Hierarchical MWW Zeolites by Soft and

Hard Template Routes

Anderson Joel Schwanke and Sibele Pergher

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Hierarchical Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
MCM-22 Zeolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Soft Templating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Soft Templates for Post-synthetic Modication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Soft Templates for Direct Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Dual Templating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Hard Templating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Conclusions and Further Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Abstract
This chapter will discuss the exciting area of nanomaterial engineering that
focuses on obtaining porous solids with improved efciency in catalysis. Lamel-
lar zeolites, also called two-dimensional zeolites, with MWW topologies are
potential candidates to substitute the commercial zeolitic catalysts produced
thus far. Advances to obtain MWW zeolites with hierarchical porous structures
by soft and hard templating approaches will be presented. The hierarchical
concept is based on the generation of mesoporous regions combined with the
microporosity of zeolites. The aim is to alleviate diffusional limitations encoun-
tered by large molecules (reactants, intermediates, and products) that cannot
access the microporous channels (<2 nm) of the zeolites, which decrease their
catalytic activities. The details and preparation procedures to obtain hierarchical
MWW zeolites by soft and hard templates as well as the chemistry associated

A.J. Schwanke (*) S. Pergher

Laboratrio de Peneiras Moleculares (LABPEMOL), Universidade Federal do Rio
Grande do Norte UFRN, Natal, RN, Brazil
e-mail: anderson-js@live.com; sibelepergher@gmail.com

# Springer International Publishing AG 2018 1

L.M.T. Martnez et al. (eds.), Handbook of Ecomaterials,
https://doi.org/10.1007/978-3-319-48281-1_89-1
2 A.J. Schwanke and S. Pergher

with the interactions between templates and the zeolite structures will be
described.

Introduction

Zeolites are microporous crystalline inorganic solids composed of tetrahedral TO4

(T = Si, Al, P, Ge, Ga, etc.) units that form well-dened regular pore systems with
molecular dimensions up to 2 nm. These materials are a special class of molecular
sieves with high surface area used for a wide range of applications in adsorption,
separation, and catalysis [13]. In addition, applications for zeolites have been
explored in new elds, such as medical [4], biotechnology [5], luminescence [6]
cosmetics [7], and food industry elds [8]. However, zeolite-based aluminosilicates
have strong acid centers provided by aluminum in the structure and play key roles as
heterogeneous catalysts for hydrocarbon conversions (cracking, isomerization,
alkylation, methanol-to-olen and methanol-to-gasoline conversion, biomass
upgrading, and others [1, 9]). The use of zeolites as catalysts is environmentally
friendly and offers economic advantages, such as lower energy requirements, recov-
ery and recycling, reduced corrosion, improved selectivity, and high activity.
In contrast, the microporous channels of zeolites impose considerable restrictions
on the access of reactants and products that have molecular dimensions larger than
2 nm, limiting the reactions only on their external surface. Currently, several efforts
have converged to develop zeolitic materials with facilitated diffusion of reactants
and products. These efforts can be divided into three strategies:

1. The synthesis of zeolites with extra-large pores (greater than 12 tetrahedral units,
12 MR) up to 2 nm. The formation of these zeolites is based on the use of
phosphates or germanosilicates as inorganic sources and bulky organic special
templates as structural directing agents (SDAs). This strategy involves the con-
sideration that most commercial zeolites, such as beta, ZSM-5, mordenite,
ferrierite, and zeolites X and Y, have maximum pore sizes of 0.74 nm [10].
However, the synthesis of SDAs combined with the stability of the formed
products poses difculties that need to be overcome to be industrially relevant
[11].
2. The preparation of zeolites in the form of nanoparticles (1100 nm), also called
nanosized zeolites, and the decrease of traditional micrometer-sized particles of
zeolitic crystals to the nanoscale increase the external surface and provide the
rapid diffusion of reactants and products. However, separating nanosized zeolites
from their reaction mixtures is difcult, which challenges their large-scale
implementation.
3. Obtaining hierarchical porosity (mesopores and/or macropores) combined with
the microporosity of the zeolite using soft and hard templating approaches.

The soft templating strategies comprise the use of surfactants [12, 13] and
mesoscale cationic polymers [14]. Hard templating involves the use of rigid solids
Hierarchical MWW Zeolites by Soft and Hard Template Routes 3

with or without porosity, such as carbon particles (spheres, carbon nanotubes, and
carbon bers) [1517], polymers (polystyrene and polyurethane) [18, 19], biological
materials (starch and bacteria) [20, 21], carbonized rice husk [22], and inorganic
sources (diatomite, mesoporous silica, and CaCO3) [2225]. The focus of these
approaches is on zeolites with faujasite (FAU) (X and Y) and Mobil Five (MFI)
(ZSM-5 and silicalite-1) topologies that are the most valuable in catalysis.
This chapter will cover another unique zeolitic framework topology that has
attracted much attention. This includes two-dimensional zeolites with an MWW
topology, including MCM-22. The formation of this zeolite is preceded by a two-
dimensional lamellar zeolitic precursor (LZP), allowing modication to create
highly designed porous structures with controlled procedures of swelling,
desilication, delamination, and pillaring [2628].

Hierarchical Zeolites

In the study of materials, for a material to be considered hierarchical, it must have

more than one scale length, and each structural element must have a distinct but
complementary function. Within the class of porous materials, the denition of
hierarchy is often used for systems possessing a certain number of pores with
different distributions, which can be bi- or multimodal, regardless of whether two
or more types of pores are interconnected. However, according to the previously
mentioned denition of hierarchy, each structural element (the pores in this case)
must have a different but complementary function.
Hierarchical porous materials are classied as Type I porous systems, in which
each pore level (larger) is divided into several species of smaller pores. Type II
systems consist of interconnected pores of different sizes, where the larger pores
intersect the system of smaller pores, branching them to create a continuous system
of large pores. In both cases, the main objective of hierarchical systems is to provide
rapid and widespread distribution by subdivision.
Zeolites are crystalline materials with channels and cavities in the microporous
range (02 nm). These materials are versatile solids that act as molecular sieves,
adsorbents, ionic separators, and solid acids. Because of these properties, zeolites are
extensively used for environmental remediation and energy efciency. In catalysis,
zeolites represent 40% of the solid catalysts used in the chemical industry [1]. In the
petrochemical industry, zeolite Y is used in FCC (uid catalytic cracking) plants to
produce gasoline with a higher octane rating and gases (olens) with more economic
value [1]. The main characteristics of the zeolites are their well-dened microporous
channels with shape selectivity. This pore size of <2 nm not only allows the access
of small molecules with high technological interest but also excludes bulk mole-
cules, which cannot access the active sites located in the microporous channels,
imposing diffusion limitations for reactants, intermediates, and products.
In micropores, congurational diffusion prevails because of the tight t of
molecules and the pore size. This diffusion regime is typical in solids and is
characterized by low diffusion coefcients, which can be up to 23 orders of
4 A.J. Schwanke and S. Pergher

magnitude lower than those observed in Knudsen (mesopores) and molecular

(macropores) regimes. The diffusion in micropores considerably reduces the trans-
port of different reactants to the active sites as well as decreases the transport of
reactants to favor the conversion of these molecules into undesirable by-products
and coke precursors [29].
Many efforts have been made to generate materials with larger porosity and that
combine the unique characteristics of zeolites, such as cation exchange capacity,
hydrothermal stability, and acidity. Some of these efforts led to the discovery of
ordered mesoporous silica, known as the M41S family (MCM-41, MCM-48, and
MCM-50) and SBA-15 [3032]. These materials are based on supramolecular arrays
of surfactants with controllable pore sizes depending on the size of the surfactants
used. For MCM-41 and SBA-15, the pores can be controlled to sizes of 210 and
530 nm, respectively. These discoveries between 1992 and 1995 represent mile-
stones in the synthesis of new porous materials. Therefore, successive studies to
understand the assembly and interactions between surfactants and inorganic species
as well as their mechanisms of formation represent a large part of the research history
of hierarchical zeolites [3336].
Several attempts have been made to endow ordered mesoporous silica (especially,
MCM-41 and SBA-15) with the same characteristics as zeolites (especially, FCC),
such as hydrothermal stability and acidity [37]. In these efforts, post-synthesis
hydrothermal procedures and post-synthesis incorporation of aluminum were stud-
ied [38, 39]. Unfortunately, from the standpoint of stability, their formed structures
of amorphous walls were less stable than zeolites, and MCM-41 prepared with
aluminum as an acid catalyst exhibited catalytic behavior similar to silica-alumina
mixtures with moderate Brnsted acid sites [40].
Thus, for hierarchical zeolites, there is a need to create additional pore systems in
zeolitic materials to integrate them into hierarchical models to facilitate the diffusion
of molecules to the active sites. This hierarchical connection may be inter-/
intracrystalline or even a combination of the two.

MCM-22 Zeolite

The three-dimensional zeolite MCM-22 has two independent multidimensional pore

systems. One of these pore systems is accessed by 10 MR windows with sinusoidal
(0.40
0.50 nm) and bidirectional (0.40
0.55 nm) channels. The other pore
system consists of supercavities with a free internal diameter of 0.71 nm (12 MR)
and an internal height of 1.82 nm interconnected through double 6-membered rings
(D6 MR), which are also accessed by both sides of the bidirectional 10 MR channels
(Fig. 1a).
Zeolite MCM-22 has a two-dimensional lamellar zeolitic precursor (LZP) that
precedes its calcination. This LZP has an organic template (HMI, hexa-
methyleneimine) conned in its cavity, and each individual MWW lamella has a
thickness of 2.5 nm [41]. After calcination, the HMI molecules are removed, and the
silanol groups between lamellae are condensed to form the three-dimensional
Hierarchical MWW Zeolites by Soft and Hard Template Routes 5

Fig. 1 The structures (a) and XRD patterns (b) of the two-dimensional lamellar zeolitic precursor
(LZP) and three-dimensional MCM-22 zeolite. Scanning electron microscopy image of zeolite
MCM-22 (c)

structure of the MCM-22 zeolite. The product resulting from the direct crystalliza-
tion of the MWW structure (without passing through the LZP precursor) is called
MCM-49 [42].
6 A.J. Schwanke and S. Pergher

The X-ray diffraction (XRD) patterns of the LZP and MCM-22 zeolite are shown
in Fig.1b. The LZP 2D-(P)MCM-22 shows a peak in the 2 range between 3.3 and
6.6 corresponding to the (001) and (002) planes of the MWW zeolitic lamellar
stacking. Intralamellar diffraction peaks are observed at 2 = 7.1 , 25.1 , and 26.2 ,
which are assigned to the (100), (220), and (310) planes, respectively. The
interlamellar peaks at 2 = 8 and 10 are assigned to the (101) and (102) planes.
The XRD pattern of the three-dimensional zeolite MCM-22 did not show peaks for
the (001) and (002) planes due to the loss of the lamellar structure after calcination.
Regarding the location of aluminum in the structure of MCM-22, an infrared
spectroscopy study with adsorbed pyridine reported that, for samples with Si/
Al = 10, 14, and 30, most sites (5070%) were located in the supercavities. The
other sites were located in the sinusoidal channels (2030%) or connected to the
hexagonal prisms between the supercavities (10% for Si/Al = 10 and 14 and 20% for
Si/Al = 30) [43].

Soft Templating

The soft templating strategies for the preparation of hierarchical MWW-type zeolites
use surfactants. The surfactants are often quaternary ammonium ions intercalated
between individual MWW lamellae of the LZP used in a post-synthetic procedure
called swelling. Another class of surfactants is the dual templates. The dual tem-
plates are added directly in the synthesis gel and act as bifunctional organic mole-
cules combining a head group as a SDA (to direct the formation of a specic zeolite
structure) and a long alkyl chain to avoid lamellae (to grow and order along c-axis
and create mesoporosity by the space generated after their removal). For conve-
nience, the soft templates are divided into soft templates for post-synthetic modi-
cation and soft templates for direct synthesis.

Soft Templates for Post-synthetic Modification

The chemistry associated with the swelling of the LZP using soft templates for post-
synthetic modication is schematized in Fig. 3 and is based on the following: (1) a
high pH, where silanol groups (Si-OH) are deprotonated (Si-O). (2) The
deprotonated silanol groups repel each other and attract cations (in this case,
positively charged surfactant molecules). (3) The deprotonation also breaks the
hydrogen bonds that keep the lamellae interacting [44]. There is an additional factor
present in these three steps: the presence of other cations that could compete and
interfere with the swelling procedure.
The XRD patterns of the swelling treatment with surfactants are shown in Fig. 2.
The swelling procedure resulted in overlapping of the (101) and (102) diffraction
bands, yielding only a broad peak located between 2 = 8 10 , indicating the
partial loss of the vertically aligned order in the stacking direction, i.e., along the c-
axis [45]. In addition, the (001) diffraction band from the precursor at 2 = 3.3
Hierarchical MWW Zeolites by Soft and Hard Template Routes 7

Fig. 2 General scheme of the chemistry associated with the swelling of the MWW-type LZP and
the increase of basal spacing monitored by XRD

(basal spacing of 2.7 nm) was shifted to a lower angle at 2 = 1.9 (basal spacing of
4.5 nm) in the swollen sample. The basal spacing of 4.5 nm, subtracted from the
thickness of an individual MWW lamella (2.5 nm), indicates an interlamellar region
of 2 nm that is occupied by surfactants.
The correlation between the XRD and thermogravimetric results (to quantify the
interacting organics) could be used to predict the type of accommodation of the
surfactants between the interlamellar regions considering the molecular size of the
surfactants [46].
The swollen precursor opens many possibilities to create delaminated and pillared
hierarchical zeolites. The rst example of an MWW-type zeolite with a hierarchical
8 A.J. Schwanke and S. Pergher

Fig. 3 Scheme of the post-synthetic procedures of swelling the MWW-type precursor with
surfactants and pillaring and delaminating to create hierarchical porosity

structure is called MCM-36 (Mobil Composition of Matter no. 36) and was obtained
by a pillaring procedure [28, 47]. For the formation of pillars, the swollen LZP is
added with an appropriate oxide precursor, such as an alkoxide source, i.e., TEOS
(tetraethyl orthosilicate), that partially lls the interlamellar region. The organic
material between the lamellae is removed by calcination, and simultaneously, solid
oxides are formed from the alkoxide maintaining the lamellae separation and
creating interlamellar mesoporosity (Fig. 3). MCM-36 possesses mesopores with
sizes between 2 and 4 nm and a surface area of 896 m2 g1. The increase of the open
structure of MCM-36 was evaluated by the adsorption of large hydrocarbon mole-
cules, such as 1,3,5-trimethylbenze, displaying a value of 0.040 mg/g, while MCM-
22 showed negligible adsorption. The pillaring of two-dimensional LZP led to the
formation of other lamellar zeolitic pillared materials, such as ITQ-36 (FER) [48],
MCM-39 (NSI) [49], and IPC-1PI [50].
Another successful preparation of a hierarchical MWW material was obtained
after treatment of the swollen precursor and is called ITQ-2 (Insttuto de Tecnologa
Qumica no. 2). ITQ-2 was the rst delaminated zeolite and was obtained by the
treatment of the swollen precursor under sonication with an acid solution and a
further calcination step [27]. This treatment creates interlamellar mesoporosity
similar to a house of cards due to an edge-to-face orientation of MWW lamellae
(Fig. 3). The prepared material possessed a surface area exceeding 700 m2 g1,
allowing bulk molecules to access the active sites and favoring the diffusion of
reactants and products and increasing their lifetime. ITQ-2 showed superior catalytic
activity compared to the MCM-22 zeolite for the cracking of bulky molecules, such
as 1,3-diisopropylbenzene and vacuum gas oil in gasoline and diesel. The delami-
nation procedure established a novel route for the preparation of hierarchical
Hierarchical MWW Zeolites by Soft and Hard Template Routes 9

zeolites, which can be applied to other lamellar zeolites, such as ITQ-6 (FER) [51]
and ITQ-18 (NSI) [52].
Both delaminated ITQ-2 and pillared MCM-36 were obtained from a swollen
precursor intermediate using hexadecyltrimethylammonium cations as soft tem-
plates. The swelling procedure of the LZPs is typically the most important step for
the modication of lamellar zeolites. For the LPZ of MCM-22, a high pH is required
to separate the lamellae, which are bound by strong interactions (hydrogen bonds).
The MWW structure has a single pyramidal silicon atom at the T6 (Fig. 1) position
on the surface, which is an ideal center for this type of bonding. In addition,
interactions of the silanol groups between lamellae with possible participation by
HMI are involved [44]. After calcination, these atoms are bridged with oxygen (Si-
O-Si) between the lamellae.
Different swelling treatments were reported using hydroxide surfactants, such as
CTAOH (hexadecyltrimethylammonium hydroxide) and mixtures of CTAB (hexa-
decyltrimethylammonium bromide) with a hydroxide source (NaOH, TMAOH,
TEAOH, or TPAOH) at 95  C [44]. In these cases, swelling with mixtures of
CTAB and TPAOH showed similar results compared to swelling with CTAOH.
The hypothesis was based on the size of the TPA cation (0.45 nm), which is larger
than others and prevents it from entering the interlamellar region, leaving CTAB as
the only viable alternative. This hypothesis was based on the opening of the
interlamellar region (0.42 nm), which is narrower than the size of the TPA cation.
However, a later study by the same authors contested this hypothesis of size
exclusion by showing that it is possible to obtain swollen MWW-type LZPs
(MCM-22 and MCM-56) with CTAB and TMAOH solutions [53].
The initial preparation for the swelling of the MWW-type LZP is traditionally
carried out with a surfactant and a hydroxide source (TPAOH) at high pH (~1314)
and temperatures between 95 and 100  C for 3 days [47]. Consequently, the
dissolution of silica and the possible formation of undesired M41S-like mesophases
may occur once the reactants (silica, surfactant, and basic media) and temperature are
similar to the syntheses of ordered mesoporous silica.
Years later, a procedure for the swelling of MWW precursors was carried out
using milder conditions at room temperature over 24 h [26]. This swelling at room
temperature followed by successive washing cycles of the precursor produced
swollen precursors with a high degree of order with preserved lamellar structures.
The pillared material possessed strong acid sites, which were catalytically conrmed
in cracking, isomerization, and alkylation reactions [54]. On the other hand, efforts
to use the swollen LZP at room temperature followed by the delamination procedure
(using sonication and acidication) demonstrated that swollen LZP is not organized
in a typical house of cards orientation of lamellae as for ITQ-2 and that the
swelling is reversible, as the lamellae restore the stacking structure of the LZP.
A recent study showed that the swelling procedure of the MWW-type LZP using
surfactants with different sizes (C18TA, C16TA, and C12TA) combined with treat-
ment under room temperature or 80  C generated particular arrangements of surfac-
tants in the interlamellar region that resulted in pillared materials with different pore
architectures, surface areas, and acidities. These materials were active for the
10 A.J. Schwanke and S. Pergher

catalytic dehydration of fructose to 5-hydroxymethylfurfural (5-HMF), which is a

valuable platform derived from biomass used for the production of fuels, polymers
and ne chemicals, and pharmaceuticals [46].
To obtain a greener and economical procedure for the swelling of the MWW
precursor, the same authors demonstrated reuse of the recyclable swelling solution at
room temperature. After the swelling step, the solution was separated from the solid
and reused three times. Furthermore, no adjustments of pH or reactant supplemen-
tation were required. The pillared material showed a surface area of 777 m2 g1,
mesopore sizes of 24 nm, and a basal spacing of 4.5 nm [55].
Another interesting strategy for a swelling procedure was reported based on the
weakening of the interlamellar interactions [56]. The LZP of MCM-56 (an MWW
zeolite with partially disorganized lamellae) obtained by direct synthesis with a high
amount of aluminum (Si/Al = 11) was used. As the amount of aluminum (more than
5 or 6 Al atoms per unit cell) increased, aluminum can no longer be located in the
structure of the lamella and instead populate its surface, in particular, the T6
pyramidal sites (Fig. 3). Consequently, the substitution of the silanol groups (Si-
OH by Al-OH) generates a negative charge deciency (Al3+) and requires the
presence of charge compensating cations for neutralization (Al-OH-Na+). With
this weakening, the lamellae are more susceptible to swelling. The swelling step was
carried out at room temperature with mixtures of CTACl and NaOH (which are
cheaper than TPA, TEA, and TMA hydroxides), which was previously reported as
not possible.
The insertion of silica pillars created interlamellar mesoporosity but also blocked
a portion of the active sites present on the surface of the MWW zeolite leading to a
decreased catalytic activity [57]. An alternative to compensate this blockage is the
insertion of active species in the pillars, which act as acid-basic or redox sites
combined with the acidity of the zeolitic structure and generate accessibility to the
interlamellar mesoporosity regions. MCM-36 materials with mixed pillars of BaO-
Al2O3, Al2O3-SiO2, MgO-Al2O3-SiO2, and BaO-Al2O3-SiO2 were reported showing
mesoporous sizes between 2 and 4 nm, and the MgO-Al2O3-MCM-36 material
showed higher N2 yield (77%) than MCM-22 zeolite (22%) for the reduction of
NOx emissions formed during the regeneration of coked cracking catalysts in FCC
units [58, 59]. MCM-36 with Si/Ti as mixed pillars was reported and applied as a
catalyst for cyclohexene epoxidation. However, adjustments to the Si/Ti ratio must
be done to avoid the formation of an octahedral titanium extraframework [60].
Not only inorganic and rigid pillars can be formed but also organic pillars can be
formed between interlamellar regions to generate multifunctional organic-inorganic
catalytic materials with hierarchical structures. This strategy uses the stabilization of
aryl silsesquioxane molecules between the MWW lamellae [61]. The swollen MWW
precursor was used as an intermediate and was added with a solution of 1,4-bis
(triethoxysilyl)benzene (BTEB) that acted as a pillaring agent. To remove the CTAB
used for the swelling, an acid extraction process was performed (Fig. 4a). An
additional step was required to incorporate amino groups onto the bridged benzene
groups in the interlayer space. The XRD pattern of the nal material (MWW-BTEB-
NH2) showed expanded lamellae with a basal spacing of 4.1 nm, a surface area of
Hierarchical MWW Zeolites by Soft and Hard Template Routes 11

C
590
tion
cina MWW-P-CAL
Cali

id
Ac tion MWW-BTEB
CT c
MWW-P MA x tra
* BTEB
E

HMI
CTMA
Arylic groups
MWW-CTMA
MWW-CTMA-BTEB

Fig. 4 Scheme of the formation of multifunctional MWW-BTEB with organic pillars (a) and a
simulated model representing the pillars linked with the T6 pyramidal sites (Adapted with permis-
sion from Ref. [61]. Copyright 2010 American Chemical Society)

556 m2 g1, and mesopores formed by intercalation of the organic basic amino
groups incorporated on the aryl molecules (Fig. 4b).
The multifunctional performance of the catalyst was investigated with a cascade
reaction that requires acid and base sites. Consequently, the acid sites were provided
by the MWW lamellae, and the base sites were provided by the amino groups in the
aryl molecules forming the organic pillars. The reaction used was an acetal hydro-
lysis followed by a Knoevenagel condensation, where benzaldehyde dimethyl acetal
was hydrolyzed to produce benzaldehyde (by the acid sites), and after, benzaldehyde
reacted with malononitrile to give benzylidene malononitrile. The catalytic results
showed a product yield of 96% and selectivity of 99% after 7.2 h of reaction. If
MWW-BTEB reacted without the amino groups, a yield of only 11% and selectivity
12 A.J. Schwanke and S. Pergher

Fig. 5 Transmission electron micrographs of MCM-49 (a) and hierarchical MCM-49 zeolites after
2 h (b) and 22 h (c) of desilication treatment (Adapted from Ref. [62]. Copyright 2015 with
permission from Elsevier)

of 51% were obtained. In addition, the blank reaction was also performed with the
swollen precursor, showing that the Knoevenagel condensation does not occur.
All the abovementioned procedures make use of surfactants to generate MWW
swollen materials to create interlamellar mesopores (by pillaring or delamination).
Post-synthetic modication is capable of creating hierarchical MWW-type materials
with intralamellar mesopores using a procedure with a zeolite in a CTAB and NaOH
mixed solution, a specic temperature, and different times [62]. The role of CTAB
was attributed to form a protective lm adsorbed on the surface of MCM-49, while
the alkali media (OH) attacked regions with defects that are not completely
protected by CTAB molecules, removing fragments from the zeolitic structure
(Fig. 5). This removal created more uniform mesopores (24 nm) with an increasing
treatment time (0.52.0 h). In addition, CTAB played a key role in protecting the
zeolite from uncontrollable dissolution when the treatment time extended even up to
22 h, showing similar morphologies (see Fig. 5b,c). It is important to mention that
treatments with only NaOH solution easily cracked the lamellae into small crystals
and the integrity of MWW crystals was not maintained [63].
Hierarchical MWW Zeolites by Soft and Hard Template Routes 13

Hierarchical acidic MCM-49 showed improved catalytic activity for the alkyl-
ation reaction of benzene with ethylene compared to traditional acidic MCM-49. The
results showed similar initial catalytic activities for ethylene conversion of 63% and
60.8%, but different deactivation rates of 40% and 39.2% were observed within the
same time on stream. The low deactivation of hierarchical MCM-49 was attributed
to improved diffusion of the reactant and products of the intralamellar mesopores.

Soft Templates for Direct Synthesis

Recently, a novel material called ECNU-7 (East China Normal University no. 7) was
synthesized, and the swollen material with an MWW framework topology was
prepared with a zeolite seed and CTAB-assisted dissolution-recrystallization route
[64]. The authors demonstrated that the silicate fragments dissolved in the liquid
combined with 1,3-bis(cyclohexyl)imidazolium hydroxide as a SDA containing
MWW-type building units that acted as nutrients for the crystallization at 150  C
for 72 h, as shown in the scheme of Fig. 6a. The XRD results showed a basal spacing
of 5 nm, and TEM analysis (Fig. 6b) showed lamellae separated by distances of 1.9
and 1.8 nm for the swollen Al-ECNU-7P. The pillared product showed the same
basal spacing (5 nm) and a surface area of 701 m2 g1.
Another product obtained by the direct calcination of the swollen precursor (Al-
ECNU-7P) showed partially condensed and delaminated (Fig. 6c) lamellae and a
surface area of 512 m2 g1. The catalytic behaviors of the samples were evaluated
for the acylation of anisole with anhydride to obtain p-methoxyacetophenone ( p-
MAP) as the main product. The pillared sample showed a superior yield of 48.7%,
and the Al-ECNU-7 sample showed 37.1% yield, compared to 17.3% of the MCM-
22 zeolite. For the reaction of cracking 1,3,5-triisopropylbenzene (TIPB), Al-
ECNU-7 showed three times higher conversion than the traditional MCM-22
zeolite.

Dual Templating

The use of dual templates for the preparation of MWW-type materials was rst
reported in 2015 and is based on the formation of individual MWW-type lamella
using dual templating to form ITQ-2 by a direct synthesis (called DS-ITQ-2 (direct
synthesis ITQ-2)) [65]. In this approach, N-hexadecyl-N0 -methyl-DABCO (C16C1)
was used as a dual template, as shown in Fig. 7. DABCO has a similar structure to
the HMI structure used as a SDA in the MCM-22 synthesis, while the C16 tail
avoided zeolitic growth and order along the c-axis. The authors demonstrated that
the yield of the synthesis was 78% and approximately 70% of the material consisted
of mono- and bi-lamellae with an MWW structure. The surface area of DS-ITQ-2
was 545 m2 g1, and its microporous volume was higher than that of ITQ-2, which is
associated with the structural integrity of the material combined with the generated
interlamellar mesoporosity. The catalytic evaluation for the liquid-phase alkylation
 14

Fig. 6 Zeolite seed and CTAB-assisted dissolution-recrystallization route to obtain swollen Al-ECNU-7P, pillared Al-ECNU-7, and delaminated Al-ECNU-7
MWW-type materials (a). TEM micrographs of swollen (b) and delaminated (c) samples (The TEM micrographs were adapted from Ref. [64]. Copyright 2016
American Chemical Society)
A.J. Schwanke and S. Pergher
Hierarchical MWW Zeolites by Soft and Hard Template Routes 15

Fig. 7 Scheme of the direct synthesis procedure to obtain DS-ITQ-2

of benzene with propene showed that DS-ITQ-2 demonstrated activity comparable

to ITQ-2 with lower catalyst deactivation.
In the same year, another direct synthesis of a delaminated MWW zeolite, called
MIT-1 (Massachusetts Institute of Technology no. 1), was performed using a strat-
egy very similar to DS-ITQ-2 [66]. However, the dual template used was a mixture
of trimethyladamantylammonium hydroxide (TMAda+OH) and CTAB separated
by alkyl chain linkers with 4, 5, or 6 carbon atoms (see Fig. 8a). According to the
authors, the zeolite structure was directed by the Ada-OH head group, which is
surrounded by the cavities, whereas the region between the ammonium diquaternary
surfactants stabilized the pore mouth (Fig. 8b). After calcination, MIT-1 was formed,
showing MWW lamellae delaminated, as indicated by the micrographs in Fig. 8c,d.
The authors mentioned that the linker directly interfered with the crystallinity of the
product: with linkers with 4- and 6-carbon chains, the materials reached the highest
crystallinity in 14 and 22 days, respectively. With the linker with a 5-carbon chain,
30 days was required to obtain a crystalline product. MIT-1 possessed a surface area
exceeding 500 m2 g1, and its catalytic behavior was tested in the Friedel-Crafts
alkylation reaction of benzene with benzyl alcohol, showing a threefold increase in
catalytic activity compared to the MCM-22 and MCM-56 zeolites.

Hard Templating

The rst study using hard templates for the synthesis of MWW zeolites was reported
in 2010 [67]. In the procedure, carbon spheres with particle sizes of 48 m were
used directly in the synthesis gel, as shown in Fig. 9a. According to the authors, the
formation of nest-like hollow hierarchical MCM-22 microspheres (Fig. 9b) resulted
from a combination of conditions during the nucleation and crystallization, such as
the rotation of the autoclaves (to ensure a homogeneous dispersion of carbon
spheres) and the interactions between them and the MWW precursor. Infrared
spectroscopy analysis of the carbon spheres conrmed the presence of COH and
COOH groups that can strongly interact via hydrogen bonds with the OH, Si-O, Al-
O, and NH groups of the MWW precursor.
XRD patterns with similar crystallinities compared to traditional MCM-22 and
mesoporosity formed by the random orientation of crystal particles were observed.
 16

Fig. 8 Scheme of synthesis of MIT-1 (a) and the simulated conformation of Ada-4-16 on the surface of the MWW zeolite. Transmission (c) and scanning
electron micrographs of MIT-1 (Adapted from Ref. [66]. Published by Royal Society of Chemistry)
A.J. Schwanke and S. Pergher
 Hierarchical MWW Zeolites by Soft and Hard Template Routes

Fig. 9 Scheme of the preparation of nest-like hollow hierarchical MCM-22 microspheres using carbon spheres as hard templates (a) and a micrograph of a
formed hollow sphere after calcination (b) (The micrograph was reprinted with permission from Ref. [67]. Copyright 2010 American Chemical Society)
17
18 A.J. Schwanke and S. Pergher

Fig. 10 Scheme of the transformation of the amorphous mesoporous walls of SBA-15 into a
crystalline MWW zeolite by VTP assisted by lling the mesopores with carbon. The crystallization
without carbon resulted in a collapsed mesostructure (Adapted from Ref. [68]. Copyright 2011 with
permission from Elsevier)

The acidic form of the MCM-22 hollow spheres and the traditional MCM-22 were
impregnated with molybdenum and catalytically evaluated for methane
dehydroaromatization (MDA), which is a promising route for the direct conversion
of methane into high-value-added chemicals. The catalyst exhibited a high CH4
conversion and a higher yield of benzene (2530%) and catalyst lifetime than
traditional MCM-22. According to the authors, these results are associated with
the formation of intercrystalline mesopores, which improved the mass transport of
reactants to the active sites.
Silica has also been used as a hard template to obtain a MCM-22/SBA-15
composite. Figure 10 shows the strategy using mesoporous silica (SBA-15) as
hard template, which was based on the partial transformation of the amorphous
mesopore walls of SBA-15 into a crystalline MWW zeolite assisted by a vapor-
phase transformation (VPT) [68]. The authors noted that the carbonization step lled
the mesopores serving as the support of the structure and prevented its collapse. In
addition, carbon served as a diffusion controller of HMI to conduct nucleation on the
silica walls. Slow crystallization was also a key step to avoid the excess growth of
the zeolite and the collapse of the mesoporous structure.
The presence of micropores was conrmed by thermal-programmed desorption
(TPD) of benzene, which can trap inside the supercavities on the external surface of
the MCM-22 zeolite, and the acidity was conrmed by ammonia-TPD.

Conclusions and Further Outlook

Zeolites are versatile solids used for a wide range of applications in different elds.
As catalysts, zeolites play key roles to obtain products with high yields and selec-
tivities with lower required energy and recyclability. Many efforts have been targeted
Hierarchical MWW Zeolites by Soft and Hard Template Routes 19

in obtaining zeolites with hierarchical porous structures, which can increase their
efciency, especially when bulky molecules are involved that cannot access their
active sites. Two-dimensional zeolites with MWW structures offer great potential as
catalysts due to their hierarchical pore structures, such as delaminated, pillared, and
desilicated structures, obtained by soft and hard templating strategies. Many
advances have been made in the past few years to obtain MWW zeolites with
intercalated surfactants. Among them, DS-ITQ-2, MIT-1, and ECNU-7 are success-
ful examples of hierarchical materials obtained by direct synthesis, which represent
huge advances in the last 3 years. On the other hand, the study of hard templating
strategies to obtain hierarchical MWW zeolites still possesses many opportunities
for the use of rigid templates, such as carbon (spheres, bers, and nanotubes),
biological (starch and bacteria), and inorganic (silica, diatomites, and CaCO3)
sources. Many targets of these materials have been the processing of biomass
derivatives to generate high-value-added products and intermediates, which can
gradually replace compounds derived from fossil fuels. The search for materials
with structures containing hierarchical pores is a fascinating area, and the vast eld
of zeolite applications makes these materials highly valued.

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