crystals indicates lack of promising methodology for tailoring acid–base properties of
regularity and provides no further clue. The typical graphical zeolitic catalysts.
representation of pillared materials as regular well shaped
props is unlikely representative of real situation. The most
6. Adsorption and catalytic opportunities
general description can be that in between zeolite layers there
is a layer of amorphous silica with channels, mainly of the size While pillared and delaminated materials exhibit large surface
2–3 nm, whether regular or not is unknown, but certainly areas comparable with mesoporous materials not too many
allowing access to the surface pockets of MWW sheets. examples of their adsorption studies have appeared in the
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The very attractive layered MFI derivative announced literature in contrast to the latter. This might be due to more
recently18 was also subjected to the above pillaring treatment.25 complex synthetic procedures when related to easier and
The process was deemed successful and it was claimed that the straightforward one-pot syntheses of mesoporous molecular
generated pillars were not amorphous but also had the MFI sieves although some textural features of e.g. SBA-15 (surface
structure concluded from TEM images. The regions identified roughness53) can limit application and understanding of
as pillars appear commensurate with the adjacent layers. It adsorption on them. In contrast, catalytic studies are rather
results in a continuous regular pattern of apparent MFI pores frequent evidencing some advantages over 3D zeolites.
suggesting congruent underlying structure extending vertically Mesoporous materials modified with different amines offer
through several layers. As the first and clearly unexpected case high capacities for CO2 adsorption.54 However, ITQ-6
of ‘crystalline pillars’ this result requires further validation, (delaminated FER material) modified by different aminopropyl
and presents intriguing possibilities for catalytic activity and groups exhibits higher adsorption efficiency in the whole
structure stability. region of CO2 pressures, defined as the number of adsorbed
Pillaring represents a kind of permanent layer separation, CO2 molecules per one amine ligand.55 This could indicate
while as discussed above the pillar structure and distribution that smooth surface of ITQ-6 layers is more adequate for
between layers can be generally characterized as disordered the spreading of aminopropyl groups resulting in a higher
(except for the MFI claim25). The recent stabilization of adsorbed amount of CO2 per amine group.
MCM-22P in its expanded form by silylation21 may be viewed In catalysis, the accessibility of large external surface of
as discrete ordered pillaring. In fact, it provides the first delaminated or pillared materials is crucial as most of the
example of ordered pillaring. It was initially demonstrated reactions over these catalysts would occur on the external
with Ti-MWW, as Ti-YNU-1,22 and subsequently extended to zeolite surface. Delaminated or pillared catalysts with a large
standard MWW and then other layered precursors.21 The net and well organized external surface of tiny zeolitic crystals
result of this process is a larger pore version of MCM-22, allow accessibility of active sites for bulky organic molecules,
effectively with 12-ring channels between the layers vs. 10-ring which would be otherwise sterically restricted by the channel
in the conventional MWW. The connecting moiety is identified entrances of conventional zeolites.
as Si(OH)2 with remaining 2 valences spanning adjacent While the entire area of modified layered zeolite structures is
MWW layers though the T1 sites.22,51 of general fundamental interest the ultimate practical goal is to
The pillaring procedures discussed above were carried out gain advantage compared with the parent zeolite. In fact, in
with silica reagents, which proved most convenient and order to be a viable candidate for development beyond
effective to date. The corresponding pillaring reagents are liquids laboratory the benefits must be substantial to offset the cost
with possibly the right balance of reactivity towards organics, and trouble associated with additional, often demanding
polymerization and hydrolysis. To date there is no control over processing steps. Improved performance relative to the parent
the pillar distribution and size as the intercalated swelling zeolite may be also treated as evidence that the attempted
substance seems to determine final interlayer porosity. These modification has been indeed successful. This may be
are clearly variables that may require fundamental studies. exemplified by MWW, which itself is a highly active zeolite,

Table 2 Comparison of catalytic performance of different zeolites in C4 alkylation

Stability/g alkylate
Catalyst SiO2/Al2O3 T/1C Yield (wt/wt) C8 (wt%) Me3C5/Me2C6 Octane # RON/MON per g catalyst
MCM-22, MCM-49 o 20 150 — — — — —
MCM-36 430 150 2.1 53 2.4 91–93 23
Zeolite beta 24–30 90 2.0 69 2.2 91–93 12.5
Faujasite, EMT 10–12 80 1.3–2.0 72–76 4.1–4.2 91–97 2.1–44.8
HF n.a. 32 2.0 90 7.6 94–97 100
H2SO4 n.a. 7 2.0 81 6.4 94–96 8.7

This journal is c The Royal Society of Chemistry 2011 Catal. Sci. Technol., 2011, 1, 43–53 49
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thus if attempted modification fails the product is still likely to BEA and MWW for bulky substrates.61 When small substrates
exhibit high activity. were used similar conversions were achieved evidencing the
The evidence of catalytic enhancement upon pillaring of a similar role of acid sites in all materials. Steric exclusion of
zeolite was provided originally by MCM-36.56,57 It must be bulkier substrates, not accessing zeolite channels, made ITQ-2
appreciated that in its original form it contains roughly 50% favourable for these reactions. The yield of acetalization
by weight of amorphous silica, which is inactive and in many of 2-acetonaphthalene with propylene glycol increased in
processes, such as cracking, MCM-36 performance may the order BEA (5%) o MWW (20%) o ITQ-2 (63%)61
appear like ‘diluted’ MCM-22. However, in some processes (Scheme 1)
the superiority of MCM-36 was without any doubt. In the The literature reports about catalytic activity of MCM-56
report by Schweitzer and van den Oosterkamp56 the published paint a somewhat inconsistent picture. Juttu and Lobo found
patent data were compiled to compare activity of several their preparation to be largely inactive, which they attributed
zeolites in olefin alkylation of isobutane, which is an important to coiling of the sheets observed in micrographs.62 A comparison
industrial process currently practised in the refineries with HF between ITQ-2 and MCM-56 in large molecules conversion
and sulfuric acid as catalysts. Zeolites are in general inferior to was reported to favour the former material.45 As mentioned
liquid acid catalysts in this process but MCM-36 showed good above, MCM-56 appeared superior to MWW (MCM-22 and
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performance in particular with regard to resistance to MCM-49) in liquid phase alkylation, which can be interpreted
deactivation as shown in Table 2. In contrast, MCM-22 as advantage because of disordered/delaminated nature. The
activity was poor providing low yields and product quality. alkylation reactions studied in a gas phase led to the conclusion
Evidently the expanded interlayer space offered advantages that the reactions proceed exclusively on the external surface
compensating the acid site dilution (less active zeolite and of tiny MWW sheet crystals.63,64 This supports the superior
presence of amorphous silica pillars). The benefits of more catalytic activity of MCM-56, as this 2D zeolite exhibits much
open structure were revealed in a liquid phase ethylbenzene larger external surface. One must factor in the intermediate
synthesis by MCM-56.58 The monolayer MCM-56 showed nature of MCM-56 during synthesis, which may cause isolation
higher activity than the conventional 3D zeolites with of product, either too early or too late and consequently not
analogous framework, MCM-22 and MCM-49. having the optimal performance.
m-Xylene transformation at 350 1C has been developed to Comparison of ITQ-2 and MWW modified with Mo was
estimate the activity and selectivity of the three pore systems in carried out by Martinez and co-workers65 for methane
MCM-22 materials (sinusoidal channels, supercages and dehydroaromatization. ITQ-2 produced more naphthalene
external cups).59 Compared with regular MCM-22, pillaring and less benzene than MWW. The selectivity to benzene was
caused a great change in the distribution of the activity: only substantially improved by surface dealumination of the ITQ-2
approximately 15% of m-xylene transformation occurred in zeolite with simultaneous decrease in naphthalene formation.
the 10-ring intralayer pores in MCM-36 vs. more than 70% in Molecular dynamics simulation and treatment of the external
the parent MCM-22 sample. The rest, i.e. 85% of the activity surface evidenced the primary formation of naphthalene on
of MCM-36 (30% in MCM-22) is attributed to surface the active sites located at the external surface of ITQ-2.65
pockets, which may be accessible to larger molecules. Recently, Lima et al. reported on the preparation of
Maheshwari et al.60 reported that a milder swelling and delaminated zeolite derived from the layered material
pillaring process prevents destruction of the material and Nu-6(1).66 This delaminated catalyst exhibited conversion of
improved retention of zeolitic layers. As a result, higher about 80–85% in the liquid phase cyclodehydration of xylose
conversions of MCM-36 prepared at room temperature to furfural with moderate furfural yields.
compared with those of high temperature treatment were Relatively flat external surface of delaminated materials
achieved in vacuum gas–oil cracking and transformations of offers nice opportunity to attached organometallic complexes.
aromatics. ITQ-2 and ITQ-6 were studied also in Heck and Suzuki
ITQ-2 prepared from MWW lamellar precursor and having coupling reactions. In this case, Schiff base 2-tert-butyl-
surface areas larger than 700 m2 g1, showed superiority over 4-methyl-6{(E)-[(2S)-1-(1-arylmethyl)pyrrolidinyl] imino}-
MWW and MCM-36 in vacuum oil cracking. ITQ-2 exhibited methylphenol (aryl = phenyl, 1-naphthyl, 2-naphthyl) were
higher conversion and yield of gasoline than other catalysts used as anchoring ligands. After addition of Pd acetate high
and similar yield of diesel as MCM-36. ITQ-2 is also highly activity was achieved with recyclability and no leaching.67
active in reaction leading to the preparation of fine chemicals. Continuing this research, group of Corma immobilized
In particular, ITQ-2 was superior for dimethylacetals and mononuclear asymmetrical N-heterocyclic carbene-gold
tetrahydropyranylation of alcohols and phenols over zeolites 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
Scheme 1 Reaction scheme of the formation of 2-methyl-2-naphthyl- reaction proceeded at the presence of methylalumoxane as
4-methyl-1,3-dioxolane. co-catalyst.

50 Catal. Sci. Technol., 2011, 1, 43–53 This journal is c The Royal Society of Chemistry 2011
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Catalytic investigations of delaminated materials were 7. Summary and challenges


extended to Ti-containing catalysts.70 Corma et al. demonstrated
that Ti-ITQ-6 is highly active in hexene and norbornene Up-to-date, 10 frameworks have been recognized as having a
epoxidation and this catalyst showed higher activity than layered precursor but not all among them have been prepared by
Ti-FER or Ti-BEA. High stability of the conversion is due both the direct (3D assembly) and indirect (layered precursor)
to exclusive tetrahedral coordination of Ti in the silica matrix, synthesis pathway. More layered precursors are expected based
which was maintained even after the reaction.70 High activity on the fact that some long well-known conventional frameworks
of delaminated Ti-zeolites was confirmed for cyclooctene and have been found only recently to have a lamellar form.
cyclododecene by group of Tatsumi.71 Zeolite MWW with Particularly encouraging is the case of MFI because of its 3D
titanium demonstrated exceptional activity as an oxidation pore system. One may wonder if structures with isotropic
catalyst and has been extensively studied since.72–74 The distribution of density, i.e. the same in 3D, are also capable of
corresponding lamellar precursor form became attractive for showing layered precursors but we cannot point to a specific
modifications, previously discussed and implemented in principle that may rule out lamellar forms for most, possibly all
practice, like delaminated and pillared forms. In fact, the first frameworks, as hypothesized earlier.23 The recent MFI case is
example of the precursor stabilized in the expanded form, now also remarkable as apparently the first one where template was
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designated IEZ-MWW, was obtained in the Ti-MWW system designed specifically for the purpose. In general, new precursors
and designated Ti-YNU-1.22 Its crystal structure was determined have been obtained accidentally thus availability of rational
by Rietveld refinement.22 This material showed enhanced approaches is needed as it could facilitate further progress and
activity compared with other titanosilicates and attributed directed expansion. In short, better understanding of factors
by the authors to ‘formation of twelve-rings. . ., which results affecting pathway selection for the framework or layer assembly
in increased steric accessibility. . .’. Subsequently, attempts would be very helpful. As the lamellar MFI provides layers with
were made to swell Ti-MWW to synthesize delaminated and 10-ring channels through the layer it might be desirable to obtain
pillared derivatives. The former was reported to be superior to layers with bigger channels like 12-ring and higher. This implies
TS-1, Ti-Beta, conventional 3D Ti-MWW and Ti-MCM-41 in that precursors of zeolites like FAU, EMT or BEA would be
the epoxidation of a wide range of bulky alkenes with highly valuable.
hydrogen peroxide.75 Ti-MCM-36 synthesized by standard Simultaneously, the area expands in terms of new layered
procedure was tested for 1-hexene and propylene epoxidation architectures demonstrated. Here MCM-22 shows most
reactions using H2O2 as an oxidant and reported superior diversity with 6 different types of layer assemblies, while the
performance of Ti-MCM-36 over Ti-MCM-22 or TS-1.76 Both other frameworks are being gradually modeled on the
reports provided XRD patterns of the final catalysts but known MWW materials. Aside from ‘standard’ layered
without analysis to verify layer packing. precursor forms, MWW afforded rather unexpected remarkable
Superior catalytic behaviour of delaminated and pillar materials spontaneously (MCM-56) or by post-synthesis
zeolites in some acid and oxidation reactions is usually modification (IZE-MWW). This suggests that additional
attributed to high surface areas of these catalysts and easy structure types are possible and should be anticipated with
accessibility of the active sites on the external surface. Surface enough effort and ingenuity. As the number of possibilities is
areas of external surface are at the range of 700–900 cm2 g1 increasing (different frameworks and layer packings) the
and are comparable with surface areas of mesoporous attempts may become more selective with elements of design
molecular sieves. Recent results of Gil et al. showed the and focus on most promising precursors. It is easy to visualize
invariance and homogeneity of the concentration of Brønsted ordered pillared materials with controlled pillar population
sites on the external surface for the series of MCM-22 and and density, which would enable tailoring of large pore size of
MCM-49 with different Si/Al ratios.77 zeolitic structures.
Combination of inorganic (zeolitic) layers with organic In contrast to the framework rigidity and immutability, the
pillars represents another interesting approach to prepare lamellar forms offer the first and basically open-ended
active catalysts. Kuroda et al. showed that layered octosilicate opportunity for post-synthesis modifications. The structural
can be treated with 1,4-bis(trichloro- and dichloromethyl-silyl) aspect has been already discussed in the paragraphs throughout
benzenes to prepare microporous inorganic–organic hybrids.78 this narrative. There is of course the option to use additional
They subsequently hydrolyzed the chlorosilane moieties and compositions, e.g. for pillars or other layer spacers, or just as
the resultant silanols were close enough to enable condensation deposits on the surface to modify properties. Delaminated
into a Si–O–Si interlayer bridge. Very recently, a novel layered materials may be made into mixtures with different layer
zeolitic organic–inorganic material (MWW-BTEB) has been topologies, as a fundamental option, but it may also turn
reported by group of Corma79 combining intercalation and out to offer practical benefits.
stabilization of arylic silsesquioxane molecules between inorganic Another area of development may be the synthesis in terms
zeolitic MWW layers. 1,4-Bis(triethoxysilyl)benzene (BTEB) of direct preparation without pre-swelling or at least without
was used as organic linker being aminated after the synthesis. separation of intermediates of modified structures. Typically
The reported approach led to the of bifunctional acid–base the modifications require several step procedures, which
catalysts exhibiting the acid sites of zeolitic nature combined increases cost offsetting potential benefits offered by the more
with basic sites of the organic structure. This bifunctional open structures. The only example to date is MCM-56, as the
catalyst was studied in a two-step cascade reaction that of delaminated zeolite obtained in one step, suggesting other may
benzaldehyde dimethylacetal into benzylidene malononitrile.79 be possible, too.

This journal is c The Royal Society of Chemistry 2011 Catal. Sci. Technol., 2011, 1, 43–53 51
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For now we know very little about the factors deciding with cost of large-scale production shall be targeted for
whether the structure will propagate directly in 3D structure or industrial application.
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. Acknowledgements
It was proposed19 that aluminium may play a significant role
J.Č. thanks the Academy of Sciences of the Czech Republic
in this process but it is not well understood at this time.
(KAN100400701) and the Grant Agency of the Czech
Catalytic examples are rather broad covering area of
Republic (104/09/0561 and 203/08/0604).
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
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